[ CAS No. 33719-74-3 ] {[proInfo.proName]}

Name: 33719-74-3|1,3-Dichloro-5-methoxybenzene|98%
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Quality Control of [ 33719-74-3 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 33719-74-3 ]

Product Details of [ 33719-74-3 ]

CAS No. :	33719-74-3	MDL No. :	MFCD00000589
Formula :	C₇H₆Cl₂O	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	SSNXYMVLSOMJLU-UHFFFAOYSA-N
M.W :	177.03	Pubchem ID :	36588
Synonyms :

Safety of [ 33719-74-3 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P280-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H315-H319-H332-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 33719-74-3 ]

* 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 [ 33719-74-3 ]
Downstream synthetic route of [ 33719-74-3 ]

[ 33719-74-3 ] Synthesis Path-Upstream 1~18

1
[ 33719-74-3 ]
[ 65262-96-6 ]

Reference： [1] Journal of the American Chemical Society, 2016, vol. 138, # 41, p. 13493 - 13496

2
[ 33719-74-3 ]
[ 591-35-5 ]
[ 65262-96-6 ]
[ 7051-16-3 ]

Reference： [1] Tetrahedron, 1983, vol. 39, # 1, p. 193 - 198

3
[ 33719-74-3 ]
[ 124-41-4 ]
[ 591-35-5 ]
[ 65262-96-6 ]
[ 7051-16-3 ]

Reference： [1] Tetrahedron, 1983, vol. 39, # 1, p. 193 - 198
[2] Tetrahedron, 1983, vol. 39, # 1, p. 193 - 198

4
[ 33719-74-3 ]
[ 100-96-9 ]
[ 10272-06-7 ]

Reference： [1] Organic Letters, 2015, vol. 17, # 23, p. 5934 - 5937

5
[ 33719-74-3 ]
[ 591-35-5 ]
[ 65262-96-6 ]
[ 7051-16-3 ]

Reference： [1] Tetrahedron, 1983, vol. 39, # 1, p. 193 - 198

6
[ 33719-74-3 ]
[ 124-41-4 ]
[ 591-35-5 ]
[ 65262-96-6 ]
[ 7051-16-3 ]

Reference： [1] Tetrahedron, 1983, vol. 39, # 1, p. 193 - 198
[2] Tetrahedron, 1983, vol. 39, # 1, p. 193 - 198

7
[ 33719-74-3 ]
[ 62089-34-3 ]

Reference： [1] Tetrahedron Letters, 1989, vol. 30, # 38, p. 5093 - 5096

8
[ 33719-74-3 ]
[ 6480-66-6 ]

Reference： [1] Chemical Research in Toxicology, 1999, vol. 12, # 8, p. 690 - 699
[2] Synthesis, 2011, # 7, p. 1045 - 1054

9
[ 33719-74-3 ]
[ 6480-66-6 ]
[ 93839-14-6 ]

Reference： [1] Synthesis, 2011, # 7, p. 1045 - 1054

10
[ 124-38-9 ]
[ 33719-74-3 ]
[ 82477-67-6 ]

Yield	Reaction Conditions	Operation in experiment
41%	Stage #1: With magnesium; ethylene dibromide In tetrahydrofuran for 2 h; Heating / reflux	Magnesium turnings (Fluka purum for Grignard reactions) were pre-treated in the following way: The turnings were placed in a glass sintered funnel and 0.1 M of hydrochloric acid was poured onto them. The turnings were stirred with a glass rod for a few seconds and then the acid was washed away with 3 portions of water. Finally, the turnings were washed with 2 portions of acetone and bottled. Tetrahydrofuran (100 mL, 99.95percent) was dried by adding RedAl [(1] g, 70percent wt. in toluene). Pre-treated magnesium turnings (5 g, 200 mmol) were placed in a round bottomed flask, and were flushed with nitrogen 3 times. Dichloroanisole (26 g, 146 mmol) was dissolved in THF (100 mL, [REDAI-DRIED)] and dibromoethane (1.8 g, 10 mmol) was added. The reaction mixture was flushed with nitrogen and then refluxed for 2 hours. Heating was interrupted and dry ice (10 g) was added portionwise over 2 minutes. When all of the dry ice was dissolved, the reaction mixture was poured into ice containing hydrochloric acid (400 mL, 2 M). Extractive work up (ether, 300 mL) gave 11.2 g, 60.2 mmol (yield: [41percent)] of the sub-title compound. [LH-NMR] (500 MHz; [ACETONE-D6)] : A 7.57 (m, [I H),] 7.49 (m, 1H), 7.23 (m, 1H), 3. 91 (s, 3H)

Reference： [1] Patent: WO2003/101956, 2003, A1, . Location in patent: Page 55
[2] Journal of Medicinal Chemistry, 1984, vol. 27, # 5, p. 577 - 585

11
[ 33719-74-3 ]
[ 82477-67-6 ]

Yield	Reaction Conditions	Operation in experiment
41%	Stage #1: With magnesium; ethylene dibromide In tetrahydrofuran for 2 h; Heating / reflux Stage #2: With hydrogenchloride In tetrahydrofuran; water	Magnesium turnings (Fluka purum for Grignard reactions) were pre-treated in the following way: The turnings were placed in a glass sintered funnel and 0.1 M of hydrochloric acid was poured onto them. The turnings were stirred with a glass rod for a few seconds and then the acid was washed away with 3 portions of water. Finally, the turnings were washed with 2 portions of acetone and bottled. Tetrahydrofuran (100 mL, 99.95percent) was dried by adding RedAl (1 g, 70percent wt. in toluene). Pre-treated magnesium turnings (5 g, 200 mmol) were placed in a round bottomed flask, and were flushed with nitrogen 3 times. Dichloroanisole (26 g, 146 mmol) was dissolved in THF (100 mL, RedAl-dried) and dibromoethane (1.8 g, 10 mmol) was added. The reaction mixture was flushed with nitrogen and then refluxed for 2 hours. Heating was interrupted and dry ice (10 g) was added portionwise over 2 minutes. When all of the dry ice was dissolved, the reaction mixture was poured into ice containing hydrochloric acid (400 mL, 2 M). Extractive work up (ether, 300 mL) gave 11.2 g, 60.2 mmol (yield: 41percent) of the sub-title compound. [0408] 1H-NMR (500 MHz; acetone-d6): δ7.57 (m, 1H), 7.49 (m, 1H), 7.23 (m, 1H), 3.91 (s, 3H).

Reference： [1] Patent: US2004/19033, 2004, A1, . Location in patent: Page/Page column 21

12
[ 33719-74-3 ]
[ 100948-83-2 ]
[ 74672-01-8 ]

Reference： [1] Chemical Research in Toxicology, 1999, vol. 12, # 8, p. 690 - 699
[2] Synthesis, 2011, # 7, p. 1045 - 1054

13
[ 50-00-0 ]
[ 33719-74-3 ]
[ 82772-93-8 ]
[ 78444-52-7 ]

Reference： [1] Patent: EP1864971, 2007, A1, . Location in patent: Page/Page column 134-135

14
[ 4885-02-3 ]
[ 33719-74-3 ]
[ 82772-93-8 ]

Reference： [1] Journal of Medicinal Chemistry, 1987, vol. 30, # 3, p. 486 - 494

15
[ 33719-74-3 ]
[ 82772-93-8 ]

Reference： [1] Bioorganic and medicinal chemistry, 2003, vol. 11, # 16, p. 3457 - 3474
[2] Journal of Medicinal Chemistry, 1988, vol. 31, # 1, p. 72 - 83

16
[ 33719-74-3 ]
[ 68-12-2 ]
[ 164650-68-4 ]

Yield	Reaction Conditions	Operation in experiment
54%	Stage #1: With magnesium; ethylene dibromide In tetrahydrofuran at 0 - 25℃; for 3 h; Heating / reflux Stage #3: With hydrogenchloride; water In tetrahydrofuran	3,5-Dichloroanisole (74.0 g, 419 mmol) in THF (200 mL) was added dropwise to magnesium metal (14.2 g, 585 mmol, pre-washed with 0.5 N HCl) in THF (100 mL) at 25° C. After the addition, 1,2-dibromoethane (3.9 g, 20.8 mmol) was added dropwise. The resultant dark brown mixture was heated at reflux for 3 h. The mixture was cooled to 0° C., and N,N-dimethylformamide (60 mL) was added in one portion. The mixture was partitioned with diethyl ether (3400 mL) and 6N HCl (500 mL). The combined organic extracts were washed with brine (300 mL), dried (Na₂SO₄), filtered and concentrated in vacuo to give an oil. Flash chromatography (2) on silica gel eluding with Hex:EtOAc (4:1) afforded the sub-title compound (38.9 g, 54percent/) as a yellow oil. ¹H NMR (300 MHz, CDCl₃) δ9.90 (s, 1H), 7.53 (s, 1H), 7.38 (s, 1H), 7.15 (s, 1H), 3.87 (s, 3H).
54%	Stage #1: With magnesium; ethylene dibromide In tetrahydrofuran for 3 h; Heating / reflux Stage #2: at 0℃;	3,5-Dichloroanisole (74.0 g, 419 mmol) in THF (200 [ML)] was added dropwise to magnesium metal (14.2 g, 585 mmol, pre-washed with 0.5 N [HC1)] in THF (100 [ML)] at [25°C.] After the addition, 1,2-dibromoethane (3.9 g, 20.8 mmol) was added dropwise. The resultant dark brown mixture was heated at reflux for 3 h. The mixture was cooled to [0°C,] and [N, N-DIMETHYLFORMAMIDE] (60 mL) was added in one portion. The mixture was partitioned with diethyl ether (3 x 400 mL) and 6N HCl (500 mL). The combined organic extracts were washed with brine (300 mL), dried [(NA2S04),] filtered and concentrated in vacuo to give an oil. Flash chromatography (2x) on silica gel eluting with Hex: EtOAc (4: 1) afforded the sub- title compound (38.9 g, 54percent) as a yellow oil. [APOS;H] NMR (300 MHz, [CDC13)] [8] 9.90 (s, 1H), 7.53 (s, 1H), 7.38 (s, 1H), 7.15 (s, 1H), 3.87 (s, 3H).
54%	Stage #1: With magnesium; ethylene dibromide In tetrahydrofuran for 3 h; Heating / reflux Stage #2: at 0℃;	[5-DICHLOROANISOLE] (74.0 g, 419 mmol) in THF (200 mL) was added dropwise to magnesium metal (14.2 g, 585 mmol, pre-washed with 0.5 N HC1) in THF (100 mL) at [25°C.] After the addition, 1,2-dibromoethane (3.9 g, 20.8 mmol) was added dropwise. The resultant dark brown mixture was heated at reflux for 3 h. The mixture was cooled to [0°C,] and N, N-dimethylformamide (60 mL) was added in one portion. The mixture was partitioned with diethyl ether (3 x 400 mL) and 6N HCI (500 mL). The combined organic extracts were washed with brine (300 [ML),] dried [(NA2SO4),] filtered and concentrated in vacuo to give an oil. Flash chromatography (2x) on silica gel eluting with Hex: EtOAc (4: 1) afforded the sub- title compound (38.9 g, 54percent) as a yellow oil. 'H NMR (300 MHz, [CDC13)] 8 9.90 (s, 1H), 7.53 (s, 1H), 7.38 (s, 1H), 7.15 (s, 1H), 3.87 (s, 3H).

54%

Stage #1: With magnesium; ethylene dibromide In tetrahydrofuran for 3 h; Heating / reflux
Stage #2: at 0℃;

3, [5-DICHLOROANISOLE] (74.0 g, 419 mmol) in THF (200 mL) was added dropwise to magnesium metal (14.2 g, 585 mmol, pre-washed with 0.5 N HCI) in THF (100 mL) at [25°C.] After the addition, 1,2-dibromoethane (3.9 g, 20.8 mmol) was added dropwise. The resultant dark brown mixture was heated at reflux for 3 h. The mixture was cooled to [0°C,] and N, N-dimethylformamide (60 mL) was added in one portion. The mixture was partitioned with diethyl ether (3 x 400 mL) and 6N HCI (500 mL). The combined organic extracts were washed with brine (300 mL), dried [(NA2SO4),] filtered and concentrated in vacuo to give an oil. Flash chromatography (2x) on silica gel eluting with Hex: EtOAc (4: 1) afforded the sub-title compound (38.9 g, 54percent) as a yellow oil. 'H NMR (300 MHz, [CDCI3)] A 9.90 (s, 1H), 7.53 (s, 1H), 7.38 (s, 1H), 7.15 (s, 1H), 3.87 (s, 3H).

Reference： [1] Patent: US2004/19033, 2004, A1, . Location in patent: Page/Page column 16
[2] Patent: WO2003/101423, 2003, A1, . Location in patent: Page 19
[3] Patent: WO2003/101424, 2003, A1, . Location in patent: Page 21
[4] Patent: WO2003/101956, 2003, A1, . Location in patent: Page 39; 40

17
[ 33719-74-3 ]
[ 106-93-4 ]
[ 164650-68-4 ]

Yield	Reaction Conditions	Operation in experiment
54%	Stage #1: With magnesium In tetrahydrofuran for 3 h; Heating / reflux Stage #2: With N,N-dimethyl-formamide In tetrahydrofuran at 0℃;	3,5-Dichloroanisole [(74.] 0 g, 419 mmol) in THF (200 mL) was added dropwise to magnesium metal (14.2 g, 585 mmol, pre-washed with 0.5 N [HCL)] in THF (100 [ML)] at [25°C.] After the addition, 1,2-dibromoethane (3.9 g, 20.8 mmol) was added dropwise. The resultant dark brown mixture was heated at reflux for 3 h. The mixture was cooled to [0°C,] and [N, N-] dimethylformamide (60 mL) was added in one portion. The mixture was partitioned with diethyl ether (3 x 400 mL) and 6N HCl (500 mL). The combined organic extracts were washed with brine (300 mL), dried (Na2SO4), filtered and concentrated in vacuo to give an oil. Flash chromatography (2x) on silica gel eluting with Hex: EtOAc (4: 1) afforded the sub-title compound [(38.] 9 g, 54percent) as a yellow oil. [APOS;H] NMR (300 MHz, [CDCL3)] 8 9.90 (s, 1H), 7.53 (s, 1H), 7.38 (s, 1H), 7.15 (s, [1H),] 3.87 (s, 3H).

Reference： [1] Patent: WO2003/101957, 2003, A1, . Location in patent: Page 29

18
[ 33719-74-3 ]
[ 164650-68-4 ]

Reference： [1] Patent: US6255301, 2001, B1,

[ 33719-74-3 ] Synthesis Path-Downstream 1~87

1
[ 108-70-3 ]
[ 124-41-4 ]
[ 33719-74-3 ]

Yield	Reaction Conditions	Operation in experiment
98%	In dimethyl sulfoxide; at 80 - 90℃;	A 1 L three-necked flask is charged with 100 g (551 mmoles) of <strong>[108-70-3]1,3,5-trichlorobenzene</strong> that is placed in suspension in 400 mL of dimethylsulfoxide. This suspension is heated to 80 C., under agitation, then 119.06 g of a 30% solution of sodium methanolate are added drop-wise, i.e. 661.2 mmoles of sodium methanolate. Heating is continued up to 90 C., still under agitation, for 3 hours 10. After this time, the content of the flask is lowered too ambient temperature and it is poured into 4 L of iced water. A white solid is precipitated. This solid is recovered by filtering, washed three times with 250 mL of iced water, then vacuum died at ambient temperature. This gives 95.55 g of 3,5-dichloroanisole in the form of a white powder whose analysis by GC-MS (under the same conditions as previously) shows that it has a degree of purity of 96%. The yield is 98%.

Reference： [1]Patent: US2013/178655,2013,A1 .Location in patent: Paragraph 0071; 0072; 0073; 0074; 0075; 0076; 0077; 0078
[2]Tetrahedron,1983,vol. 39,p. 193 - 198
[3]Journal of the Chemical Society. Perkin transactions II,1982,p. 1593 - 1598
[4]Recueil des Travaux Chimiques des Pays-Bas,1918,vol. 37,p. 105

2
[ 591-35-5 ]
[ 77-78-1 ]
[ 33719-74-3 ]

Yield	Reaction Conditions	Operation in experiment
100%	With potassium carbonate In acetone for 3h;
100%	With potassium carbonate In acetone for 3h; Ambient temperature;
	With sodium hydroxide

Reference： [1]Tatsuta, Kuniaki; Itoh, Manabu [Tetrahedron Letters, 1993, vol. 34, # 52, p. 8443 - 8444]
[2]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[3]Blanksma [Recueil des Travaux Chimiques des Pays-Bas, 1908, vol. 27, p. 36]

3
[ 4885-02-3 ]
[ 33719-74-3 ]
[ 82772-93-8 ]

Reference： [1]Journal of Medicinal Chemistry,1987,vol. 30,p. 486 - 494

4
[ 124-38-9 ]
[ 33719-74-3 ]
[ 82477-67-6 ]

Yield	Reaction Conditions	Operation in experiment
41%		Magnesium turnings (Fluka purum for Grignard reactions) were pre-treated in the following way: The turnings were placed in a glass sintered funnel and 0.1 M of hydrochloric acid was poured onto them. The turnings were stirred with a glass rod for a few seconds and then the acid was washed away with 3 portions of water. Finally, the turnings were washed with 2 portions of acetone and bottled. Tetrahydrofuran (100 mL, 99.95%) was dried by adding RedAl [(1] g, 70% wt. in toluene). Pre-treated magnesium turnings (5 g, 200 mmol) were placed in a round bottomed flask, and were flushed with nitrogen 3 times. Dichloroanisole (26 g, 146 mmol) was dissolved in THF (100 mL, [REDAI-DRIED)] and dibromoethane (1.8 g, 10 mmol) was added. The reaction mixture was flushed with nitrogen and then refluxed for 2 hours. Heating was interrupted and dry ice (10 g) was added portionwise over 2 minutes. When all of the dry ice was dissolved, the reaction mixture was poured into ice containing hydrochloric acid (400 mL, 2 M). Extractive work up (ether, 300 mL) gave 11.2 g, 60.2 mmol (yield: [41%)] of the sub-title compound. [LH-NMR] (500 MHz; [ACETONE-D6)] : A 7.57 (m, [I H),] 7.49 (m, 1H), 7.23 (m, 1H), 3. 91 (s, 3H)

Reference： [1]Patent: WO2003/101956,2003,A1 .Location in patent: Page 55
[2]Journal of Medicinal Chemistry,1984,vol. 27,p. 577 - 585

5
[ 33719-74-3 ]
[ 124-41-4 ]
[ 591-35-5 ]
[ 65262-96-6 ]
[ 7051-16-3 ]

Yield	Reaction Conditions	Operation in experiment
1: 40% 2: 7% 3: 51%	In N,N,N,N,N,N-hexamethylphosphoric triamide at 120℃;
1: 51% 2: 7% 3: 40%	In N,N,N,N,N,N-hexamethylphosphoric triamide at 120℃; for 1h;

Reference： [1]Testaferri, L.; Tiecco, M.; Tingoli, M.; Chianelli, D.; Montanucci, M. [Tetrahedron, 1983, vol. 39, # 1, p. 193 - 198]
[2]Testaferri, L.; Tiecco, M.; Tingoli, M.; Chianelli, D.; Montanucci, M. [Tetrahedron, 1983, vol. 39, # 1, p. 193 - 198]

6
[ 33719-74-3 ]
[ 591-35-5 ]

Yield	Reaction Conditions	Operation in experiment
67%	With boron triiodide-N,N-diethylaniline In benzene for 4h; Ambient temperature;
	With hydrogen bromide In water Reflux;

Reference： [1]Narayana, Chatla; Padmanabhan, Seetharamaiyer; Kabalka, George W. [Tetrahedron Letters, 1990, vol. 31, # 48, p. 6977 - 6978]
[2]Mangin, Loïc P.; Zargarian, Davit [Dalton Transactions, 2017, vol. 46, # 46, p. 16159 - 16170]

7
[ 33719-74-3 ]
[ 591-35-5 ]
[ 65262-96-6 ]
[ 7051-16-3 ]

Yield	Reaction Conditions	Operation in experiment
1: 51% 2: 40% 3: 7%	With sodium methylate In N,N,N,N,N,N-hexamethylphosphoric triamide at 120℃; for 1h;

Reference： [1]Testaferri, L.; Tiecco, M.; Tingoli, M.; Chianelli, D.; Montanucci, M. [Tetrahedron, 1983, vol. 39, # 1, p. 193 - 198]

8
[ 33719-74-3 ]
[ 54135-82-9 ]

Yield	Reaction Conditions	Operation in experiment
87%	With trichloroisocyanuric acid In N,N-dimethyl-formamide for 1h;
87%	With 1,3,5-trichloro-2,4,6-triazine In N,N-dimethyl-formamide for 1h; Ambient temperature;
	With chlorine

Reference： [1]Tatsuta, Kuniaki; Itoh, Manabu [Tetrahedron Letters, 1993, vol. 34, # 52, p. 8443 - 8444]
[2]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[3]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

9
[ 33719-74-3 ]
[ 77-78-1 ]
[ 82477-66-5 ]

Reference： [1]Tetrahedron Letters,1989,vol. 30,p. 5093 - 5096

10
[ 33719-74-3 ]
[ 100948-83-2 ]
[ 74672-01-8 ]

Reference： [1]Chemical Research in Toxicology,1999,vol. 12,p. 690 - 699
[2]Synthesis,2011,p. 1045 - 1054

11
[ 50-00-0 ]
[ 33719-74-3 ]
[ 86111-47-9 ]

Yield	Reaction Conditions	Operation in experiment
30%	Stage #1: formaldehyd; 3,5-dichloroanisole With hydrogenchloride; sulfuric acid In water at 60℃; Stage #2: With sodium hydroxide In 1,4-dioxane; water for 3h; Heating;
30%	With hydrogenchloride; sulfuric acid In water at 60℃;	9; 40 Example 40; (2,6-Dichloro-4-methoxy-phenyl)-methanol; Scheme 9 A mixture of 3,5 DICHLOROANISOLE (16.; 39 g, 92.59 MMOL), HC1 (250 mL of concentrated solution), and sulfuric acid (2.5 ML of concentrated solution) was stirred at 60°C overnight. The mixture was cooled to room temperature and the organic layer was removed. The aqueous layer was extracted with dichloromethane (2 x 100 mL). The combined organic layers were washed with water and the solvent was removed by evaporation. To the remaining oil was added NAOH (180 ML of 1N solution) and dioxane (85 mL). The mixture was stirred at reflux for 3 hours and cooled to room temperature. The organic layer was removed and the aqueous layer was extracted with dichloromethane (3 x 100 mL). The combined organic layers were washed with water, washed with brine, dried over sodium sulfate, and filtered. The residue was purified on silica (90% hexanes-10% ethyl acetate) to yield 5.82 g (30%) of the title compound as a white solid : mp 71-72°C ; IHNMR (CDCL3) : 8 1. 88 (1H, s), 3.73 (3H, s), 4.81 (2H, s), 6.81 (2H, s); MS (EI) M/Z 206/208/210 (M+ ). Anal. for C8H8C1202 : Calc'd : C: 46.41 H: 3.89 Found: C: 46.38 H: 3.69.
26.6%	Stage #1: formaldehyd; 3,5-dichloroanisole With hydrogenchloride; sulfuric acid In water at 100℃; for 16h; Stage #2: With sodium hydroxide	3a; 3b Synthesis of Compound 1 To a mixture of 3,5-dichloroanisole (18 g, 97.6 mmol, 1.00 equiv), Paraformaldehyde (4.26 g, 128 mmol, 1.31 equiv) and cone, hydrochloric acid (180 mL) was added cone, sulfuric acid (1.80 mL) at room temperature. After refluxing at 100 °C for 16 hours, the mixture was cooled to room temperature, he resulting mixture was extracted with ethyl acetate (5 x SO mL). The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. To the residue were added 1,4-dioxane (100 mL) and a sodium hydroxide aqueous solution (203 mL, 1 M). The mixture was refluxed at 100 °C for 3 hours. The reaction solution was cooled to room temperature, followed by extraction with DCM (5 x SO mL). The organic layer was dried over anhydrous sodium sulfate, filtered and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluting with 85:15 PE/EA) to afford (2,6-dichloro-4-methoxyphenyl)methanol (5.6 g, 26.6%) as a white solid. GCMS (ES, m/z): 206,208.

26.6%	Stage #1: formaldehyd; 3,5-dichloroanisole With hydrogenchloride; sulfuric acid In water at 100℃; for 16h; Stage #2: With sodium hydroxide	3a; 3b Synthesis of Compound 1 To a mixture of 3,5-dichloroanisole (18 g, 97.6 mmol, 1.00 equiv), Paraformaldehyde (4.26 g, 128 mmol, 1.31 equiv) and cone, hydrochloric acid (180 mL) was added cone, sulfuric acid (1.80 mL) at room temperature. After refluxing at 100 °C for 16 hours, the mixture was cooled to room temperature, he resulting mixture was extracted with ethyl acetate (5 x SO mL). The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. To the residue were added 1,4-dioxane (100 mL) and a sodium hydroxide aqueous solution (203 mL, 1 M). The mixture was refluxed at 100 °C for 3 hours. The reaction solution was cooled to room temperature, followed by extraction with DCM (5 x SO mL). The organic layer was dried over anhydrous sodium sulfate, filtered and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluting with 85:15 PE/EA) to afford (2,6-dichloro-4-methoxyphenyl)methanol (5.6 g, 26.6%) as a white solid. GCMS (ES, m/z): 206,208.
4.67 g	Stage #1: formaldehyd; 3,5-dichloroanisole With hydrogenchloride; sulfuric acid In water at 100℃; for 8h; Stage #2: With water; sodium hydroxide In 1,4-dioxane at 100℃; for 3h;	11 Preparation Example 11 Preparation Example 11 To a mixture of 1,3-dichloro-5-methoxybenzene (10.0 g), paraformaldehyde (2.21 g), and concentrated hydrochloric acid (100 mL) was added concentrated sulfuric acid (1.00 mL) at room temperature. After heating and refluxing at 100°C for 8 hours, and leaving to be cooled to room temperature, water was added thereto, followed by extraction with ethyl acetate. The organic layer was washed with water, a saturated aqueous sodium hydrogen carbonate solution, and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. To the residue were added dioxane (56.0 mL) and a 1 M aqueous sodium hydroxide solution (113 mL), followed by heating and refluxing at 100°C for 3 hours. The reaction solution was left to be cooled, and then water was added thereto, followed by extraction with chloroform. The organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain (2,6-dichloro-4-methoxyphenyl)methanol (4.67 g).

Reference： [1]Edsall Jr., Richard J; Harris, Heather A; Manas, Eric S; Mewshaw, Richard E [Bioorganic and medicinal chemistry, 2003, vol. 11, # 16, p. 3457 - 3474]
[2]Current Patent Assignee: PFIZER INC - WO2004/99122, 2004, A2 Location in patent: Page 18; 35
[3]Current Patent Assignee: PAKINAX - WO2022/31, 2022, A1 Location in patent: Page/Page column 69; 70; 73; 74
[4]Current Patent Assignee: PAKINAX - WO2022/31, 2022, A1 Location in patent: Page/Page column 69; 70; 73; 74
[5]Current Patent Assignee: ASTELLAS PHARMA INC. - EP2757093, 2014, A1 Location in patent: Paragraph 0144

12
[ 33719-74-3 ]
[ 2845-89-8 ]
[ 100-66-3 ]

Yield	Reaction Conditions	Operation in experiment
	With tetraethylammonium bromide In methanol Electrolysis; Title compound not separated from byproducts;
	With [(NHC)Pd(allyl)Cl]; sodium hydroxide In isopropyl alcohol at 60℃; for 18h;

Reference： [1]Kranz, Olaf; Voss, Jürgen [Zeitschrift fur Naturforschung, B: Chemical Sciences, 2003, vol. 58, # 12, p. 1187 - 1200]
[2]Collinson, John-Michael; Wilton-Ely, James D.E.T.; Díez-González, Silvia [Catalysis Communications, 2016, vol. 87, p. 78 - 81]

13
[ 110-00-9 ]
[ 33719-74-3 ]
7-chloro-5-methoxy-1,4-dihydro-1,4-epoxidonaphthalene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	With n-butyllithium; diisopropylamine In tetrahydrofuran at -78 - 0℃; for 3h;

Reference： [1]Lautens, Mark; Schmid, Gavin A; Chau, Anh [Journal of Organic Chemistry, 2002, vol. 67, # 23, p. 8043 - 8053]

14
[ 33719-74-3 ]
Potassium; 3,5-dichloro-phenolate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With Triton X-114; potassium thioacyanate at 180℃; for 6h;

Reference： [1]Bhattacharya, Apurba; Patel, Nitin C.; Vasques, Tomas; Tichkule, Ritesh; Parmar, Gaurang; Wu, Jiejun [Tetrahedron Letters, 2006, vol. 47, # 4, p. 565 - 567]

15
[ 33719-74-3 ]
[ 89-75-8 ]
[ 934562-64-8 ]

Yield	Reaction Conditions	Operation in experiment
85%	With aluminium trichloride In nitrobenzene at -78 - 20℃; for 25h;
85%	With aluminum (III) chloride In nitrobenzene at -78 - 20℃; for 25h;
80%	Stage #1: 3,5-dichloroanisole; 2,4-dichlorobenzoyl chloride With aluminum (III) chloride In nitromethane at -78 - 20℃; for 25h; Stage #2: With sodium hydroxide In diethyl ether; nitromethane at 0℃;	2; 2.1.1; 3.1; III.1 Anhydrous AlCl3 (4.5 g, 33.9 mmol) was placed in a round bottom flask and PhNO2 (150 mL) was added. At -78° C. 2,4-dichlorobenzoyl chloride (4.7 mL, 33.9 mmol) and 3,5-dichloro anisole (5.0 g, 28.2 mmol) were added. The reaction mixture was kept at the same temperature for 1 h and warmed to rt over 24 h. The reaction mixture was diluted with Et2O (50 mL) at 0° C. and quenched with 1N NaOH (30 mL). The reaction mixture was stirred vigorously until a white precipitate had been formed. The precipitates were filtered and washed with CH2Cl2 (50, 30, and 20 mL). The combined organic solvents were dried (Na2SO4), filtered, and concentrated under vacuum at 10 mmHg. Purification by silica gel chromatography (4:1, hexanes:CHCl3) to provide (2,6-dichloro-4-methoxyphenyl)(2,4-dichlorophenyl)methanone (8.3 g, 85%) as a white powder. 1H NMR (300 MHz, CDCl3): δ 7.68 (d, J=8.2 Hz, 1H), 7.54 (d, J=2.1 Hz, 1H), 7.37 (dd, J=8.1, 2.1 Hz, 1H), 6.95 (s, 2H), 3.87 (s, 3H); 13C NMR (75 MHz, CDCl3): δ 197.6, 163.8, 142.0, 138.3, 137.7, 136.4, 130.3, 129.9, 127.8, 122.9, 118.4, 117.9, 114.6, 56.1; IR (film): 1619 cm-1, 1584, 1553, 1400, 1309; HRMS (FAB): C14H8Cl4O2 (M+Na1) calcd. 370.91761, found 370.91765.; Compounds of the invention, such as the (2,6-dichloro-4-methoxyphenyl)(2,4-dichlorophenyl)methyl hydrazinecarboxylate derivative 5b (Scheme 3-1), which were conveniently synthesized by Friedel-Crafts reactions followed by NaBH4 reduction, and CDI-mediated urethane formation reactions, are stable to various acidic conditions such as 1015% TFA, 30% HF, 2N HCl, HBr/AcOH, TiCl4, ZnCl2, AlCl3, B(C6F5)3, BCl3, BBr3, TMSOTf, and La(OTf)3 at rt. These compounds are also stable to bases such as 40% NH4OH, 10% LiOH, 6N NaOH, TlOEt, and DBU at rt. Moreover they are stable against and nucleophiles such as primary and secondary amines at 80° C., and NH2NH2 at rt. However, The urethane 5b could conveniently be deprotected by using 20% TFA in CH2Cl2 to afford hydrazine.TFA salt and (2,6-dichloro-4-methoxyphenyl)(2,4-dichlorophenyl)methyl 2,2,2-trifluoroacetate in quantitative yields.

80%	With aluminum (III) chloride In nitrobenzene
71%	With aluminium trichloride In dichloromethane at -78 - 20℃; for 6h;
	With aluminum (III) chloride In nitrobenzene

Reference： [1]Kurosu, Michio; Biswas, Kallolmay; Narayanasamy, Prabagaran; Crick, Dean C. [Synthesis, 2007, # 16, p. 2513 - 2516]
[2]Kurosu, Michio; Li, Kai [Organic Letters, 2009, vol. 11, # 4, p. 911 - 914]
[3]Current Patent Assignee: COLORADO STATE UNIVERSITY SYSTEM - US2008/200719, 2008, A1 Location in patent: Page/Page column 6; 15-16; 18-19
[4]Location in patent: scheme or table Kurosu, Michio; Narayanasamy, Prabagaran; Crick, Dean C. [Heterocycles, 2007, vol. 73, # C, p. 169 - 175]
[5]Kurosu, Michio; Biswas, Kallolmay; Crick, Dean C. [Organic Letters, 2007, vol. 9, # 6, p. 1141 - 1144]
[6]Location in patent: scheme or table Wang, Yong; Kurosu, Michio [Tetrahedron, 2012, vol. 68, # 24, p. 4797 - 4804]

16
[ 50-00-0 ]
[ 33719-74-3 ]
[ 82772-93-8 ]
[ 78444-52-7 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sulfuric acid; In water; at 60℃; for 16.0h;	A mixture of 3,5-dichloroanisole (5.0 g), paraformaldehyde (1.1 g), concentrated hydrochloric acid (50 mL) and concentrated sulfuric acid (0.5 mL) was stirred at 60C for 16 hr. The reaction mixture was poured into ice, and the mixture was extracted with diethyl ether (100 mL). The extract was washed successively with water, saturated sodium hydrogencarbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and a mixture of the obtained pale-yellow oil (6.57 g), 1N sodium hydroxide (56 mL) and dioxane (28 mL) was heated under reflux for 3 hr. The reaction mixture was extracted with dichloromethane (50 mL), and the extract was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (hexane-ethyl acetate 9:1) to give a mixture (3:1) of (2,6-dichloro-4-methoxyphenyl)methanol and (2,4-dichloro-6-methoxyphenyl)methanol.Reference Example 39A 1H NMR (300 MHz, CDCl3) delta ppm 1.95 (t, J=6.8 Hz, 1 H), 3.80 (s, 3H), 4.89 (d, J=6.8 Hz, 2 H), 6.88 (s, 2 H).Reference Example 40A 1H NMR (300 MHz, CDCl3) delta ppm 2.20 (t, J=6.8 Hz, 1 H), 3.88 (s, 3H), 4.81 (d, J=6.8 Hz, 2 H), 6.81 (s, 1 H), 7.04 (s, 1 H)

Reference： [1]Patent: EP1864971,2007,A1 .Location in patent: Page/Page column 134-135

17
[ 33719-74-3 ]
[ 934562-65-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 71 percent / anhydrous AlCl₃ / CH₂Cl₂ / 6 h / -78 - 20 °C 2: 97 percent / NaBH₄ / methanol / 0 °C

Reference： [1]Kurosu, Michio; Biswas, Kallolmay; Crick, Dean C. [Organic Letters, 2007, vol. 9, # 6, p. 1141 - 1144]

18
[ 33719-74-3 ]
[ 74390-79-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 71 percent / anhydrous AlCl₃ / CH₂Cl₂ / 6 h / -78 - 20 °C 2: 96 percent / aq. HBr; AcOH / 6 h / 110 °C

Reference： [1]Kurosu, Michio; Biswas, Kallolmay; Crick, Dean C. [Organic Letters, 2007, vol. 9, # 6, p. 1141 - 1144]

19
[ 33719-74-3 ]
[ 934562-66-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 71 percent / anhydrous AlCl₃ / CH₂Cl₂ / 6 h / -78 - 20 °C 2: 96 percent / aq. HBr; AcOH / 6 h / 110 °C 3: 92 percent / potassium carbonate / dimethylformamide / 6 h / 20 °C

Reference： [1]Kurosu, Michio; Biswas, Kallolmay; Crick, Dean C. [Organic Letters, 2007, vol. 9, # 6, p. 1141 - 1144]

20
[ 33719-74-3 ]
[ 60964-09-2 ]

Reference： [1]Bioorganic and medicinal chemistry,2003,vol. 11,p. 3457 - 3474

21
[ 33719-74-3 ]
[ 82772-93-8 ]

Reference： [1]Bioorganic and medicinal chemistry,2003,vol. 11,p. 3457 - 3474
[2]Journal of Medicinal Chemistry,1988,vol. 31,p. 72 - 83

22
[ 33719-74-3 ]
[ 634192-33-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: HCl; H₂SO₄ / H₂O / 60 °C 1.2: 30 percent / NaOH / dioxane; H₂O / 3 h / Heating 2.1: MnO₂ / benzene / Heating 3.1: BBr₃ / CH₂Cl₂ / 0 - 20 °C 4.1: 87 percent / pyridine / CH₂Cl₂ / 0 - 20 °C 5.1: 50 percent / Na₂CO₃ / Pd(PPh₃)4 / 1,2-dimethoxy-ethane; H₂O / 95 °C

Reference： [1]Edsall Jr., Richard J; Harris, Heather A; Manas, Eric S; Mewshaw, Richard E [Bioorganic and medicinal chemistry, 2003, vol. 11, # 16, p. 3457 - 3474]

23
[ 33719-74-3 ]
[ 634192-37-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1.1: HCl; H₂SO₄ / H₂O / 60 °C 1.2: 30 percent / NaOH / dioxane; H₂O / 3 h / Heating 2.1: MnO₂ / benzene / Heating 3.1: BBr₃ / CH₂Cl₂ / 0 - 20 °C 4.1: 87 percent / pyridine / CH₂Cl₂ / 0 - 20 °C 5.1: 39 percent / Na₂CO₃ / Pd(PPh₃)4 / 1,2-dimethoxy-ethane; H₂O / 95 °C 6.1: 85 percent / BBr₃ / CH₂Cl₂ / 0 - 20 °C

Reference： [1]Edsall Jr., Richard J; Harris, Heather A; Manas, Eric S; Mewshaw, Richard E [Bioorganic and medicinal chemistry, 2003, vol. 11, # 16, p. 3457 - 3474]

24
[ 33719-74-3 ]
3',5'-dichloro-4'-hydroxymethyl-biphenyl-4-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1.1: HCl; H₂SO₄ / H₂O / 60 °C 1.2: 30 percent / NaOH / dioxane; H₂O / 3 h / Heating 2.1: MnO₂ / benzene / Heating 3.1: BBr₃ / CH₂Cl₂ / 0 - 20 °C 4.1: 87 percent / pyridine / CH₂Cl₂ / 0 - 20 °C 5.1: 50 percent / Na₂CO₃ / Pd(PPh₃)4 / 1,2-dimethoxy-ethane; H₂O / 95 °C 6.1: 81 percent / NaBH₄ / ethanol / 1 h / 20 °C

Reference： [1]Edsall Jr., Richard J; Harris, Heather A; Manas, Eric S; Mewshaw, Richard E [Bioorganic and medicinal chemistry, 2003, vol. 11, # 16, p. 3457 - 3474]

25
[ 33719-74-3 ]
[ 634192-54-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: HCl; H₂SO₄ / H₂O / 60 °C 1.2: 30 percent / NaOH / dioxane; H₂O / 3 h / Heating 2.1: MnO₂ / benzene / Heating 3.1: BBr₃ / CH₂Cl₂ / 0 - 20 °C 4.1: 87 percent / pyridine / CH₂Cl₂ / 0 - 20 °C 5.1: 39 percent / Na₂CO₃ / Pd(PPh₃)4 / 1,2-dimethoxy-ethane; H₂O / 95 °C

Reference： [1]Edsall Jr., Richard J; Harris, Heather A; Manas, Eric S; Mewshaw, Richard E [Bioorganic and medicinal chemistry, 2003, vol. 11, # 16, p. 3457 - 3474]

26
[ 33719-74-3 ]
3',5'-dichloro-3-fluoro-4'-hydroxymethyl-biphenyl-4-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 7 steps 1.1: HCl; H₂SO₄ / H₂O / 60 °C 1.2: 30 percent / NaOH / dioxane; H₂O / 3 h / Heating 2.1: MnO₂ / benzene / Heating 3.1: BBr₃ / CH₂Cl₂ / 0 - 20 °C 4.1: 87 percent / pyridine / CH₂Cl₂ / 0 - 20 °C 5.1: 39 percent / Na₂CO₃ / Pd(PPh₃)4 / 1,2-dimethoxy-ethane; H₂O / 95 °C 6.1: 85 percent / BBr₃ / CH₂Cl₂ / 0 - 20 °C 7.1: 94 percent / NaBH₄ / ethanol / 20 °C

Reference： [1]Edsall Jr., Richard J; Harris, Heather A; Manas, Eric S; Mewshaw, Richard E [Bioorganic and medicinal chemistry, 2003, vol. 11, # 16, p. 3457 - 3474]

27
[ 33719-74-3 ]
[ 6480-66-6 ]

Reference： [1]Chemical Research in Toxicology,1999,vol. 12,p. 690 - 699
[2]Synthesis,2011,p. 1045 - 1054

28
[ 33719-74-3 ]
[ 98273-17-7 ]

Yield	Reaction Conditions	Operation in experiment
77%	With iodine; silver sulfate In acetonitrile at 20℃; for 72h; Inert atmosphere;
	Multi-step reaction with 3 steps 1: HNO₃; H₂SO₄ / CH₂Cl₂ / 18 h / 20 °C 2: 7 percent / Na₂S₂O₄ / aq. ethanol / 2 h / Heating
	Multi-step reaction with 2 steps 1.1: sulfuric acid; nitric acid / dichloromethane / 18 h 1.2: 14 h / Heating 2.1: sulfuric acid; potassium iodide; sodium nitrite / water / 18 h / 0 °C / Heating

	Multi-step reaction with 3 steps 1: sulfuric acid; nitric acid / dichloromethane / 18 h 2: sodium dithionite / ethanol; water / 14 h / Heating 3: sulfuric acid; potassium iodide; sodium nitrite / water / 18 h / 0 °C / Heating
65 %Chromat.	With iodine; silver sulfate In acetonitrile at 20℃; for 42h; regioselective reaction;	4.2. General procedure for the iodination of chlorinated benzene derivatives 1a-i General procedure: The respective silver salt (0.32 g, 1 mmol) and iodine (0.25 g, 1 mmol) were typically added to a stirred solution of the benzene derivative 1a-i (1 mmol) in dichloromethane (3 mL). The reaction mixture was allowed to stir at room temperature for approximately 16 h (see refPreviewPlaceHolderTable 1, refPreviewPlaceHolderTable 2, refPreviewPlaceHolderTable 3, refPreviewPlaceHolderTable 4, refPreviewPlaceHolderTable 5 and refPreviewPlaceHolderTable 6). The reaction mixture was cooled with ice-cold water, quenched with an aqueous solution of sodium metabisulfite (0.2 mL) and, in the case of anilines, 2 M NaOH (0.2 mL). The mixture was filtered through Celite and the residue was washed with dichloromethane (3×3 mL). The combined filtrate was washed with aqueous sodium bicarbonate (3 mL), water (3 mL), and brine (3 mL). The combined organic phases were dried over Na2SO4 and the solvent was removed under reduced pressure. The residue was redissolved in dichloromethane (10 mL) and the percent conversion of the starting material and the yields of the iodination products were determined by GC-MS using diethylene glycol di-n-butyl ether as internal standard. The relative response factor for the respective analyte (RRFA) was calculated from a calibration standard containing known amounts of the internal standard and the respective analytes using the formula RRFA=AIS·MA/(AA·MIS), where AIS is the peak area of the internal standard, AA is the area of an analyte (i.e., starting material or iodination product), MA is the mass of the analyte and MIS is the mass of the internal standard. The mass of the analyte in the reaction mixture was determined as MA=(RRFA·MIS·AA)/AIS. All samples were analyzed at least in duplicate. The iodination products of selected reactions were separated by column chromatography to obtain milligram quantities for their characterization and use as analytical standards. In the case of 3g, the isolated quantities were not sufficient for 13C NMR analysis.

Reference： [1]Bender, Aaron M.; Griggs, Nicholas W.; Gao, Chao; Trask, Tyler J.; Traynor, John R.; Mosberg, Henry I. [ACS Medicinal Chemistry Letters, 2015, vol. 6, # 12, p. 1199 - 1203]
[2]Waller, Stephen C.; He, You Ai; Harlow, Greg R.; He, You Qun; Mash, Eugene A.; Halpert, James R. [Chemical Research in Toxicology, 1999, vol. 12, # 8, p. 690 - 699]
[3]Joshi; Vyas; Duffel; Parkin; Lehmler [Synthesis, 2011, # 7, p. 1045 - 1054]
[4]Joshi; Vyas; Duffel; Parkin; Lehmler [Synthesis, 2011, # 7, p. 1045 - 1054]
[5]Location in patent: experimental part Joshi, Sudhir N.; Vyas, Sandhya M.; Wu, Huimin; Duffel, Michael W.; Parkin, Sean; Lehmler, Hans-Joachim [Tetrahedron, 2011, vol. 67, # 39, p. 7461 - 7469]

29
[ 33719-74-3 ]
[ 93839-14-6 ]

Reference： [1]Chemical Research in Toxicology,1999,vol. 12,p. 690 - 699

30
[ 33719-74-3 ]
[ 54300-74-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature
	Multi-step reaction with 3 steps 1: Cl₂ 2: nitrating agent 3: reducing agent
	Multi-step reaction with 3 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd/C / dimethylformamide; ethanol / 4 h

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]
[3]Tatsuta, Kuniaki; Itoh, Manabu [Tetrahedron Letters, 1993, vol. 34, # 52, p. 8443 - 8444]

31
[ 33719-74-3 ]
[ 151143-59-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C
	Multi-step reaction with 2 steps 1: Cl₂ 2: nitrating agent
	Multi-step reaction with 2 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C

32
[ 33719-74-3 ]
[ 155499-03-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C
	Multi-step reaction with 4 steps 1: Cl₂ 2: nitrating agent 3: reducing agent
	Multi-step reaction with 4 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd/C / dimethylformamide; ethanol / 4 h 4: 91 percent / acetic acid / 1 h / 70 - 80 °C

33
[ 33719-74-3 ]
[ 155499-04-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h
	Multi-step reaction with 5 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: NBS
	Multi-step reaction with 5 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd/C / dimethylformamide; ethanol / 4 h 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / NBS / dimethylformamide / 1 h / -5 °C

34
[ 33719-74-3 ]
[ 131956-35-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 8 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 1.) BuLi / 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane, 15 min 7: 95 percent / isocyanuric acid / dimethylformamide / 1.5 h / Ambient temperature 8: 66 percent / Cu-powder / quinoline / 0.12 h / 210 °C
	Multi-step reaction with 8 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: NBS 6: 1.) BuLi 7: trichloroisocyanuric acid 8: quinoline / Cu / Heating
	Multi-step reaction with 8 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd/C / dimethylformamide; ethanol / 4 h 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / NBS / dimethylformamide / 1 h / -5 °C 6: 81 percent / n-BuLi / tetrahydrofuran / -78 - 20 °C 7: 95 percent / trichloroisocyanuric acid / dimethylformamide / 2 h 8: 65 percent / Cu / quinoline / 0.12 h / 210 °C

35
[ 33719-74-3 ]
[ 155499-05-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 1.) BuLi / 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane, 15 min
	Multi-step reaction with 6 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: NBS 6: 1.) BuLi
	Multi-step reaction with 6 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd/C / dimethylformamide; ethanol / 4 h 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / NBS / dimethylformamide / 1 h / -5 °C 6: 81 percent / n-BuLi / tetrahydrofuran / -78 - 20 °C

36
[ 33719-74-3 ]
[ 155499-06-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 7 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 1.) BuLi / 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane, 15 min 7: 95 percent / isocyanuric acid / dimethylformamide / 1.5 h / Ambient temperature
	Multi-step reaction with 7 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: NBS 6: 1.) BuLi 7: trichloroisocyanuric acid
	Multi-step reaction with 7 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd/C / dimethylformamide; ethanol / 4 h 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / NBS / dimethylformamide / 1 h / -5 °C 6: 81 percent / n-BuLi / tetrahydrofuran / -78 - 20 °C 7: 95 percent / trichloroisocyanuric acid / dimethylformamide / 2 h

37
[ 33719-74-3 ]
[ 131956-34-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 9 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 1.) BuLi / 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane, 15 min 7: 95 percent / isocyanuric acid / dimethylformamide / 1.5 h / Ambient temperature 8: 66 percent / Cu-powder / quinoline / 0.12 h / 210 °C 9: 91 percent / AlCl₃ / benzene / 14 h / Ambient temperature
	Multi-step reaction with 9 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: NBS 6: 1.) BuLi 7: trichloroisocyanuric acid 8: quinoline / Cu / Heating 9: AlCl₃

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

38
[ 33719-74-3 ]
(+)-neopyrrolomycin [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 11 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 1.) BuLi / 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane, 15 min 7: 95 percent / isocyanuric acid / dimethylformamide / 1.5 h / Ambient temperature 8: 66 percent / Cu-powder / quinoline / 0.12 h / 210 °C 9: 91 percent / AlCl₃ / benzene / 14 h / Ambient temperature 10: pyridine / CH₂Cl₂ / 1) 5 deg C, 30 min; 2) room temperature, 30 min 11: 86 percent / NaOMe / methanol / 0.5 h
	Multi-step reaction with 11 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: NBS 6: 1.) BuLi 7: trichloroisocyanuric acid 8: quinoline / Cu / Heating 9: AlCl₃ 11: KOH
	Multi-step reaction with 9 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd/C / dimethylformamide; ethanol / 4 h 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / NBS / dimethylformamide / 1 h / -5 °C 6: 81 percent / n-BuLi / tetrahydrofuran / -78 - 20 °C 7: 95 percent / trichloroisocyanuric acid / dimethylformamide / 2 h 8: 65 percent / Cu / quinoline / 0.12 h / 210 °C 9: 82 percent / AlCl₃ / various solvent(s) / 14 h

39
[ 33719-74-3 ]
(-)-neopyrrolomycin [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 11 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 1.) BuLi / 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane, 15 min 7: 95 percent / isocyanuric acid / dimethylformamide / 1.5 h / Ambient temperature 8: 66 percent / Cu-powder / quinoline / 0.12 h / 210 °C 9: 91 percent / AlCl₃ / benzene / 14 h / Ambient temperature 10: pyridine / CH₂Cl₂ / 1) 5 deg C, 30 min; 2) room temperature, 30 min 11: 87 percent / NaOMe / methanol / 0.5 h
	Multi-step reaction with 11 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: NBS 6: 1.) BuLi 7: trichloroisocyanuric acid 8: quinoline / Cu / Heating 9: AlCl₃ 11: KOH
	Multi-step reaction with 9 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd/C / dimethylformamide; ethanol / 4 h 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / NBS / dimethylformamide / 1 h / -5 °C 6: 81 percent / n-BuLi / tetrahydrofuran / -78 - 20 °C 7: 95 percent / trichloroisocyanuric acid / dimethylformamide / 2 h 8: 65 percent / Cu / quinoline / 0.12 h / 210 °C 9: 85 percent / AlCl₃ / various solvent(s) / 14 h

40
[ 33719-74-3 ]
(-)-neopyrrolomycin potassium salt [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 12 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 1.) BuLi / 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane, 15 min 7: 95 percent / isocyanuric acid / dimethylformamide / 1.5 h / Ambient temperature 8: 66 percent / Cu-powder / quinoline / 0.12 h / 210 °C 9: 91 percent / AlCl₃ / benzene / 14 h / Ambient temperature 10: pyridine / CH₂Cl₂ / 1) 5 deg C, 30 min; 2) room temperature, 30 min 11: 87 percent / NaOMe / methanol / 0.5 h 12: 83 percent / t-BuOK / ethanol / 0.08 h / 0 - 5 °C
	Multi-step reaction with 10 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd/C / dimethylformamide; ethanol / 4 h 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / NBS / dimethylformamide / 1 h / -5 °C 6: 81 percent / n-BuLi / tetrahydrofuran / -78 - 20 °C 7: 95 percent / trichloroisocyanuric acid / dimethylformamide / 2 h 8: 65 percent / Cu / quinoline / 0.12 h / 210 °C 9: 85 percent / AlCl₃ / various solvent(s) / 14 h 10: 84 percent / t-BuOK / ethanol / 0.08 h / 5 °C

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta, Kuniaki; Itoh, Manabu [Tetrahedron Letters, 1993, vol. 34, # 52, p. 8443 - 8444]

41
[ 33719-74-3 ]
(+)-neopyrrolomycin potassium salt [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 12 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 1.) BuLi / 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane, 15 min 7: 95 percent / isocyanuric acid / dimethylformamide / 1.5 h / Ambient temperature 8: 66 percent / Cu-powder / quinoline / 0.12 h / 210 °C 9: 91 percent / AlCl₃ / benzene / 14 h / Ambient temperature 10: pyridine / CH₂Cl₂ / 1) 5 deg C, 30 min; 2) room temperature, 30 min 11: 86 percent / NaOMe / methanol / 0.5 h 12: 84 percent / t-BuOK / ethanol / 0.08 h / 0 - 5 °C
	Multi-step reaction with 10 steps 1: 87 percent / trichloroisocyanuric acid / dimethylformamide / 1 h 2: 87 percent / fum. HNO₃/H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd/C / dimethylformamide; ethanol / 4 h 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / NBS / dimethylformamide / 1 h / -5 °C 6: 81 percent / n-BuLi / tetrahydrofuran / -78 - 20 °C 7: 95 percent / trichloroisocyanuric acid / dimethylformamide / 2 h 8: 65 percent / Cu / quinoline / 0.12 h / 210 °C 9: 82 percent / AlCl₃ / various solvent(s) / 14 h 10: 92 percent / t-BuOK / ethanol / 0.08 h / 5 °C

42
[ 33719-74-3 ]
2-(1H-pyrrol-1-yl)-3,4,5-trichlorophenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 91 percent / AlCl₃ / benzene / 14 h / Ambient temperature
	Multi-step reaction with 5 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: 91 percent / AlCl₃, benzene / 14 h / Ambient temperature

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

43
[ 33719-74-3 ]
2-(2-chloro-1H-pyrrol-1-yl)-3,4,5-trichlorophenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 55 percent / N-chlorosuccinimide / dimethylformamide / 14 h / Ambient temperature 6: 68 percent / AlCl₃ / benzene / 14 h / Ambient temperature
	Multi-step reaction with 6 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: 55 percent / N-chlorosuccinimide / dimethylformamide / 15 h / Ambient temperature 6: 67 percent / AlCl₃, benzene / 14 h / Ambient temperature

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

44
[ 33719-74-3 ]
2-(2-bromo-1H-pyrrol-1-yl)-3,4,5-trichlorophenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 88 percent / AlCl₃ / benzene / 14 h / Ambient temperature
	Multi-step reaction with 6 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: NBS 6: 87 percent / AlCl₃, benzene / 14 h / Ambient temperature

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

45
[ 33719-74-3 ]
2-(3-chloro-1H-pyrrol-1-yl)-3,4,5-trichlorophenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 9 percent / N-chlorosuccinimide / dimethylformamide / 14 h / Ambient temperature 6: 82 percent / AlCl₃ / benzene / 14 h / Ambient temperature
	Multi-step reaction with 6 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: 9 percent / N-chlorosuccinimide / dimethylformamide / 15 h / Ambient temperature 6: 81 percent / AlCl₃, benzene / 14 h / Ambient temperature

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

46
[ 33719-74-3 ]
[ 155589-89-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 9 percent / N-chlorosuccinimide / dimethylformamide / 14 h / Ambient temperature
	Multi-step reaction with 5 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: 9 percent / N-chlorosuccinimide / dimethylformamide / 15 h / Ambient temperature

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

47
[ 33719-74-3 ]
[ 155589-88-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 55 percent / N-chlorosuccinimide / dimethylformamide / 14 h / Ambient temperature
	Multi-step reaction with 5 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: 55 percent / N-chlorosuccinimide / dimethylformamide / 15 h / Ambient temperature

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

48
[ 33719-74-3 ]
[ 155589-86-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 76 percent / NIS / dimethylformamide / 1) ice-cooling, 1 h; 2) room temperature, overnight
	Multi-step reaction with 5 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: 77 percent / N-iodosuccinimide / dimethylformamide / 15 h / Ambient temperature

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

49
[ 33719-74-3 ]
2-(2,4-dichloro-1H-pyrrol-1-yl)-3,4,5-trichlorophenol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 7 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 55 percent / N-chlorosuccinimide / dimethylformamide / 14 h / Ambient temperature 6: 53 percent / isocyanuric trichloride / dimethylformamide / 2 h / 0 - 5 °C 7: 92 percent / AlCl₃ / benzene / 14 h / Ambient temperature
	Multi-step reaction with 7 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: 55 percent / N-chlorosuccinimide / dimethylformamide / 15 h / Ambient temperature 6: 52 percent / trichloroisocyanuric acid / dimethylformamide / 2 h / 0 - 10 °C 7: AlCl₃, benzene / Ambient temperature

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

50
[ 33719-74-3 ]
[ 155589-90-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 55 percent / N-chlorosuccinimide / dimethylformamide / 14 h / Ambient temperature 6: 53 percent / isocyanuric trichloride / dimethylformamide / 2 h / 0 - 5 °C
	Multi-step reaction with 6 steps 1: Cl₂ 2: nitrating agent 3: reducing agent 5: 55 percent / N-chlorosuccinimide / dimethylformamide / 15 h / Ambient temperature 6: 52 percent / trichloroisocyanuric acid / dimethylformamide / 2 h / 0 - 10 °C

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]
[2]Tatsuta; Itoh [Journal of Antibiotics, 1994, vol. 47, # 2, p. 262 - 265]

51
[ 33719-74-3 ]
(+/-)-neopyrrolomycin potassium salt [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 10 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 1.) BuLi / 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane, 15 min 7: 95 percent / isocyanuric acid / dimethylformamide / 1.5 h / Ambient temperature 8: 66 percent / Cu-powder / quinoline / 0.12 h / 210 °C 9: 91 percent / AlCl₃ / benzene / 14 h / Ambient temperature 10: 84 percent / t-BuOK / ethanol / 0.08 h / 0 - 5 °C

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]

52
[ 33719-74-3 ]
O-<N-(p-tolylsulfonyl)-L-phenylalanyl>neopyrrolomycin [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 10 steps 1: 87 percent / isocyanuric trichloride / dimethylformamide / 1 h / Ambient temperature 2: 87 percent / fum. HNO₃, conc. H₂SO₄ / acetic anhydride / 0.5 h / 0 °C 3: 76 percent / H₂ / Pd-C / dimethylformamide; ethanol / 4 h / Ambient temperature 4: 91 percent / acetic acid / 1 h / 70 - 80 °C 5: 92 percent / N-bromosuccinimide / dimethylformamide / 1 h 6: 1.) BuLi / 1) THF, hexane, -78 deg C, 10 min; 2) THF, hexane, 15 min 7: 95 percent / isocyanuric acid / dimethylformamide / 1.5 h / Ambient temperature 8: 66 percent / Cu-powder / quinoline / 0.12 h / 210 °C 9: 91 percent / AlCl₃ / benzene / 14 h / Ambient temperature 10: pyridine / CH₂Cl₂ / 1) 5 deg C, 30 min; 2) room temperature, 30 min

Reference： [1]Tatsuta; Itoh [Bulletin of the Chemical Society of Japan, 1994, vol. 67, # 5, p. 1449 - 1455]

53
[ 33719-74-3 ]
[ 86111-47-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 1.) n-BuLi, TMEDA, 3.) SOCl₂, 4.) pyridine 2: 90 percent / LiAlH₄ / diethyl ether / 3 h / 0 °C
	Multi-step reaction with 2 steps 1: conc. HCl, comc. H₂SO₄ / 7 h / 60 °C 2: NaOH / dioxane / 3 h / Heating

Reference： [1]Pascal, Robert A.; Chen, Y.-C. Jack [Journal of Organic Chemistry, 1985, vol. 50, # 3, p. 408 - 410]
[2]Karl, Johann; Gust, Ronald; Spruss, Thilo; Schneider, Martin R.; Schoenenberg, Helmut; et al. [Journal of Medicinal Chemistry, 1988, vol. 31, # 1, p. 72 - 83]

54
[ 33719-74-3 ]
[ 94278-70-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 1.) n-BuLi, TMEDA, 3.) SOCl₂, 4.) pyridine 2: 90 percent / LiAlH₄ / diethyl ether / 3 h / 0 °C 3: 30percent aq. HBr, AcOH / 1.5 h / Ambient temperature
	Multi-step reaction with 2 steps 1: hydrogenchloride; sulfuric acid / water / 7 h / 60 °C / Inert atmosphere 2: phosphorus tribromide / dichloromethane / 2 h / 20 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1: hydrogenchloride; sulfuric acid / water / 16 h / 100 °C 2: phosphorus tribromide / dichloromethane / 1 h / 0 °C

Reference： [1]Pascal, Robert A.; Chen, Y.-C. Jack [Journal of Organic Chemistry, 1985, vol. 50, # 3, p. 408 - 410]
[2]Chignen Possi, Kelvine; Mulumba, Mukandila; Omri, Samy; Garcia-Ramos, Yesica; Tahiri, Houda; Chemtob, Sylvain; Ong, Huy; Lubell, William D. [Journal of Medicinal Chemistry, 2017, vol. 60, # 22, p. 9263 - 9274]
[3]Current Patent Assignee: PAKINAX - WO2022/31, 2022, A1

55
[ 33719-74-3 ]
[ 28023-86-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 1.) <1,2-bis(diphenylphosphino)ethane>nickel(II) chloride, 2.) 10percent aq. HCl / 1.) Et₂O, reflux, 54 h 2: 75 percent / Me₃SiI / CH₂Cl₂ / 90 h / Ambient temperature

Reference： [1]Naka, Kensuke; Sadownik, Andrzej; Regen, Steven L. [Journal of the American Chemical Society, 1993, vol. 115, # 6, p. 2278 - 2286]

56
[ 33719-74-3 ]
tridecaethylene glycol 3',5'-diphenylphenyl ether [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: 1.) <1,2-bis(diphenylphosphino)ethane>nickel(II) chloride, 2.) 10percent aq. HCl / 1.) Et₂O, reflux, 54 h 2: 75 percent / Me₃SiI / CH₂Cl₂ / 90 h / Ambient temperature 3: 1.) NaH / 1.) THF, 2.) THF, reflux, 4 h 4: conc. HCl / CHCl₃; methanol / 1 h / Ambient temperature

Reference： [1]Naka, Kensuke; Sadownik, Andrzej; Regen, Steven L. [Journal of the American Chemical Society, 1993, vol. 115, # 6, p. 2278 - 2286]

57
[ 33719-74-3 ]
C₆₃H₈₀O₁₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 1.) <1,2-bis(diphenylphosphino)ethane>nickel(II) chloride, 2.) 10percent aq. HCl / 1.) Et₂O, reflux, 54 h 2: 75 percent / Me₃SiI / CH₂Cl₂ / 90 h / Ambient temperature 3: 1.) NaH / 1.) THF, 2.) THF, reflux, 4 h

Reference： [1]Naka, Kensuke; Sadownik, Andrzej; Regen, Steven L. [Journal of the American Chemical Society, 1993, vol. 115, # 6, p. 2278 - 2286]

58
[ 33719-74-3 ]
[ 62089-34-3 ]

Reference： [1]Tetrahedron Letters,1989,vol. 30,p. 5093 - 5096

59
[ 33719-74-3 ]
[ 115475-80-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 9 steps 1: 1.) Rieke Mg / 1.) THF r.t.; 2.) THF r.t. 2: 1.) Rieke Mg / 1.) THF r.t.; 2.) THF r.t. 3: KOH, H₂O / methanol 4: SOCl₂ / benzene 5: 2.) SOCl₂ / 1.) CH₂Cl₂; 6: 1.) n-BuLi; 2.) MAD / 1.) THF, -45 deg C; 2.) toluene/THF, -78 deg C 7: 95 percent / 0.6 M HCl / tetrahydrofuran; H₂O / Heating 8: 98 percent / K₂CO₃ / CH₂Cl₂ 9: 82 percent / H₂ / Pd/C / tetrahydrofuran

Reference： [1]Hart, David J.; Merriman, Gregory H. [Tetrahedron Letters, 1989, vol. 30, # 38, p. 5093 - 5096]

60
[ 33719-74-3 ]
[ 106-93-4 ]
[ 164650-68-4 ]

Yield	Reaction Conditions	Operation in experiment
54%		3,5-Dichloroanisole [(74.] 0 g, 419 mmol) in THF (200 mL) was added dropwise to magnesium metal (14.2 g, 585 mmol, pre-washed with 0.5 N [HCL)] in THF (100 [ML)] at [25C.] After the addition, 1,2-dibromoethane (3.9 g, 20.8 mmol) was added dropwise. The resultant dark brown mixture was heated at reflux for 3 h. The mixture was cooled to [0C,] and [N, N-] dimethylformamide (60 mL) was added in one portion. The mixture was partitioned with diethyl ether (3 x 400 mL) and 6N HCl (500 mL). The combined organic extracts were washed with brine (300 mL), dried (Na2SO4), filtered and concentrated in vacuo to give an oil. Flash chromatography (2x) on silica gel eluting with Hex: EtOAc (4: 1) afforded the sub-title compound [(38.] 9 g, 54%) as a yellow oil. ['H] NMR (300 MHz, [CDCL3)] 8 9.90 (s, 1H), 7.53 (s, 1H), 7.38 (s, 1H), 7.15 (s, [1H),] 3.87 (s, 3H).

Reference： [1]Patent: WO2003/101957,2003,A1 .Location in patent: Page 29

61
[ 33719-74-3 ]
[ 82477-67-6 ]

Yield	Reaction Conditions	Operation in experiment
41%		Magnesium turnings (Fluka purum for Grignard reactions) were pre-treated in the following way: The turnings were placed in a glass sintered funnel and 0.1 M of hydrochloric acid was poured onto them. The turnings were stirred with a glass rod for a few seconds and then the acid was washed away with 3 portions of water. Finally, the turnings were washed with 2 portions of acetone and bottled. Tetrahydrofuran (100 mL, 99.95%) was dried by adding RedAl (1 g, 70% wt. in toluene). Pre-treated magnesium turnings (5 g, 200 mmol) were placed in a round bottomed flask, and were flushed with nitrogen 3 times. Dichloroanisole (26 g, 146 mmol) was dissolved in THF (100 mL, RedAl-dried) and dibromoethane (1.8 g, 10 mmol) was added. The reaction mixture was flushed with nitrogen and then refluxed for 2 hours. Heating was interrupted and dry ice (10 g) was added portionwise over 2 minutes. When all of the dry ice was dissolved, the reaction mixture was poured into ice containing hydrochloric acid (400 mL, 2 M). Extractive work up (ether, 300 mL) gave 11.2 g, 60.2 mmol (yield: 41%) of the sub-title compound. [0408] 1H-NMR (500 MHz; acetone-d6): delta7.57 (m, 1H), 7.49 (m, 1H), 7.23 (m, 1H), 3.91 (s, 3H).

Reference： [1]Patent: US2004/19033,2004,A1 .Location in patent: Page/Page column 21

62
[ 33719-74-3 ]
4-bromo-3,5-dichloroanisole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; N-Bromosuccinimide In water; acetone at 20℃; for 0.5h;	1.A A solution of 5.0 grams (0.028 mole) of l,3-dichloro-5-methoxybenzene (commercially available) in 35 mL of acetone was stirred and 5.0 grams (0.028 mole) of N-bromosuccinimide, then one mL of aqueous 10% hydrochloric acid were added. Upon completion of additions the reaction mixture was stirred at ambient temperature during a 30-minute period. After this time the reaction mixture was concentrated under reduced pressure to a residue. The residue was slurried in 20 mL of hexane and an insoluble material was removed by filtration. The filtrate was concentrated under reduced pressure, yielding 4.8 grams of the subject compound. The NMR spectrum was consistent with the proposed structure.

Reference： [1]Current Patent Assignee: FMC CORP - WO2006/47438, 2006, A2 Location in patent: Page/Page column 22-23

63
[ 33719-74-3 ]
[ 775287-78-0 ]
[ 35509-63-8 ]

Yield	Reaction Conditions	Operation in experiment
	With chlorosulfonic acid; thionyl chloride at -10 - 20℃; for 3h;	XV PREPARATION XV; 2,6-dichloro-4-methoxybenzenesulphonyl chloride and 2,4-dichloro-6-methoxybenzenesulphonyl chloride; A solution is prepared of 15 g (84.7 mM) of 3,5-dichloroanisole in 8 ml of thionyl chloride that is cooled to -10° C., and 6 ml (90 mM) of chlorosulphonic acid are then added dropwise. The reaction mixture is then agitated for 3 hours at ambient temperature, and then poured over a mixture of ice and ethyl acetate. The organic phase is separated, dried over magnesium sulphate and concentrated under reduced pressure. The residue from evaporation is used, without other purification, in the next step.

Reference： [1]Current Patent Assignee: ABBOTT LABORATORIES INC - US2006/178360, 2006, A1 Location in patent: Page/Page column 7

64
bis(triphenylphosphine)-nickel(II)chloride [ No CAS ]
[ 33719-74-3 ]
[ 100-58-3 ]
[ 141748-37-0 ]

Yield	Reaction Conditions	Operation in experiment
	With ammonium chloride In tetrahydrofuran; methanol; diethyl ether	29.A A. A. 3.5-diphenyl-anisole To a mixture of 150 cc of tetrahydrofuran and 34 cc of a 3M solution of phenylmagnesium bromide in diethylether at 40° C. under an argon atmosphere, are added 15 g of 3,5-dichloroanisole and 5.5 g of bis(triphenylphosphine)nickel(II) chloride. The resultant black mixture is heated for 6 hours to 65° C. and then poured into 400 cc of a saturated aqueous solution of ammonium chloride. After extraction with ethyl acetate (3*150 cc), the combined organic extracts are washed with water, dried (MgSO4) and concentrated in vacuo. The resultant residue is flash chromatographed on silica gel (30-60 mm; eluent: 20:0.1 n-hexane/ethyl acetate) and recrystallized from 20 cc of methanol to give 3,5-diphenyl-anisole as a white solid. (m.p.=93°-94° C.)

Reference： [1]Current Patent Assignee: SANOFI - US5366982, 1994, A

65
[ 33719-74-3 ]
[ 164650-68-4 ]

Yield	Reaction Conditions	Operation in experiment
	With ethidium Bromide; In tetrahydrofuran; magnesium; N,N-dimethyl-formamide;	(i) 3-Methoxy-5-chlorobenzaldehyde 3,5-Dichloroanisol (1.1 g; 6.8 mmol) was added in portions to magnesium chips (0.20 g; 8.2 mmol) in THF (dry, 20 mL). After the first addition, EtBr (0.1 mL) was added to start the reaction. After total addition the reaction mixture was stirred at 60 C. overnight, whereafter the mixture was cooled to 0 C., and DMF was added. After stirring for 1 hour, the mixture was poured onto HCl/aq, concentrated, and extracted with ether (3*50 mL). The combined organic phase was washed with water, dried (Na2SO4), and concentrated, yielding 2.35 g of the sub-title compound. 1H-NMR (300 MHz; CDCl3): delta 9.91 (s, 1H); 7.43 (t, 1H); 7.28 (t, 1H); 7.15 (t, 1H); 3.87 (s, 3H).

Reference： [1]Patent: US6255301,2001,B1

66
[ 929626-16-4 ]
[ 33719-74-3 ]

Yield	Reaction Conditions	Operation in experiment
193 mg	With copper dichloride In methanol at 90℃;

Reference： [1]Murphy, Jaclyn M.; Liao, Xuebin; Hartwig, John F. [Journal of the American Chemical Society, 2007, vol. 129, # 50, p. 15434 - 15435]

67
[ 33719-74-3 ]
[ 68-12-2 ]
[ 164650-68-4 ]

Yield	Reaction Conditions	Operation in experiment
54%		3,5-Dichloroanisole (74.0 g, 419 mmol) in THF (200 mL) was added dropwise to magnesium metal (14.2 g, 585 mmol, pre-washed with 0.5 N HCl) in THF (100 mL) at 25 C. After the addition, 1,2-dibromoethane (3.9 g, 20.8 mmol) was added dropwise. The resultant dark brown mixture was heated at reflux for 3 h. The mixture was cooled to 0 C., and N,N-dimethylformamide (60 mL) was added in one portion. The mixture was partitioned with diethyl ether (3400 mL) and 6N HCl (500 mL). The combined organic extracts were washed with brine (300 mL), dried (Na2SO4), filtered and concentrated in vacuo to give an oil. Flash chromatography (2) on silica gel eluding with Hex:EtOAc (4:1) afforded the sub-title compound (38.9 g, 54%/) as a yellow oil. 1H NMR (300 MHz, CDCl3) delta9.90 (s, 1H), 7.53 (s, 1H), 7.38 (s, 1H), 7.15 (s, 1H), 3.87 (s, 3H).
54%		3,5-Dichloroanisole (74.0 g, 419 mmol) in THF (200 [ML)] was added dropwise to magnesium metal (14.2 g, 585 mmol, pre-washed with 0.5 N [HC1)] in THF (100 [ML)] at [25C.] After the addition, 1,2-dibromoethane (3.9 g, 20.8 mmol) was added dropwise. The resultant dark brown mixture was heated at reflux for 3 h. The mixture was cooled to [0C,] and [N, N-DIMETHYLFORMAMIDE] (60 mL) was added in one portion. The mixture was partitioned with diethyl ether (3 x 400 mL) and 6N HCl (500 mL). The combined organic extracts were washed with brine (300 mL), dried [(NA2S04),] filtered and concentrated in vacuo to give an oil. Flash chromatography (2x) on silica gel eluting with Hex: EtOAc (4: 1) afforded the sub- title compound (38.9 g, 54%) as a yellow oil. ['H] NMR (300 MHz, [CDC13)] [8] 9.90 (s, 1H), 7.53 (s, 1H), 7.38 (s, 1H), 7.15 (s, 1H), 3.87 (s, 3H).
54%		[5-DICHLOROANISOLE] (74.0 g, 419 mmol) in THF (200 mL) was added dropwise to magnesium metal (14.2 g, 585 mmol, pre-washed with 0.5 N HC1) in THF (100 mL) at [25C.] After the addition, 1,2-dibromoethane (3.9 g, 20.8 mmol) was added dropwise. The resultant dark brown mixture was heated at reflux for 3 h. The mixture was cooled to [0C,] and N, N-dimethylformamide (60 mL) was added in one portion. The mixture was partitioned with diethyl ether (3 x 400 mL) and 6N HCI (500 mL). The combined organic extracts were washed with brine (300 [ML),] dried [(NA2SO4),] filtered and concentrated in vacuo to give an oil. Flash chromatography (2x) on silica gel eluting with Hex: EtOAc (4: 1) afforded the sub- title compound (38.9 g, 54%) as a yellow oil. 'H NMR (300 MHz, [CDC13)] 8 9.90 (s, 1H), 7.53 (s, 1H), 7.38 (s, 1H), 7.15 (s, 1H), 3.87 (s, 3H).

54%

3, [5-DICHLOROANISOLE] (74.0 g, 419 mmol) in THF (200 mL) was added dropwise to magnesium metal (14.2 g, 585 mmol, pre-washed with 0.5 N HCI) in THF (100 mL) at [25C.] After the addition, 1,2-dibromoethane (3.9 g, 20.8 mmol) was added dropwise. The resultant dark brown mixture was heated at reflux for 3 h. The mixture was cooled to [0C,] and N, N-dimethylformamide (60 mL) was added in one portion. The mixture was partitioned with diethyl ether (3 x 400 mL) and 6N HCI (500 mL). The combined organic extracts were washed with brine (300 mL), dried [(NA2SO4),] filtered and concentrated in vacuo to give an oil. Flash chromatography (2x) on silica gel eluting with Hex: EtOAc (4: 1) afforded the sub-title compound (38.9 g, 54%) as a yellow oil. 'H NMR (300 MHz, [CDCI3)] A 9.90 (s, 1H), 7.53 (s, 1H), 7.38 (s, 1H), 7.15 (s, 1H), 3.87 (s, 3H).

Reference： [1]Patent: US2004/19033,2004,A1 .Location in patent: Page/Page column 16
[2]Patent: WO2003/101423,2003,A1 .Location in patent: Page 19
[3]Patent: WO2003/101424,2003,A1 .Location in patent: Page 21
[4]Patent: WO2003/101956,2003,A1 .Location in patent: Page 39; 40

68
[ 121-43-7 ]
[ 33719-74-3 ]
[ 1221263-05-3 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 3,5-dichloroanisole With n-butyllithium In tetrahydrofuran at -100℃; Stage #2: Trimethyl borate In tetrahydrofuran; diethyl ether at 20℃; for 2h;	59 Method 13A; General procedure: To the benzene in THF (0.4 M) at -100° C. (liq. N2 and 1:1 MeOH:acetone) was added the n-BuLi (1.1 eq, 1.6 M) over 20 minutes. The reaction was stirred for a further 45 minutes. B(OMe)3 was added slowly in ether over 20 minutes. The reaction was allowed to warm to RT over 2 hours. The reaction was quenched with ice and diluted with 2M HCl and EtOAc. The reaction was stirred for 30 minutes and then the product was extracted with EtOAc (×3). The combined organic layers were dried with brine and then MgSO4. The product was filtered and evaporated to dryness to leave a colourless oil/solid. The residue was taken on as is.

Reference： [1]Current Patent Assignee: OTSUKA HOLDINGS CO LTD - US2009/215777, 2009, A1 Location in patent: Page/Page column 45; 59

69
[ 50-00-0 ]
[ 33719-74-3 ]
[ 911718-18-8 ]
[ 86111-47-9 ]

Yield	Reaction Conditions	Operation in experiment
1: 25% 2: 15%	With hydrogenchloride; sulfuric acid In water at 60℃; for 7h; Inert atmosphere;
1: 7.9 g 2: 3.74 g	Stage #1: formaldehyd; 3,5-dichloroanisole With hydrogenchloride; sulfuric acid In water at 70℃; for 7h; Inert atmosphere; Stage #2: With sodium hydroxide In 1,4-dioxane; water for 7h; Reflux; Inert atmosphere;

Reference： [1]Chignen Possi, Kelvine; Mulumba, Mukandila; Omri, Samy; Garcia-Ramos, Yesica; Tahiri, Houda; Chemtob, Sylvain; Ong, Huy; Lubell, William D. [Journal of Medicinal Chemistry, 2017, vol. 60, # 22, p. 9263 - 9274]
[2]Location in patent: experimental part Tietze, Lutz F.; Vock, Carsten A.; Krimmelbein, Ilga K.; Nacke, Linda [Synthesis, 2009, # 12, p. 2040 - 2060]

70
[ 591-35-5 ]
[ 616-38-6 ]
[ 33719-74-3 ]

Yield	Reaction Conditions	Operation in experiment
100%	With 1,8-diazabicyclo[5.4.0]undec-7-ene at 90℃; Inert atmosphere;

Reference： [1]Location in patent: experimental part Tietze, Lutz F.; Vock, Carsten A.; Krimmelbein, Ilga K.; Nacke, Linda [Synthesis, 2009, # 12, p. 2040 - 2060]

71
[ 33719-74-3 ]
4-bromo-3,5-dichloroanisole [ No CAS ]
[ 73931-43-8 ]

Yield	Reaction Conditions	Operation in experiment
25%	With hydrogenchloride; N-Bromosuccinimide In water; acetone at 20℃; for 0.5h;
	With hydrogenchloride; N-Bromosuccinimide; water In acetone at 20℃; for 0.0833333h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Joshi; Vyas; Duffel; Parkin; Lehmler [Synthesis, 2011, # 7, p. 1045 - 1054]
[2]Location in patent: experimental part Tietze, Lutz F.; Vock, Carsten A.; Krimmelbein, Ilga K.; Nacke, Linda [Synthesis, 2009, # 12, p. 2040 - 2060]

72
[ 33719-74-3 ]
[ 6480-66-6 ]
[ 93839-14-6 ]

Reference： [1]Synthesis,2011,p. 1045 - 1054

73
[ 33719-74-3 ]
[ 1271523-34-2 ]
[ 1335097-17-0 ]
[ 98273-17-7 ]

Yield	Reaction Conditions	Operation in experiment
28%Chromat.; 11%Chromat.; 48%Chromat.	With iodine; silver sulfate; In hexane; at 20℃; for 16.0h;	General procedure: The respective silver salt (0.32 g, 1 mmol) and iodine (0.25 g, 1 mmol) were typically added to a stirred solution of the benzene derivative 1a-i (1 mmol) in dichloromethane (3 mL). The reaction mixture was allowed to stir at room temperature for approximately 16 h (see refPreviewPlaceHolderTable 1, refPreviewPlaceHolderTable 2, refPreviewPlaceHolderTable 3, refPreviewPlaceHolderTable 4, refPreviewPlaceHolderTable 5 and refPreviewPlaceHolderTable 6). The reaction mixture was cooled with ice-cold water, quenched with an aqueous solution of sodium metabisulfite (0.2 mL) and, in the case of anilines, 2 M NaOH (0.2 mL). The mixture was filtered through Celite and the residue was washed with dichloromethane (3×3 mL). The combined filtrate was washed with aqueous sodium bicarbonate (3 mL), water (3 mL), and brine (3 mL). The combined organic phases were dried over Na2SO4 and the solvent was removed under reduced pressure. The residue was redissolved in dichloromethane (10 mL) and the percent conversion of the starting material and the yields of the iodination products were determined by GC-MS using diethylene glycol di-n-butyl ether as internal standard. The relative response factor for the respective analyte (RRFA) was calculated from a calibration standard containing known amounts of the internal standard and the respective analytes using the formula RRFA=AIS·MA/(AA·MIS), where AIS is the peak area of the internal standard, AA is the area of an analyte (i.e., starting material or iodination product), MA is the mass of the analyte and MIS is the mass of the internal standard. The mass of the analyte in the reaction mixture was determined as MA=(RRFA·MIS·AA)/AIS. All samples were analyzed at least in duplicate. The iodination products of selected reactions were separated by column chromatography to obtain milligram quantities for their characterization and use as analytical standards. In the case of 3g, the isolated quantities were not sufficient for 13C NMR analysis.

Reference： [1]Tetrahedron,2011,vol. 67,p. 7461 - 7469

74
[ 33719-74-3 ]
[ 1271523-34-2 ]
[ 98273-17-7 ]

Reference： [1]Chemistry - A European Journal,2013,vol. 19,p. 4480 - 4495
[2]Tetrahedron,2011,vol. 67,p. 7461 - 7469

75
[ 33719-74-3 ]
[ 1335097-17-0 ]
[ 98273-17-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 7 %Chromat. 2: 9 %Chromat.	With iodine; silver sulfate In dichloromethane at 20℃; for 60h; regioselective reaction;	4.2. General procedure for the iodination of chlorinated benzene derivatives 1a-i General procedure: The respective silver salt (0.32 g, 1 mmol) and iodine (0.25 g, 1 mmol) were typically added to a stirred solution of the benzene derivative 1a-i (1 mmol) in dichloromethane (3 mL). The reaction mixture was allowed to stir at room temperature for approximately 16 h (see refPreviewPlaceHolderTable 1, refPreviewPlaceHolderTable 2, refPreviewPlaceHolderTable 3, refPreviewPlaceHolderTable 4, refPreviewPlaceHolderTable 5 and refPreviewPlaceHolderTable 6). The reaction mixture was cooled with ice-cold water, quenched with an aqueous solution of sodium metabisulfite (0.2 mL) and, in the case of anilines, 2 M NaOH (0.2 mL). The mixture was filtered through Celite and the residue was washed with dichloromethane (3×3 mL). The combined filtrate was washed with aqueous sodium bicarbonate (3 mL), water (3 mL), and brine (3 mL). The combined organic phases were dried over Na2SO4 and the solvent was removed under reduced pressure. The residue was redissolved in dichloromethane (10 mL) and the percent conversion of the starting material and the yields of the iodination products were determined by GC-MS using diethylene glycol di-n-butyl ether as internal standard. The relative response factor for the respective analyte (RRFA) was calculated from a calibration standard containing known amounts of the internal standard and the respective analytes using the formula RRFA=AIS·MA/(AA·MIS), where AIS is the peak area of the internal standard, AA is the area of an analyte (i.e., starting material or iodination product), MA is the mass of the analyte and MIS is the mass of the internal standard. The mass of the analyte in the reaction mixture was determined as MA=(RRFA·MIS·AA)/AIS. All samples were analyzed at least in duplicate. The iodination products of selected reactions were separated by column chromatography to obtain milligram quantities for their characterization and use as analytical standards. In the case of 3g, the isolated quantities were not sufficient for 13C NMR analysis.

Reference： [1]Location in patent: experimental part Joshi, Sudhir N.; Vyas, Sandhya M.; Wu, Huimin; Duffel, Michael W.; Parkin, Sean; Lehmler, Hans-Joachim [Tetrahedron, 2011, vol. 67, # 39, p. 7461 - 7469]

76
[ 33719-74-3 ]
[ 4136-95-2 ]
[ 1380572-64-4 ]

Yield	Reaction Conditions	Operation in experiment
80%	With aluminum (III) chloride In nitrobenzene at 0 - 20℃;	4.2. (2,6-Dichloro-4-methoxyphenyl)(2,4,6-trichlorophenyl) methanone (4b) Anhydrous AlCl3 (450 mg, 3.4 mmol) was added to PhNO2 (10 mL). The reaction mixture was cooled to 0 °C, and 2,4,6-trichlorobenzoyl chloride (0.53 mL, 3.4 mmol) and 3,5-dichloroanisole (500 mg, 2.82 mmol) were added. The reaction mixture was stirred at rt for 24 h, then it was diluted with Et2O (10 mL) at 0 °C and quenched by 1 N NaOH (∼3 mL). The mixture was stirred vigorously until precipitate was formed. Filter and wash the precipitate with DCM. The organic layer was dried over Na2SO4 and concentrated to give the crude product. Purification by silica gel chromatography (hexanes/EtOAc=20/1) provided 4b (867 mg, 80%). 1H NMR (CDCl3, 500 MHz) 7.36 (s, 2H), 6.88 (s, 2H), 3.85 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 194.25, 163.33, 141.89, 138.12, 136.31, 129.29, 127.78, 117.65, 57.03; IR (film): 1633, 1557, 1388, 1341 cm-1; HRMS (EI) m/z=382.8967 calcd for C14H8Cl5O2 (MH+); found: 382.8975.

Reference： [1]Location in patent: experimental part Wang, Yong; Kurosu, Michio [Tetrahedron, 2012, vol. 68, # 24, p. 4797 - 4804]

77
[ 33719-74-3 ]
[ 271242-20-7 ]
2'-iodo-5'-methoxy-4,4''-bis[2-(triisopropylsilyl)ethynyl]-1,1':3',1''-terphenyl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	Stage #1: 3,5-dichloroanisole With [bis-(trifluoroacetoxy)iodo]benzene; iodine In dichloromethane at 20℃; for 2.5h; Stage #2: (2-(4-bromophenyl)ethynyl)triisopropylsilane With tert.-butyl lithium In diethyl ether; pentane at 10 - 20℃; for 15h; Stage #3: With iodine In diethyl ether; pentane at 0℃; for 1h;

Reference： [1]Aggarwal, A. Vikas; Jester, Stefan-S.; Taheri, Sara Mehdizadeh; Foerster, Stephan; Hoeger, Sigurd [Chemistry - A European Journal, 2013, vol. 19, # 14, p. 4480 - 4495]

78
[ 124-38-9 ]
[ 33719-74-3 ]
[ 94278-69-0 ]
[ 94294-09-4 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 3,5-dichloroanisole With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran; hexane at -78℃; for 1.5h; Inert atmosphere; Stage #2: carbon dioxide Stage #3: With hydrogenchloride In water at 0℃; Overall yield = 57 %; Overall yield = 3.5 g;
2.2 g	Stage #1: 3,5-dichloroanisole With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran at -78℃; for 2h; Stage #2: carbon dioxide In tetrahydrofuran for 2h;	4 2,4-Dichloro-6-methoxybenzoic acid To solution of nBuLi (2.5 M in hexanes) (8.8 ml, 22 mmol) in tetrahydrofuran (20 ml) at - 78 °C was added N,N,N’,N’-tetramethylethylenediamine (3.6 ml, 23 mmol) and the solution was stirred for 30 minutes at -78 oC. A solution of 1,3-dichloro-5-methoxybenzene(3.0 g, 17 mmol) in tetrahydrofuran (7.0 mL) was added slowly, and the reaction mixture was stirred for an additional 1.5 h. Crushed solid carbon dioxide (C02) was added portionwise, and the reaction warmed to room temperature over 2 h. Kept adding crushed CO2 over this time period. The reaction mixture was then poured into iN HC1, and extracted 3x with dichloromethane. The combined organic layers were dried over magnesium sulfate, andfiltered. The solution was poured into dichloromethane and basified with iN aqueous sodium hydroxide solution. The aqueous layer was washed with dichloromethane, and then acidified with iN aqueous HC1 solution. This solution was extracted 3x with dichloromethane. The combined organic extracts were dried over magnesium sulfate, filtered and concentrated to give 2.2g of a pale green solid as a mixture of regioisomers. The mixture was taken into thenext step without purification.

Reference： [1]Liang, Jun; Van Abbema, Anne; Balazs, Mercedesz; Barrett, Kathy; Berezhkovsky, Leo; Blair, Wade; Chang, Christine; Delarosa, Donnie; Devoss, Jason; Driscoll, Jim; Eigenbrot, Charles; Ghilardi, Nico; Gibbons, Paul; Halladay, Jason; Johnson, Adam; Kohli, Pawan Bir; Lai, Yingjie; Liu, Yanzhou; Lyssikatos, Joseph; Mantik, Priscilla; Menghrajani, Kapil; Murray, Jeremy; Peng, Ivan; Sambrone, Amy; Shia, Steven; Shin, Young; Smith, Jan; Sohn, Sue; Tsui, Vickie; Ultsch, Mark; Wu, Lawren C.; Xiao, Yisong; Yang, Wenqian; Young, Judy; Zhang, Birong; Zhu, Bing-Yan; Magnuson, Steven [Journal of Medicinal Chemistry, 2013, vol. 56, # 11, p. 4521 - 4536]
[2]Current Patent Assignee: UNIVERSITY OF MICHIGAN - WO2015/138326, 2015, A1 Location in patent: Page/Page column 59

79
[ 33719-74-3 ]
[ 75-36-5 ]
[ 157487-30-4 ]

Yield	Reaction Conditions	Operation in experiment
40%	Stage #1: acetyl chloride With aluminum (III) chloride In dichloromethane at 0℃; for 0.5h; Stage #2: 3,5-dichloroanisole In dichloromethane at 20℃; for 2h;	1-(2,6-Dichloro-4-methoxyphenyi)ethanone (10-2). A mixture of aluminum chloride (4.50 g, 33.9 mmol) and acetyl chloride (2.40 mL, 33.9 mmol) in CH2Cl2 (20.0 mL) was stirred at 0 °C for 30 min. The reaction mixture was slowly added with 1,3-dichloro-5- methoxybenzene (10-1, 2.00 g, 11.3 mmol) in CH2Cl2 (10.0 mL), and the resultant solution was stirred at room temperature for additional 2.0 h. The solution was basified with saturatedaqueous NaHCO3. The organic layer was separated, dried over MgSO4(s), and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to give 1-(2,6-dichloro-4-methoxyphenyl)ethanone (10-2, 1.0 g, 4.6 mmol) as yellow oil in 40% yield: 1H NMR (CDCl3, 500 MHz) δ 7.01 (d, J = 1.6 Hz, 2 H), 6.82 (d, J= 1.6 Hz, 2 H), 3.83 (s, 3 H), 2.49 (s, 3 H).

Reference： [1]Current Patent Assignee: DEVELOPMENT CENTER FOR BIOTECHNOLOGY; CHINA PETROCHEMICAL DEVELOPMENT CORPORATION - WO2013/82324, 2013, A1 Location in patent: Paragraph 00118

80
[ 33719-74-3 ]
[ 100-96-9 ]
[ 1445972-33-7 ]

Yield	Reaction Conditions	Operation in experiment
	With dicyclohexyl(2',4',6'-triisopropyl-5-methoxy-3,4,6-trimethyl-[1,1'-biphenyl]-2-yl)phosphine; C₅₀H₇₀NO₄PPdS; C₅₀H₇₀NO₄PPdS; dicyclohexyl(2',4',6'-triisopropyl-4-methoxy-3,5,6-trimethyl-[1,1'-biphenyl]-2-yl)phosphine; ammonia; sodium t-butanolate In 1,4-dioxane at 80℃; for 24h; Inert atmosphere;

Reference： [1]Cheung, Chi Wai; Surry, David S.; Buchwald, Stephen L. [Organic Letters, 2013, vol. 15, # 14, p. 3734 - 3737]

81
[ 33719-74-3 ]
[ 94294-09-4 ]

Yield	Reaction Conditions	Operation in experiment
	With N,N,N,N,-tetramethylethylenediamine; carbon dioxide In tetrahydrofuran	4 2,4-Dichloro-6-methoxybenzoic acid 2,4-Dichloro-6-methoxybenzoic acid Procedure followed J. Org. Chem. 1985, 50, 408-410 To solution of nBuLi (2.5 M in hexanes) (8.8 ml, 22 mmol) in tetrahydrofuran (20 ml) at -78° C. was added N,N,N',N'-tetramethylethylenediamine (3.6 ml, 23 mmol) and the solution was stirred for 30 minutes at -78° C. A solution of 1,3-dichloro-5-methoxybenzene (3.0 g, 17 mmol) in tetrahydrofuran (7.0 mL) was added slowly, and the reaction mixture was stirred for an additional 1.5 h. Crushed solid carbon dioxide (CO2) was added portionwise, and the reaction warmed to room temperature over 2 h. Kept adding crushed CO2 over this time period. The reaction mixture was then poured into IN HCl, and extracted 3* with dichloromethane. The combined organic layers were dried over magnesium sulfate, and filtered. The solution was poured into dichloromethane and basified with IN aqueous sodium hydroxide solution. The aqueous layer was washed with dichloromethane, and then acidified with IN aqueous HCl solution. This solution was extracted 3* with dichloromethane. The combined organic extracts were dried over magnesium sulfate, filtered and concentrated to give 2.2 g of a pale green solid as a mixture of regioisomers. The mixture was taken into the next step without purification.

Reference： [1]Current Patent Assignee: UNIVERSITY OF MICHIGAN - US2015/250769, 2015, A1

82
[ 33719-74-3 ]
[ 100-96-9 ]
[ 10272-06-7 ]

Reference： [1]Organic Letters,2015,vol. 17,p. 5934 - 5937

83
[ 33719-74-3 ]
[ 65262-96-6 ]

Yield	Reaction Conditions	Operation in experiment
82%	With copper acetylacetonate; N<SUP>1</SUP>-(4-hydroxy-2,6-dimethylphenyl)-N<SUP>2</SUP>-(4-hydroxy-3,5-dimethylphenyl)oxalamide; water In water; dimethyl sulfoxide at 130℃; for 24h; Schlenk technique; Inert atmosphere;

Reference： [1]Xia, Shanghua; Gan, Lu; Wang, Kailiang; Li, Zheng; Ma, Dawei [Journal of the American Chemical Society, 2016, vol. 138, # 41, p. 13493 - 13496]

84
[ 110-89-4 ]
[ 33719-74-3 ]
1,1′-(5-methoxy-1,3-phenylene)dipiperidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	With potassium <i>tert</i>-butylate In toluene at 155℃; for 24h; Autoclave;

Reference： [1]Micheletti, Gabriele; Boga, Carla; Forlani, Luciano; Del Vecchio, Erminia; Zanna, Nicola; Mazzanti, Andrea; Monari, Magda [European Journal of Organic Chemistry, 2017, vol. 2017, # 5, p. 964 - 974]

85
[ 33719-74-3 ]
[ 79-05-0 ]
N-(3-chloro-5-methoxyphenyl)propionamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With copper(I) oxide; potassium phosphate; N<SUP>1</SUP>,N<SUP>2</SUP>-bis(thiophen-2-ylmethyl)oxalamide In <i>tert</i>-butyl alcohol at 130℃; for 24h; Schlenk technique;

Reference： [1]De, Subhadip; Yin, Junli; Ma, Dawei [Organic Letters, 2017, vol. 19, # 18, p. 4864 - 4867]

86
[ 33719-74-3 ]
[ 4659-45-4 ]
[ 34786-96-4 ]

Yield	Reaction Conditions	Operation in experiment
72%	With aluminum (III) chloride at 0 - 110℃; for 15h; Inert atmosphere;

Reference： [1]Nocera, Giuseppe; Young, Allan; Palumbo, Fabrizio; Emery, Katie J.; Coulthard, Graeme; McGuire, Thomas; Tuttle, Tell; Murphy, John A. [Journal of the American Chemical Society, 2018, vol. 140, # 30, p. 9751 - 9757]

87
[ 33719-74-3 ]
mggnesium bis-diisopropylamide [ No CAS ]
C₇H₅Cl₂MgO⁽¹⁺⁾*C₆H₁₄N^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In toluene at 70℃; for 1h; Inert atmosphere; Schlenk technique; regioselective reaction;

Reference： [1]Hess, Andreas; Alandini, Nurtalya; Guersoy, Yusuf C.; Knochel, Paul [Angewandte Chemie - International Edition, 2022, vol. 61, # 29][Angew. Chem., 2022, vol. 134, # 29]

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Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
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P308	IF exposed or concerned:
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P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
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P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
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P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
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. 33719-74-3 ] {[proInfo.proName]}

Quality Control of [ 33719-74-3 ]

Related Doc. of [ 33719-74-3 ]

Product Details of [ 33719-74-3 ]

Safety of [ 33719-74-3 ]

Application In Synthesis of [ 33719-74-3 ]

[ 33719-74-3 ] Synthesis Path-Upstream 1~18

[ 33719-74-3 ] Synthesis Path-Downstream 1~87

Related Functional Groups of [ 33719-74-3 ]

Aryls

Chlorides

Ethers

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 33719-74-3 ]