[ CAS No. 850864-54-9 ]

Name: 850864-54-9|Ethyl 6-chloro-3-methylpicolinate|98%
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Product Details of [ 850864-54-9 ]

CAS No. :	850864-54-9	MDL No. :	MFCD18416525
Formula :	C₉H₁₀ClNO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	N/A
M.W :	199.63 g/mol	Pubchem ID :	-
Synonyms :

Safety of [ 850864-54-9 ]

Signal Word:	Danger	Class:	6.1
Precautionary Statements:	P261-P264-P270-P271-P280-P302+P352-P304+P340-P310-P330-P361-P403+P233-P405-P501	UN#:	2810
Hazard Statements:	H301-H311-H331	Packing Group:	Ⅲ
GHS Pictogram:

Application In Synthesis of [ 850864-54-9 ]

* 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 [ 850864-54-9 ]
Downstream synthetic route of [ 850864-54-9 ]

[ 850864-54-9 ] Synthesis Path-Upstream 1~1

1
[ 850864-54-9 ]
[ 1201924-32-4 ]

Yield	Reaction Conditions	Operation in experiment
99%	With water; lithium hydroxide In tetrahydrofuran at 20℃; for 12 h;	A mixture of A56-3 (800 mg, 4.0 mmol) and LiOH (480 mg, 20.0 mmol) in 7 mL THF/H₂CX6 : 1) was stirred at r.t. overnight. After acified by 6 N HC1 to pH = 4. The aqueous phase was extracted withethyl acetate. The combined organic phases were dried over Na₂S0₄ and the solvent was removed by vacuum to give A56-4 as a white solid (680 mg, 99percent). H NMR (400 MHz, CDC1₃) δ 10.97 (br s, 1H), 7.69 (d, / = 8.0 Hz, 1H), 7.48 (d, / = 8.0 Hz, 1H), 2.75 (s, 3H).

Reference： [1] Patent: WO2018/17435, 2018, A1, . Location in patent: Paragraph 00139-00140

[ 850864-54-9 ] Synthesis Path-Downstream 1~32

1
[ 850864-53-8 ]
[ 850864-54-9 ]

Yield	Reaction Conditions	Operation in experiment
86%	With N,N-dimethyl-formamide; trichlorophosphate In dichloromethane at 0 - 20℃;	22.8.C Alternative synthesis of 3-[[6-[3-(hydroxymethyl)phenyl]-3-methyl-pyridine-2- carbonyllamino -2.4-dimethyl-benzoic acid (Example 22). Scheme 8. Step C. Phosphorous oxychloride (1.16 L, 12.4 mol) is added dropwise at 0 °C over ~1 hour to a solution of DMF (2.45 L, 24.8 mol) and methylene chloride (4.5 L) The reaction is stirred for 30 minutes at 0 °C, then ethyl 3 -methyl- 1-oxido-pyridin-l- ium-2-carboxylate (450 g, 2.48 mol) is added. The reaction is allowed to slowly warm overnight to room temperature, and the reaction mixture is poured into ice water (10 L). The pH is adjusted with 10% sodium carbonate to pH~8, and the mixture is stirred for 1 hour. The layers are separated, and the aqueous layer is extracted with methylene chloride (2 x 2 L). The combined organic layers are dried over sodium sulfate, filtered, and concentrated under reduced pressure to give ethyl 6-chloro-3-methyl-pyridine-2- carboxylate as a beige semi solid (425 g, 86%). MS (m/z) 200 [M+H]+.
83%	With trichlorophosphate In N,N-dimethyl-formamide at 0℃;
68%	With N,N-dimethyl-formamide; trichlorophosphate at 0 - 20℃; for 12h;	6.3 Step 3: ethyl 6-chloro-3-methylpicolinate To a stirred 20 mL DMF solution at 0°C, POCl3 (3.77 g, 24.6 mmol) was added dropwise. After stirred at 0°C for 30 min, a DMF solution of A56-2 (2.23 g, 12.3 mmol) was added. The reaction was carried out at r.t. overnight. After quenched with water, the mixture was basified by NaHC03. The aqueous phase was extracted with petroleum ether : ethyl acetate = 1 : 1. The combined organic phases were dried over Na2S04 and the solvent was removed by vacuum to give A56-3 as a pail oil (1.68 g, 68%). H NMR (400 MHz, CDC13) δ 7.56 (d, / = 8.0 Hz, 1H), 7.35 (d, / = 8.0 Hz, 1H), 4.45 (q / = 7.0 Hz, 2H), 2.53 (s, 3H), 1.43 (t, / = 7.0 Hz, 3H).

With trichlorophosphate In N,N-dimethyl-formamide at 0℃; for 1h; Cooling with ice;

69.c c) 6-Chloro-3-methyl-pyridine-2-carboxylic acid ethyl ester[0343] 3-Methyl-pyridine-N-oxide-2-carboxylic acid ethyl ester (680 mg, 3.76 mmol) was dissolved in DMF (30 mL) and cooled in ice bath. POCl3 (0.42 mL, 4.51 mmol) was added, and the mixture was stirred at 0°C for 1 h, and then at r.t. for 16 h. The mixture was neutralized with saturated NaHC03, and extracted with CH2CI2. The organic layer was dried over MgS04 and concentrated in vacuo. The crude product was purified by silica gel chromatography (0-5% MeOH/CH2Cl2) to give 650 mg of the title compound as a viscous oil. MS: (+) m/z 200.20 (M+l).

Reference： [1]Current Patent Assignee: ELI LILLY & CO - WO2015/94912, 2015, A1 Location in patent: Page/Page column 31
[2]Location in patent: body text Lee, Ki Yong; Seob Lee, Kwang; Jin, Changbae; Lee, Yong Sup [European Journal of Medicinal Chemistry, 2009, vol. 44, # 3, p. 1331 - 1334]
[3]Current Patent Assignee: ACCRO BIOSCIENCE; ZHANG - WO2018/17435, 2018, A1 Location in patent: Paragraph 00137-00138
[4]Current Patent Assignee: FIBROGEN, INC. - WO2012/106472, 2012, A1 Location in patent: Page/Page column 125

2
[ 850864-54-9 ]
[ 1146964-94-4 ]

Yield	Reaction Conditions	Operation in experiment
40%	With dichloro-acetic acid; water Reflux;
	Stage #1: ethyl 6-chloro-3-methyl-pyridine-2-carboxylate With dichloro-acetic acid In water for 1h; Reflux; Stage #2: With sodium hydrogencarbonate In dichloromethane; water	69.d d) 3-Methyl-6-oxo-l , 6-dihydro-pyridine-2-carboxylic acid ethyl ester[0344] A mixture of 6-chloro-3-methyl-pyridine-2-carboxylic acid ethyl ester (650 mg, 3.26 mmol), dichloroacetic acid (5 mL) and water (0.5 mL) was refluxed for 1 h. After cooling to r.t., the mixture was neutralized with saturated NaHC03 and extracted with CH2CI2. The organic layer was dried over MgSC>4 and concentrated in vacuo. The crude product was purified by silica gel chromatography (0-10% MeOH/CH2Cl2) to give 230 mg of the title compound as a white solid. MS: (+) m/z 182.25 (M+l).

Reference： [1]Location in patent: body text Lee, Ki Yong; Seob Lee, Kwang; Jin, Changbae; Lee, Yong Sup [European Journal of Medicinal Chemistry, 2009, vol. 44, # 3, p. 1331 - 1334]
[2]Current Patent Assignee: FIBROGEN, INC. - WO2012/106472, 2012, A1 Location in patent: Page/Page column 125

3
[ 4021-07-2 ]
[ 850864-54-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: thionyl chloride / 5 h / -20 °C / Reflux 2: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 16 h / 20 °C 3: trichlorophosphate / N,N-dimethyl-formamide / 1 h / 0 °C / Cooling with ice
	Multi-step reaction with 3 steps 1: sulfuric acid / 19 h / Reflux 2: acetic acid; dihydrogen peroxide / water monomer / 4.5 h / 60 °C 3: trichlorophosphate; N,N-dimethyl-formamide / dichloromethane / 0 - 20 °C
	Multi-step reaction with 3 steps 1: thionyl chloride / 12 h / 0 °C / Reflux 2: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 12 h / 0 - 20 °C 3: trichlorophosphate; N,N-dimethyl-formamide / 12 h / 0 - 20 °C

Multi-step reaction with 2 steps 1.1: thionyl chloride / 80 °C 2.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 20 °C 2.2: 20 °C

Reference： [1]Current Patent Assignee: FIBROGEN, INC. - WO2012/106472, 2012, A1
[2]Current Patent Assignee: ELI LILLY & CO - WO2015/94912, 2015, A1
[3]Current Patent Assignee: ACCRO BIOSCIENCE; ZHANG - WO2018/17435, 2018, A1
[4]Hao, Yongjin; He, Sudan; Li, Zhanhui; Lu, Haohao; Ma, Haikuo; Tian, Sheng; Wang, Jingrui; Wu, Shuwei; Yang, Chengkui; Yang, Qing; Yang, Tao; Zhang, Xiaohu [European Journal of Medicinal Chemistry, 2022, vol. 228]

4
[ 58997-10-7 ]
[ 850864-54-9 ]

Yield	Reaction Conditions	Operation in experiment
70%	Stage #1: ethyl 3-methylpyridine-2-carboxylate With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; Stage #2: With trichlorophosphate In N,N-dimethyl-formamide at 20℃;	6.1.3. Ethyl 6-chloro-3-methylpicolinate (9) To a solution of 8 (2.6 g, 16 mmol) in dichloromethane (50 mL)was added 3-chloroperbenzoic acid (3.8 g, 19 mmol) at 0 C. Thereactionwas stirred at room temperature overnight, then quenchedwith saturated sodium sulfite aqueous solution (20 mL) andwashed with saturated NaHCO3 aqueous solution (20 mL3). Theorganic layer was dried over Na2SO4, filtered and concentrated togive the intermediate as a brown solid. To another flask, POCl3(3.8 g, 25 mmol) was added dropwise in DMF (15 mL) and cooled to0 C. A solution of the brown solid in DMF (5 mL) was addeddropwise at 0 C. The reaction was stirred at room temperatureovernight. The reaction mixture was poured into ice water (50 mL)and neutralized using saturated NaHCO3 aqueous solution topH 7, then extracted with ethyl acetate (30 mL3). The combinedorganic layer was dried over Na2SO4, filtered and concentrated. Theresidue was purified by silica gel column chromatography (petroleumether/ethyl acetate 50/1) to give the desired product (2.2 g,70%) as a colorless oil. 1H NMR (400 MHz, CDCl3) d 7.56 (d,J 8.0 Hz, 1H), 7.35 (d, J 8.4 Hz, 1H), 4.44 (q, J 6.8 Hz, 2H), 2.53(s, 3H), 1.43 (t, J 6.8 Hz, 3H). MS (ESI/APCI) m/z 222.0 [MNa].
70%	Stage #1: ethyl 3-methylpyridine-2-carboxylate With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; Stage #2: With trichlorophosphate In N,N-dimethyl-formamide at 20℃;	6.1.3. Ethyl 6-chloro-3-methylpicolinate (9) To a solution of 8 (2.6 g, 16 mmol) in dichloromethane (50 mL)was added 3-chloroperbenzoic acid (3.8 g, 19 mmol) at 0 C. Thereactionwas stirred at room temperature overnight, then quenchedwith saturated sodium sulfite aqueous solution (20 mL) andwashed with saturated NaHCO3 aqueous solution (20 mL3). Theorganic layer was dried over Na2SO4, filtered and concentrated togive the intermediate as a brown solid. To another flask, POCl3(3.8 g, 25 mmol) was added dropwise in DMF (15 mL) and cooled to0 C. A solution of the brown solid in DMF (5 mL) was addeddropwise at 0 C. The reaction was stirred at room temperatureovernight. The reaction mixture was poured into ice water (50 mL)and neutralized using saturated NaHCO3 aqueous solution topH 7, then extracted with ethyl acetate (30 mL3). The combinedorganic layer was dried over Na2SO4, filtered and concentrated. Theresidue was purified by silica gel column chromatography (petroleumether/ethyl acetate 50/1) to give the desired product (2.2 g,70%) as a colorless oil. 1H NMR (400 MHz, CDCl3) d 7.56 (d,J 8.0 Hz, 1H), 7.35 (d, J 8.4 Hz, 1H), 4.44 (q, J 6.8 Hz, 2H), 2.53(s, 3H), 1.43 (t, J 6.8 Hz, 3H). MS (ESI/APCI) m/z 222.0 [MNa].
	Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 16 h / 20 °C 2: trichlorophosphate / N,N-dimethyl-formamide / 1 h / 0 °C / Cooling with ice

	Multi-step reaction with 2 steps 1: acetic acid; dihydrogen peroxide / water monomer / 4.5 h / 60 °C 2: trichlorophosphate; N,N-dimethyl-formamide / dichloromethane / 0 - 20 °C
	Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 12 h / 0 - 20 °C 2: trichlorophosphate; N,N-dimethyl-formamide / 12 h / 0 - 20 °C

Reference： [1]Hao, Yongjin; He, Sudan; Li, Zhanhui; Lu, Haohao; Ma, Haikuo; Tian, Sheng; Wang, Jingrui; Wu, Shuwei; Yang, Chengkui; Yang, Qing; Yang, Tao; Zhang, Xiaohu [European Journal of Medicinal Chemistry, 2022, vol. 228]
[2]Hao, Yongjin; He, Sudan; Li, Zhanhui; Lu, Haohao; Ma, Haikuo; Tian, Sheng; Wang, Jingrui; Wu, Shuwei; Yang, Chengkui; Yang, Qing; Yang, Tao; Zhang, Xiaohu [European Journal of Medicinal Chemistry, 2022, vol. 228]
[3]Current Patent Assignee: FIBROGEN, INC. - WO2012/106472, 2012, A1
[4]Current Patent Assignee: ELI LILLY & CO - WO2015/94912, 2015, A1
[5]Current Patent Assignee: ACCRO BIOSCIENCE; ZHANG - WO2018/17435, 2018, A1

5
[ 850864-54-9 ]
[ 1392839-43-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: dichloro-acetic acid / water / 1 h / Reflux 2: potassium carbonate; lithium bromide; tetrabutylammomium bromide / toluene; water / 0.67 h / 80 °C