Carbon Disulfide → ethyl 2-cyano-3,3-bis(benzylthio)acrylate

HRID 1696190Notes

Reaction equation

HRID 1696190 reaction equation
[H-].[Na+].[C:3]([CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7])#[N:4].[C:11](=[S:13])=[S:12].[CH2:14](Br)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>CN(C)C=O>[C:3]([C:5](=[C:11]([S:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[S:12][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:6]([O:8][CH2:9][CH3:10])=[O:7])#[N:4]

Participants

6

Reactant 4

HCID 6348Carbon DisulfideHCID 7498Benzyl BromideHCID 7764Ethyl cyanoacetateHCID 24758Sodium hydride

Product 1

HCID 2755377ethyl 2-cyano-3,3-bis(benzylthio)acrylateYield 82%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent4×

Conditions

Temperature
10 °C

Procedure

Under nitrogen atmosphere, sodium hydride (60%, 6.77 g) was added to dimethylformamide (75 mL). Thereto was added dropwise a solution of ethyl cyanoacetate (9.57 g) in dimethylformamide (15 mL) under cooling (internal temperature: ca. 10° C.) over a period of 15 minutes, and the mixture was stirred at room temperature for 10 minutes. Thereto was added dropwise a solution of carbon disulfide (5.09 mL) in dimethylformamide (12 mL) under cooling (internal temperature ≦10° C.) over a period of 20 minutes. The mixture was stirred at room temperature overnight, and thereto was added dropwise a solution of benzyl bromide (20.1 mL) in dimethylformamide (23 mL) under cooling (internal temperature ≦25° C.). The mixture was stirred at 70° C. for 7 hours and at room temperature overnight. The reaction mixture was poured in ice-water, and the mixture was stirred. The precipitates were collected by filtration and recrystallized from hot ethanol. The resultant crystals were washed with cold ethanol to give ethyl 2-cyano-3,3-bis(benzylthio)acrylate (25.63 g, yield: 82%) as a colorless solid.

Workup

  1. temperatureunder cooling (internal temperature ≦10° C.) over a period of 20 minutes
  2. stirringThe mixture was stirred at room temperature overnight
  3. temperatureunder cooling (internal temperature ≦25° C.)
  4. stirringThe mixture was stirred at 70° C. for 7 hours and at room temperature overnight
  5. stirringthe mixture was stirred
  6. filtrationThe precipitates were collected by filtration
  7. customrecrystallized from hot ethanol
  8. washThe resultant crystals were washed with cold ethanol

Sources & evidence

ORD record
ord-378d9f694d444309b4b5e9120a4ba39e
Source dataset
uspto-grants-2012_04
Patent number
US08163759B2

Reaction notes

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