Benzyl Alcohol → Benzyl 6-chloropyridine-3-carboxylate

HRID 595177Notes

Reaction equation

HRID 595177 reaction equation
S(Cl)(Cl)=O.[Cl:5][C:6]1[CH:14]=[CH:13][C:9]([C:10]([OH:12])=[O:11])=[CH:8][N:7]=1.[CH2:15](O)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.Cl>C1(C)C=CC=CC=1.N1C=CC=CC=1>[Cl:5][C:6]1[CH:14]=[CH:13][C:9]([C:10]([O:12][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[O:11])=[CH:8][N:7]=1

Participants

7

Reactant 4

HCID 244Benzyl AlcoholHCID 313Hydrochloric AcidHCID 24386Thionyl ChlorideHCID 792226-Chloronicotinic acid

Product 1

HCID 51057995Benzyl 6-chloropyridine-3-carboxylate

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
110 °C

Procedure

Sulfurous dichloride (6.8 g, 57 mmol) was added to a solution of 6-chloronicotinic acid (4.5 g, 28.5 mmol) in toluene (40 mL) at 0° C. The mixture was stirred at 110° C. for 2 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure. Benzyl alcohol (4.65 g, 43.1 mmol), pyridine (6.9 mL) and toluene (50 mL) were added to the residue. The mixture was stirred at 25° C. for 3 hours. HCl (20 mL, 4 N) was added and the mixture was extracted with toluene. The toluene layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to afford benzyl 6-chloronicotinate. MS ESI calc'd. for C13H11ClNO2 [M+H]+ 248. found 248. 1HNMR (400 MHz, DMSO-d6) δ 8.94 (d, J=2.0 Hz, 1H), 8.34-8.31 (m, 1H), 7.67 (d, J=8.4 Hz, 1H), 7.50-7.17 (m, 5H), 5.38 (s, 2H).

Workup

  1. temperatureAfter cooling to room temperature
  2. concentrationthe mixture was concentrated under reduced pressure
  3. stirringThe mixture was stirred at 25° C. for 3 hours
  4. extractionthe mixture was extracted with toluene
  5. dry with materialThe toluene layer was dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-64b007c156904fc9b983e462a66973c1
Source dataset
uspto-grants-2016_01
Patent number
US09242984B2

Reaction notes

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