[ CAS No. 13731-82-3 ] {[proInfo.proName]}

Name: 13731-82-3|2,5-Dibromoterephtalic acid|98%
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Quality Control of [ 13731-82-3 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 13731-82-3 ]

Product Details of [ 13731-82-3 ]

CAS No. :	13731-82-3	MDL No. :	MFCD00204593
Formula :	C₈H₄Br₂O₄	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	VUTICWRXMKBOSF-UHFFFAOYSA-N
M.W :	323.92	Pubchem ID :	83690
Synonyms :

Calculated chemistry of [ 13731-82-3 ]

Physicochemical Properties

Num. heavy atoms :	14
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.0
Num. rotatable bonds :	2
Num. H-bond acceptors :	4.0
Num. H-bond donors :	2.0
Molar Refractivity :	55.76
TPSA :	74.6 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.6 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.11
Log Po/w (XLOGP3) :	2.36
Log Po/w (WLOGP) :	2.61
Log Po/w (MLOGP) :	2.64
Log Po/w (SILICOS-IT) :	2.01
Consensus Log Po/w :	2.15

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	0.0
Bioavailability Score :	0.56

Water Solubility

Log S (ESOL) :	-3.52
Solubility :	0.0978 mg/ml ; 0.000302 mol/l
Class :	Soluble
Log S (Ali) :	-3.57
Solubility :	0.0878 mg/ml ; 0.000271 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-2.83
Solubility :	0.484 mg/ml ; 0.00149 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	0.0
Synthetic accessibility :	1.65

Safety of [ 13731-82-3 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 13731-82-3 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 13731-82-3 ]
Downstream synthetic route of [ 13731-82-3 ]

[ 13731-82-3 ] Synthesis Path-Upstream 1~12

1
[ 1074-24-4 ]
[ 13731-82-3 ]

Yield	Reaction Conditions	Operation in experiment
96%	With pyridine; potassium permanganate In water	The inventive diindenothiophene derivatives can be produced by any of the methods that are conventionally known to persons having ordinary skill in the art. For instance, the above-mentioned compound of formula (2) can be prepared by a method comprising the following steps:
84%	Stage #1: With acetic acid In water at 120 - 150℃; for 2 h; Stage #2: With oxygen In water at 180℃; for 4 - 10 h;	Example 1; This example illustrates the production of 2,5- dibromoterephthalic acid from 2 , 5-dibromo-l , 4- dimethylbenzene .In a stirred autoclave with internal cooling coil and reflux condenser, 2 , 5-dibromo-l , 4 -dimethylbenzene (372 mmol) was combined with a solution containing Co(OAc)₂-4H₂0 (2.5 mmol), Mn (OAc) ₂ .bul. 4H₂O (2.5 mmol), Zr(OAc)₄ (0.25 mmol), and NaBr (5 mmol) in 500 g of 97percent acetic acid. The mixture was stirred at a constant rate using a gas dispersing stirrer for better gas mixing and the mixture was heated to 150°C for 2 h (this stage is noted as "T-I" in Table 1) , followed by increasing the temperature to 180°C for 4 h (this stage is noted as "T-2" in Table 1) . While the reaction was heating, air was continuously blown through the system with 400 psig (2.76 MPa) back pressure. After reaction completion, the pressure was released and the reactor was allowed to cool to 50°C. The product was discharged, rinsing the reactor twice with 50 g acetic acid to collect further product. The white solid was collected via suction filtration, washed with water, and dried under vacuum to yield 31O g (84percent) of the product 2 , 5-dibromoterephthalic acid as a white solid with a purity of 99percent, as determined by ¹H NMR.; Examples 2-5; These examples illustrate the effect of varying the stages, times and temperatures on 2,5- dibromoterephthalic acid net yield and purity. Examples 2-5 were carried out using the procedure of Example 1 except as noted in Table 1. The product 2,5- dibromoterephthalic acid in each case was a white solid <n="17"/>with a purity of at least 99 molpercent
42%	With potassium permanganate In water; <i>tert</i>-butyl alcohol for 18 h; Reflux	Iodine (78 mg, 0.33 mmol) was added to p-xylene (6.13 mL, 50.0 mmol), the mixture was cooled to 0 °C, and bromine (5.20 mL, 101 mmol) was added dropwise over 10 min. The ice bath was removed and the reaction stirred at rt for 16 h in the absence of light. The reaction was quenched with 20percent aq. KOH and stirred for 15 min while the solution became colorless. The solid precipitate was filtered and rinsed 2 x with 100 mL of H₂O. The solids were recrystallized in ethanol to afford a white solid (9.19 g, 70percent). ¹H NMR (CDCl₃): δ 7.40 (s, 2H), 2.34 (s, 6H). 1,4–dibromo-2,5-dimethylbenzene (5.93 g, 22.5 mmol) and KMnO₄ (15.72 g, 99.5 mmol) were added to 80 mL of t-BuOH:H₂O (1:1). Celite (14 g) was added to the flask and the reaction was refluxed for 18 h. The reaction mixture was cooled to rt, filtered over celite and the filter was washed with hot H₂O (100mL) and EtOAc (50mL). The filtrate was then acidified to pH=1 with conc. HCl. The white suspension was then extracted 3x with 100 mL of EtOAc. The combined organic extracts were dried over MgSO₄ and excess solvent was removed under vacuum to obtain a white solid (3.06 g, 42percent) which was not purified further. ¹H NMR (DMSO-d6): δ 8.01 (s, 2H). 2,5–dibromoterephthalic acid (2.04 g, 6.30 mmol) dissolved in 35 mL of MeOH and refluxed for 30 min. Thionyl chloride (9.00 mL, 124 mmol) was then carefully added and the reaction was refluxed 12 hours. The reaction flask was cooled to room temperature, 50 mL of water was carefully added, and the reaction was extracted 3x with 75 mL of Et₂O. The combined organics were washed with 3 x with 50 mL of sat. NaHCO₃ and dried with MgSO₄. The solvent was removed under vacuum and the solids recrystallized in MeOH to yield a white crystalline solid (1.65g, 74percent), mp = 134-136 C (lit.³ mp 134-137 C). ¹H NMR (CDCl₃): δ 8.06 (s, 2H), 3.96 (s, 6H). The ¹H NMR matches the known spectrum.³

Reference： [1] Patent: US2010/168444, 2010, A1, . Location in patent: Page/Page column 4-8
[2] Bulletin of the Korean Chemical Society, 2011, vol. 32, # 5, p. 1781 - 1783
[3] Patent: WO2008/82501, 2008, A1, . Location in patent: Page/Page column 15-16
[4] Journal of the American Chemical Society, 2014, vol. 136, # 43, p. 15414 - 15421
[5] Chemical Communications, 2010, vol. 46, # 35, p. 6503 - 6505
[6] Journal of Fluorescence, 2016, vol. 26, # 4, p. 1295 - 1307
[7] Journal of Solution Chemistry, 2017, vol. 46, # 5, p. 1005 - 1023
[8] Crystal Growth and Design, 2016, vol. 16, # 7, p. 3993 - 4004
[9] Advanced Synthesis and Catalysis, 2018, vol. 360, # 8, p. 1590 - 1594
[10] Organic Letters, 2014, vol. 16, # 1, p. 106 - 109
[11] Tetrahedron, 2015, vol. 71, # 2, p. 283 - 292
[12] Journal of the American Chemical Society, 1993, vol. 115, # 11, p. 4935 - 4936
[13] Macromolecules, 2004, vol. 37, # 21, p. 7945 - 7954
[14] New Journal of Chemistry, 2006, vol. 30, # 5, p. 667 - 670
[15] Journal of Organic Chemistry USSR (English Translation), 1968, vol. 4, p. 1547 - 1550[16] Zhurnal Organicheskoi Khimii, 1968, vol. 4, p. 1609 - 1613
[17] Chemistry - A European Journal, 2001, vol. 7, # 23, p. 5118 - 5134
[18] Journal fuer Praktische Chemie (Leipzig), 1933, vol. <2> 138, p. 103,106
[19] Electrochimica Acta, 2011, vol. 56, # 16, p. 5616 - 5623
[20] Journal of Materials Chemistry C, 2015, vol. 3, # 16, p. 4086 - 4092
[21] Electrochemistry Communications, 2018, vol. 93, p. 71 - 75

2
[ 20871-01-6 ]
[ 13731-82-3 ]

Reference： [1] Journal of the American Chemical Society, 1994, vol. 116, # 26, p. 11723 - 11736
[2] Chemistry - A European Journal, 2008, vol. 14, # 36, p. 11328 - 11342
[3] Chemische Berichte, 1885, vol. 18, p. 1762
[4] Journal fuer Praktische Chemie (Leipzig), 1933, vol. <2> 138, p. 103,106

3
[ 106-42-3 ]
[ 13731-82-3 ]

Reference： [1] Journal fuer Praktische Chemie (Leipzig), 1933, vol. <2> 138, p. 103,106
[2] Electrochimica Acta, 2011, vol. 56, # 16, p. 5616 - 5623
[3] Tetrahedron, 2015, vol. 71, # 2, p. 283 - 292
[4] Journal of Materials Chemistry C, 2015, vol. 3, # 16, p. 4086 - 4092
[5] Crystal Growth and Design, 2016, vol. 16, # 7, p. 3993 - 4004

4
[ 63525-48-4 ]
[ 13731-82-3 ]

Reference： [1] Chemistry - A European Journal, 2001, vol. 7, # 23, p. 5118 - 5134

5
[ 18870-11-6 ]
[ 13731-82-3 ]

Reference： [1] Journal of Organic Chemistry USSR (English Translation), 1968, vol. 4, p. 1547 - 1550[2] Zhurnal Organicheskoi Khimii, 1968, vol. 4, p. 1609 - 1613

6
[ 7697-37-2 ]
[ 13731-82-3 ]

Reference： [1] Chemische Berichte, 1880, vol. 13, p. 903

7
[ 69065-15-2 ]
[ 7697-37-2 ]
[ 13731-82-3 ]

Reference： [1] Chemische Berichte, 1880, vol. 13, p. 903

8
[ 67-56-1 ]
[ 13731-82-3 ]
[ 18014-00-1 ]

Yield	Reaction Conditions	Operation in experiment
74%	for 12 h; Reflux	Iodine (78 mg, 0.33 mmol) was added to p-xylene (6.13 mL, 50.0 mmol), the mixture was cooled to 0 °C, and bromine (5.20 mL, 101 mmol) was added dropwise over 10 min. The ice bath was removed and the reaction stirred at rt for 16 h in the absence of light. The reaction was quenched with 20percent aq. KOH and stirred for 15 min while the solution became colorless. The solid precipitate was filtered and rinsed 2 x with 100 mL of H₂O. The solids were recrystallized in ethanol to afford a white solid (9.19 g, 70percent). ¹H NMR (CDCl₃): δ 7.40 (s, 2H), 2.34 (s, 6H). 1,4–dibromo-2,5-dimethylbenzene (5.93 g, 22.5 mmol) and KMnO₄ (15.72 g, 99.5 mmol) were added to 80 mL of t-BuOH:H₂O (1:1). Celite (14 g) was added to the flask and the reaction was refluxed for 18 h. The reaction mixture was cooled to rt, filtered over celite and the filter was washed with hot H₂O (100mL) and EtOAc (50mL). The filtrate was then acidified to pH=1 with conc. HCl. The white suspension was then extracted 3x with 100 mL of EtOAc. The combined organic extracts were dried over MgSO₄ and excess solvent was removed under vacuum to obtain a white solid (3.06 g, 42percent) which was not purified further. ¹H NMR (DMSO-d6): δ 8.01 (s, 2H). 2,5–dibromoterephthalic acid (2.04 g, 6.30 mmol) dissolved in 35 mL of MeOH and refluxed for 30 min. Thionyl chloride (9.00 mL, 124 mmol) was then carefully added and the reaction was refluxed 12 hours. The reaction flask was cooled to room temperature, 50 mL of water was carefully added, and the reaction was extracted 3x with 75 mL of Et₂O. The combined organics were washed with 3 x with 50 mL of sat. NaHCO₃ and dried with MgSO₄. The solvent was removed under vacuum and the solids recrystallized in MeOH to yield a white crystalline solid (1.65g, 74percent), mp = 134-136 C (lit.³ mp 134-137 C). ¹H NMR (CDCl₃): δ 8.06 (s, 2H), 3.96 (s, 6H). The ¹H NMR matches the known spectrum.³

Reference： [1] Bulletin of the Korean Chemical Society, 2011, vol. 32, # 5, p. 1781 - 1783
[2] Journal of the American Chemical Society, 1994, vol. 116, # 26, p. 11723 - 11736
[3] Tetrahedron, 2015, vol. 71, # 2, p. 283 - 292
[4] Journal of Organic Chemistry, 1959, vol. 24, p. 26
[5] Bulletin de la Societe Chimique de France, 1958, p. 1418,1420
[6] Journal of Organic Chemistry, 1959, vol. 24, p. 26
[7] Bulletin de la Societe Chimique de France, 1958, p. 1418,1420
[8] Macromolecules, 2004, vol. 37, # 21, p. 7945 - 7954

9
[ 13731-82-3 ]
[ 18014-00-1 ]

Reference： [1] Journal of the American Chemical Society, 2014, vol. 136, # 6, p. 2432 - 2440

10
[ 67-56-1 ]
[ 13731-82-3 ]
[ 18014-00-1 ]
[ 114537-99-4 ]

Reference： [1] Bulletin de la Societe Chimique de France, 1958, p. 1418,1420

11
[ 64-17-5 ]
[ 13731-82-3 ]
[ 18013-97-3 ]

Yield	Reaction Conditions	Operation in experiment
96%	Reflux	The inventive diindenothiophene derivatives can be produced by any of the methods that are conventionally known to persons having ordinary skill in the art. For instance, the above-mentioned compound of formula (2) can be prepared by a method comprising the following steps:

Reference： [1] Patent: US2010/168444, 2010, A1, . Location in patent: Page/Page column 4-8
[2] Organic Letters, 2014, vol. 16, # 1, p. 106 - 109
[3] Crystal Growth and Design, 2016, vol. 16, # 7, p. 3993 - 4004
[4] Chemical Communications, 2010, vol. 46, # 35, p. 6503 - 6505
[5] Chemistry - A European Journal, 2008, vol. 14, # 36, p. 11328 - 11342
[6] Electrochimica Acta, 2011, vol. 56, # 16, p. 5616 - 5623
[7] Journal of Materials Chemistry C, 2015, vol. 3, # 16, p. 4086 - 4092

12
[ 13731-82-3 ]
[ 18013-97-3 ]

Reference： [1] Chemische Berichte, 1885, vol. 18, p. 1762
[2] Gazzetta Chimica Italiana, 1888, vol. 18, p. 303
[3] New Journal of Chemistry, 2006, vol. 30, # 5, p. 667 - 670

[ 13731-82-3 ] Synthesis Path-Downstream 1~88

1
[ 67-56-1 ]
[ 13731-82-3 ]
[ 18014-00-1 ]

Yield	Reaction Conditions	Operation in experiment
95%	With sulfuric acid;Heating; Reflux;	2,5-Dibromo-1,4-terephthalic acid (16.2 g, 0.05 mol) was dissolved in methanol (30 ml).Slowly add concentrated sulfuric acid (10ml).Heating and stirring reflux for 10h~16h,cool down,filter,Wash three times with methanol (5ml),Dry in vacuo (16.7 g, 47.5 mmol),Yield: 95%,
74%	With thionyl chloride; for 12h;Reflux;	Iodine (78 mg, 0.33 mmol) was added to p-xylene (6.13 mL, 50.0 mmol), the mixture was cooled to 0 C, and bromine (5.20 mL, 101 mmol) was added dropwise over 10 min. The ice bath was removed and the reaction stirred at rt for 16 h in the absence of light. The reaction was quenched with 20% aq. KOH and stirred for 15 min while the solution became colorless. The solid precipitate was filtered and rinsed 2 x with 100 mL of H2O. The solids were recrystallized in ethanol to afford a white solid (9.19 g, 70%). 1H NMR (CDCl3): delta 7.40 (s, 2H), 2.34 (s, 6H). 1,4-dibromo-2,5-dimethylbenzene (5.93 g, 22.5 mmol) and KMnO4 (15.72 g, 99.5 mmol) were added to 80 mL of t-BuOH:H2O (1:1). Celite (14 g) was added to the flask and the reaction was refluxed for 18 h. The reaction mixture was cooled to rt, filtered over celite and the filter was washed with hot H2O (100mL) and EtOAc (50mL). The filtrate was then acidified to pH=1 with conc. HCl. The white suspension was then extracted 3x with 100 mL of EtOAc. The combined organic extracts were dried over MgSO4 and excess solvent was removed under vacuum to obtain a white solid (3.06 g, 42%) which was not purified further. 1H NMR (DMSO-d6): delta 8.01 (s, 2H). 2,5-dibromoterephthalic acid (2.04 g, 6.30 mmol) dissolved in 35 mL of MeOH and refluxed for 30 min. Thionyl chloride (9.00 mL, 124 mmol) was then carefully added and the reaction was refluxed 12 hours. The reaction flask was cooled to room temperature, 50 mL of water was carefully added, and the reaction was extracted 3x with 75 mL of Et2O. The combined organics were washed with 3 x with 50 mL of sat. NaHCO3 and dried with MgSO4. The solvent was removed under vacuum and the solids recrystallized in MeOH to yield a white crystalline solid (1.65g, 74%), mp = 134-136 C (lit.3 mp 134-137 C). 1H NMR (CDCl3): delta 8.06 (s, 2H), 3.96 (s, 6H). The 1H NMR matches the known spectrum.3

Reference： [1]Bulletin of the Korean Chemical Society,2011,vol. 32,p. 1781 - 1783
[2]Journal of the American Chemical Society,1994,vol. 116,p. 11723 - 11736
[3]Patent: CN110054581,2019,A .Location in patent: Paragraph 0033-0035
[4]Tetrahedron,2015,vol. 71,p. 283 - 292
[5]Journal of Organic Chemistry,1959,vol. 24,p. 26
[6]Journal of Organic Chemistry,1959,vol. 24,p. 26

2
[ 67-56-1 ]
[ 13731-82-3 ]
[ 18014-00-1 ]
[ 114537-99-4 ]

Reference： [1]Bulletin de la Societe Chimique de France,1958,p. 1418,1420

3
[ 13731-82-3 ]
[ 2550-73-4 ]

Reference： [1]Journal of Organic Chemistry,1959,vol. 24,p. 26

4
[ 13731-82-3 ]
[ 610-92-4 ]

Yield	Reaction Conditions	Operation in experiment
> 98%		In a round bottom flask with reflux condenser, 1.00 g (3.1 mmol) of 2,5-dibromoterephthalic acid was combined with 10 mL of H2O. 0.85 g of Na2CO3 (7.8 mmol) was added to this mixture. Subsequently, 0.12 mL (0.031 mmol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile was added, followed by addition of 0.12 mL (0.062 mmol, 2 mol %) of 0.5 M rac-trans-N,N'-Dimethylcyclohexane-1,2-diamine (Ligand F). The reaction mixture was heated to 90 C. with stirring, then stirred for 18 h at 90 C. A sample was taken after 6 h and analyzed by 1H NMR. No starting material was detected. After 18 h, the conversion of 2-bromo-5-hydroxyterephthalic acid was larger than 99%, and the product selectivity to 2,5-dihydroxyterephthalic acid was above 98%. After cooling to 25 C., the reaction mixture was acidified with 15% HCl, producing a light green precipitate. The precipitate was filtered and washed with water and dried. The water phase did not show any detectable organic products by 1H NMR analysis. The purity of the solid product was determined to >98%.
97%		Under nitrogen, 5.00 g (15.4 mmol) of 2,5-dibromoterephthalic acid was combined with 20 g of H2O. 1.71 g (16.1 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 2.38 g (22.5 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 28 mg of CuBr and 50 mg of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved to give a blue-purple solution. This solution was added to the stirred reaction mixture at 90 C. under nitrogen and stirred for 2 h at 90 C. After cooling to 25 C., the reaction mixture was acidified with 15% HCl, producing a yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 2.96 g (15 mmol, 97% yield) 2,5-dihydroxyterphtalic acid was collected. The purity was determined by 1H NMR to be >98%.
92%		Under nitrogen, 2.00 g (6.2 mmol) of 2,5-dibromoterephthalic acid was combined with 15 g of H2O; 0.679 g (6.4 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 0.940 g (9.0 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 9 mg (0.06 mmol) (0.01 mol equiv) of CuBr and 25 mg (0.14 mmol) (0.02 mol equiv) of 2,2',6,6'-tetramethylheptanedione-3,5 were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved. This solution was added to the stirred reaction mixture via syringe at 80 C. under nitrogen and stirred for 30 h at 80 C. After cooling to 25 C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 1.26 g of crude 2,5-dihydroxyterephthalic acid and 2-hydroxyterephthalic acid was collected. The purity of 2,5-dihydroxyterephthalic acid was determined by 1H NMR to be about 89%. The net yield of 2,5-dihydroxyterephthalic acid was determined to be 92%.

72%		Under nitrogen, 2.00 g (6.2 mmol) of 2,5-dibromooterephthalic acid were combined with 10 g of H2O, 0.679 g (6.4 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 0.950 g (9.0 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 9 mg (0.01 mol equiv) of CuBr and 40 mg (0.02 mol equiv) of N,N'-dimesityl-2,3-diiminobutane were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved. This solution was added to the stirred reaction mixture via syringe at 80 C. under nitrogen and stirred for 30 h at 80 C. After cooling to 25 C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 1.09 g of crude 2,5-dihydroxyterephthalic acid was collected. The purity of 2,5-dihydroxyterephthalic acid was determined by 1H NMR to be about 81%. The net yield of 2,5-dihydroxyterephthalic acid was determined to be 72%.
97 - 99%Spectr.		Eight 2 mL reaction vials were each charged with 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid, followed by various amounts of 0.5 M aqueous sodium carbonate solution as shown in Table 3. Each of the mixtures was then treated with 0.003 mL of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL of 0.5 M rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). The reaction vials were closed and loaded into an 8-well reactor. The reactor was then sealed. About 12 psi (83 kPa) of N2 pressure was applied. The reactor was heated to 90 C. and held at that temperature for 5 hours, then allowed to cool to room temperature. The reaction mixture was then acidified with 15% aqueous HCl, producing a light green precipitate. The precipitate was filtered, washed with water, dried, and analyzed by 1H NMR in DMSO-d6. Results are presented in Table 3.
		These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.
		These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.
		These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.
		These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.
		These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.
		These examples demonstrate the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using different copper compounds and rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F). Under nitrogen, a predetermined amount of 2,5-dibromoterephthalic acid (set forth in Table 4) was combined with about the five times the weight H2O, and a predetermined amount of Na2CO3 (set forth in Table 4) was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Separately a predetermined amount of the copper compound (set forth in Table 4) and of rac-trans-N,N'-dimethylcyclohexane-1,2-diamine (Ligand F) were combined with 2 mL H2O under exclusion of air. For CuBr and CuCl the resulting mixture was subsequently stirred under an air atmosphere for about 30 seconds until the copper salt was dissolved before it was added to the reaction mixture. For CuBr2, CuSO4, Cu(OTf)(Toluene) and Cu(OTf)2, the resulting catalyst solutions were added to the stirred reaction mixture via syringe at 80 C. under exclusion of air and stirred at 80 C. Samples were taken periodically to follow the conversion to DHTA. Table 4 gives the results as derived by 1H NMR spectroscopy. Times given indicate the approximate reaction time to reach the given conversion of starting material II.

Reference： [1]Patent: US7345194,2008,B1 .Location in patent: Page/Page column 15
[2]Patent: US7345194,2008,B1 .Location in patent: Page/Page column 14-15
[3]Patent: US7345195,2008,B1 .Location in patent: Page/Page column 9
[4]Patent: US7378547,2008,B1 .Location in patent: Page/Page column 12
[5]Journal of Fluorescence,2016,vol. 26,p. 1295 - 1307
[6]Journal of Solution Chemistry,2017,vol. 46,p. 1005 - 1023
[7]Journal of the Indian Chemical Society,1957,vol. 34,p. 321
[8]Patent: US7345194,2008,B1 .Location in patent: Page/Page column 17-18
[9]Patent: US7345194,2008,B1 .Location in patent: Page/Page column 18
[10]Patent: US7345194,2008,B1 .Location in patent: Page/Page column 18
[11]Patent: US7345194,2008,B1 .Location in patent: Page/Page column 18
[12]Patent: US7345194,2008,B1 .Location in patent: Page/Page column 18
[13]Patent: US7345194,2008,B1 .Location in patent: Page/Page column 18
[14]Patent: US7345194,2008,B1 .Location in patent: Page/Page column 18

5
[ 13731-82-3 ]
[ 13815-90-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With oxalyl dichloride; N,N-dimethyl-formamide In benzene at 80℃;
100%	With oxalyl dichloride
100%	With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane for 3h; Inert atmosphere; Reflux;

96%	With oxalyl dichloride; N,N-dimethyl-formamide In toluene at 40℃;
85%	With thionyl chloride
	With phosphorus pentachloride
	With oxalyl dichloride Yield given;
	With thionyl chloride for 10h; Heating;
	With thionyl chloride for 4h; Heating;
	With thionyl chloride In dichloromethane for 2h; Heating;	23 Example 23 Synthesis of 2,5-dibromo-4-(2,3-dihydro-pyrido[4,3-b][1,4]oxazin-4-carbonyl)-benzoic acid (compound 23) In a 20 ml flask, 2,5-dibromo-terephthalic acid (100 mg, 0.31 mmol) and N,N-dimethyl formamide (3 drops) were dissolved in thionyl chloride (2 ml). After stirring for 2 hours at 800, the reaction mixture was cooled to room temperature and concentrated. Crude 2,5-dibromo-terephthaloic dichloride (112 mg, 0.31 mmol) was dissolved in dichloromethane (6 ml) and was added to 3,4-dihydro-2H-pyrido[4,3-b][1,4]oxazine (20.9 mg, 0.15 mmol) dissolved in dichloromethane (1 ml). Triethylamine (3 drops) were slowly added thereto and stirred at room temperature for 16 hours. After completion of the reaction, the residue was purified by preparative LC/Mass to obtain the target compound 23, i.e., 2,5-dibromo-4-(2,3-dihydro-pyrido[4,3-b][1,4]oxazin-4-carbonyl)-benzoic acid, as white solid (23 mg, 5%).
	With thionyl chloride; N,N-dimethyl-formamide for 3h; Reflux;	4.3.3. 2,5-Dibromobenzene-1,4-diamide (8) The mixture of 2,5-dibromotetrephthalic acid (1.5 g, 4.6 mmol), thionyl chloride (20 mL), a drop of DMF was refluxed for 3 h. Thionyl chloride was removed by co-evaporation with toluene (20 mL) with rotary evaporation. The concentrated crude product was dissolved in dioxane (20 mL). Ammonium hydroxide (20 mL, concd) was added dropwisely to the mixture and stirred overnight at room temperature. The precipitate was filtered and washed with dioxane to afford the pure product as a white solid (1.22 g, 76%).
	With thionyl chloride for 10h; Reflux;
	With thionyl chloride
	With thionyl chloride
	With thionyl chloride In N,N-dimethyl-formamide at 80℃; for 1h; Inert atmosphere;
	With thionyl chloride for 3h; Inert atmosphere; Reflux;
	With thionyl chloride In N,N-dimethyl-formamide for 6h; Reflux;
	With thionyl chloride; N,N-dimethyl-formamide In dichloromethane Inert atmosphere; Reflux;
	With thionyl chloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 24h;
	With thionyl chloride; N,N-dimethyl-formamide at 80℃; for 3h;
	With pyridine; phosphorus pentachloride In toluene at 80 - 90℃; for 1h;	1.1 1) Step 1 1) Step 1 (0227) (0228) 9.72 grams (g) of 2,5-dibromoterephthalic acid (MW=323.92 grams per mole (g/mol), 30 millimoles (mmol), 1.0 equivalents (eq)) is placed in 260 mL of toluene, and the mixture is stirred. Subsequently, 18.74 g of PCl5 (MW=208.24 g/mol, 90 mmol, 3.0 eq) and one drop of pyridine are added thereto, and the obtained mixture is heated at 80 to 90° C. After the crystals are completely dissolved, the mixture is additionally stirred for one hour. Subsequently, the reaction solution is distilled, to obtaining a yellow oily compound. Then, 50 milliliters (mL) of N,N-dimethyl acetamide is added thereto, and the obtained mixture is uniformly stirred (a mixed solution A). In a separate vessel, hydroquinone (MW=110.11 g/mol, 300 mmol, 10.0 eq) is added to 50 mL of N,N-dimethyl acetamide and heated until the solid is completely dissolved. Then, 12.14 g of triethylamine (MW=101.19 g/mol, 120 mmol, 4.0 eq) is added to the solution and mixed (a mixed solution B). The mixed solution B is slowly added to the mixed solution A, and the mixture is stirred at room temperature for 1 hour. When the reaction is complete, the reaction solution is poured into 1,600 mL of purified water to form crystals. The crystallization solution is then heated for about 1 hour and filtered while heated, to obtain pink crystals. Additionally, 1,000 mL of water is added thereto, and the mixture is heated and stirred for about 1 hour. The resultant is filtered while heated, and crystals obtained therefrom are vacuum-dried in a drying oven (60° C.) for greater than or equal to 12 hours, to obtain 11.12 g of a gray compound I-1 (a yield of 73%). The compound I-1 is used in the following reaction without an additional purification. (0229) 1H NMR (DMSO-d6) 300 MHz, δ, ppm: 6.8 (d, 4H), 7.2 (d, 4H), 8.4 (s, 2H), 9.6 (s, 2H
	With thionyl chloride for 10h; Reflux;
	With thionyl chloride; N,N-dimethyl-formamide at 90℃; for 1h; Inert atmosphere;
	With thionyl chloride at 120℃; for 10h;	1.1; 2.1; 3.1; 4.1; 5.1; 6.1; 7.1 Step 1, Synthesis of Intermediate 2,5-Dibromo-terephthaloyltoluene (II) Weigh 2,5-dibromoterephthalic acid (IV) 3.25g (10mmol)Adding to 40 ml of thionyl chloride (S0Cl2), heating at 120 ° C for 10 h,Excess thionyl chloride is removed in vacuo,3,6-dibromo terephthaloyl chloride was obtained; 2.30 g (25 mmol) of toluene was weighed,Anhydrous aluminum trichloride catalyst 2.67 g (20 mmol) was dissolved in dichloromethane.Then, it was added dropwise to 3,6-dibromo terephthaloyl chloride, and the reaction was stirred at room temperature for 8 hours.After the reaction is completed, a large amount of ice water is added to obtain a solid.Then, recrystallization was carried out to obtain a total of 3.35 g of the intermediate 2,5-dibromo-p-benzoyltoluene (hydrazine).
	With thionyl chloride for 10h; Reflux; Inert atmosphere;	2,5-Dibromoterephthalic acid (7.01 g, 21.0 mmol) was added to50 mL thionyl chloride, and then reflux for 10 h. The solvent was thenremoved under vacuum to obtain 2, 5-dibromoterephthaloyl dichloride,which was used in the next step without purification.
	With thionyl chloride for 10h; Reflux;	1; 2; 3 2,5-dibromoterephthalic acid (4.88 g, 15 mmol) was added to 50 mL of thionyl chloride (SOCl2).After heating to reflux for 10 hours, excess thionyl chloride was removed in vacuo.2,5-Dibromoterephthaloyl chloride was obtained.Methylene chloride containing toluene (7.25 g, 55 mmol) and anhydrous aluminum trichloride (6.01 g, 45 mmol) catalyst was added dropwise to the above 2,5-dibromo terephthaloyl chloride, and the mixture was reacted at room temperature for 8 hours.
	With thionyl chloride for 3h; Reflux;
	With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 60℃;	1-4 Compound 1-3 Synthesis Into a 3 L reaction flask, add compound 1-5 (100 g, 308.7 mmol, 1eq), add dichloromethane (1 L), add oxalyl chloride (62.6 mL, 740.9 mmol, 2.4 eq), and stir.Add N, N-dimethylformamide (DMF, 0.22 mL, 3.1 mmol, 0.01 eq) to the reaction and stir for 10 minutes.The oil-bath is used to raise the temperature of the bath to 60 ° C. and stir at reflux overnight. After cooling the reaction temperature to room temperature (25 ), the solvent (Dichloromethane (MC)) is concentrated using a reduced pressure pump.Dichloromethane (1 L) was added to the concentrate, followed by aluminum chloride (90.6 g, 679.2 mmol, 2.2 eq).Cool the reactant to 0 ° C using an ice-bath and dilute n-hexylbenzene (174.5 mL, 926.2 mmol, 3 eq) in dichloromethane (200 mL) and slowly add dropwise to the reaction.The reaction is stirred overnight at room temperature (25 ° C.).After completion of the reaction, the reaction solution is slowly poured into cooling water (purified water / ice = 1/1, 1.5 L) and stirred vigorously.The organic layer was separated and then 1N NaOH (in purified water, 1.5 L),Wash each with purified water (1 L).The separated organic layer was dried over anhydrous MgSO 4, filtered, and the organic layer was removed using an evaporatior.The concentrate is recrystallized with Dichloromethane / MeOH and filtered, and the filtered solid is washed with MeOH.The washed solid was dried overnight in a vacuum oven (temp. = 90 ° C.) to afford intermediate compound 1-3 (141.8 g, 2 steps overall 75%).
	With thionyl chloride In N,N-dimethyl-formamide; toluene for 2h; Reflux;
	With thionyl chloride In N,N-dimethyl-formamide at 80℃; for 1h;	1.2 (2) Synthesis of 2,5-dibromoterephthaloyl chloride: At 80°C,DMF (360uL, 4.6mmol),2,5-Dibromoterephthalic acid (30g, 93mmol) andMix thionyl chloride (150mL), react for 1h,The resulting product is subjected to vacuum distillation to obtain 2,5-dibromoterephthaloyl chloride,No purification is required to proceed directly to the next reaction.

Reference： [1]Lamba, Jaydeep J. S.; Tour, James M. [Journal of the American Chemical Society, 1994, vol. 116, # 26, p. 11723 - 11736]
[2]Tour, James M.; Rawlett, Adam M.; Kozaki, Masatoshi; Yao, Yuxing; Jagessar, Raymond C.; Dirk, Shawn M.; Price, David W.; Reed, Mark A.; Zhou, Chong-Wu; Chen, Jia; Wang, Wenyong; Campbell, Ian [Chemistry - A European Journal, 2001, vol. 7, # 23, p. 5118 - 5134]
[3]Garcia, Rosalva C.; Pech, Matthew J.; Sommer, Roger; Gorman, Christopher B. [Journal of Organic Chemistry, 2019, vol. 84, # 23, p. 15079 - 15086]
[4]Location in patent: experimental part Nielsen, Christian B.; Arnbjerg, Jacob; Johnsen, Mette; Joorgensen, Mikkel; Ogilby, Peter R. [Journal of Organic Chemistry, 2009, vol. 74, # 23, p. 9094 - 9104]
[5]Location in patent: scheme or table Lee, Myunggun; Hahn, So-Jung; Poduval, Mithrabinda K.K.; Kim, Tae-Hyun [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 8, p. 2776 - 2778]
[6]Claus [Journal fur praktische Chemie (Leipzig 1954), 1888, vol. <2> 37, p. 18]
[7]Tour, James M.; Lamba, Jaydeep J. S. [Journal of the American Chemical Society, 1993, vol. 115, # 11, p. 4935 - 4936]
[8]Qiu, Song; Lu, Ping; Liu, Xiao; Shen, Fangzhong; Liu, Linlin; Ma, Yuguang; Shen, Jiacong [Macromolecules, 2003, vol. 36, # 26, p. 9823 - 9829]
[9]Wang, Hong-Yu; Feng, Jia-Chun; Wen, Gui-An; Jiang, Hong-Ji; Wan, Jun-Hua; Zhu, Rui; Wang, Chuan-Ming; Wei, Wei; Huang, Wei [New Journal of Chemistry, 2006, vol. 30, # 5, p. 667 - 670]
[10]Current Patent Assignee: JW PHARMACEUTICAL DO.,LTD. - US2011/28467, 2011, A1 Location in patent: Page/Page column 23
[11]Location in patent: experimental part Cheng, Jian-Zhang; Lin, Chao-Chen; Chou, Pi-Tai; Chaskar, Atul; Wong, Ken-Tsung [Tetrahedron, 2011, vol. 67, # 4, p. 734 - 739]
[12]Location in patent: experimental part Wu, Yonggang; Hao, Xiaohui; Wu, Junling; Jin, Jia; Ba, Xinwu [Macromolecules, 2010, vol. 43, # 2, p. 731 - 738]
[13]Ricci, Antonella; Chiarini, Marco; Apicella, Maria Teresa; Compagnone, Dario; Del Carlo, Michele; Lo Sterzo, Claudio; Prodi, Luca; Bonacchi, Sara; Villamaina, Diego; Zaccheroni, Nelsi [Tetrahedron Letters, 2013, vol. 54, # 4, p. 303 - 307]
[14]Jung, In Hwan; Lo, Wai-Yip; Jang, Jaeyoung; Chen, Wei; Zhao, Donglin; Landry, Erik S.; Lu, Luyao; Talapin, Dmitri V.; Yu, Luping [Chemistry of Materials, 2014, vol. 26, # 11, p. 3450 - 3459]
[15]Ie, Yutaka; Ueta, Masashi; Nitani, Masashi; Tohnai, Norimitsu; Miyata, Mikiji; Tada, Hirokazu; Aso, Yoshio [Chemistry of Materials, 2012, vol. 24, # 16, p. 3285 - 3293]
[16]Lee, Sae Youn; Yasuda, Takuma; Park, In Seob; Adachi, Chihaya [Dalton Transactions, 2015, vol. 44, # 18, p. 8356 - 8359]
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[18]Shi, Xueliang; Kueh, Weixiang; Zheng, Bin; Huang, Kuo-Wei; Chi, Chunyan [Angewandte Chemie - International Edition, 2015, vol. 54, # 48, p. 14412 - 14416][Angew. Chem., 2015, vol. 54, # 48, p. 14620 - 14624,5]
[19]Esiner, Serkan; Van Pruissen, Gijs W.P.; Wienk, Martijn M.; Janssen, René A.J. [Journal of Materials Chemistry A, 2016, vol. 4, # 14, p. 5107 - 5114]
[20]Schäfer, Julian; Holzapfel, Marco; Mladenova, Boryana; Kattnig, Daniel; Krummenacher, Ivo; Braunschweig, Holger; Grampp, Günter; Lambert, Christoph [Journal of the American Chemical Society, 2017, vol. 139, # 17, p. 6200 - 6209]
[21]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD. - US2017/197906, 2017, A1 Location in patent: Paragraph 0227; 0228; 0229
[22]Fang, Mei; Huang, Jinjin; Chang, Si-Ju; Jiang, Yi; Lai, Wen-Yong; Huang, Wei [Journal of Materials Chemistry C, 2017, vol. 5, # 23, p. 5797 - 5809]
[23]Sato, Chihiro; Suzuki, Shuichi; Okada, Keiji; Kozaki, Masatoshi [Chemistry - An Asian Journal, 2018, vol. 13, # 23, p. 3729 - 3736]
[24]Current Patent Assignee: HUZHOU UNIVERSITY - CN109180506, 2019, A Location in patent: Paragraph 0041-0044; 0047; 0048; 0050; 0051; 0053; 0054
[25]Cao, Jian; Shan, Tong; Wang, Ji-Kang; Xu, Yun-Xiang; Ren, Xiancheng; Zhong, Hongliang [Dyes and Pigments, 2019, vol. 165, p. 354 - 360]
[26]Current Patent Assignee: HUZHOU UNIVERSITY - CN109293563, 2019, A Location in patent: Paragraph 0032-0045
[27]Ma, Fulong; Cheng, Yu; Zheng, Yu; Ji, Hefang; Hasrat, Kamran; Qi, Zhengjian [Journal of Materials Chemistry C, 2019, vol. 7, # 30, p. 9413 - 9422]
[28]Current Patent Assignee: CMDL CO LTD - KR2019/113044, 2019, A Location in patent: Page/Page column 10-15
[29]Rodrigues, Ana Clara B.; Wetterling, Dario; Scherf, Ullrich; Seixas de Melo, J. Sérgio [Chemistry - A European Journal, 2021, vol. 27, # 29, p. 7826 - 7830]
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6
[ 13731-82-3 ]
[ 18013-97-3 ]

Reference： [1]Chemische Berichte,1885,vol. 18,p. 1762
[2]New Journal of Chemistry,2006,vol. 30,p. 667 - 670

7
[ 20871-01-6 ]
[ 13731-82-3 ]

Yield	Reaction Conditions	Operation in experiment
94%	With potassium permanganate; sodium hydrogencarbonate for 144h; Heating;
86%	With potassium permanganate In water for 144h; Reflux;
86%	With potassium permanganate; water for 144h; Reflux;	1 Compound 5-3 Synthesis Compound 5-4 (6.6 g, 19.5 mmol) was added to a 250 mL reaction flask, purified water (50 mL) was added thereto, potassium permanganate (8.7 g, 55 mmol) was added thereto, and the suspension was stirred.The reaction is stirred at reflux for 6 days.The reaction is filtered using celite-pad.Conc the filtrate. Acidify with HCl solution until the color disappears.The resulting solid was filtered to give compound 5-3 (5.7 g, 86%).

	With alkaline permanganate
	With potassium permanganate; potassium carbonate

Reference： [1]Lamba, Jaydeep J. S.; Tour, James M. [Journal of the American Chemical Society, 1994, vol. 116, # 26, p. 11723 - 11736]
[2]Cocherel, Nicolas; Poriel, Cyril; Rault-Berthelot, Joelle; Barriere, Frederic; Audebrand, Nathalie; Slawin, Alexandra M. Z.; Vignau, Laurence [Chemistry - A European Journal, 2008, vol. 14, # 36, p. 11328 - 11342]
[3]Current Patent Assignee: CMDL CO LTD - KR2019/113044, 2019, A Location in patent: Paragraph 0097; 0101-0102
[4]Schultz [Chemische Berichte, 1885, vol. 18, p. 1762]
[5]Marzin [Journal fur praktische Chemie (Leipzig 1954), 1933, vol. <2> 138, p. 103,106]

8
[ 1074-24-4 ]
[ 13731-82-3 ]

Yield	Reaction Conditions	Operation in experiment
96%	With pyridine; potassium permanganate In water	The inventive diindenothiophene derivatives can be produced by any of the methods that are conventionally known to persons having ordinary skill in the art. For instance, the above-mentioned compound of formula (2) can be prepared by a method comprising the following steps:
91%	With pyridine; potassium permanganate In water for 24h; Reflux;
90%	With chromium(VI) oxide; sulfuric acid In acetic acid at 20℃; for 24h;

85%	With potassium permanganate In <i>tert</i>-butyl alcohol at 25 - 100℃;	1 Synthesis of Compound 1-5 1,4-Dibromo-2,5-dimethylbenzene (100 g, 378.8 mmol, 1 eq) and tert-Buthanol (650 mL) were added to a 3 L reaction flask and suspended.Potassium permanganate (131.7 g, 833.4 mmol, 2.2 eq) is slowly added dropwise.The temperature of the bath is raised to 100 ° C. using an oil bath, followed by stirring under reflux for 1 hour.Cool the temperature of the reaction to room temperature (25 ° C.) and then slowly add dropwise addition of Potassium permanganate (131.7 g, 833.4 mmol, 2.2 eq).The temperature of the bath was again raised to 100 ° C., followed by stirring under reflux overnight.Cool the temperature of the reaction to room temperature (25 ° C.), then add purified water (400 mL) to the reaction and stir.The reaction solution was filtered using celite-pad (300 g) and the filtered pad was washed with purified water (500 mL).The solvent (tert-BuOH) of the filtrate was concentrated under reduced pressure, followed by conc. The HCl solution is slowly added dropwise until the pH of the reactant reaches 1 = 1 and then stirred for 2 hours (precipitation as solid product crystals). The resulting solid is filtered and the filtered solid is washed with purified water until the pH of the filtrate is 7.The washed solid was dried overnight in a vacuum oven (temp. = 90 ° C.) to afford intermediate compound 1-5 (104.3 g, 85%).
84%	Stage #1: 2,5-dibromo-p-xylene With acetic acid In water at 120 - 150℃; for 2h; Stage #2: With oxygen In water at 180℃; for 4 - 10h;	1; 2; 3; 4; 5 Example 1; This example illustrates the production of 2,5- dibromoterephthalic acid from 2 , 5-dibromo-l , 4- dimethylbenzene .In a stirred autoclave with internal cooling coil and reflux condenser, 2 , 5-dibromo-l , 4 -dimethylbenzene (372 mmol) was combined with a solution containing Co(OAc)2-4H20 (2.5 mmol), Mn (OAc) 2 • 4H2O (2.5 mmol), Zr(OAc)4 (0.25 mmol), and NaBr (5 mmol) in 500 g of 97% acetic acid. The mixture was stirred at a constant rate using a gas dispersing stirrer for better gas mixing and the mixture was heated to 150°C for 2 h (this stage is noted as "T-I" in Table 1) , followed by increasing the temperature to 180°C for 4 h (this stage is noted as "T-2" in Table 1) . While the reaction was heating, air was continuously blown through the system with 400 psig (2.76 MPa) back pressure. After reaction completion, the pressure was released and the reactor was allowed to cool to 50°C. The product was discharged, rinsing the reactor twice with 50 g acetic acid to collect further product. The white solid was collected via suction filtration, washed with water, and dried under vacuum to yield 31O g (84%) of the product 2 , 5-dibromoterephthalic acid as a white solid with a purity of 99%, as determined by 1H NMR.; Examples 2-5; These examples illustrate the effect of varying the stages, times and temperatures on 2,5- dibromoterephthalic acid net yield and purity. Examples 2-5 were carried out using the procedure of Example 1 except as noted in Table 1. The product 2,5- dibromoterephthalic acid in each case was a white solid with a purity of at least 99 mol%
82.7%	Stage #1: 2,5-dibromo-p-xylene With potassium permanganate In water; <i>tert</i>-butyl alcohol for 19h; Reflux; Stage #2: With hydrogenchloride In water
81%	With pyridine; potassium permanganate In water Reflux;
81%	With pyridine; potassium permanganate In water
81%	With pyridine; potassium permanganate In water
65%	With potassium permanganate In water; <i>tert</i>-butyl alcohol for 4h; Reflux;
55%	Stage #1: 2,5-dibromo-p-xylene With pyridine Reflux; Stage #2: With potassium permanganate In water Reflux; Stage #3: With potassium permanganate; potassium hydroxide In water at 90℃;
51%	With potassium permanganate In water; <i>tert</i>-butyl alcohol for 19h; Reflux;
47%	Stage #1: 2,5-dibromo-p-xylene With potassium permanganate In pyridine; water Reflux; Stage #2: With potassium hydroxide In water at 90℃; for 1.66667h;
42%	With potassium permanganate In water; <i>tert</i>-butyl alcohol for 18h; Reflux;	4 Dimethyl 2,5-dibromoterephthalate (6). Iodine (78 mg, 0.33 mmol) was added to p-xylene (6.13 mL, 50.0 mmol), the mixture was cooled to 0 °C, and bromine (5.20 mL, 101 mmol) was added dropwise over 10 min. The ice bath was removed and the reaction stirred at rt for 16 h in the absence of light. The reaction was quenched with 20% aq. KOH and stirred for 15 min while the solution became colorless. The solid precipitate was filtered and rinsed 2 x with 100 mL of H2O. The solids were recrystallized in ethanol to afford a white solid (9.19 g, 70%). 1H NMR (CDCl3): δ 7.40 (s, 2H), 2.34 (s, 6H). 1,4-dibromo-2,5-dimethylbenzene (5.93 g, 22.5 mmol) and KMnO4 (15.72 g, 99.5 mmol) were added to 80 mL of t-BuOH:H2O (1:1). Celite (14 g) was added to the flask and the reaction was refluxed for 18 h. The reaction mixture was cooled to rt, filtered over celite and the filter was washed with hot H2O (100mL) and EtOAc (50mL). The filtrate was then acidified to pH=1 with conc. HCl. The white suspension was then extracted 3x with 100 mL of EtOAc. The combined organic extracts were dried over MgSO4 and excess solvent was removed under vacuum to obtain a white solid (3.06 g, 42%) which was not purified further. 1H NMR (DMSO-d6): δ 8.01 (s, 2H). 2,5-dibromoterephthalic acid (2.04 g, 6.30 mmol) dissolved in 35 mL of MeOH and refluxed for 30 min. Thionyl chloride (9.00 mL, 124 mmol) was then carefully added and the reaction was refluxed 12 hours. The reaction flask was cooled to room temperature, 50 mL of water was carefully added, and the reaction was extracted 3x with 75 mL of Et2O. The combined organics were washed with 3 x with 50 mL of sat. NaHCO3 and dried with MgSO4. The solvent was removed under vacuum and the solids recrystallized in MeOH to yield a white crystalline solid (1.65g, 74%), mp = 134-136 C (lit.3 mp 134-137 C). 1H NMR (CDCl3): δ 8.06 (s, 2H), 3.96 (s, 6H). The 1H NMR matches the known spectrum.3
	With methanol; sodium hydroxide; di-tert-butyl peroxide; 3 A molecular sieve; hydrogen bromide; oxygen; cobalt(II) acetate; hydrogen cation; acetic acid Multistep reaction;
	With pyridine; potassium permanganate
	With sodium hydroxide; potassium permanganate In water for 12h; Heating;
	Multi-step reaction with 2 steps 1: NH₃, O₂, H₂O / Sn-V catalyst / 380 - 420 °C 2: aq. NaOH
	Multi-step reaction with 2 steps 1: aq. KMnO₄; pyridine 2: aq. KMnO₄
	Multi-step reaction with 2 steps 1: aqueous nitric acid 2: aqueous potassium carbonate; potassium permanganate
	With pyridine; potassium permanganate; water
	With potassium permanganate
	With pyridine; potassium permanganate In water
	Multi-step reaction with 2 steps 1: nitric acid; water / 144 h / Reflux 2: water; potassium permanganate / 144 h / Reflux

Reference： [1]Current Patent Assignee: ETERNAL MATERIALS CO., LTD. - US2010/168444, 2010, A1 Location in patent: Page/Page column 4-8
[2]Al-Fayaad, Hydar A.; Athukorala Arachchige, Kasun S.; Clegg, Jack K. [CrystEngComm, 2020, vol. 22, # 32, p. 5310 - 5315]
[3]Location in patent: scheme or table Pham, Van Chung; Huh, Geun; Kim, Jungahn; Choo, Dong Joon; Lee, Jae Yeol [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 5, p. 1781 - 1783]
[4]Current Patent Assignee: CMDL CO LTD - KR2019/113044, 2019, A Location in patent: Paragraph 0054-0055; 0057-0058
[5]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2008/82501, 2008, A1 Location in patent: Page/Page column 15-16
[6]Ishibashi, Jacob S.A.; Marshall, Jonathan L.; Mazire, Audrey; Lovinger, Gabriel J.; Li, Bo; Zakharov, Lev N.; Dargelos, Alain; Graciaa, Alain; Chrostowska, Anna; Liu, Shih-Yuan [Journal of the American Chemical Society, 2014, vol. 136, # 43, p. 15414 - 15421]
[7]Chen, Yi-Chun; Yu, Chao-Ying; Fan, Yu-Ling; Hung, Ling-I.; Chen, Chih-Ping; Ting, Ching [Chemical Communications, 2010, vol. 46, # 35, p. 6503 - 6505]
[8]Jadhav, Manoj M.; Rhyman, Lydia; Ramasami, Ponnadurai; Sekar, Nagaiyan [Journal of Fluorescence, 2016, vol. 26, # 4, p. 1295 - 1307]
[9]Jadhav, Manoj M.; Alswaidan, Ibrahim A.; Rhyman, Lydia; Ramasami, Ponnadurai; Sekar, Nagaiyan [Journal of Solution Chemistry, 2017, vol. 46, # 5, p. 1005 - 1023]
[10]Zhang, Xiu-Tang; Fan, Li-Ming; Fan, Wei-Liu; Li, Bin; Liu, Guang-Zeng; Liu, Xin-Zheng; Zhao, Xian [Crystal Growth and Design, 2016, vol. 16, # 7, p. 3993 - 4004]
[11]Rodrigues, Ana Clara B.; Wetterling, Dario; Scherf, Ullrich; Seixas de Melo, J. Sérgio [Chemistry - A European Journal, 2021, vol. 27, # 29, p. 7826 - 7830]
[12]Ning, Xiao-Shan; Liang, Xin; Hu, Kang-Fei; Yao, Chuan-Zhi; Qu, Jian-Ping; Kang, Yan-Biao [Advanced Synthesis and Catalysis, 2018, vol. 360, # 8, p. 1590 - 1594]
[13]Cai, Liping; Moehl, Thomas; Moon, Soo-Jin; Decoppet, Jean-David; Humphry-Baker, Robin; Xue, Zhaosheng; Bin, Liu; Zakeeruddin, Shaik M; Graetzel, Michael [Organic Letters, 2014, vol. 16, # 1, p. 106 - 109]
[14]Dressler, Justin J.; Miller, Sarah A.; Meeuwsen, Brian T.; Riel, Asia Marie S.; Dahl, Bart J. [Tetrahedron, 2015, vol. 71, # 2, p. 283 - 292]
[15]Tour, James M.; Lamba, Jaydeep J. S. [Journal of the American Chemical Society, 1993, vol. 115, # 11, p. 4935 - 4936]
[16]Sung, Hsiao-Hsien; Lin, Hong-Cheu [Macromolecules, 2004, vol. 37, # 21, p. 7945 - 7954]
[17]Wang, Hong-Yu; Feng, Jia-Chun; Wen, Gui-An; Jiang, Hong-Ji; Wan, Jun-Hua; Zhu, Rui; Wang, Chuan-Ming; Wei, Wei; Huang, Wei [New Journal of Chemistry, 2006, vol. 30, # 5, p. 667 - 670]
[18]Suvorov,B.V. et al. [Journal of Organic Chemistry USSR (English Translation), 1968, vol. 4, p. 1547 - 1550][Zhurnal Organicheskoi Khimii, 1968, vol. 4, p. 1609 - 1613]
[19]Tour, James M.; Rawlett, Adam M.; Kozaki, Masatoshi; Yao, Yuxing; Jagessar, Raymond C.; Dirk, Shawn M.; Price, David W.; Reed, Mark A.; Zhou, Chong-Wu; Chen, Jia; Wang, Wenyong; Campbell, Ian [Chemistry - A European Journal, 2001, vol. 7, # 23, p. 5118 - 5134]
[20]Marzin [Journal fur praktische Chemie (Leipzig 1954), 1933, vol. <2> 138, p. 103,106]
[21]Location in patent: scheme or table Mikroyannidis; Suresh; Roy; Sharma [Electrochimica Acta, 2011, vol. 56, # 16, p. 5616 - 5623]
[22]Xue, Pengchong; Sun, Jiabao; Chen, Peng; Gong, Peng; Yao, Boqi; Zhang, Zhenqi; Qian, Chong; Lu, Ran [Journal of Materials Chemistry C, 2015, vol. 3, # 16, p. 4086 - 4092]
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[24]Current Patent Assignee: CMDL CO LTD - KR2019/113044, 2019, A

Yield	Reaction Conditions	Operation in experiment
	With nitric acid at 300℃; im Rohr;

10
[ 63525-48-4 ]
[ 13731-82-3 ]

Reference： [1]Chemistry - A European Journal,2001,vol. 7,p. 5118 - 5134

11
[ 13731-82-3 ]
C₈H₂Br₂O₄^(2-)*2Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate In water at 50 - 75℃;	1 Under nitrogen 10 mmol of 2,5-dibromoterephthalic acid was stirred with a solution of 25 mmol Na2CO3 in 10 mL H2O at 50-75° C. until all of the 2,5-dibromoterephthalic acid was dissolved. Separately, 0.01 mmol of the copper compound [Example 1 and Examples 2 and 3 (Comparative)] or 0.05 mmol of Cu powder [Example 4 (Comparative)], respectively, was mixed with 1 mL of deionized water and 0.02 mmol of the ligand (Examples 1-3) or no ligand [Examples 2-4 (Comparative)], respectively, and the resulting copper containing mixture was added to the reaction mixture containing 2,5-dibromoterephthalic acid and Na2CO3 in H2O. The resulting reaction mixture was heated at the given temperature and for the given time (Table 1). After cooling to ambient temperature, the reaction mixtures were carefully acidified with 35% aqueous HCl. The products were isolated by filtration, washed with water and dried under vacuum. The crude reaction product was analyzed by 1H NMR (d6-dmso). The results are summarized in Table 1. TABLE 1 CONV SEL T Cu Ligand Example Ligand (% mol) (% mol) (° C.) t (h) source Structure 1 Proline 100 91 80 3CuBr2
	With sodium carbonate In water for 1h; Heating / reflux;	1; 2 Example 1. This example demonstrates the formation of 2,5-dihydroxyterephthalic acid from 2,5-dibromoterephthalic acid using CuBr and N,N'-dimesityl-2,3-diiminobutane Under nitrogen, 2.00 g (6.2 mmol) of 2,5-dibromoterephthalic acid were combined with 10 g of H2O; 0.679 g (6.4 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 0.950 g (9.0 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 9 mg (0.01 mol equiv) of CuBr and 40 mg (0.02 mol equiv) of N,N'-dimesityl-2,3-diiminobutane were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved. This solution was added to the stirred reaction mixture via syringe at 80° C. under nitrogen and stirred for 30 h at 80° C. After cooling to 25° C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 1.09 g of crude 2,5-dihydroxyterephthalic acid was collected. The purity of 2,5-dihydroxyterephthalic acid was determined by 1H NMR to be about 81%. The net yield of 2,5-dihydroxyterephthalic acid was determined to be 72%. Example 2. Under nitrogen, 3.24 g (10 mmol) of 2,4-dibromoterephthalic acid was combined with 10 g of H2O; 1.10 g (10.4 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 1.54 g (14.5 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 minutes. Separately, 22 mg (0.01 mol equiv) of CuBr2 and 69 mg (0.02 mol equiv) of N,N'-di(trifluoromethylbenzene)-2,3-diiminoethane were combined under nitrogen, followed by addition of 2 mL H2O under air. This solution was added to the stirred reaction mixture via syringe at with 80° C. under nitrogen and stirred for 26 h at 80° C. After cooling to 25° C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The precipitate was filtered and washed with water and dried. The conversion and selectivity of 2,4-hydroxyterephthalic acid were determined to be 100% and 72%, respectively, by 1H NMR. The net yield was determined to be 72%.

Reference： [1]Current Patent Assignee: DUPONT DE NEMOURS INC - US7339076, 2008, B1 Location in patent: Page/Page column 8-9
[2]Current Patent Assignee: DUPONT DE NEMOURS INC - US7355070, 2008, B1 Location in patent: Page/Page column 9-10

12
[ 13731-82-3 ]
[ 610-92-4 ]
2-bromo-5-hydroxy-terephthalic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	48 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water at 20℃;	41 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	37 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)

	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	45 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	44 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	35 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	46 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	43 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	36 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water at 20℃;	40 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	33 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	39 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	47 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	38 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	34 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	42 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	49 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I) bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 8. For Example 50 (Comparative), no ligand was used. The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 8. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 8. TABLE 8 Examples 33~49 Ligand CONV SEL SEL Ligand Code Example (II, %) (VII, %) (I, %) Structure A 33 >99 <1 84 B 34 >99 <1 94 C 35 92 5% 12 D 36 >99 <1 90 E 37 98 4 12 F 38 >99 <1 >98 G 39 >99 <1 82 H 40 83 9 10 I 41 >99 <1 55 J 42 >99 <1 76 K 43 >99 <1 96 L 44 >99 <1 11 M 45 >99 2 58 N 46 >99 3 49 P 47 >99 <1 99 R 48 >99 <1 75 - 49 31 32 2 No ligand (Comparative) (Comparative)
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	3 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	19 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	11 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	7 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	18 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	14 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	5 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	16 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	13 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	6 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	10 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	9 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water at 20℃;	8 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	15 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	4 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	12 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	A Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	17 Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.
	Stage #1: 2,5-dibromoterephtalic acid With sodium hydroxide; water; sodium acetate In acetonitrile at 90℃; for 3h; Sealed vial; Stage #2: With hydrogenchloride In water; acetonitrile at 20℃;	B Under a nitrogen atmosphere, to a 2 mL vial with magnetic stir bar was added 25 mg (0.077 mmol) of 2,5-dibromoterephthalic acid (“DBTA”), followed by 0.308 mL (0.308 mmol) of 1.0 M aqueous sodium hydroxide and 0.169 mL (0.169 mmol) of 1.0 M aqueous sodium acetate. The mixture was then treated with 0.003 mL (0.00077 mol, 1 mol %) of 0.23 M copper(I)bromide in acetonitrile and 0.003 mL (0.00154 mmol, 2 mol %) of the diamine ligand as noted below in Table 2, or half the amount for tetraamine ligand (Comparative Example A) or twice the amount in the case of pyridine (Q). For Comparative Example B, no ligand was used.The reactor vial was then sealed under nitrogen and placed in a sealed reactor block. After 3 hours at 90° C., the reaction mixture was allowed to cool to room temperature. The reaction mixture was acidified with 15% aqueous HCl, producing a precipitate. The precipitate was filtered and washed with H2O and the dried product was analyzed by 1H NMR. Percent conversion of DBTA (II) for each ligand is presented in Table 2. Selectivities for DHTA (I) and the intermediate 2-bromo-5-dihydroxyterephalic acid (VII) are also presented in Table 2. Using either a methyl-bearing tertiary tetraamine (Ligand O, Comparative Example A) or no ligand (Comparative Example B) resulted in lower conversion than using the ligands of the working examples.

Reference： [1]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[2]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[3]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[4]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[5]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[6]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[7]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[8]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[9]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[10]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[11]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[12]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[13]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[14]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[15]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[16]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[17]Current Patent Assignee: DUPONT DE NEMOURS INC - US7335791, 2008, B1 Location in patent: Page/Page column 25-31
[18]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[19]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[20]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[21]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[22]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[23]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[24]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[25]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[26]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[27]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[28]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[29]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[30]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[31]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[32]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-16
[33]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[34]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[35]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17
[36]Current Patent Assignee: DUPONT DE NEMOURS INC - US7345194, 2008, B1 Location in patent: Page/Page column 15-17

13
[ 13731-82-3 ]
[ 791717-65-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: SOCl₂ / 4 h / Heating 2: 2.1 g / 4 h / Heating 3: 95 percent / hydrazine monohydrate / methanol / Heating
	Multi-step reaction with 2 steps 1: H₂SO₄ 2: 83 percent / NH₂NH₂*H₂O / methanol / 24 h / Heating

Reference： [1]Wang, Hong-Yu; Feng, Jia-Chun; Wen, Gui-An; Jiang, Hong-Ji; Wan, Jun-Hua; Zhu, Rui; Wang, Chuan-Ming; Wei, Wei; Huang, Wei [New Journal of Chemistry, 2006, vol. 30, # 5, p. 667 - 670]
[2]Sung, Hsiao-Hsien; Lin, Hong-Cheu [Macromolecules, 2004, vol. 37, # 21, p. 7945 - 7954]

14
[ 13731-82-3 ]
[ 136296-63-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: thionyl chloride / 10 h / Heating 2: 72 percent / aluminium trichloride / benzene / 48 h / 20 °C
	Multi-step reaction with 2 steps 1: thionyl chloride / toluene; N,N-dimethyl-formamide / 2 h / Reflux 2: aluminum (III) chloride / dichloromethane / 24 h / 0 - 20 °C

Reference： [1]Qiu, Song; Lu, Ping; Liu, Xiao; Shen, Fangzhong; Liu, Linlin; Ma, Yuguang; Shen, Jiacong [Macromolecules, 2003, vol. 36, # 26, p. 9823 - 9829]
[2]Rodrigues, Ana Clara B.; Wetterling, Dario; Scherf, Ullrich; Seixas de Melo, J. Sérgio [Chemistry - A European Journal, 2021, vol. 27, # 29, p. 7826 - 7830]

15
[ 13731-82-3 ]
C₃₈H₄₄Br₂N₄O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: H₂SO₄ 2: 83 percent / NH₂NH₂*H₂O / methanol / 24 h / Heating 3: 73 percent / pyridine; NMP / 12 h 4: 74 percent / POCl₃ / 130 °C

Reference： [1]Sung, Hsiao-Hsien; Lin, Hong-Cheu [Macromolecules, 2004, vol. 37, # 21, p. 7945 - 7954]

16
[ 13731-82-3 ]
[ 791717-67-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: H₂SO₄ 2: 83 percent / NH₂NH₂*H₂O / methanol / 24 h / Heating 3: 73 percent / pyridine; NMP / 12 h

Reference： [1]Sung, Hsiao-Hsien; Lin, Hong-Cheu [Macromolecules, 2004, vol. 37, # 21, p. 7945 - 7954]

17
[ 13731-82-3 ]
2,5-bis(p-bromobenzyl)-1,4-dibromobenzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 100 percent / oxalyl chloride 2: 60 percent / aluminum chloride / CH₂Cl₂ / 0 - 20 °C 3: 88 percent / trifluoromethanesulfonic acid; triethylsilane / CH₂Cl₂ / 3 h / 20 °C

Reference： [1]Tour, James M.; Rawlett, Adam M.; Kozaki, Masatoshi; Yao, Yuxing; Jagessar, Raymond C.; Dirk, Shawn M.; Price, David W.; Reed, Mark A.; Zhou, Chong-Wu; Chen, Jia; Wang, Wenyong; Campbell, Ian [Chemistry - A European Journal, 2001, vol. 7, # 23, p. 5118 - 5134]

18
[ 13731-82-3 ]
[ 421554-39-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 100 percent / oxalyl chloride 2: 60 percent / aluminum chloride / CH₂Cl₂ / 0 - 20 °C

19
[ 13731-82-3 ]
[ 421554-40-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: 100 percent / oxalyl chloride 2.1: 60 percent / aluminum chloride / CH₂Cl₂ / 0 - 20 °C 3.1: 88 percent / trifluoromethanesulfonic acid; triethylsilane / CH₂Cl₂ / 3 h / 20 °C 4.1: tert-BuLi / tetrahydrofuran; diethyl ether; pentane / -78 - 0 °C 4.2: 58 percent / iodine / tetrahydrofuran; diethyl ether; pentane / -78 - 20 °C

20
[ 13731-82-3 ]
thioacetic acid <i>S</i>-(4-{4-(4-acetylsulfanyl-phenylethynyl)-2,5-bis-[4-(4-acetylsulfanyl-phenylethynyl)-benzyl]-phenylethynyl}-phenyl) ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: 100 percent / oxalyl chloride 2.1: 60 percent / aluminum chloride / CH₂Cl₂ / 0 - 20 °C 3.1: 88 percent / trifluoromethanesulfonic acid; triethylsilane / CH₂Cl₂ / 3 h / 20 °C 4.1: tert-BuLi / tetrahydrofuran; diethyl ether; pentane / -78 - 0 °C 4.2: 58 percent / iodine / tetrahydrofuran; diethyl ether; pentane / -78 - 20 °C 5.1: 35 percent / copper(I) iodide; triphenylphosphine; diisopropylethylamine / bis(dibenylideneacetone)palladium⁽⁰⁾ / tetrahydrofuran / 29 h / 20 °C

21
[ 13731-82-3 ]
[ 148079-53-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: ClCOCOCl 2: 70 percent

Reference： [1]Tour, James M.; Lamba, Jaydeep J. S. [Journal of the American Chemical Society, 1993, vol. 115, # 11, p. 4935 - 4936]

22
[ 13731-82-3 ]
1,4-bis(1'-oxo-n-tridecane)-2,5-dibromobenzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: ClCOCOCl 2: 64 percent

Reference： [1]Tour, James M.; Lamba, Jaydeep J. S. [Journal of the American Chemical Society, 1993, vol. 115, # 11, p. 4935 - 4936]

23
[ 106-42-3 ]
[ 13731-82-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: iodine; bromine / 10 - 15 °C 2: aqueous nitric acid 3: aqueous potassium carbonate; potassium permanganate
	Multi-step reaction with 2 steps 1: bromine; iodine / dichloromethane 2: pyridine; potassium permanganate; water
	Multi-step reaction with 2 steps 1: bromine; iodine / dichloromethane / 16 h / 0 - 20 °C / Darkness 2: potassium permanganate / water; <i>tert</i>-butyl alcohol / 18 h / Reflux

	Multi-step reaction with 2 steps 1: bromine 2: potassium permanganate
	Multi-step reaction with 2 steps 1: dihydrogen peroxide; bromine / dichloromethane / 24 h / 5 °C 2: potassium permanganate / <i>tert</i>-butyl alcohol; water / 4 h / Reflux
	Multi-step reaction with 2 steps 1.1: iodine / dichloromethane / 1 h / 0 °C 1.2: 16 h / 0 - 20 °C / Darkness 2.1: pyridine / Reflux 2.2: Reflux 2.3: 90 °C

Reference： [1]Marzin [Journal fur praktische Chemie (Leipzig 1954), 1933, vol. <2> 138, p. 103,106]
[2]Mikroyannidis; Suresh; Roy; Sharma [Electrochimica Acta, 2011, vol. 56, # 16, p. 5616 - 5623]
[3]Dressler, Justin J.; Miller, Sarah A.; Meeuwsen, Brian T.; Riel, Asia Marie S.; Dahl, Bart J. [Tetrahedron, 2015, vol. 71, # 2, p. 283 - 292]
[4]Xue, Pengchong; Sun, Jiabao; Chen, Peng; Gong, Peng; Yao, Boqi; Zhang, Zhenqi; Qian, Chong; Lu, Ran [Journal of Materials Chemistry C, 2015, vol. 3, # 16, p. 4086 - 4092]
[5]Zhang, Xiu-Tang; Fan, Li-Ming; Fan, Wei-Liu; Li, Bin; Liu, Guang-Zeng; Liu, Xin-Zheng; Zhao, Xian [Crystal Growth and Design, 2016, vol. 16, # 7, p. 3993 - 4004]
[6]Rodrigues, Ana Clara B.; Wetterling, Dario; Scherf, Ullrich; Seixas de Melo, J. Sérgio [Chemistry - A European Journal, 2021, vol. 27, # 29, p. 7826 - 7830]

24
[ 13731-82-3 ]
[ 50880-39-2 ]

Yield	Reaction Conditions	Operation in experiment
94%	Stage #1: 2,5-dibromoterephtalic acid With thionyl chloride; N,N-dimethyl-formamide for 3h; Inert atmosphere; Reflux; Stage #2: With ammonium hydroxide In 1,4-dioxane for 1h;	1 Synthesis of Compound 1 2,5-Dibromoterephthalic acid (14.7 g, 45.2 mmol), thionyl chloride (16.6 g, 14.0 mmol), a few drops of dimethylformamide (DMF) were placed in a two-neck flask under a nitrogen atmosphere, and refluxed under heating for 3 hours. Thereafter, toluene (50 mL) was added thereto, and thionyl chloride was removed through azeotropy therewith. The resulting deposit was dissolved in dioxane (20 mL), and the resulting solution was added dropwise to concentrated aqueous ammonia (60 mL), followed by stirring for 1 hour. The deposit was filtered to provide white powder (12.2 g, 94%).
	Multi-step reaction with 2 steps 1: PCl₅ 2: diethyl ether; ammonia
	Multi-step reaction with 2 steps 1: thionyl chloride; N,N-dimethyl-formamide / 3 h / Reflux 2: ammonium hydroxide / 1,4-dioxane / 20 °C

	Stage #1: 2,5-dibromoterephtalic acid With thionyl chloride In N,N-dimethyl-formamide Stage #2: With ammonium hydroxide
	Multi-step reaction with 2 steps 1: thionyl chloride; N,N-dimethyl-formamide / 3 h / 80 °C 2: ammonium hydroxide / 1,4-dioxane / 12 h / 20 °C
	Multi-step reaction with 2 steps 1: oxalyl dichloride; N,N-dimethyl-formamide / dichloromethane / 3 h / Inert atmosphere; Reflux 2: ammonium hydroxide / 0.08 h / 20 °C

Reference： [1]Current Patent Assignee: KYULUX, INC. - US2019/345095, 2019, A1 Location in patent: Paragraph 0204; 0205
[2]Claus [Journal fur praktische Chemie (Leipzig 1954), 1888, vol. <2> 37, p. 18]
[3]Cheng, Jian-Zhang; Lin, Chao-Chen; Chou, Pi-Tai; Chaskar, Atul; Wong, Ken-Tsung [Tetrahedron, 2011, vol. 67, # 4, p. 734 - 739]
[4]Current Patent Assignee: KYULUX, INC. - US9502668, 2016, B2 Location in patent: Page/Page column 133
[5]Schäfer, Julian; Holzapfel, Marco; Mladenova, Boryana; Kattnig, Daniel; Krummenacher, Ivo; Braunschweig, Holger; Grampp, Günter; Lambert, Christoph [Journal of the American Chemical Society, 2017, vol. 139, # 17, p. 6200 - 6209]
[6]Garcia, Rosalva C.; Pech, Matthew J.; Sommer, Roger; Gorman, Christopher B. [Journal of Organic Chemistry, 2019, vol. 84, # 23, p. 15079 - 15086]

25
[ 743460-48-2 ]
[ 13731-82-3 ]
[ 864751-39-3 ]

Yield	Reaction Conditions	Operation in experiment
100%	With N-ethyl-N,N-diisopropylamine; HATU In DMF (N,N-dimethyl-formamide) at 20℃; for 3h;	11 N-{2-[4-(Biphenyl-2-ylcarbamoyloxy)piperidin-1-yl]ethyl}-2,5-dibromo-N-methylterephthalamic Acid Preparation 11 N-{2-[4-(Biphenyl-2-ylcarbamoyloxy)piperidin-1-yl]ethyl}-2,5-dibromo-N-methylterephthalamic Acid To a 100 mL flask containing the product of Preparation 2 (2.5 g, 7.1 mmol) in DMF (20 mL) was added 2,5-dibromoterephthalic acid (6.88 g, 21.2 mmol) followed by DIPEA (1.6 mL, 9.2 mmol) and HATU (3.23 g, 8.5 mol). The yellow slurry was stirred at room temperature for 3 hours (all material in solution following completion of reaction). The reaction mixture was diluted with DCM (200 mL). To the solution was added 1N NaOH (150 mL) and MeOH (minimal amount added in order to dissolve the fine white precipitate that was observed following the addition of base). The solution was transferred to a separatory funnel and the aqueous layer discarded. The organic layer was washed with 1N HCl (1*150 mL), dried over sodium sulfate, filtered and the solvent removed under reduced pressure to provide 7 g of the title compound (>100% yield due to the presence of residual DMF). This material was used without further purification. MS m/z: [M+H+] calcd f for C29H29Br2N3O5, 659.4; found, 660.3. Rf=3.39 min (2-90 ACN: H2O, reverse phase HPLC).

Reference： [1]Current Patent Assignee: THERAVANCE BIOPHARMA, INC. - US2005/203133, 2005, A1 Location in patent: Page/Page column 27

26
[ 13731-82-3 ]
[ 124-41-4 ]
C₁₀H₈O₆^(2-)*2Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	In methanol for 8h; Heating / reflux;	1 In an air and moisture free environment, 4.2 g (77 mmol) of sodium methoxide was combined with 125 g of anhydrous methanol, followed by the addition of 5 g (15 mmol) of 2, 5-dibromoterephthalic acid. Separately, 103 mg (0.03 mol equiv) of CuBr2 and 132 mg (0.06 mol equiv) of rac-trans-N,N-dimethylcyclohexane-l , 2-diamine were combined under nitrogen, followed by addition of anhydrous methanol to dissolve. This solution was then added to form the reaction mixture. The reaction mixture was heated to reflux with stirring for 8 h, remaining under a nitrogen atmosphere. After cooling, the product was filtered, washed with hot MeOH and dried to yield 3.5 g (14.5 mmol) of the white solid as the bis-sodium salt. The purity was determined to be 97% by 1H NMR. The net isolated yield was determined to be 95%.
	In methanol for 8h; Heating / reflux;	1 In an air and moisture free environment, 4.2 g (77 mmol) of sodium methoxide is combined with 125 g of anhydrous methanol, followed by the addition of 5 g (15 mmol) of 2 , 5-dibromoterephthalic acid. Separately, 103 mg (0.03 mol equiv) of CuBr2 and 0.06 mol equiv of 2 , 2 ' , 6 , 6 ' -tetramethylheptanedione-3 , 5 are combined under nitrogen, followed by addition of anhydrous methanol to dissolve. This solution is then added to form the reaction mixture. The reaction mixture is heated to reflux with stirring for 8 h, remaining under a nitrogen atmosphere. After cooling, the product is filtered, washed with hot MeOH and dried to yield a white solid as the bis-sodium salt. The isolated salt is then acidified with hydrochloric acid. The purity is over 95% and the net isolated yield is over 90%
	In methanol for 8h; Heating / reflux;	1 Example 1; In an air and moisture free environment, 4.2 g (77 mmol) of sodium methoxide is combined with 125 g of anhydrous methanol, followed by the addition of 5 g (15 mmol) of 2 , 5-dibromoterephthalic acid. Separately, 103 mg (0.03 mol equiv) of CuBr2 and 0.06 mol equiv of - N, N' -dimesityl-2 , 3-diiminobutaneare combined under nitrogen, followed by addition of anhydrous methanol to dissolve. This solution is then added to form the reaction mixture. The reaction mixture is heated to reflux with stirring for 8 h, remaining under a nitrogen atmosphere. After cooling, the product is filtered, washed with hot MeOH and dried to yield a white solid as the bis-sodium salt

Reference： [1]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2008/79218, 2008, A1 Location in patent: Page/Page column 23-24
[2]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2008/79225, 2008, A1 Location in patent: Page/Page column 22
[3]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2008/82551, 2008, A1 Location in patent: Page/Page column 22

27
[ 67-56-1 ]
[ 13731-82-3 ]
[ 124-41-4 ]
C₁₀H₈O₆^(2-)*2Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	for 8h; Heating / reflux;	1 Example 1; In an air and moisture free environment, 4.2 g (77 mmol) of sodium methoxide is combined with 125 g of anhydrous methanol, followed by the addition of 5 g (15 mmol) of 2 , 5-dibromoterephthalic acid. Separately, 103 mg (0.03 mol equiv) of CuBr2 and 0.06 mol equiv of valine are combined under nitrogen, followed by- addition of anhydrous methanol to dissolve. This solution is then added to form the reaction mixture. The reaction mixture is heated to reflux with stirring for 8 h, remaining under a nitrogen atmosphere. After cooling, the product is filtered, washed with hot MeOH and dried to yield white solid as the bis-sodium salt. The isolated salt is then acidified with hydrochloric acid. The purity is over 95% and the net isolated yield is over 90%.

Reference： [1]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2008/82510, 2008, A1 Location in patent: Page/Page column 19-20

28
[ 13731-82-3 ]
[ 636-94-2 ]
[ 610-92-4 ]

Yield	Reaction Conditions	Operation in experiment
92%		Under nitrogen, 2.00 g (6.2 mmol) of 2,5-dibromoterephthalic acid was combined with 15 g of H2O; 0.679 g (6.4 mmol) of Na2CO3 was then added. The mixture was heated to reflux with stirring for 30 min, remaining under a nitrogen atmosphere. Another 0.940 g (9.0 mmol) of Na2CO3 was added to the reaction mixture and reflux was continued for 30 min. Separately, 9 mg (0.06 mmol)(0.01 mol equiv) of CuBr and 25 mg (0.14 mmol)(0.02 mol equiv) of 2,2',6,6'-tetramethylheptanedione-3,5 were combined with 2 mL H2O under nitrogen. The resulting mixture was stirred under an air atmosphere until the CuBr was dissolved. This solution was added to the stirred reaction mixture via syringe at 80 C. under nitrogen and stirred for 30 h at 80 C. After cooling to 25 C., the reaction mixture was acidified with HCl (conc.), producing a dark yellow precipitate. The yellow precipitate was filtered and washed with water. After drying, a total of 1.26 g of crude 2,5-dihydroxyterephthalic acid and 2-hydroxyterephthalic acid was collected. The purity of 2,5-dihydroxyterephthalic acid was determined by 1H NMR to be about 89%. The net yield of 2,5-dihydroxyterephthalic acid was determined to be 92%.

Reference： [1]Patent: US7351856,2008,B1 .Location in patent: Page/Page column 10-11

29
[ 111-87-5 ]
[ 13731-82-3 ]
[ 58613-37-9 ]

Yield	Reaction Conditions	Operation in experiment
87%	With toluene-4-sulfonic acid In toluene at 110℃; for 20h;

Reference： [1]Fortage, Jerome; Boixel, Julien; Blart, Errol; Hammarstroem, Leif; Becker, Hans Christian; Odobel, Fabrice [Chemistry - A European Journal, 2008, vol. 14, # 11, p. 3467 - 3480]

30
[ 64-17-5 ]
[ 13731-82-3 ]
[ 18013-97-3 ]

Yield	Reaction Conditions	Operation in experiment
96%	sulfuric acid;Reflux;	The inventive diindenothiophene derivatives can be produced by any of the methods that are conventionally known to persons having ordinary skill in the art. For instance, the above-mentioned compound of formula (2) can be prepared by a method comprising the following steps:
76%	With sulfuric acid; for 72h;Reflux;	Compound 5-3 (5.5 g, 17 mmol) in a 250 mL reaction flask,Add ethanol (150 mL) and conc. Add sulfuric acid (6.7 g, 68 mmol) and stir. The reaction is stirred at reflux for 3 days.After completion of the reaction, the solvent was concentrated under reduced pressure, and the filtrate was purified by column chromatography to obtain Compound 5-2 (4.9 g, 76%).
		Take 10g of 2,5-dibromo terephthalic acidIn a 100 mL round bottom flask,Add 20 mL of thionyl chloride with stirring.Heating backExcessive evaporation under normal pressure after 10 hoursDichlorosulfoxide gives the corresponding acid chloride.Slowly add at 0 C cooling10mL absolute ethanol,After the addition is completed,Stir at room temperature for 6 hours.The solvent was evaporated to give diethyl 2,5-dibromophthalate.

Reference： [1]CrystEngComm,2019,vol. 21,p. 4192 - 4199
[2]Patent: US2010/168444,2010,A1 .Location in patent: Page/Page column 4-8
[3]Organic Letters,2014,vol. 16,p. 106 - 109
[4]Crystal Growth and Design,2016,vol. 16,p. 3993 - 4004
[5]Chemical Communications,2010,vol. 46,p. 6503 - 6505
[6]Chemistry - A European Journal,2008,vol. 14,p. 11328 - 11342
[7]Patent: KR2019/113044,2019,A .Location in patent: Paragraph 0097; 0104-0105
[8]Electrochimica Acta,2011,vol. 56,p. 5616 - 5623
[9]Journal of Materials Chemistry C,2015,vol. 3,p. 4086 - 4092
[10]Patent: CN108947933,2018,A .Location in patent: Paragraph 0035; 0036

31
[ 13731-82-3 ]
[ 18870-11-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: thionyl chloride; N,N-dimethyl-formamide / 3 h / Reflux 2: ammonium hydroxide / 1,4-dioxane / 20 °C 3: trichlorophosphate / 12 h / 135 °C
	Multi-step reaction with 2 steps 1: thionyl chloride / N,N-dimethyl-formamide 2: trichlorophosphate
	Multi-step reaction with 3 steps 1: thionyl chloride; N,N-dimethyl-formamide / 3 h / 80 °C 2: ammonium hydroxide / 1,4-dioxane / 12 h / 20 °C 3: trichlorophosphate / 12 h / 125 °C

Multi-step reaction with 3 steps 1: oxalyl dichloride; N,N-dimethyl-formamide / dichloromethane / 3 h / Inert atmosphere; Reflux 2: ammonium hydroxide / 0.08 h / 20 °C 3: trichlorophosphate / 1 h / 110 °C / Inert atmosphere

Reference： [1]Cheng, Jian-Zhang; Lin, Chao-Chen; Chou, Pi-Tai; Chaskar, Atul; Wong, Ken-Tsung [Tetrahedron, 2011, vol. 67, # 4, p. 734 - 739]
[2]Current Patent Assignee: KYULUX, INC. - US9502668, 2016, B2
[3]Schäfer, Julian; Holzapfel, Marco; Mladenova, Boryana; Kattnig, Daniel; Krummenacher, Ivo; Braunschweig, Holger; Grampp, Günter; Lambert, Christoph [Journal of the American Chemical Society, 2017, vol. 139, # 17, p. 6200 - 6209]
[4]Garcia, Rosalva C.; Pech, Matthew J.; Sommer, Roger; Gorman, Christopher B. [Journal of Organic Chemistry, 2019, vol. 84, # 23, p. 15079 - 15086]

32
[ 76-37-9 ]
[ 13731-82-3 ]
[ 1268628-20-1 ]

Yield	Reaction Conditions	Operation in experiment
72%		Example 2 . Preparation of 2,5-bis (2,2,3,3- tetrafluoropropoxy) terephthalic acid; A flask was charged with 5 mL of anhydrous THF and 8.1 mmol of sodium hydride . A solution of 1.5 g (11.4 mmol) of <strong>[76-37-9]2,2,3,3-tetrafluoropropanol</strong> (HCF2CF2CH2OH) in 5 mL of THF was added dropwise. When gas evolution was complete, 2 , 5-dibromoterephthalic acid (1.51 mmol) was added to the colorless solution. Next, a mixture of CuBr2 (0.13 mmol) and 1 ,2-bis (methylamino) cyclohexane (0.22 mmol) in 0.5 g of HCF2CF2CH2OH was added to the solution. The resulting pale blue slurry was heated at 60 C for two days. The product was isolated by treating the cooled reaction product with 0.5 N HCl, then with water, and washing the precipitate with water. Yield: 0.465 g, 72%.NMR analysis: XH (CD3OD) : 7.56 (s, 2H) , 6.39 (tt, 52.8 and 5.7 Hz, 2H) , 4.52 (tt, 12.0 and 1.3 Hz, 4H) .
72%		Example 2 . Preparation of 2, 5-bis (2, 2, 3, 3- tetrafluoropropoxy) terephthalic acid; A flask was charged with 5 mL of anhydrous THF and 8.1 mmol of sodium hydride. A solution of 1.5 g(11.4 mmol) of 2 , 2 , 3 , 3-tetrafluoropropanol (HCF2CF2CH2OH) in 5 mL of THF was added dropwise. When gas evolution was complete, 2 , 5-dibromoterephthalic acid (1.51 mmol) was added to the colorless solution. Next, a mixture of CuBr2 (0.13 mmol) and 1 , 2-bis (methylamino) cyclohexane (0.22 mmol) in 0.5 g of HCF2CF2CH2OH was added to the solution. The resulting pale blue slurry was heated at 60C for two days. The product was isolated by treating the cooled reaction product with 0.5 N HC1, then with water, and washing the precipitate with water. Yield: 0.465 g, 72%.NMR analysis: XH (CD3OD) : 7.56 (s, 2H) , 6.39 (tt, 52.8 and 5.7 Hz, 2H) , 4.52 (tt, 12.0 and 1.3 Hz, 4H) .
		Example 2 . Preparation of 2,5-bis (2,2,3,3- tetrafluoropropoxy) terephthalic acid; A flask is charged with 5 mL of anhydrous THF and 8.1 mmol of sodium hydride . A solution of 1.5 g (11.4 mmol) of <strong>[76-37-9]2,2,3,3-tetrafluoropropanol</strong> (HCF2CF2CH2OH) in 5 mL of THF is added dropwise. When gas evolution is complete, 2, 5-dibromoterephthalic acid (1.51 mmol) is added to the colorless solution. Next, a mixture of CuBr2 (0.13 mmol) and N-methylanthranilic acid (0.22 mmol) in 0.5 g of HCF2CF2CH2OH is added to the solution. The resulting pale blue slurry is heated at 60 C for two days. The product 2,5-bis (2,2,3,3- tetrafluoropropoxy) terephthalic acidis isolated by treating the cooled reaction product with 0.5 N HC1, then with water, and washing the precipitate with water.

		Example 2 . Preparation of 2, 5-bis (2, 2, 3, 3- tetrafluoropropoxy) terephthalic acidA flask is charged with 5 mL of anhydrous THF and 8.1 mmol of sodium hydride.; A solution of 1.5 g (11.4 mmol) of 2 , 2 , 3 , 3-tetrafluoropropanol (HCF2CF2CH2OH) in 5 mL of THF is added dropwise. When gas evolution is complete, 2 , 5-dibromoterephthalic acid (1.51 mmol) is added to the colorless solution. Next, a mixture of CuBr2 (0.13 mmol) and N, N' -di ( trifluoromethylbenzene) -2 , 3- diiminoethane(0.22 mmol) in 0.5 g of HCF2CF2CH2OH is added to the solution. The resulting pale blue slurry is heated at 60C for two days. The product 2, 5-bis (2, 2, 3, 3- tetrafluoropropoxy) terephthalic acidis isolated by treating the cooled reaction product with 0.5 N HC1, then with water, and washing the precipitate with water.
		Example 2 . Preparation of 2, 5-bis (2, 2, 3, 3- tetrafluoropropoxy) terephthalic acid; A flask is charged with 5 mL of anhydrous THF and 8.1 mmol of sodium hydride. A solution of 1.5 g (11.4 mmol) of 2, 2, 3, 3-tetrafluoropropanol (HCF2CF2CH2OH) in 5 mL of THF is added dropwise. When gas evolution is complete, 2 , 5-dibromoterephthalic acid (1.51 mmol) is added to the colorless solution. Next, a mixture of CuBr2 (0.13 mmol) and 2, 4-pentanedione (0.22 mmol) in 0.5 g of HCF2CF2CH2OH is added to the solution. The resulting pale blue slurry is heated at 60C for two days. The product 2,5- bis (2, 2, 3, 3-tetrafluoropropoxy) terephthalic acid is isolated by treating the cooled reaction product with 0.5 N HC1, then with water, and washing the precipitate with water .

Reference： [1]Patent: WO2011/28851,2011,A2 .Location in patent: Page/Page column 27
[2]Patent: WO2011/28872,2011,A2 .Location in patent: Page/Page column 33
[3]Patent: WO2011/28852,2011,A2 .Location in patent: Page/Page column 27
[4]Patent: WO2011/28862,2011,A2 .Location in patent: Page/Page column 30
[5]Patent: WO2011/28866,2011,A2 .Location in patent: Page/Page column 28-29

33
[ 75-89-8 ]
[ 13731-82-3 ]
[ 1268628-19-8 ]

Yield	Reaction Conditions	Operation in experiment
71%	Stage #1: 2,2,2-trifluoroethanol With sodium hydride In tetrahydrofuran Stage #2: 2,5-dibromoterephtalic acid In tetrahydrofuran; 2,2,2-trifluoroethanol at 60℃; for 96h; Stage #3: With hydrogenchloride In tetrahydrofuran; water	1 Example 1 Preparation of 2, 5-bis (2,2,2- trifluoroethoxy) terephthalic acid; To a solution of 8 mL 2,2,2-trifluoroethanol ( CF3CH2OH) in 15 mL of THF was carefully added 0.19 g (7.9 mmol) of sodium hydride. When gas evolution wascomplete, 0.488 g (1.5 mmol) of 2 , 5-dibromoterephthalic acid was added to the solution, followed by addition of a solution of CuBr2 (0.092 mmol) and 1,2- bis (methylamino) cyclohexane (0.19 mmol) in 1.5 mL ofCF3CH2OH . The resulting pale blue slurry was heated at 60°C for four days. Aqueous HCI (1 N) was added to precipitate the product. The product was washed with water, then dissolved in methanol, and the resulting solution was filtered. The methanol was removed under vacuum to give the product as colorless microcrystals. Yield: 0.384 g, 71 %. Elemental analysis: Calculated for Ci2H8F606: C, 39.80 %; H, 2.23 %. Found: C, 39.93%, 2.31 %.MR analysis: XH (CD3OD) : 7.53 (s, 2H) , 4.57 (q, 8.5 Hz, 4H)13C (CD3OD) : 167.7, 152.9, 128.2, 124.9 (q, 277 Hz), 120.4, 69.1 (q, 35.4 Hz) .
71%	Stage #1: 2,2,2-trifluoroethanol With sodium hydride In tetrahydrofuran Stage #2: 2,5-dibromoterephtalic acid In tetrahydrofuran; 2,2,2-trifluoroethanol at 60℃; for 96h; Stage #3: With hydrogenchloride In tetrahydrofuran; water	1 Example 1 Preparation of 2 , 5-bis (2 , 2 , 2- trifluoroethoxy) terephthalic acid; To a solution of 8 mL 2 , 2 , 2-trifluoroethanol (CF3CH2OH) in 15 mL of THF was carefully added 0.19 g (7.9 mmol) of sodium hydride. When gas evolution wascomplete, 0.488 g (1.5 mmol) of 2 , 5-dibromoterephthalic acid was added to the solution, followed by addition of a solution of CuBr2 (0.092 mmol) and 1,2- bis (methylamino) cyclohexane (0.19 mmol) in 1.5 mL ofCF3CH2OH. The resulting pale blue slurry was heated at 60°C for four days. Aqueous HCI (1 N) was added toprecipitate the product. The product was washed with water, then dissolved in methanol, and the resulting solution was filtered. The methanol was removed under vacuum to give the product as colorless microcrystals .Yield: 0.384 g, 71 %.Elemental analysis: Calculated for Ci2H8F606 : C, 39.80 %;H, 2.23 %. Found: C, 39.93%, 2.31 %. NMR analysis: lH (CD3OD) : 7.53 (s, 2H) , 4.57 (q, 8.5 Hz,4H)13C (CD3OD) : 167.7, 152.9, 128.2, 124.9 (q, 277 Hz),120.4, 69.1 (q, 35.4 Hz) .
	Stage #1: 2,2,2-trifluoroethanol With sodium hydride In tetrahydrofuran Stage #2: 2,5-dibromoterephtalic acid In tetrahydrofuran; 2,2,2-trifluoroethanol at 60℃; for 96h; Stage #3: With hydrogenchloride In tetrahydrofuran; water	1 Example 1 Preparation of 2, 5-bis (2,2,2- trifluoroethoxy) terephthalic acid; To a solution of 8 mL 2,2,2-trifluoroethanol (CF3CH2OH) in 15 mL of THF is carefully added 0.19 g (7.9 mmol) of sodium hydride. When gas evolution is complete, 0.488 g (1.5 mmol) of 2 , 5-dibromoterephthalic acid was added to the solution, followed by addition of a solution of CuBr2 (0.092 mmol) and valine (0.19 mmol) in 1.5 mL of CF3CH2OH. The resulting pale blue slurry is heated at 60°C for four days. Aqueous HC1 (1 N) is added to precipitate the product. The product is washed with water, then dissolved in methanol, and the resulting solution is filtered. The methanol is removed under vacuum to give the product 2,5-bis (2,2,2- trifluoroethoxy) terephthalic acid as colorlessmicrocrystals .

	Stage #1: 2,2,2-trifluoroethanol With sodium hydride In tetrahydrofuran Stage #2: 2,5-dibromoterephtalic acid In tetrahydrofuran; 2,2,2-trifluoroethanol at 60℃; for 96h; Stage #3: With hydrogenchloride In tetrahydrofuran; water	1 Example 1 Preparation of 2 , 5-bis (2 , 2 , 2- trifluoroethoxy) terephthalic acid; To a solution of 8 mL 2 , 2 , 2-trifluoroethanol(CF3CH2OH) in 15 mL of THF is carefully added 0.19 g (7.9 mmol) of sodium hydride. When gas evolution is complete, 0.488 g (1.5 mmol) of 2 , 5-dibromoterephthalic acid was added to the solution, followed by addition of a solution of CuBr2 (0.092 mmol) and N, N' -dimesityl-2 , 3-diiminobutane(0.19 mmol) in 1.5 mL of CF3CH2OH. The resulting pale blue slurry is heated at 60°C for four days. Aqueous HCI(1 N) is added to precipitate the product. The product is washed with water, then dissolved in methanol, and the resulting solution is filtered. The methanol is removed under vacuum to give the product 2 , 5-bis (2 , 2 , 2- trifluoroethoxy) terephthalic acid as colorlessmicrocrystals .
	Stage #1: 2,2,2-trifluoroethanol With sodium hydride In tetrahydrofuran Stage #2: 2,5-dibromoterephtalic acid In tetrahydrofuran; 2,2,2-trifluoroethanol at 60℃; for 96h; Stage #3: With hydrogenchloride In tetrahydrofuran; water	1 Example 1 Preparation of 2 , 5-bis (2 , 2 , 2- trifluoroethoxy) terephthalic acid; To a solution of 8 mL 2 , 2 , 2-trifluoroethanol (CF3CH2OH) in 15 mL of THF is carefully added 0.19 g (7.9 mmol) of sodium hydride. When gas evolution is complete, 0.488 g (1.5 mmol) of 2 , 5-dibromoterephthalic acid was added to the solution, followed by addition of a solution of CuBr2 (0.092 mmol) and 2, 2', 6,6'- tetramethylheptanedione-3 , 5 (0.19 mmol) in 1.5 mL ofCF3CH2OH. The resulting pale blue slurry is heated at 60°C for four days. Aqueous HC1 (1 N) is added toprecipitate the product. The product is washed with water, then dissolved in methanol, and the resulting solution is filtered. The methanol is removed under vacuum to give the product 2 , 5-bis (2 , 2 , 2- trifluoroethoxy) terephthalic acid as colorlessmicrocrystals .

Reference： [1]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2011/28851, 2011, A2 Location in patent: Page/Page column 26-27
[2]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2011/28872, 2011, A2 Location in patent: Page/Page column 32-33
[3]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2011/28852, 2011, A2 Location in patent: Page/Page column 26-27
[4]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2011/28862, 2011, A2 Location in patent: Page/Page column 29
[5]Current Patent Assignee: DUPONT DE NEMOURS INC - WO2011/28866, 2011, A2 Location in patent: Page/Page column 28

34
[ 13731-82-3 ]
[ 915224-39-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: sulfuric acid 2: bis-triphenylphosphine-palladium(II) chloride / tetrahydrofuran / 24 h / Inert atmosphere; Reflux
	Multi-step reaction with 2 steps 1.1: sulfuric acid / 72 h / Reflux 2.1: bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol / toluene / 0.25 h / 100 °C / Inert atmosphere 2.2: 24 h / 100 °C / Inert atmosphere 2.3: 12 h / 20 °C / Inert atmosphere

Reference： [1]Mikroyannidis; Suresh; Roy; Sharma [Electrochimica Acta, 2011, vol. 56, # 16, p. 5616 - 5623]
[2]Cai, Liping; Moehl, Thomas; Moon, Soo-Jin; Decoppet, Jean-David; Humphry-Baker, Robin; Xue, Zhaosheng; Bin, Liu; Zakeeruddin, Shaik M; Graetzel, Michael [Organic Letters, 2014, vol. 16, # 1, p. 106 - 109]

35
[ 13731-82-3 ]
[ 1314019-18-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: sulfuric acid 2: bis-triphenylphosphine-palladium(II) chloride / tetrahydrofuran / 24 h / Inert atmosphere; Reflux 3: trichlorophosphate / 1,2-dichloro-ethane / 17 h / Reflux

Reference： [1]Mikroyannidis; Suresh; Roy; Sharma [Electrochimica Acta, 2011, vol. 56, # 16, p. 5616 - 5623]

36
6-[4-(4-pentyl-cyclohexyl)-phenoxy]-hexan-1-ol [ No CAS ]
[ 13731-82-3 ]
bis(6-(4-(4-pentylcyclohexyl)phenoxy)hexyl) 2,5-dibromoterephthalate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%	With triphenylphosphine; diethylazodicarboxylate In tetrahydrofuran; toluene at 20℃; Inert atmosphere;

Reference： [1]Jeong, Yong Soo; Akagi, Kazuo [Journal of Materials Chemistry, 2011, vol. 21, # 28, p. 10472 - 10481]

37
[ 13731-82-3 ]
[ 111232-16-7 ]
[ 1314135-89-1 ]

Yield	Reaction Conditions	Operation in experiment
26%	With triphenylphosphine; diethylazodicarboxylate In tetrahydrofuran; toluene at 20℃; Inert atmosphere;

Reference： [1]Jeong, Yong Soo; Akagi, Kazuo [Journal of Materials Chemistry, 2011, vol. 21, # 28, p. 10472 - 10481]

38
[ 110-89-4 ]
[ 13731-82-3 ]
[ 1050611-59-0 ]

Yield	Reaction Conditions	Operation in experiment
83%	Stage #1: 2,5-dibromoterephtalic acid With thionyl chloride; N,N-dimethyl-formamide for 1h; Inert atmosphere; Reflux; Stage #2: piperidine With triethylamine at 0 - 20℃; for 2h;	2 Synthesis of Compound D 1,4-Dibromo-2,5-benzenedicarboxylic acid (10 g, 30.87 mmol), a catalytic amount of DMF and an excess of thionyl chloride were placed in a recovery flask. The gas in the recovery flask was replaced with nitrogen, followed by refluxing for one hour. After the reaction, thionyl chloride was evaporated under vacuum. Next, this was cooled to 0° C., and triethylamine (25.89 mL, 185.2 mmol) was then added and piperidine (18.36 mL, 185.2 mmol) was further added dropwise. After the dropwise addition, the mixture was stirred at room temperature. After two hours, water was added, followed by extraction with dichloromethane. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The generated solid was washed with methanol to provide a white solid compound D (11.76 g, yield: 83%). The analysis results and the chemical formula of the resulting compound D are as follows. [0251] 1H NMR (400 MHz, CDCl3): δ 7.44 (s, 2H) [0252] GC-MS (DI): m/z=457 (M+).

Reference： [1]Current Patent Assignee: OSAKA UNIVERSITY; Sumitomo Chemical (w/o Dongwoo Fine-Chem); SUMITOMO CHEMICAL COMPANY LIMITED - US2013/41123, 2013, A1 Location in patent: Paragraph 0250; 0251; 0252

39
[ 13731-82-3 ]
[ 71-36-3 ]
[ 58613-36-8 ]

Yield	Reaction Conditions	Operation in experiment
89%	With sulfuric acid at 120℃; for 12h;
81%	With sulfuric acid for 15h;

Reference： [1]Audibert, Edwige; Gianga, Tiberiu-M.; Kociok-Köhn, Gabriele; Pantoş, G. Dan; Trandafir, Anamaria [Chemical Science, 2020, vol. 11, # 35, p. 9685 - 9690]
[2]Ota, Shinya; Minami, Sojiro; Hirano, Koji; Satoh, Tetsuya; Ie, Yutaka; Seki, Shu; Aso, Yoshio; Miura, Masahiro [RSC Advances, 2013, vol. 3, # 30, p. 12356 - 12365]

40
cobalt(II) nitrate hexahydrate [ No CAS ]
[ 83524-76-9 ]
[ 13731-82-3 ]
[Co(methylenebis(3,5-dimethylpyrazole))(Br-BDC)](H₂O)_0.5} [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	In water at 120℃; for 24h; Autoclave;

Reference： [1]Guo, Xiang-Guang; Yang, Wen-Bin; Wu, Xiao-Yuan; Zhang, Qi-Kai; Lin, Lang; Yu, Rongmin; Lu, Can-Zhong [CrystEngComm, 2013, vol. 15, # 18, p. 3654 - 3663]

41
cadmium(II) nitrate tetrhydrate [ No CAS ]
[ 83524-76-9 ]
[ 13731-82-3 ]
[Cd(methylenebis(3,5-dimethylpyrazole))(Br-BDC)_0.5(Br-HBDC)] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	In water at 120℃; for 48h; Autoclave;

Reference： [1]Guo, Xiang-Guang; Yang, Wen-Bin; Wu, Xiao-Yuan; Zhang, Qi-Kai; Lin, Lang; Yu, Rongmin; Lu, Can-Zhong [CrystEngComm, 2013, vol. 15, # 18, p. 3654 - 3663]

42
[ 13731-82-3 ]
[ 1509939-07-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 10 steps 1.1: sulfuric acid / 72 h / Reflux 2.1: bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol / toluene / 0.25 h / 100 °C / Inert atmosphere 2.2: 24 h / 100 °C / Inert atmosphere 2.3: 12 h / 20 °C / Inert atmosphere 3.1: potassium hydroxide / water; ethanol / Reflux 4.1: oxalyl dichloride / dichloromethane; N,N-dimethyl-formamide / 20 °C 5.1: aluminum (III) chloride / dichloromethane / 0 - 20 °C 6.1: potassium hydroxide; hydrazine hydrate / diethylene glycol / 24 h / 180 °C 7.1: potassium <i>tert</i>-butylate / dimethyl sulfoxide / 1 h / 80 °C 7.2: 85 - 90 °C 8.1: trichlorophosphate / 1,2-dichloro-ethane / 4 h / 0 °C / Inert atmosphere 8.2: 2 h / 20 °C 9.1: N-Bromosuccinimide / tetrahydrofuran / 0 - 20 °C / Inert atmosphere 10.1: potassium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene / 24 h / Inert atmosphere; Reflux

43
[ 13731-82-3 ]
[ 1446707-47-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 11 steps 1.1: sulfuric acid / 72 h / Reflux 2.1: bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol / toluene / 0.25 h / 100 °C / Inert atmosphere 2.2: 24 h / 100 °C / Inert atmosphere 2.3: 12 h / 20 °C / Inert atmosphere 3.1: potassium hydroxide / water; ethanol / Reflux 4.1: oxalyl dichloride / dichloromethane; N,N-dimethyl-formamide / 20 °C 5.1: aluminum (III) chloride / dichloromethane / 0 - 20 °C 6.1: potassium hydroxide; hydrazine hydrate / diethylene glycol / 24 h / 180 °C 7.1: potassium <i>tert</i>-butylate / dimethyl sulfoxide / 1 h / 80 °C 7.2: 85 - 90 °C 8.1: trichlorophosphate / 1,2-dichloro-ethane / 4 h / 0 °C / Inert atmosphere 8.2: 2 h / 20 °C 9.1: N-Bromosuccinimide / tetrahydrofuran / 0 - 20 °C / Inert atmosphere 10.1: potassium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene / 24 h / Inert atmosphere; Reflux 11.1: piperidine / chloroform; acetonitrile / 65 °C / Inert atmosphere

44
[ 13731-82-3 ]
[ 1209012-29-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: sulfuric acid / 72 h / Reflux 2.1: bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol / toluene / 0.25 h / 100 °C / Inert atmosphere 2.2: 24 h / 100 °C / Inert atmosphere 2.3: 12 h / 20 °C / Inert atmosphere 3.1: potassium hydroxide / water; ethanol / Reflux 4.1: oxalyl dichloride / dichloromethane; N,N-dimethyl-formamide / 20 °C

45
[ 13731-82-3 ]
[ 1209012-28-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: sulfuric acid / 72 h / Reflux 2.1: bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol / toluene / 0.25 h / 100 °C / Inert atmosphere 2.2: 24 h / 100 °C / Inert atmosphere 2.3: 12 h / 20 °C / Inert atmosphere 3.1: potassium hydroxide / water; ethanol / Reflux
	Multi-step reaction with 3 steps 1: sulfuric acid / water / 25 °C / Reflux; Inert atmosphere 2: tris-(o-tolyl)phosphine; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾ / tetrahydrofuran / 3 h / Reflux; Inert atmosphere 3: sodium hydroxide / water; methanol / 16 h / Reflux
	Multi-step reaction with 3 steps 1: sulfuric acid / 25 °C / Inert atmosphere; Reflux 2: tris-(o-tolyl)phosphine; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾ / tetrahydrofuran / 3 h / Reflux; Inert atmosphere 3: sodium hydroxide; water / methanol / 16 h / Reflux

Reference： [1]Cai, Liping; Moehl, Thomas; Moon, Soo-Jin; Decoppet, Jean-David; Humphry-Baker, Robin; Xue, Zhaosheng; Bin, Liu; Zakeeruddin, Shaik M; Graetzel, Michael [Organic Letters, 2014, vol. 16, # 1, p. 106 - 109]
[2]Current Patent Assignee: WAYS TECHNICAL CORPORATION LIMITED - TWI706955, 2020, B
[3]Current Patent Assignee: WAYS TECH - CN112390813, 2021, A

46
[ 13731-82-3 ]
[ 1209012-30-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: sulfuric acid / 72 h / Reflux 2.1: bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol / toluene / 0.25 h / 100 °C / Inert atmosphere 2.2: 24 h / 100 °C / Inert atmosphere 2.3: 12 h / 20 °C / Inert atmosphere 3.1: potassium hydroxide / water; ethanol / Reflux 4.1: oxalyl dichloride / dichloromethane; N,N-dimethyl-formamide / 20 °C 5.1: aluminum (III) chloride / dichloromethane / 0 - 20 °C

47
[ 13731-82-3 ]
[ 1209012-31-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1.1: sulfuric acid / 72 h / Reflux 2.1: bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol / toluene / 0.25 h / 100 °C / Inert atmosphere 2.2: 24 h / 100 °C / Inert atmosphere 2.3: 12 h / 20 °C / Inert atmosphere 3.1: potassium hydroxide / water; ethanol / Reflux 4.1: oxalyl dichloride / dichloromethane; N,N-dimethyl-formamide / 20 °C 5.1: aluminum (III) chloride / dichloromethane / 0 - 20 °C 6.1: potassium hydroxide; hydrazine hydrate / diethylene glycol / 24 h / 180 °C
	Multi-step reaction with 5 steps 1.1: sulfuric acid / water / 25 °C / Reflux; Inert atmosphere 2.1: tris-(o-tolyl)phosphine; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾ / tetrahydrofuran / 3 h / Reflux; Inert atmosphere 3.1: sodium hydroxide / water; methanol / 16 h / Reflux 4.1: phosgene; N,N-dimethyl-formamide / dichloromethane / 16 h / 20 °C / Cooling with ice 4.2: 4.5 h / 20 °C / Cooling with ice 5.1: hydrazine; potassium hydroxide / diethylene glycol / 24 h / 160 - 170 °C / Cooling with ice
	Multi-step reaction with 5 steps 1.1: sulfuric acid / 25 °C / Inert atmosphere; Reflux 2.1: tris-(o-tolyl)phosphine; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾ / tetrahydrofuran / 3 h / Reflux; Inert atmosphere 3.1: sodium hydroxide; water / methanol / 16 h / Reflux 4.1: N,N-dimethyl-formamide; oxalyl dichloride / dichloromethane / 16 h / 0 - 20 °C 4.2: 4.5 h / 0 - 20 °C 5.1: hydrazine hydrate; potassium hydroxide / diethylene glycol / 24 h / 160 - 170 °C

48
[ 13731-82-3 ]
[ 1509939-03-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 7 steps 1.1: sulfuric acid / 72 h / Reflux 2.1: bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol / toluene / 0.25 h / 100 °C / Inert atmosphere 2.2: 24 h / 100 °C / Inert atmosphere 2.3: 12 h / 20 °C / Inert atmosphere 3.1: potassium hydroxide / water; ethanol / Reflux 4.1: oxalyl dichloride / dichloromethane; N,N-dimethyl-formamide / 20 °C 5.1: aluminum (III) chloride / dichloromethane / 0 - 20 °C 6.1: potassium hydroxide; hydrazine hydrate / diethylene glycol / 24 h / 180 °C 7.1: potassium <i>tert</i>-butylate / dimethyl sulfoxide / 1 h / 80 °C 7.2: 85 - 90 °C

49
[ 13731-82-3 ]
[ 1509939-04-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 8 steps 1.1: sulfuric acid / 72 h / Reflux 2.1: bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol / toluene / 0.25 h / 100 °C / Inert atmosphere 2.2: 24 h / 100 °C / Inert atmosphere 2.3: 12 h / 20 °C / Inert atmosphere 3.1: potassium hydroxide / water; ethanol / Reflux 4.1: oxalyl dichloride / dichloromethane; N,N-dimethyl-formamide / 20 °C 5.1: aluminum (III) chloride / dichloromethane / 0 - 20 °C 6.1: potassium hydroxide; hydrazine hydrate / diethylene glycol / 24 h / 180 °C 7.1: potassium <i>tert</i>-butylate / dimethyl sulfoxide / 1 h / 80 °C 7.2: 85 - 90 °C 8.1: trichlorophosphate / 1,2-dichloro-ethane / 4 h / 0 °C / Inert atmosphere 8.2: 2 h / 20 °C

50
[ 13731-82-3 ]
[ 1509939-05-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 9 steps 1.1: sulfuric acid / 72 h / Reflux 2.1: bis-triphenylphosphine-palladium(II) chloride; 2,6-di-tert-butylphenol / toluene / 0.25 h / 100 °C / Inert atmosphere 2.2: 24 h / 100 °C / Inert atmosphere 2.3: 12 h / 20 °C / Inert atmosphere 3.1: potassium hydroxide / water; ethanol / Reflux 4.1: oxalyl dichloride / dichloromethane; N,N-dimethyl-formamide / 20 °C 5.1: aluminum (III) chloride / dichloromethane / 0 - 20 °C 6.1: potassium hydroxide; hydrazine hydrate / diethylene glycol / 24 h / 180 °C 7.1: potassium <i>tert</i>-butylate / dimethyl sulfoxide / 1 h / 80 °C 7.2: 85 - 90 °C 8.1: trichlorophosphate / 1,2-dichloro-ethane / 4 h / 0 °C / Inert atmosphere 8.2: 2 h / 20 °C 9.1: N-Bromosuccinimide / tetrahydrofuran / 0 - 20 °C / Inert atmosphere

51
[ 13731-82-3 ]
[ 18014-00-1 ]

Reference： [1]Journal of the American Chemical Society,2014,vol. 136,p. 2432 - 2440

52
europium(III) chloride hexahydrate [ No CAS ]
[ 865169-07-9 ]
[ 13731-82-3 ]
Eu⁽³⁺⁾*C₂₀H₁₁N₄O₂^(1-)*C₈H₂Br₂O₄^(2-) [ No CAS ]

Reference： [1]Inorganic Chemistry,2014,vol. 53,p. 10952 - 10963

53
[ 13731-82-3 ]
[ 6046-93-1 ]
[ 121-44-8 ]
[Cu(Br₂BDC)₂](HTEA)₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
48.4%	In methanol at 90℃; for 24h; Autoclave; High pressure;	2.1 2.2.1. Compound [Cu(Br2BDC)2](HTEA)2 (1) 0.154 g (0.771 mmol) Cu(CH3COO)2H2O was mixed with0.500 g (1.54 mmol) 2,5-dibromoterephthalic acid and 0.22 mLtriethylamine (TEA) in 1.0 mL methanol. The reaction mixture wastransferred to a 300 400 Teflon bag, which was then sealed andplaced in a 45 mL Teflon-lined autoclave. The autoclave was placedin an oven and was heated up to 90 C in 12h, kept at 90C for12 h, then cooled to 30 C in 18 h. The resulting products were thenfiltered using a vacuum filtration system and washed withmethanol.Blue crystals of 1 were obtained in 48.4% yield (0.340 g,0.373mmol). CHN-analysis: Anal. Calc. for [Cu(Br2BDC)2](TEA)2 (1):C, 36.89; H, 3.98; N, 3.07. Found: C, 36.69; H, 3.83; N, 2.98%.

Reference： [1]Liu, Xin; Valentine, Haley L.; Pan, Wei-Ping; Cao, Yan; Yan, Bangbo [Inorganica Chimica Acta, 2016, vol. 447, p. 162 - 167]

54
[ 64-18-6 ]
cobalt(II) nitrate hexahydrate [ No CAS ]
[ 13731-82-3 ]
[ 33513-42-7 ]
[Co₂(2,5-dibromoterephthalate)(HCOO)₂(dimethylformamide)₂] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78.2%	at 150℃; for 24h; Autoclave; High pressure;	2.2.2. Compound [Co2(Br2BDC)(HCOO)2(DMF)2] (2) A mixture of 2,5-dibromoterephthalic (0.077 g; 0.238 mmol),formic acid (0.021 g; 0.45 mmol), Co(NO3)26H2O (0.138 g;0.474 mmol) and 4.0 mL DMF was placed in a 300 400 Teflon bag.The bag was sealed and placed in a 45 ml Teflon-line autoclave.The autoclave was then placed in an oven programmed and heatedat 150 C for 24 h. After cooled naturally, the products were filteredand washed with DI water. Pink crystals were obtained in 78.2%yield (0.119 g, 0.176 mmol). CHN-analysis: Anal. Calc. for C,28.43; H, 2.68; N, 4.14. Found: C, 28.61; H, 2.65; N, 4.04%.

Reference： [1]Liu, Xin; Valentine, Haley L.; Pan, Wei-Ping; Cao, Yan; Yan, Bangbo [Inorganica Chimica Acta, 2016, vol. 447, p. 162 - 167]

55
C₂₂H₃₁N₄O₆Pol [ No CAS ]
[ 13731-82-3 ]
C₅₂H₆₂Br₂N₈O₁₄Pol₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In 1-methyl-pyrrolidin-2-one	General N-acylation Procedure of Peptides General procedure: Following completion of the oligopeptide sequence and deprotection of the last amino acid residue, the resin (0.3 mmol peptide) was treated with 2,5-dibromoterephthalic acid (0.1 eq.) that was activated by PyBOP (0.2 eq.) and diisopropylethylamine (10 eq.) for 12 hours in NMP. After coupling, the resin was filtered, washed 2x with NMP and DCM and resubjected to treatment with 2,5-dibromoterephthalic acid (0.05 eq.) that was activated by PyBOP (0.10 eq.) and diisopropylethylamine (10 eq.) for 12 hours in NMP. After coupling, the resin was filtered, washed 2x with NMP and DCM and subjected to a blank coupling cycle using PyBOP (0.2 eq.) and diisopropylethylamine (10 eq.) for 1-2 hours in NMP to yield maximum coupling of diacid with oligopeptide. After completion, the resin was subjected to a standard wash cycle: 3x NMP, methanol and DCM.

Reference： [1]Kale, Tejaswini S.; Tovar, John D. [Tetrahedron, 2016, vol. 72, # 40, p. 6084 - 6090]

56
[ 13731-82-3 ]
Wang-DFGG amide [ No CAS ]
C₅₀H₅₈Br₂N₈O₁₄Pol₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In 1-methyl-pyrrolidin-2-one	General N-acylation Procedure of Peptides General procedure: Following completion of the oligopeptide sequence and deprotection of the last amino acid residue, the resin (0.3 mmol peptide) was treated with 2,5-dibromoterephthalic acid (0.1 eq.) that was activated by PyBOP (0.2 eq.) and diisopropylethylamine (10 eq.) for 12 hours in NMP. After coupling, the resin was filtered, washed 2x with NMP and DCM and resubjected to treatment with 2,5-dibromoterephthalic acid (0.05 eq.) that was activated by PyBOP (0.10 eq.) and diisopropylethylamine (10 eq.) for 12 hours in NMP. After coupling, the resin was filtered, washed 2x with NMP and DCM and subjected to a blank coupling cycle using PyBOP (0.2 eq.) and diisopropylethylamine (10 eq.) for 1-2 hours in NMP to yield maximum coupling of diacid with oligopeptide. After completion, the resin was subjected to a standard wash cycle: 3x NMP, methanol and DCM.

Reference： [1]Kale, Tejaswini S.; Tovar, John D. [Tetrahedron, 2016, vol. 72, # 40, p. 6084 - 6090]

57
[ 13731-82-3 ]
Wang-DFAA amide [ No CAS ]
C₅₄H₆₆Br₂N₈O₁₄Pol₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In 1-methyl-pyrrolidin-2-one	General N-acylation Procedure of Peptides General procedure: Following completion of the oligopeptide sequence and deprotection of the last amino acid residue, the resin (0.3 mmol peptide) was treated with 2,5-dibromoterephthalic acid (0.1 eq.) that was activated by PyBOP (0.2 eq.) and diisopropylethylamine (10 eq.) for 12 hours in NMP. After coupling, the resin was filtered, washed 2x with NMP and DCM and resubjected to treatment with 2,5-dibromoterephthalic acid (0.05 eq.) that was activated by PyBOP (0.10 eq.) and diisopropylethylamine (10 eq.) for 12 hours in NMP. After coupling, the resin was filtered, washed 2x with NMP and DCM and subjected to a blank coupling cycle using PyBOP (0.2 eq.) and diisopropylethylamine (10 eq.) for 1-2 hours in NMP to yield maximum coupling of diacid with oligopeptide. After completion, the resin was subjected to a standard wash cycle: 3x NMP, methanol and DCM.

Reference： [1]Kale, Tejaswini S.; Tovar, John D. [Tetrahedron, 2016, vol. 72, # 40, p. 6084 - 6090]

58
[ 13731-82-3 ]
Wang-DFGA amide [ No CAS ]
C₅₂H₆₂Br₂N₈O₁₄Pol₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In 1-methyl-pyrrolidin-2-one	General N-acylation Procedure of Peptides General procedure: Following completion of the oligopeptide sequence and deprotection of the last amino acid residue, the resin (0.3 mmol peptide) was treated with 2,5-dibromoterephthalic acid (0.1 eq.) that was activated by PyBOP (0.2 eq.) and diisopropylethylamine (10 eq.) for 12 hours in NMP. After coupling, the resin was filtered, washed 2x with NMP and DCM and resubjected to treatment with 2,5-dibromoterephthalic acid (0.05 eq.) that was activated by PyBOP (0.10 eq.) and diisopropylethylamine (10 eq.) for 12 hours in NMP. After coupling, the resin was filtered, washed 2x with NMP and DCM and subjected to a blank coupling cycle using PyBOP (0.2 eq.) and diisopropylethylamine (10 eq.) for 1-2 hours in NMP to yield maximum coupling of diacid with oligopeptide. After completion, the resin was subjected to a standard wash cycle: 3x NMP, methanol and DCM.

Reference： [1]Kale, Tejaswini S.; Tovar, John D. [Tetrahedron, 2016, vol. 72, # 40, p. 6084 - 6090]

59
[ 13731-82-3 ]
[ 108-67-8 ]
(2,5-dibromo-1,4-phenylene)bis(mesitylmethanone) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: 2,5-dibromoterephtalic acid With thionyl chloride In dichloromethane for 24h; Reflux; Stage #2: 1,3,5-trimethyl-benzene With aluminum (III) chloride In dichloromethane at 0 - 20℃; for 12h;
65%	Stage #1: 2,5-dibromoterephtalic acid With thionyl chloride In dichloromethane for 12h; Reflux; Stage #2: 1,3,5-trimethyl-benzene With aluminum (III) chloride In dichloromethane Cooling with ice; Reflux;

Reference： [1]Dong, Shaoqiang; Herng, Tun Seng; Gopalakrishna, Tullimilli Y.; Phan, Hoa; Lim, Zheng Long; Hu, Pan; Webster, Richard D.; Ding, Jun; Chi, Chunyan [Angewandte Chemie - International Edition, 2016, vol. 55, # 32, p. 9316 - 9320][Angew. Chem., 2016, vol. 128, p. 9462 - 9466]
[2]Chen, Yang; Kueh, Huilin; Gopalakrishna, Tullimilli Y.; Dong, Shaoqiang; Han, Yi; Chi, Chunyan [Organic Letters, 2019]

60
[ 13731-82-3 ]
[ 114460-21-8 ]
[Ca(dbt)(H₂O)]_n [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%	With [2,2]bipyridinyl; potassium hydroxide In ethanol; water at 120℃; for 72h; Sealed tube; High pressure;

Reference： [1]Sun, Yuexin; Sun, Yayong; Zheng, Hao; Wang, Hongli; Han, Yi; Yang, Yu; Wang, Lei [CrystEngComm, 2016, vol. 18, # 44, p. 8664 - 8671]

61
[ 553-26-4 ]
[ 13731-82-3 ]
[ 114460-21-8 ]
(4,4′-bpy)_0.5[Ca(dbt)(H₂O)₂]_n [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With potassium hydroxide In ethanol; water at 120℃; for 72h; Sealed tube; High pressure;

Reference： [1]Sun, Yuexin; Sun, Yayong; Zheng, Hao; Wang, Hongli; Han, Yi; Yang, Yu; Wang, Lei [CrystEngComm, 2016, vol. 18, # 44, p. 8664 - 8671]

62
[ 1762-34-1 ]
[ 13731-82-3 ]
[ 114460-21-8 ]
[Ca(H-dbt)₂(5,5′-dmbpy)₂]_n [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With potassium hydroxide In ethanol; water at 120℃; for 72h; Sealed tube; High pressure;

Reference： [1]Sun, Yuexin; Sun, Yayong; Zheng, Hao; Wang, Hongli; Han, Yi; Yang, Yu; Wang, Lei [CrystEngComm, 2016, vol. 18, # 44, p. 8664 - 8671]

63
[ 13731-82-3 ]
[ 114460-21-8 ]
[ 25372-07-0 ]
(H₂-dib)[Ca₃(dbt)₄(H₂O)₄·2H₂O]_n [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With potassium hydroxide In ethanol; water at 120℃; for 72h; Sealed tube; High pressure;

Reference： [1]Sun, Yuexin; Sun, Yayong; Zheng, Hao; Wang, Hongli; Han, Yi; Yang, Yu; Wang, Lei [CrystEngComm, 2016, vol. 18, # 44, p. 8664 - 8671]

64
[ 1004-38-2 ]
[ 13731-82-3 ]
2C₄H₇N₅*C₈H₄Br₂O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	In ethanol; water; for 0.5h;	General procedure: To a 10 ml of ethanol-H2O mixed solution containing H2NPA(0.20 mmol) and <strong>[1004-38-2]TAP</strong>I (0.10 mmol) was stirred for half an hourcontinually. The resulting clear solution was evaporated at20e25 C, and an irregular, colorless bulk crystal was obtained afterseven days. The resulting crystals were filtered and dried afterrinsed with ethanol-H2O mixed solution. Yield: 70%. Analysiscalculated for C12H14N6O7: C, 40.64; H, 3.95; N, 23.71%. Found: C,40.35; H, 4.00; N, 23.51%. Infrared spectrum (KBr disc, cm1):3441s, 3409s, 3208m, 3082m, 2416w, 1679s, 1651s, 1607s, 1569s,1538s, 1454m, 1431m, 1413m, 1351s, 1261m, 1155m, 1133w, 1077w,972w, 912m, 843w, 830m, 810m, 782s, 763m, 705s, 661w, 587m,532s.

Reference： [1]Journal of Molecular Structure,2017,vol. 1136,p. 59 - 68

65
[ 104-51-8 ]
[ 13731-82-3 ]
[ 197370-00-6 ]

Yield	Reaction Conditions	Operation in experiment
72%	Stage #1: 2,5-dibromoterephtalic acid With thionyl chloride for 10h; Reflux; Stage #2: 1-butylbenzene With aluminium trichloride In dichloromethane at 25℃; for 2h;

66
[ 13731-82-3 ]
(2-bromo-5-(7-(diphenylamino)-9,9-dimethyl-9H-fluoren-2-yl)-1,4-phenylene)bis((4-butylphenyl)methanone) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: thionyl chloride / 10 h / Reflux 1.2: 2 h / 25 °C 2.1: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / ethanol; toluene / 24 h / 85 °C / Inert atmosphere
	Multi-step reaction with 3 steps 1: thionyl chloride / 10 h / Reflux 2: aluminum (III) chloride / dichloromethane / 2 h / 20 °C 3: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / toluene / 24 h / 95 °C / Inert atmosphere

Reference： [1]Jiang, Yi; Fang, Mei; Chang, Si-Ju; Huang, Jin-Jin; Chu, Shuang-Quan; Hu, Shan-Ming; Liu, Cheng-Fang; Lai, Wen-Yong; Huang, Wei [Chemistry - A European Journal, 2017, vol. 23, # 23, p. 5448 - 5458]
[2]Fang, Mei; Huang, Jinjin; Chang, Si-Ju; Jiang, Yi; Lai, Wen-Yong; Huang, Wei [Journal of Materials Chemistry C, 2017, vol. 5, # 23, p. 5797 - 5809]

67
[ 13731-82-3 ]
(4,4''-dibromo-[1,1':4',1''-terphenyl]-2,2'',5,5''-tetrayl)tetrakis((4-butylphenyl)methanone) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: thionyl chloride / 10 h / Reflux 1.2: 2 h / 25 °C 2.1: potassium hydroxide; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / tetrahydrofuran / 120 °C / Microwave irradiation
	Multi-step reaction with 3 steps 1: thionyl chloride / 10 h / Reflux 2: aluminum (III) chloride / dichloromethane / 2 h / 20 °C 3: potassium hydroxide; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / tetrahydrofuran / 0.17 h / 120 °C / Sealed tube; Microwave irradiation

68
[ 13731-82-3 ]
(4-bromo-4'''-(diphenylamino)-[1,1':4',1'':4'',1'''-quaterphenyl]-2,2'',5,5''-tetrayl)tetrakis((4-butylphenyl)methanone) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: thionyl chloride / 10 h / Reflux 1.2: 2 h / 25 °C 2.1: potassium hydroxide; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / tetrahydrofuran / 120 °C / Microwave irradiation 3.1: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / ethanol; toluene / 24 h / 85 °C / Inert atmosphere
	Multi-step reaction with 4 steps 1: thionyl chloride / 10 h / Reflux 2: aluminum (III) chloride / dichloromethane / 2 h / 20 °C 3: potassium hydroxide; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / tetrahydrofuran / 0.17 h / 120 °C / Sealed tube; Microwave irradiation 4: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / toluene; water / 24 h / 95 °C / Inert atmosphere

69
[ 13731-82-3 ]
(4-bromo-4'-(diphenylamino)-[1,1'-biphenyl]-2,5-diyl)bis((4-butylphenyl)methanone) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: thionyl chloride / 10 h / Reflux 1.2: 2 h / 25 °C 2.1: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / ethanol; toluene / 24 h / 85 °C / Inert atmosphere
	Multi-step reaction with 3 steps 1: thionyl chloride / 10 h / Reflux 2: aluminum (III) chloride / dichloromethane / 2 h / 20 °C 3: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / toluene; ethanol / 24 h / 95 °C / Inert atmosphere

70
[ 67-56-1 ]
cobalt(II) acetate dihydrate [ No CAS ]
[ 13731-82-3 ]
[ 52550-63-7 ]
[Co(1,4-bis(2-methylimidazol-1-yl) butane)_0.5(bdc-Br₂)]·CH₃OH}_n [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
35.67%		A mixture of Co(OAc)2·2H2O (0.049g, 0.2mmol), H2bdc-Br2 (0.064g, 0.2mmol) and <strong>[52550-63-7]bib</strong> (0.044g, 0.2mmol) was dissolved in 10mL of the component solvent (H2O/CH3OH=1:1) and stirred for 30min. The pH of the reaction mixture was adjusted to 7 by adding NH3·H2O(w=1%). Then the reaction mixture was transferred to a 25mL stainless steel Teflon lined autoclave and sealed followed by heating at 160C for 3 days. The resulted purple block crystals were collected by filtration and characterized. Yield: 35.67% (based on Co). Anal. Calcd for C15H15Br2N2O5Co: C, 34.51% H, 2.90%N, 5.37%. Found: C, 34.47%H, 2.86%N, 5.43%. IR (KBrcm-1)3457s, 3220s, 2941m, 2677w, 1890w, 1600w, 1421m, 1331w, 1200m, 1004m, 933m, 894m, 809w, 770w, 668m, 517m.

Reference： [1]Journal of Molecular Structure,2017,vol. 1147,p. 192 - 196

71
[ 13731-82-3 ]
(3S,4S)-N₃,N₄-bis(((1S,2R)-2-phenylcyclopropyl)carbamoyl)pyrrolidine-3,4-dicarboxamide hydrochloride [ No CAS ]
(3S,3’S,4S,4’S)-1,1’-(2,5-dibromoterephthaloyl)-bis(N3,N4-bis((1S,2R)-2-phenylcylopropyl)pyrrolidine-3,4-dicarboxamide) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 23℃; for 18h;

Reference： [1]Morin; Wang, Ying; Jones, Brian T.; Mifune, Yuto; Su, Lijing; Shi, Hexin; Moresco, Eva Marie Y.; Zhang, Hong; Beutler, Bruce; Boger, Dale L. [Journal of the American Chemical Society, 2018, vol. 140, # 43, p. 14440 - 14454]

72
[ 553-26-4 ]
uranyl nirate hexahydrate [ No CAS ]
[ 13731-82-3 ]
[(uranyl)(2,5-dibromoterephthalate)(4,4′-bipyridine)_0.5] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	In ethanol; water at 160℃; for 24h; Sealed tube; High pressure;	Synthesis of [(UO2) (bdc) (4,4′-bpy)0.5] (3) 0.051 g (0.10 mmol) UO2(NO3)2·6H2O dissolved in 1.0 mL ethanol,was dropwise added to 2.0 mL aqueous solution containing 0.068 g(0.20 mmol) H2bdc and 0.016 g (0.10 mmol) 4,4′-bpy. After stirred for30 min, the reaction mixture was loaded into a 15 mL tightly closedglass vessel and heated at 160 °C for one day. The yellow block-likecrystals of 3 were obtained after filtration, washed with distilled waterand EtOH, dried in vacuum oven at 40 °C. Yield: 65% based onUO2(NO3)2·6H2O. The experimental PXRD pattern of sample 3 coincideswell with the simulated pattern from single crystal X-ray diffraction(Fig. S1c). Anal. Calc. for C13H6NO6Br2U (3) (Mr=670.02): C23.28, H 1.02, N 2.09; found: C 23.32, H 1.07, N 2.02 (%). IR (KBrpellet, cm-1): 3448(w), 3108(w), 1606(vs), 1548(vs), 1411(vs),1065(w), 934(s), 777(w), 639(w). Compound 3 exhibits thermal stabilityup to about 405 °C, and the first lost weight (48.8%) occurs at405-590 °C, the second stage loss weight (11.6%) occures at590-800 °C. (Figs. S2c, S3c).

Reference： [1]Wang, Chao; Xu, Wei; Ren, Ya-Nan; Zhu, Hong-Lin; Zheng, Yue-Qing [Inorganica Chimica Acta, 2019, vol. 493, p. 29 - 37]

73
[ 13731-82-3 ]
C₇₈H₇₈O₄S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: thionyl chloride / dichloromethane / 12 h / Reflux 1.2: Cooling with ice; Reflux 2.1: potassium carbonate / N,N-dimethyl-formamide / 60 °C 3.1: potassium carbonate / N,N-dimethyl-formamide / 60 °C

Reference： [1]Chen, Yang; Kueh, Huilin; Gopalakrishna, Tullimilli Y.; Dong, Shaoqiang; Han, Yi; Chi, Chunyan [Organic Letters, 2019]

74
[ 13731-82-3 ]
C₇₈H₈₆O₄S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: thionyl chloride / dichloromethane / 12 h / Reflux 1.2: Cooling with ice; Reflux 2.1: potassium carbonate / N,N-dimethyl-formamide / 60 °C 3.1: potassium carbonate / N,N-dimethyl-formamide / 60 °C 4.1: lithium aluminium tetrahydride / tetrahydrofuran / 12 h / 20 °C

Reference： [1]Chen, Yang; Kueh, Huilin; Gopalakrishna, Tullimilli Y.; Dong, Shaoqiang; Han, Yi; Chi, Chunyan [Organic Letters, 2019]

75
[ 13731-82-3 ]
C₅₈H₅₂Br₂O₄S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: thionyl chloride / dichloromethane / 12 h / Reflux 1.2: Cooling with ice; Reflux 2.1: potassium carbonate / N,N-dimethyl-formamide / 60 °C

Reference： [1]Chen, Yang; Kueh, Huilin; Gopalakrishna, Tullimilli Y.; Dong, Shaoqiang; Han, Yi; Chi, Chunyan [Organic Letters, 2019]

76
[ 13731-82-3 ]
[ 1401211-90-2 ]
2,5-dibromo-N₁,N₄-bis(2-hexyldecyl)-N₁,N₄-di(thiophen-3-yl)terephthalamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	Stage #1: 2,5-dibromoterephtalic acid With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 20h; Schlenk technique; Inert atmosphere; Stage #2: N-(2-hexyldecyl)thiophene-3-amine With triethylamine In dichloromethane at 0 - 20℃; for 20h;	(3-2)2,5-dibromo-N1, N4-bis (2-hexyldecyl) -N1, N4-di (thiophen-3-yl) terephthalamideSynthesis of (Compound 12) 2,5-dibromoterephtalic acid(3.03 g, 9.36 mmol)And dehydrated dichloromethane (52 mL),Dehydrated N, N-dimethylformamide (DMF)(2 drops) in a Schlenk tube under a nitrogen atmosphere,Oxalyl chloride (3.56 g, 28.1 mmol) was added dropwise thereto and stirred at room temperature for 20 hours.After removing the solvent and excess oxalyl chloride under reduced pressure, dehydrated dichloromethane (16 mL) was added,Cooled to 0 ° C. with an ice bath.Thereto said compound 11 (7.82 g, 20.6 mmol) and triethylamine (1.8 mL),Dehydrated dichloromethane (20 mL) was slowly added, followed by stirring at room temperature for 20 hours.Pour pure water into the reaction solution,After extraction with hexane,Dried over sodium sulfate,The solvent was removed with an evaporator.Purification by silica gel column chromatography (hexane: chloroform = 2: 1)Compound 12 (8.68 g, yield 99%) as an oily dark green liquid was obtained.

Reference： [1]Current Patent Assignee: RICOH CO LTD; KYUSHU UNIVERSITY - JP2019/156787, 2019, A Location in patent: Paragraph 0055

77
zinc(II) nitrate hexahydrate [ No CAS ]
[ 13731-82-3 ]
1,3,5-tris(2-methyl-1H-imidazol-1-yl)benzene [ No CAS ]
C₁₈H₁₈N₆*2C₈H₂Br₂O₄^(2-)*2Zn⁽²⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%	With nitric acid In water; N,N-dimethyl-formamide at 64.84℃; for 24h; Sealed tube;

Reference： [1]Liu, Shuang; Dong, Qiubing; Wang, Daqi; Wang, Yang; Wang, Huijie; Huang, Yuhang; Wang, Suna; Liu, Lantao; Duan, Jingui [Inorganic Chemistry, 2019, vol. 58, # 23, p. 16241 - 16249]

78
zinc(II) sulfate heptahydrate [ No CAS ]
[ 13731-82-3 ]
1,4-bis(2-methylbenzimidazol-1-yl)-2-butylene [ No CAS ]
[ 1310-73-2 ]
C₂₀H₂₀N₄*Zn⁽²⁺⁾*C₈H₂Br₂O₄^(2-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
44.5%	In ethanol; water at 140℃; for 72h;	2.3. synthesis of [Zn(L)(DBT)]_n (2) The procedure was similar to that of 1, except that the mixture was replaced by ZnSO47H2O (0.200 mmol, 57.5 mg), L (0.100 mmol, 31.6mg), H2DBT (0.100 mmol, 32.4 mg), NaOH (0.200 mmol, 8.0 mg), EtOH(2.0 mL) and H2O (8.0 mL). After the mixture was cooled to room temperature,colorless crystals 2 were produced (yield: 44.5% based on Lligand). Anal. Calc. for C28H22Br2N4O4Zn (Mr 703.68): C, 47.8; H, 3.2;N, 8.0%. Found: C, 47.5; H, 3.1; N, 8.2%. IR: 2962m, 1633s, 1508m,1417m, 1312w, 1262m, 1053s, 965m, 830m, 738s.

Reference： [1]Dong, Gui-Ying; Fu, Lianshe; Li, Yue-Hua; Liu, Dong; Zhu, Hui [Journal of Solid State Chemistry, 2020, vol. 286]

79
[ 13731-82-3 ]
cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene) hexafluorophosphate [ No CAS ]
C₃₈H₃₄N₁₀⁽⁴⁺⁾*C₈H₂Br₂O₄^(2-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tetramethyl ammoniumhydroxide In dimethylsulfoxide-d6 at 24.84℃;

Reference： [1]Chen, Xu-Lang; Gao, Chao; Gong, Han-Yuan; Sessler, Jonathan L.; Shen, Yun-Jia; Sun, Xin; Wei, Gong-Ping; Xiang, Jun-Feng; Yang, Jian; Yang, Yu-Dong; Zhang, Xin [Journal of the American Chemical Society, 2020, vol. 142, # 16, p. 7443 - 7455]

80
[ 2425-77-6 ]
[ 13731-82-3 ]
1,4-dibromo-2,5-bis(2-hexyldecanoate)benzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: 2,5-dibromoterephtalic acid With thionyl chloride Reflux; Stage #2: 2-hexyldecan-1-ol With pyridine at 80℃; for 18h;

Reference： [1]Jeong, Ji-Eun; Joung, Joonyoung Francis; Kang, Minsu; Kim, Hee-Chang; Park, Sungnam; Ryu, Hwa Sook; Shim, Sang-Hee; Uddin, Mohammad Afsar; Woo, Han Young [Chemistry of Materials, 2020, vol. 32, # 15, p. 6685 - 6696]

81
[ 366-18-7 ]
zinc(II) nitrate hexahydrate [ No CAS ]
[ 13731-82-3 ]
C₈H₂Br₂O₄^(2-)*C₁₀H₈N₂*Zn⁽²⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	In water; N,N-dimethyl-formamide at 90℃; for 72h; Sealed tube;	2.4. Synthesis of [Zn(DBT) (2,20-bpy)]n (3) A mixture of Zn(NO3)26H2O (29.7 mg, 0.1 mmol), 2,20-bpy (15.6 mg, 0.1 mmol) and H2DBT (32.4 mg, 0.1 mmol) in 6 mL DMF/H2O (v/v 1:1) was sealed in a 25 mL Teflon-lined autoclave and heated at 90 C for3 days. Colorless block crystals of 3 were obtained by cooling to roomtemperature slowly in 60% yield based on H2DBT. Element analysis forC18H10Br2N2O4Zn (543.65), C, 39.78; H, 1.86; N, 5.15. Found: C, 39.56;H, 1.84; N, 5.08. IR (KBr): 3418 (m), 3083 (w), 1629 (w), 1557 (s), 1512(s), 1445 (m), 1388 (s), 1313 (m), 1050(m), 828 (w), 758 (w), 607 (m).

Reference： [1]Jiao, Shaoshao; Li, Shaoxiang; Liu, Kang; Song, Xiuyan; Wang, Lei; Zhang, Xinghao; Zhang, Yaowen [Journal of Solid State Chemistry, 2020, vol. 292]

82
[ 366-18-7 ]
zinc(II) nitrate hexahydrate [ No CAS ]
[ 13731-82-3 ]
0.5C₈H₂Br₂O₄^(2-)*2C₁₀H₈N₂*Zn⁽²⁺⁾*C₈H₃Br₂O₄^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
32%	In water; N,N-dimethyl-formamide at 100℃; for 96h; Sealed tube;	2.5. Synthesis of [Zn(DBT)0.5(2,20-bpy)2(HDBT-)]n (4) A mixture of Zn(NO3)26H2O (29.7 mg, 0.1 mmol), 2,20-bpy (15.6 mg,0.1 mmol) and H2DBT (32.3 mg, 0.1 mmol) was dissolved in 6 mL ofDMF/H2O (v/v 2:1), and then they were sealed in a 25 mL Teflon-linedautoclave. After that, the reaction autoclave was heated at 100 C for 4days. Finally, colorless block crystals of 4 were isolated in 32% yieldbased on H2DBT. Element analysis for C32H20Br3N4O6Zn (861.62), C,44.61; H, 2.34; N, 6.50. Found: C, 44.47; H, 2.26; N, 6.43. IR (KBr): 3425(m), 3072 (w), 1646 (w), 1596 (s), 1495 (m), 1444 (m), 1308 (m), 1054(m), 831 (w), 807(w), 768 (m), 600(m).

Reference： [1]Jiao, Shaoshao; Li, Shaoxiang; Liu, Kang; Song, Xiuyan; Wang, Lei; Zhang, Xinghao; Zhang, Yaowen [Journal of Solid State Chemistry, 2020, vol. 292]

83
[ 366-18-7 ]
cobalt(II) nitrate hexahydrate [ No CAS ]
[ 13731-82-3 ]
C₈H₂Br₂O₄^(2-)*C₁₀H₈N₂*H₂O*Co⁽²⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	In water; N,N-dimethyl-formamide at 120℃; for 72h; Sealed tube;	2.3. Synthesis of [Co(DBT) (2,20-bpy) (H2O)]n (2) The synthetic procedure of compound 2 was similar to that of 1,except that Zn(NO3)26H2O and 4,40-dmbpy were substituted withCo(NO3)26H2O (29.1 mg, 0.1 mmol), 2,20-bpy (15.6 mg, 0.1 mmol),respectively. Fuchsia block crystals were isolated in 65% yield based onH2DBT. Element analysis for C18H12Br2CoN2O5 (555.03), C, 38.95; H,2.18; N, 5.05. Found: C, 39.05; H, 2.06; N, 5.01. IR (KBr): ν (cm1) 3401 (s), 3055(m), 1690 (w), 1547(s), 1510 (s), 1467 (m), 1400 (s),1325 (w), 1053 (m), 833 (w), 772 (w), 612 (m).

Reference： [1]Jiao, Shaoshao; Li, Shaoxiang; Liu, Kang; Song, Xiuyan; Wang, Lei; Zhang, Xinghao; Zhang, Yaowen [Journal of Solid State Chemistry, 2020, vol. 292]

84
[ 1134-35-6 ]
zinc(II) nitrate hexahydrate [ No CAS ]
[ 13731-82-3 ]
C₈H₂Br₂O₄^(2-)*C₁₂H₁₂N₂*H₂O*Zn⁽²⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	In water; N,N-dimethyl-formamide at 120℃; for 72h; Sealed tube;	2.2. Synthesis of [Zn(DBT) (4,40-dmbpy) (H2O)]n (1) A mixture of Zn(NO3)26H2O (29.7 mg, 0.1 mmol), 4,40-dmbpy (18.4mg, 0.1 mmol) and H2DBT (32.4 mg, 0.1 mmol) in 6 mL of DMF/H2O (v/v 1:2) was sealed in a 25 mL Teflon-lined autoclave and heated at 120C for 3 days. Colorless block crystals of 1 were obtained by filtration andrinsed with ethanol and water three times with a yield of 70% based onH2DBT. Element analysis for C20H16Br2N2O5Zn (589.54), C, 40.75; H,2.74; N, 4.75. Found: C, 40.58; H, 2.80; N, 4.72. IR (KBr): ν (cm1) 3620(m), 3409(s), 2971 (s), 1697 (w), 1545(s), 1512 (s), 1477 (m), 1443(m), 1395 (s), 1325 (w), 1055 (m), 829 (w), 802 (w), 775 (w), 610 (m).

Reference： [1]Jiao, Shaoshao; Li, Shaoxiang; Liu, Kang; Song, Xiuyan; Wang, Lei; Zhang, Xinghao; Zhang, Yaowen [Journal of Solid State Chemistry, 2020, vol. 292]

85
[ 13731-82-3 ]
[ 33513-42-7 ]
C₈H₃Br₂O₄^(1-)*C₃H₇NO*Li⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50%	With [Li₂Zn₂(pivalate)₆(pyridine)₂] In acetonitrile at 130℃; for 48h; Sealed tube;	Synthesis of [Li(DMF)(HBr2-bdc)] (1). To a solution of [Li2Zn2(py)2(piv)6] (25 mg, 0.03 mmol) in DMF (0.5 mL)a solution of H2Br2-bdc (57 mg, 0.18 mmol) in DMF (0.5 mL) was added. The total volume of the reaction mixture wasbrought to 5 mL with acetonitrile. The mixture was placed in a sealed glass ampoule, heated to 130 °C with a heating rate of1 °C/min, and then left at 130 °C for 48 h. Rectangular, elongated colorless crystals formed were used to solve the structureby synchrotron single crystal XRD. The crystals obtained is the only solid-phase reaction product and the synthesis isreproduced with the yield of ∼50%.

Reference： [1]Dudko, E. R.; Fedin, V. P.; Samsonenko, D. G.; Sapianik, A. A. [Journal of Structural Chemistry, 2020, vol. 61, # 12, p. 1957 - 1964][Zh. Strukt. Kim., 2020, vol. 61, # 12, p. 2064 - 2071,8]

86
[ 103-83-3 ]
[ 13731-82-3 ]
dibenzyl 2,5-dibromoterephthalate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	Stage #1: 2,5-dibromoterephtalic acid With propynoic acid ethyl ester In 1,4-dioxane at 80℃; Stage #2: N,N'-dimethylbenzylamine In 1,4-dioxane at 80℃; for 12h;	General Procedure for the Synthesis of Dibenzyl 2,6-Pyridine-dicarboxylate (4aa) General procedure: A mixture of pyridine-2,6-dicarboxylic acid (2a, 83.5 mg, 0.5mmol, 1.0 equiv) and ethyl propiolate (3a, 157 mg, 1.6 mmol,3.2 equiv) was added a 10 mL tube along with a magnetic stirbar, and then 2 mL 1,4-dioxane was added. The tube was stirredand refluxed in oil bath at 80 °C. Subsequently, N,N-dimethylbenzylamine(1a, 202 mg, 1.5 mmol, 3 equiv) solved in 1 mL1,4-dioxane was added to the tube slowly for 10 min. And thetube was stirred again and refluxed at 80 °C for 12 h. After theremoval of the volatiles in vacuo, the crude residue was loadedon a silica gel (100-200 mesh) column and flashed with 20%ethyl acetate in petroleum ether to afford the desired product4aa in 81% yield.

Reference： [1]Sun, Feixiang; Feng, Huangdi; Huang, Liliang; Huang, Junhai [Synlett, 2021, vol. 32, # 7, p. 713 - 717]

87
[ 13731-82-3 ]
[ 86-74-8 ]
2,5-dicarbazolyl-1,4-terephthalic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58.4%	With copper(l) iodide; 18-crown-6 ether; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h; Inert atmosphere; Darkness;	3 3. Synthesis of 2,5-dicarbazolyl-1,4-terephthalic acid (DCTA) Take carbazole (10.04g, 0.06mol), 2,5-dibromo-1,4-terephthalic acid (6.48g, 0.02mol), o-dichlorobenzene (15ml), potassium carbonate (5.52g, 0.04 mol), 18-crown-6 (1.44g, 4mmol), and cuprous iodide (0.76g, 4mmol) were put into a two-necked flask, the instrument was assembled, and the reaction device was protected from light with tin foil, under the protection of nitrogen atmosphere After the reaction was heated to 180°C and stirred and refluxed for 24 hours, the reaction was cooled and filtered with suction, washed with dichloromethane, silica gel powder was added, the filtrate was removed by rotary evaporation, and the sample was loaded, separated by column chromatography, using petroleum ether and ethanol (2: 1) As an eluent, 5.80 g of yellow solid material was obtained, and the yield was 58.4%

Reference： [1]Current Patent Assignee: NANJING UNIVERSITY OF POSTS AND TELECOMMUNICATIONS - CN113461594, 2021, A Location in patent: Paragraph 0040-0042

88
[ 6960-22-1 ]
[ 13731-82-3 ]
2C₇H₈N₂O*C₈H₄Br₂O₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65.04%	In methanol at 20℃; for 600h;	e. (6-methylnicotinamide) 2: (2,5-dibromoterephthalic acid) [(Hmnic) 2 ·(dbtpa 2 -)](5) To a CH 3 OH solution (20 mL) of 2,5-dibromoterephthalic acid (64.8 mg, 0.20 mmol) was added 6-methylnicotinamide (27.2 mg, 0.20 mmol). The solution was stirred for a few minutes, then the solution was filtered into a test tube. The solution was left standing at r. t. for 25 days, colorless crystals were isolated af- ter slow evaporation of the CH 3 OH solution in air. The crystals were gathered and dried in air to get [(Hmnic) 2 ·(dbtpa 2 -)] (5). Yield: 38.8 mg, 65.04% (based on L). m. p. 204-205 °C. Anal. Calcd for C 22 H 20 Br 2 N 4 O 6 (596.24): C, 44.28; H, 3.35; N, 9.39. Found: C, 44.16; H, 3.20; N, 9.27. Infrared spectrum (KBr disk, cm -1 ): 34 4 4m( νas (NH)), 3365w( νs (NH)), 3258 m, 3157 m, 3059 m, 2958 m, 2873 m, 1692s( ν(C = O)), 1595s( νas (CO 2 -)), 1552 m, 1510 m, 1468 m, 1428 m, 1386s( νs (CO 2 -)), 1343 m, 1301 m, 1258 m, 1214 m, 1170 m, 1126 m, 1084 m, 1042 m, 996 m, 956 m, 912 m, 868 m, 824 m, 776 m, 724 m, 684 m, 642 m, 600 m.

Reference： [1]Jin, Shouwen; Liu, Bin; Shi, Chengzhe; Wang, Daqi; Wu, Yujiu; Zhou, Jingxuan [Journal of Molecular Structure, 2022, vol. 1264]

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H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 13731-82-3 ] {[proInfo.proName]}

Quality Control of [ 13731-82-3 ]

Related Doc. of [ 13731-82-3 ]

Product Details of [ 13731-82-3 ]

Calculated chemistry of [ 13731-82-3 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 13731-82-3 ]

Application In Synthesis of [ 13731-82-3 ]

[ 13731-82-3 ] Synthesis Path-Upstream 1~12

[ 13731-82-3 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 13731-82-3 ]

Aryls

Bromides

Carboxylic Acids

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 13731-82-3 ]