Water → Ethyl 3-isothiocyanatopyrrolidine-1-carboxylate

HRID 704702Notes

Reaction equation

HRID 704702 reaction equation
O.[OH-].[Na+].[NH2:4][CH:5]1[CH2:9][CH2:8][N:7]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH2:6]1.C(Cl)(=O)OCC.[C:21](=S)=[S:22]>>[N:4]([CH:5]1[CH2:9][CH2:8][N:7]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH2:6]1)=[C:21]=[S:22]

Participants

6

Reactant 5

HCID 962WaterHCID 6348Carbon DisulfideHCID 10928Ethyl chloroformateHCID 14798Sodium HydroxideHCID 13656208Ethyl 3-aminopyrrolidine-1-carboxylate

Product 1

HCID 14575268Ethyl 3-isothiocyanatopyrrolidine-1-carboxylateYield 39%

Procedure

(a-2) To 192 parts of cooled water were added portionwise 12.8 parts of sodium hydroxide. Upon complete addition, 25.3 parts of carbon disulfide were added and stirring was continued for 30 minutes at 10° C. 55 Parts of ethyl 3-aminopyrrolidinecarboxylate were added and the whole was stirred for 30 minutes at 10° C. 34.8 Parts of ethyl carbonochloridate were added dropwise (exothermic reaction) and stirring was continued for 4 hours at 60° C. After cooling, the product was extracted with methylbenzene. The extract was washed twice with water, dried, filtered and evaporated. The residue was purified by column chromatography over silica gel using a mixture of dichloromethane and ethanol (99:1 and 100:0.5 by volume) as eluents. The pure fractions were collected and the eluent was evaporated at a warm water bath at 30° C., yielding 25 parts (39.0%) of ethyl 3-isothiocyanato-1-pyrrolidinecarboxylate as a residue (interm. 6).

Workup

  1. additionwere added
  2. stirringthe whole was stirred for 30 minutes at 10° C
  3. custom(exothermic reaction)
  4. stirringstirring
  5. waitwas continued for 4 hours at 60° C
  6. temperatureAfter cooling
  7. extractionthe product was extracted with methylbenzene
  8. washThe extract was washed twice with water
  9. customdried
  10. filtrationfiltered
  11. customevaporated
  12. customThe residue was purified by column chromatography over silica gel using
  13. additiona mixture of dichloromethane and ethanol (99:1 and 100:0.5 by volume) as eluents
  14. customThe pure fractions were collected
  15. customthe eluent was evaporated at a warm water bath at 30° C.

Sources & evidence

ORD record
ord-b836103889be437589e2c00d673e05c1
Source dataset
uspto-grants-1991_01
Patent number
US04988689

Reaction notes

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