Acetonitrile → HCID 20030495, compound

HRID 232009Notes

Reaction equation

HRID 232009 reaction equation
C(#N)C.Cl.[CH3:5][N:6]([CH3:10])[CH2:7][CH2:8][SH:9].C[O-].[Na+].Cl[CH2:15][C:16](=[O:23])[CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19]>CO>[CH3:5][N:6]([CH3:10])[CH2:7][CH2:8][S:9][CH2:15][C:16](=[O:23])[CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19]

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 25798Captamine HydrochlorideHCID 69484Ethyl 4-chloroacetoacetateHCID 10942334Sodium Methoxide

Product 1

HCID 20030495HCID 20030495, compoundYield 89.7%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
40 °C

Procedure

200 ml of acetonitrile was added to 28.3 g of 2-dimethylaminoethanethiol hydrochloride, and after 80 ml of sodium methoxide-containing 28% methyl alcohol solution was added thereto with cooling in an ice bath, 32.9 g of ethyl 4-chloroacetoacetate was dropwise added thereto with cooling in an ice bath. After the dropwise addition, the whole was stirred for 2 hours at 40° C., and then the inorganic salt was separated by filtration and the resulting filtrate was dried under reduced pressure. The oily substance obtained was purified by silica gel column chromatography (with moving phase solvent of chloroform/methyl alcohol, 10/1) to obtain 41.8 g of ethyl 4-(2-dimethylaminoethylthio)acetoacetate. To 23.3 g of the ethyl 4-(2-dimethylaminoethylthio)acetoacetate thus-obtained were added 8.4 g of 3-amino-1,2,4-triazole and 4.0 ml of acetic acid, and the whole was heated under reflux for 4 hours. After the reaction, 100 ml of methyl alcohol was added to the reaction solution and stirred with cooling in an ice bath, and the crystal precipitate was taken out by filtration and recrystallized from 300 ml of methyl alcohol to obtain 10.2 g of the desired product. M.P.: 109°-110° C.

Workup

  1. additionwas added
  2. temperaturewith cooling in an ice bath
  3. temperaturewith cooling in an ice bath
  4. additionAfter the dropwise addition
  5. customthe inorganic salt was separated by filtration
  6. customthe resulting filtrate was dried under reduced pressure
  7. customThe oily substance obtained
  8. customwas purified by silica gel column chromatography (with moving phase solvent of chloroform/methyl alcohol, 10/1)

Sources & evidence

ORD record
ord-67f87a10889849f5945f42777985031d
Source dataset
uspto-grants-1989_07
Patent number
US04851321

Reaction notes

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