[ CAS No. 18013-97-3 ] {[proInfo.proName]}

Name: 18013-97-3|Diethyl 2,5-dibromoterephthalate|98%
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Quality Control of [ 18013-97-3 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 18013-97-3 ]

Product Details of [ 18013-97-3 ]

CAS No. :	18013-97-3	MDL No. :	MFCD12407163
Formula :	C₁₂H₁₂Br₂O₄	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	WXRSDHICEYICMV-UHFFFAOYSA-N
M.W :	380.03	Pubchem ID :	22146229
Synonyms :

Calculated chemistry of [ 18013-97-3 ]

Physicochemical Properties

Num. heavy atoms :	18
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.33
Num. rotatable bonds :	6
Num. H-bond acceptors :	4.0
Num. H-bond donors :	0.0
Molar Refractivity :	74.02
TPSA :	52.6 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	Yes
CYP2C9 inhibitor :	Yes
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.96 cm/s

Lipophilicity

Log Po/w (iLOGP) :	2.88
Log Po/w (XLOGP3) :	3.74
Log Po/w (WLOGP) :	3.57
Log Po/w (MLOGP) :	3.72
Log Po/w (SILICOS-IT) :	3.78
Consensus Log Po/w :	3.54

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	0.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-4.4
Solubility :	0.015 mg/ml ; 0.0000395 mol/l
Class :	Moderately soluble
Log S (Ali) :	-4.54
Solubility :	0.011 mg/ml ; 0.0000291 mol/l
Class :	Moderately soluble
Log S (SILICOS-IT) :	-5.0
Solubility :	0.00378 mg/ml ; 0.00000995 mol/l
Class :	Moderately soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	2.0
Synthetic accessibility :	2.29

Safety of [ 18013-97-3 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 18013-97-3 ]

* 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 [ 18013-97-3 ]
Downstream synthetic route of [ 18013-97-3 ]

[ 18013-97-3 ] Synthesis Path-Upstream 1~7

1
[ 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

2
[ 6165-68-0 ]
[ 18013-97-3 ]

Reference： [1] Patent: EP2696351, 2014, A2, . Location in patent: Page/Page column
[2] Patent: US8890134, 2014, B2, . Location in patent: Page/Page column

3
[ 1074-24-4 ]
[ 18013-97-3 ]

Reference： [1] New Journal of Chemistry, 2006, vol. 30, # 5, p. 667 - 670
[2] Electrochimica Acta, 2011, vol. 56, # 16, p. 5616 - 5623
[3] Organic Letters, 2014, vol. 16, # 1, p. 106 - 109
[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
[ 106-42-3 ]
[ 18013-97-3 ]

Reference： [1] Electrochimica Acta, 2011, vol. 56, # 16, p. 5616 - 5623
[2] Journal of Materials Chemistry C, 2015, vol. 3, # 16, p. 4086 - 4092
[3] Crystal Growth and Design, 2016, vol. 16, # 7, p. 3993 - 4004

5
[ 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

6
[ 20871-01-6 ]
[ 18013-97-3 ]

Reference： [1] Chemische Berichte, 1885, vol. 18, p. 1762

7
[ 64-17-5 ]
[ 13815-90-2 ]
[ 18013-97-3 ]

Reference： [1] New Journal of Chemistry, 2006, vol. 30, # 5, p. 667 - 670

[ 18013-97-3 ] Synthesis Path-Downstream 1~88

1
[ 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

2
[ 64-17-5 ]
[ 13815-90-2 ]
[ 18013-97-3 ]

Reference： [1]New Journal of Chemistry,2006,vol. 30,p. 667 - 670

3
[ 18013-97-3 ]
[ 791717-65-2 ]

Reference： [1]New Journal of Chemistry,2006,vol. 30,p. 667 - 670

4
[ 98437-23-1 ]
[ 18013-97-3 ]
[ 915224-41-8 ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5033 - 5036

5
2-(9,9-di-p-tolyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl[1,3,2]dioxaborolane [ No CAS ]
[ 18013-97-3 ]
2,5-bis-(9,9-di-p-tolyl-9H-fluoren-2-yl)-terephthalic acid diethyl ester [ No CAS ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5029 - 5032

6
[ 18013-97-3 ]
[ 68716-52-9 ]
[ 913175-30-1 ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5029 - 5032

7
[ 18013-97-3 ]
[ 5713-61-1 ]
[ 915224-39-4 ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5033 - 5036

8
[ 18013-97-3 ]
[ 98-80-6 ]
[ 24091-17-6 ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5029 - 5032

9
[ 18013-97-3 ]
4,9-dihydro-4,4,9,9-tetrakis(4-methylphenyl)-s-indaceno[1,2-b:5,6-b']dithiophene [ No CAS ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5033 - 5036
[2]Tetrahedron Letters,2011,vol. 52,p. 2764 - 2766

10
[ 18013-97-3 ]
[4-(hydroxy-di-p-tolyl-methyl)-2,5-di-thiophen-2-yl-phenyl]-di-p-tolyl-methanol [ No CAS ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5033 - 5036

11
[ 18013-97-3 ]
6,6,12,12-tetra-p-tolyl-6,12-dihydro-indeno[1,2-b]fluorene [ No CAS ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5029 - 5032

12
[ 18013-97-3 ]
[5'-(hydroxy-di-p-tolyl-methyl)-[1,1';4',1'']terphenyl-2'-yl]-di-p-tolyl-methanol [ No CAS ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5029 - 5032

13
[ 18013-97-3 ]
C₅₂H₃₈S₂ [ No CAS ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5033 - 5036

14
[ 18013-97-3 ]
[2,5-bis-benzo[b]thiophen-2-yl-4-(hydroxy-di-p-tolyl-methyl)-phenyl]-di-p-tolyl-methanol [ No CAS ]

Reference： [1]Organic Letters,2006,vol. 8,p. 5033 - 5036

15
[ 1074-24-4 ]
[ 18013-97-3 ]

Reference： [1]New Journal of Chemistry,2006,vol. 30,p. 667 - 670
[2]Electrochimica Acta,2011,vol. 56,p. 5616 - 5623
[3]Organic Letters,2014,vol. 16,p. 106 - 109
[4]Journal of Materials Chemistry C,2015,vol. 3,p. 4086 - 4092
[5]Crystal Growth and Design,2016,vol. 16,p. 3993 - 4004
[6]Patent: KR2019/113044,2019,A
[7]Patent: KR2019/113044,2019,A

16
[ 18013-97-3 ]
[ 896445-16-2 ]

Reference： [1]New Journal of Chemistry,2006,vol. 30,p. 667 - 670

17
[ 18013-97-3 ]
[ 896445-18-4 ]

Reference： [1]New Journal of Chemistry,2006,vol. 30,p. 667 - 670

18
[ 20871-01-6 ]
[ 18013-97-3 ]

Reference： [1]Chemische Berichte,1885,vol. 18,p. 1762
[2]Patent: KR2019/113044,2019,A

19
[ 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

20
[ 18013-97-3 ]
[ 302554-81-0 ]
[ 1122593-50-3 ]

Reference： [1]Chemistry - A European Journal,2008,vol. 14,p. 11328 - 11342

21
[ 110-89-4 ]
[ 18013-97-3 ]
[ 1166111-46-1 ]

Reference： [1]Angewandte Chemie - International Edition,2009,vol. 48,p. 3653 - 3656

22
[ 1193104-86-7 ]
[ 18013-97-3 ]
[ 1193104-91-4 ]

Reference： [1]Organic Letters,2009,vol. 11,p. 4942 - 4945

23
[ 1193104-83-4 ]
[ 18013-97-3 ]
[ 1193104-90-3 ]

Reference： [1]Organic Letters,2009,vol. 11,p. 4942 - 4945

24
[ 18013-97-3 ]
[ 98-80-6 ]
[ 1193104-88-9 ]

Yield	Reaction Conditions	Operation in experiment
7%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 90℃; for 36h;	To a 100 mL dry three-necked flask with a magnetic rotor and a condenser, <strong>[18013-97-3]diethyl 2,5-dibromo-terephthalate</strong> (3.80 g, 10.0 mmol, 1.0 eq) was added sequentially.Phenylboronic acid (1.21 g, 10.0 mmol, 1.0 eq), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (570 mg, 0.5 mmol, 0.05 eq),Na2CO3 (2.12 g, 20 mmol, 2.0 eq).Nitrogen gas was distilled three times, then toluene (60.0 mL) and ethanol (20.0 mL) were added.Nitrogen gas was then bubbled for 20 minutes and the mixture was placed in a 90 C oil bath for 36 hours.The mixture was cooled to room temperature, and the solvent was evaporated under reduced pressure.Eluent (petroleum ether / dichloromethane = 3: 1-1: 1) to give 3 as a white solid 256 mg, 7% yield.

Reference： [1]Organic Letters,2009,vol. 11,p. 4942 - 4945
[2]Patent: CN109678906,2019,A .Location in patent: Paragraph 0233; 0237-0239
[3]Journal of the American Chemical Society,2011,vol. 133,p. 8028 - 8039

25
[ 25069-74-3 ]
[ 18013-97-3 ]
[ 1200008-80-5 ]

Reference： [1]Journal of Organic Chemistry,2009,vol. 74,p. 9094 - 9104

26
[ 1003-09-4 ]
[ 18013-97-3 ]
[ 915224-39-4 ]

Yield	Reaction Conditions	Operation in experiment
87%		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]Chemical Communications,2010,vol. 46,p. 6503 - 6505

27
[ 18013-97-3 ]
[ 45438-80-0 ]
[ 915224-39-4 ]

Reference： [1]Journal of the American Chemical Society,2010,vol. 132,p. 11437 - 11439

28
[ 16419-60-6 ]
[ 18013-97-3 ]
[ 1197732-30-1 ]

Yield	Reaction Conditions	Operation in experiment
81%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 4h;	60 g (160 mmol) of diethyl dibromoterephthalate, 43 g (320 mmol) of o-tolylboronic acid, 365 mg (0.32 mmol) of Pd(PPh3)4 and 92 g (660 mmol) of K2CO3 are heated at the boil for 4 h in 300 ml of toluene and 300 ml of water. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water and dried over Na2SO4. The residue remaining is recrystallised twice from heptane to give colourless crystals. The yield is 51 g (127 mmol, 81%).

Reference： [1]Patent: US2011/92701,2011,A1 .Location in patent: Page/Page column 48

29
[ 16419-60-6 ]
[ 18013-97-3 ]
[ 1197732-33-4 ]

Reference： [1]Patent: US2011/92701,2011,A1

30
[ 18013-97-3 ]
[ 1310058-42-4 ]

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 2764 - 2766

31
[ 18013-97-3 ]
[ 1310058-43-5 ]

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 2764 - 2766

32
[ 18013-97-3 ]
[ 1310058-44-6 ]

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 2764 - 2766

33
[ 18013-97-3 ]
[ 1310058-45-7 ]

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 2764 - 2766

34
[ 18013-97-3 ]
[ 54663-78-4 ]
[ 915224-39-4 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tetrakis(triphenylphosphine) palladium(0); In toluene; at 120℃; for 24h;Inert atmosphere;	1.1. Under argon (Ar) protection, add 10.0 mmol (3.8 g) of <strong>[18013-97-3]diethyl 2,5-dibromo-terephthalate</strong> (Compound 1) to a 250 mL three-necked bottle.40.0mmol (17.5g) thiophen-2-yltributyltin chloride(Compound 2), 0.3 mmol (350.0 mg) of tetrakistriphenylphosphine palladium and 100 mL of toluene gave a reaction system.1.2. The reaction system of step 1.1 was reacted at 120 C for 24 h.1.3. Add water to quench the reaction. Pour the reaction solution obtained in step 1.2 into 100 mL of petroleum ether and wash with water.The organic phase was dried over anhydrous MgSO4, filtered and evaporated1.4. The crude product is separated and purified by column chromatography. The eluent is a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1..2.A pale yellow solid was obtained in an amount of 3.0 g, yield: 80%.

Reference： [1]Organic Letters,2014,vol. 16,p. 106 - 109
[2]Macromolecules,2016,vol. 49,p. 527 - 536
[3]Electrochimica Acta,2011,vol. 56,p. 5616 - 5623
[4]Patent: CN110283184,2019,A .Location in patent: Paragraph 0088; 0096-0105
[5]Tetrahedron Letters,2011,vol. 52,p. 2764 - 2766

35
[ 106-42-3 ]
[ 18013-97-3 ]

Reference： [1]Electrochimica Acta,2011,vol. 56,p. 5616 - 5623
[2]Journal of Materials Chemistry C,2015,vol. 3,p. 4086 - 4092
[3]Crystal Growth and Design,2016,vol. 16,p. 3993 - 4004

36
[ 18013-97-3 ]
[ 1314019-18-5 ]

Reference： [1]Electrochimica Acta,2011,vol. 56,p. 5616 - 5623

37
[ 18013-97-3 ]
C₃₄H₁₈N₄O₈S₂ [ No CAS ]

Reference： [1]Electrochimica Acta,2011,vol. 56,p. 5616 - 5623

38
[ 871468-23-4 ]
[ 18013-97-3 ]
[ 1301768-76-2 ]

Reference： [1]Journal of the American Chemical Society,2011,vol. 133,p. 8028 - 8039

39
[ 1301768-81-9 ]
[ 18013-97-3 ]
[ 1301768-82-0 ]

Reference： [1]Journal of the American Chemical Society,2011,vol. 133,p. 8028 - 8039

40
[ 18013-97-3 ]
[ 371193-08-7 ]
[ 1301768-74-0 ]

Reference： [1]Journal of the American Chemical Society,2011,vol. 133,p. 8028 - 8039

41
[ 18013-97-3 ]
[ 371193-08-7 ]
[ 1301768-75-1 ]

Reference： [1]Journal of the American Chemical Society,2011,vol. 133,p. 8028 - 8039

42
[ 18013-97-3 ]
[ 98-80-6 ]
[ 1301768-73-9 ]

Reference： [1]Journal of the American Chemical Society,2011,vol. 133,p. 8028 - 8039

43
[ 5720-05-8 ]
[ 18013-97-3 ]
[ 1352791-00-4 ]

Reference： [1]Angewandte Chemie - International Edition,2011,vol. 50,p. 11103 - 11106

44
[ 18013-97-3 ]
[ 1352800-79-3 ]

Reference： [1]Angewandte Chemie - International Edition,2011,vol. 50,p. 11103 - 11106

45
[ 18013-97-3 ]
[ 1352791-09-3 ]

Reference： [1]Angewandte Chemie - International Edition,2011,vol. 50,p. 11103 - 11106

46
[ 18013-97-3 ]
[ 1352791-01-5 ]

Reference： [1]Angewandte Chemie - International Edition,2011,vol. 50,p. 11103 - 11106

47
[ 18013-97-3 ]
C₂₂H₁₆Cl₂O₂ [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2011,vol. 50,p. 11103 - 11106

48
[ 18013-97-3 ]
[ 1352791-02-6 ]

Reference： [1]Angewandte Chemie - International Edition,2011,vol. 50,p. 11103 - 11106

49
[ 6165-68-0 ]
[ 18013-97-3 ]
[ 915224-39-4 ]

Yield	Reaction Conditions	Operation in experiment
81.3%	With palladium diacetate; sodium carbonate; triphenylphosphine; In tetrahydrofuran; at 70℃;Inert atmosphere;	To a solution of thiophen-2-ylboronic acid (3.20 g, 25 mmol) and<strong>[18013-97-3]diethyl 2,5-dibromo-terephthalate</strong> (3.80 g,10 mmol) in THF (80 mL)was added saturated solution of sodium carbonate (15 ml), then(Pd(AcO)2) (40 mg) and triphenylphopine (PPh3) (80 mg) wereadded under nitrogen. After stirred at 70 C overnight, the reactionwas quenched with 100 mL water and extracted with ethyl acetate.Then, the combined organic solvent was washed with brine anddried over anhydrous magnesium sulfate (MgSO4). After removingthe solvent, the compound 1 was purified with column chromatographyon silica-gel using mixture of ethyl acetate (EA) andhexane (1: 5 by volume) as a white solid (3.14 g, 81.3 %). 1H NMR(500 MHz, CDCl3, ppm), delta 7.81 (s, 2H), 7.39 (dd, J 5 Hz, J 1 Hz,2H), 7.08 (m, 4H), 4.21 (q, J 5 Hz, 4H), 1.15 (t, J 5 Hz, 6H).

Reference： [1]Journal of Polymer Science, Part A: Polymer Chemistry,2012,vol. 50,p. 371 - 377
[2]Dyes and Pigments,2017,vol. 145,p. 345 - 353
[3]Journal of Materials Chemistry C,2018,vol. 6,p. 12347 - 12354
[4]Macromolecules,2017,vol. 50,p. 7984 - 7992

50
[ 18013-97-3 ]
[ 1209012-29-2 ]

Reference： [1]Journal of Polymer Science, Part A: Polymer Chemistry,2012,vol. 50,p. 371 - 377
[2]Organic Letters,2014,vol. 16,p. 106 - 109

51
[ 1373359-06-8 ]
[ 18013-97-3 ]
C₁₂₆H₁₄₄N₂O₄ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 7297 - 7300

52
[ 1373359-06-8 ]
[ 18013-97-3 ]
C₆₉H₇₈BrNO₄ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 7297 - 7300

53
[ 18013-97-3 ]
[ 201802-67-7 ]
[ 1373359-07-9 ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 7297 - 7300

54
[ 18013-97-3 ]
[ 201802-67-7 ]
[ 1373359-09-1 ]

Reference： [1]Chemical Communications,2013,vol. 49,p. 3597 - 3599
[2]Journal of the American Chemical Society,2012,vol. 134,p. 7297 - 7300

55
[ 18013-97-3 ]
[ 1394905-73-7 ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 14913 - 14922,10

56
[ 18013-97-3 ]
[ 1394905-74-8 ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 14913 - 14922,10

57
[ 18013-97-3 ]
[ 1394905-75-9 ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 14913 - 14922,10

58
[ 103989-84-0 ]
[ 18013-97-3 ]
[ 1394905-72-6 ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 14913 - 14922,10

59
[ 18013-97-3 ]
tributyl(thieno[3,2-b]thiophen-2-yl)stannane [ No CAS ]
[ 1411976-67-4 ]

Yield	Reaction Conditions	Operation in experiment
75%	With tetrakis(triphenylphosphine) palladium(0); In toluene; for 24h;Inert atmosphere; Reflux;	A 250 mL round bottom flask was charged with <strong>[18013-97-3]diethyl 2,5-dibromo-terephthalate</strong> (9.12 g, 24 mmol), 2-tri-n-butyltin-thieno[3,2-b]thiophene (25.76 g, 60 mmol) and tetratriphenylphosphine palladium (277.3 Mg, 0.24mmol). Nitrogen gas was purged three times, and toluene (120 mL) except oxygen was added, and the mixture was refluxed under nitrogen for 24 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, and dichloromethane was evaporated. The mixture was separated by silica gel column chromatography using dichloromethane as eluent to give diethyl 2,5-bis(thieno[3,2-b]thiophen-2-yl)terephthalate (8.98 g, yield 75%).
75%	With tetrakis(triphenylphosphine) palladium(0); In N,N-dimethyl-formamide; for 4h;Inert atmosphere; Reflux;	Compound 5-2 (5 g, 13.2 mmol) in a 250 mL reaction flask under a nitrogen atmosphere,Add compound 1-2 (14.1 g, 32.9 mmol) and add N, N-dimethylformamide (50 mL) and stir.Pd (PPh3)4 (0.8 g, 0.7 mmol) was added to the reaction and stirred at reflux for 4 hours.The reaction is stirred while slowly cooling to room temperature (25 C.) (crystallization).The precipitated solid is filtered off and the filtered solid is washed with MeOH (30 mL).The filtered solid was dissolved in dichloromethane (50 mL), filtered using silica gel-pad, and the filtrate was concentrated under reduced pressure.The concentrate is recrystallized from Dichloromethane / MeOH (for 1 hour).The product solid is filtered off and the filtered solid is washed with MeOH (30 mL).The washed solid was dried overnight in a vacuum oven (temp. = 100 C.) to afford intermediate compound 5-1 (4.9 g, 75%).
19.40 g	With bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; N,N-dimethyl-formamide; for 20.5h;Reflux;	To the solution of thieno[3,2-b]thiophene (17.529 g; 125.00 mmol) in THF anhydrous ( 50 cm3) was added at -78 C n-BuLi (50.0 cm3; 25.00 mmol) over 20 minutes. The mixture was stirred with cooling for 1 hour to yield a milky white suspension. The flask was lifted out of the cooling bath and was stirred without cooling for 30 min then cooled back to -78 C again. Tributyltin chloride (35.3 cm3; 125.00 mmol) was syringed into the solution in one portion and the mixture was stirred with the cooling bath for 16 hours then at 22C for 1 hour to yield a white suspension. The solid of <strong>[18013-97-3]diethyl 2,5-dibromo-terephthalate</strong> (19.00 g; 50.00 mmol), Pd(PPh3)2CI2 (1.0 g; 1.42 mmol; 2.84 mol%) and DMF anhydrous (50.0 cm3) were added sequentially and the mixture was heated to boiling for 0.5 hour. A distillation head was installed on the flask and 100 cm3 of the solvents were removed by distillation. The residue was then stirred at reflux for an additional 20 hours. The mixture was evaporated under vacuum to remove the low boiling solvents until a solid started crashing out. Methanol (200 cm3) was added to the residue and the precipitate was suction filtered off to yield a green-yellow crystalline solid. The solid was dissolved in hot chloroform (250 cm3) then filtered through a short silica plug (15 cm) which was washed with chloroform. The filtrate was concentrated to almost dryness and the solid was triturated with methanol followed by a suction filtration to yield the product as bright yellow crystals (19.40 g, 78%). 1H- NMR (CDC , 300 MHz): delta= 1.13 (t, J = 7.2 Hz, 3H), 4.25 (q, J = 7.2 Hz, 2H), 7.28 (dd, J1 = 5.2 Hz, J2 = 0.6 Hz, 1H), 7.30 (d, J = 0.6 Hz, 1 H), 7.40 (d, J = 5.2 Hz, 1 H), 7.89 (s, 1H). 13C-NMR (CDCI3, 75 MHz): delta= 13.8, 61.8, 119.3, 119.4, 127.4, 132.0, 133.8, 134.1 , 139.3, 139.9, 142.0, 167.4.

Reference： [1]Macromolecules,2012,vol. 45,p. 9282 - 9291
[2]Patent: CN109232604,2019,A .Location in patent: Paragraph 0084; 0091-0093
[3]Patent: KR2019/113044,2019,A .Location in patent: Paragraph 0110-0113
[4]Patent: WO2013/10614,2013,A2 .Location in patent: Page/Page column 65
[5]New Journal of Chemistry,2018,vol. 42,p. 19279 - 19284

60
[ 251-41-2 ]
[ 18013-97-3 ]
[ 1411976-67-4 ]

Yield	Reaction Conditions	Operation in experiment
79%		Add thieno [3,2-b] thiophene (4.2 g, 30 mmol) to a 500 mL reaction flask under nitrogen atmosphere and dry THF (100 mL).The reaction was cooled to -78 C and then slowly added dropwise 2.5 M n-BuLi in hexane solution (12 mL, 30 mmol) to the reaction.Stir at the same temperature (-78 C) for 30 minutes, then warm the reaction at some temperature (-35 C) and then stir for a further 20 minutes.In another reaction vessel, add anhydrous zinc chloride (4.1 g, 30 mmol) to anhydrous THF (100 mL), and slowly add to the reaction.The reaction is warmed to 0 C and then stirred for 1 hour.Remove the bath and add compound 5-1 (4.6 g, 12 mmol) and Pd (PPh3) 4 (0.7 g, 0.6 mmol). The reaction is stirred at reflux overnight.After confirmation of the reaction, the reaction product was filtered using celite-pad, extracted with EA, and dried over anhydrous Na 2 SO 4.The dried reaction mixture was filtered, the filtrate was reduced under reduced pressure and purified by column chromatography to obtain a yellow solid compound 5-1 (4.8 g, 79%).

Reference： [1]Advanced Materials,2012,vol. 24,p. 6356 - 6361
[2]Patent: KR2019/113044,2019,A .Location in patent: Paragraph 0097; 0106-0107
[3]Journal of Materials Chemistry A,2014,vol. 2,p. 18988 - 18997
[4]Journal of Materials Chemistry A,2018,vol. 6,p. 395 - 403

61
[ 18013-97-3 ]
[ 1420071-64-2 ]

Reference： [1]Advanced Materials,2012,vol. 24,p. 6356 - 6361
[2]Patent: KR2019/113044,2019,A
[3]Patent: KR2019/113044,2019,A

62
[ 18013-97-3 ]
[ 1420071-65-3 ]

Reference： [1]Advanced Materials,2012,vol. 24,p. 6356 - 6361

63
[ 18013-97-3 ]
[ 81745-84-8 ]
[ 915224-39-4 ]

Yield	Reaction Conditions	Operation in experiment
4.29 g	With tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran;Inert atmosphere; Reflux;	A solution of anhydrous zinc chloride (5.4 g, 40 mmol) suspended in 30 mL anhydrous THF was added dropwise into 30 mL of 2-thienylmagnesium bromide (1 M in THF) solution at 0 C, and the reaction was kept at 0 C for another 0.5 h under argon atmosphere. A solution of diethyl 2,5-dibromoterephthalate (4.38 g, 11.5 mmol) and Pd(PPh3)4 (226 mg) in 100 mL THF was added in one portion. After the mixture was refluxed overnight, the reaction mixture were cooled to room temperature and quenched by distilled water, then extracted with diethyl ether for three times. The organic phase was combined and the solvent was removed under reduced pressure. The product was purified by chromatography (petroleum ether/ethyl acetate = 8:1, V/V) to give 4.29 g white solid with yield of 96%. 1H NMR (400 MHz, CDCl3), delta (ppm): 7.81 (s, 2H), 7.38 (dd, J = 5.2, 1.6 Hz, 2H), 7.10-7.06 (m, 4H), 4.22 (q, J = 7.2 Hz, 4H), 1.15 (t, J = 7.2 Hz, 6H). GC-MS: Cacld for C20H18O4S2, 386.48, Found: 386.15.

Reference： [1]Polymer,2013,vol. 54,p. 607 - 613

64
[ 419536-33-7 ]
[ 18013-97-3 ]
[ 1430084-03-9 ]

Yield	Reaction Conditions	Operation in experiment
32%	With palladium diacetate; potassium carbonate; triphenylphosphine; In ethanol; toluene; at 45℃; for 24h;Inert atmosphere;	Compound 2-3 (8.46 g, 29.45 mmol), diethyl 2,5-dibromoterephthalate (22.4 g, 58.9mmol), palladium (II) acetate (65 mg), triphenylphosphine (0.12g), 4M potassium carbonate (15 mL), ethanol (50 mL) and toluene (250 mL) were added to a 500 mL two-necked round bottom flask and stirred. The reaction mixture was heated at 45C with nitrogen protection for 24 h. After cooling down to room temperature, the reaction mixture was quenched with water and acidified by 6 M HCl (3mL). Thereafter, it was extracted with 3 portions of ethyl acetate and then dried over sodium sulphate. Thus, purification of residue was carried out via column chromatography to afford a white solid 5.1 g in 32% yield. 1H NMR (400MHz, CDCl3, delta): 8.25-8.14 (m, 3H), 7.97-7.84 (m,1H), 7.53-7.68 (m, 4H), 7.52-7.42 (m, 4H), 7.36-7.28 (m, 2H), 4.47 (q, J = 7.2Hz, 2H), 4.23 (q, J = 7.2 Hz, 2H), 1.46 (t, J = 7.2 Hz, 3H), 1.59 (t, J = 7.2 Hz,3H). MS(MALDI-TOF, m/z): found 542.0964 [M+H]+.

Reference： [1]Chemical Communications,2013,vol. 49,p. 3597 - 3599
[2]Journal of the Chilean Chemical Society,2015,vol. 60,p. 2971 - 2974

65
[ 1430083-99-0 ]
[ 18013-97-3 ]
[ 1430084-01-7 ]

Reference： [1]Chemical Communications,2013,vol. 49,p. 3597 - 3599

66
[ 1430747-76-4 ]
[ 18013-97-3 ]
[ 1430747-77-5 ]

Yield	Reaction Conditions	Operation in experiment
72%		The solution of 3-(1-heptyldecyl)thieno[3,2-b]thiophene (11.06 g; 29.21 mmol) in anhydrous THF (100 cm3) was cooled to -78C and n-BuLi (11.7 cm3; 29.21 mmol) was added over 10min. The mixture was stirred at the low temperature for 3 hours to yield a yellow suspension. Tributyltin chloride (8.3 cm3; 29.21 mmol) was syringed into the solution in one portion. The clear yellow solution was stirred with the cooling bath for 15h and the temperature was allowed to rise to room temperature naturally. The solid of diethyl 2,5-dibromoterephthalate (4.750 g; 12.50 mmol), Pd2(PPh3)2CI2 (264 mg; 0.38 mmol) and dry DMF(25 cm3) were added sequentially and the mixture was heated to reflux. A distillation head was fitted on the flask and ca 100 cm3 of the solvents was removed by distillation. The residual orange solution was stirred at reflux for 22 hours to yield a pale-brown solution. The solution was evaporated under vacuum to dryness. The residual pale-brown liquid was flash columned on silica eluted with 3:1 PE/dcm then with 2:1 PE/dcm to yield the product as yellow oil (8.82g, 72%). The oil turned into yellow crystals upon standing in the fume cupboard over a weekend. 1H-NMR (CDCI3, 300 MHz): delta= 0.86 (m, 6H), 1.07 (t, J = 7.1 Hz, 3H), 1.22 (m, 24H), 1.70 (m, 4H), 2.76 (m, 1 H), 4.22 (q, J = 7.2 Hz, 2H), 6.97 (s, 1H), 7.27 (s, 1 H), 7.89 (s, 1 H).

Reference： [1]Patent: WO2013/56775,2013,A1 .Location in patent: Page/Page column 71; 72

67
[ 18013-97-3 ]
[ 116886-71-6 ]
[ 1448777-69-2 ]

Yield	Reaction Conditions	Operation in experiment
59%	With tetrakis(triphenylphosphine) palladium(0); In toluene; at 110℃; for 18h;Sealed tube; Inert atmosphere;	Diethyl 2,5-dibromoterephthalate1 (11, 1.16 g, 3.06 mmol, 1 equiv), 2-(tri-nbutylstannyl)selenophene2 (3.22 g, 7.66 mmol, 2.5 equiv) and dry toluene (75 mL) were spargedwith Ar for 45 min in an oven-dried pressure vessel. After addition of Pd(PPh3)4 (177 mg, 0.153mmol, 5 mol%) to the reaction vessel, the resulting solution was sparged an additional 15 min,sealed and then stirred at 110 C for 18 h. After cooling, the reaction mixture was filteredthrough a short pad of silica gel eluting with CH2Cl2 and evaporated to dryness under reducedpressure. The crude product was purified via column chromatography (4:1 hexanes:CH2Cl2)followed by recrystallization from EtOH to yield 12 (869 mg, 59%) as light yellow crystals. 1HNMR (500 MHz, CDCl3) delta 8.11 (dd, J = 5.6, 1.2 Hz, 2H), 7.81 (s, 2H), 7.33 (dd, J = 5.6, 3.7 Hz,2H), 7.25 (dd, J = 3.7, 1.2 Hz, 2H), 4.24 (q, J = 7.2 Hz, 4H), 1.18 (t, J = 7.1 Hz, 6H); 13C NMR(151 MHz, CDCl3) delta 167.77, 146.41, 135.48, 133.72, 132.32, 131.78, 129.70, 129.28, 61.67,13.79; HRMS (ESI+) for C20H19O4Se2 (M+H)+: calcd 482.9614, found 482.9611

Reference： [1]Macromolecules,2013,vol. 46,p. 7715 - 7726
[2]Tetrahedron Letters,2015,vol. 56,p. 3235 - 3239
[3]Journal of Polymer Science, Part A: Polymer Chemistry,2013,vol. 51,p. 4550 - 4557
[4]Chemistry of Materials,2013,vol. 25,p. 3188 - 3195

68
[ 18013-97-3 ]
[ 1448777-71-6 ]

Reference： [1]Journal of Polymer Science, Part A: Polymer Chemistry,2013,vol. 51,p. 4550 - 4557

69
[ 18013-97-3 ]
[ 1448777-66-9 ]

Reference： [1]Journal of Polymer Science, Part A: Polymer Chemistry,2013,vol. 51,p. 4550 - 4557

70
[ 18013-97-3 ]
C₇₂H₉₄O₆Se₂ [ No CAS ]

Reference： [1]Macromolecules,2013,vol. 46,p. 7715 - 7726

71
[ 18013-97-3 ]
C₇₂H₉₀O₄Se₂ [ No CAS ]

Reference： [1]Macromolecules,2013,vol. 46,p. 7715 - 7726

72
[ 18013-97-3 ]
C₇₈H₁₀₆O₄Se₂Sn₂ [ No CAS ]

Reference： [1]Macromolecules,2013,vol. 46,p. 7715 - 7726

73
[ 18013-97-3 ]
[ 1509939-07-4 ]

Reference： [1]Organic Letters,2014,vol. 16,p. 106 - 109

74
[ 18013-97-3 ]
[ 1446707-47-6 ]

Reference： [1]Organic Letters,2014,vol. 16,p. 106 - 109

75
[ 18013-97-3 ]
[ 1209012-28-1 ]

Reference： [1]Organic Letters,2014,vol. 16,p. 106 - 109
[2]Macromolecules,2017,vol. 50,p. 7984 - 7992
[3]Patent: CN110283184,2019,A

76
[ 18013-97-3 ]
[ 1209012-30-5 ]

Reference： [1]Organic Letters,2014,vol. 16,p. 106 - 109
[2]Macromolecules,2017,vol. 50,p. 7984 - 7992
[3]Patent: CN110283184,2019,A

77
[ 18013-97-3 ]
[ 1209012-31-6 ]

Reference： [1]Organic Letters,2014,vol. 16,p. 106 - 109

78
[ 18013-97-3 ]
[ 1509939-03-0 ]

Reference： [1]Organic Letters,2014,vol. 16,p. 106 - 109

79
[ 18013-97-3 ]
[ 1509939-04-1 ]

Reference： [1]Organic Letters,2014,vol. 16,p. 106 - 109

80
[ 18013-97-3 ]
[ 1509939-05-2 ]

Reference： [1]Organic Letters,2014,vol. 16,p. 106 - 109

81
[ 6165-68-0 ]
[ 18013-97-3 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In toluene;	Synthesis Example 4 A compound represented by the following Chemical Formula 3A is prepared. In a 2L 3-neck round bottom flask, 500ml of toluene is degassed and charged with N2 three times, then 33.4 g (0.0879 mol, 1 eq) of 2.5-dibromoterephthalate (TCI) and 49 g (0.3517 mol, 4 eq) of K2CO3 are added. The reaction suspension is degassed and charged with N2 once then added with 7.2 g (0.0088 mol, 0.1 eq) of PdCl2 (dppf) DCM (Sigma-Aldrich Co. Ltd.). Next, the reactant is degassed and charged with N2 once then heated at 60 C for 2 hours. Then, 45 g (0.3517 mol, 4 eq) of thiophene-2-boronic acid is added to the reactant. The mixture is heated at 110 C for 16 hours. When diethyl 2.5-dibromoterephthalate still remains in the reactant, 23 g (2 eq) of thiophene-2-boronic acid is further added thereto, and 12 g (1 eq) of the thiophene-2-boronic acid is further added thereto after 40 hours.
	With potassium carbonate; In toluene;	First Step In a 2 L 3-neck round bottom flask, 500 ml of toluene is degassed and charged with N2 three times, then 33.4 g (0.0879 mol, 1 eq) of 2.5-dibromoterephthalate (TCl) and 49 g (0.3517 mol, 4 eq) of K2CO3 are added. The reaction suspension is degassed and charged with N2 once then added with 7.2 g (0.0088 mol, 0.1 eq) of PdCl2 (dppf) DCM (Sigma-Aldrich Co. Ltd.). Next, the reactant is degassed and charged with N2 once then heated at 60 C. for 2 hours. Then, 45 g (0.3517 mol, 4 eq) of thiophene-2-boronic acid is added to the reactant. The mixture is heated at 110 C. for 16 hours. When diethyl 2.5-dibromoterephthalate still remains in the reactant, 23 g (2 eq) of thiophene-2-boronic acid is further added thereto, and 12 g (1 eq) of the thiophene-2-boronic acid is further added thereto after 40 hours.

Reference： [1]Patent: EP2696351,2014,A2 .Location in patent: Page/Page column
[2]Patent: US8890134,2014,B2 .Location in patent: Page/Page column

82
[ 18013-97-3 ]
[ 142913-28-8 ]
[ 1443022-43-2 ]