Ethyl chloroformate → HCID 67928767, compound

HRID 981303Notes

Reaction equation

HRID 981303 reaction equation
[Cl:1][C:2]1[C:10]([N+:11]([O-:13])=[O:12])=[CH:9][C:5]([C:6]([OH:8])=O)=[C:4]([O:14][CH3:15])[CH:3]=1.C(Cl)(=O)OCC.[NH2:22][C@H:23]1[CH2:28][CH2:27][N:26]([C:29]([O:31][CH2:32][CH3:33])=[O:30])[CH2:25][C@H:24]1[O:34][CH3:35]>ClC(Cl)Cl.C(N(CC)CC)C>[Cl:1][C:2]1[C:10]([N+:11]([O-:13])=[O:12])=[CH:9][C:5]([C:6]([NH:22][C@H:23]2[CH2:28][CH2:27][N:26]([C:29]([O:31][CH2:32][CH3:33])=[O:30])[CH2:25][C@H:24]2[O:34][CH3:35])=[O:8])=[C:4]([O:14][CH3:15])[CH:3]=1

Participants

6

Reactant 3

HCID 10928Ethyl chloroformateHCID 128487494-Chloro-2-methoxy-5-nitrobenzoic acidHCID 13677746Ethyl cis-(4-amino-3-methoxypiperidino)formate

Product 1

HCID 67928767HCID 67928767, compoundYield 75%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolvent2×HCID 8471TriethylamineSolvent

Procedure

To a stirred and cooled (5° C.) suspension of 81 parts of 4-chloro-2-methoxy-5-nitrobenzoic acid in 1350 parts of trichloromethane were added first 35.4 parts of N,N-diethylethanamine and then 38 parts of ethyl carbonochloridate at a temperature below 5° C. The whole was stirred for 2 hours in an ice bath. A solution of 65 parts of ethyl cis-4-amino-3-methoxy-1-piperidinecarboxylate in 1125 parts of trichloromethane was added while the temperature was kept below 10° C. Stirring was continued first for 1 hour in an ice bath and then overnight at room temperature. The mixture was washed successively once with water, twice with a sodium hydroxide solution 5% and three times with water, dried, filtered and evaporated. The residue was crystallized from acetonitrile. The product was filtered off and dried, yielding 100 parts (75%) of ethyl cis-4-[(4-chloro-2-methoxy-5-nitro-benzoyl)amino]-3-methoxy-1-piperidinecarboxylate; mp. 181.3° C. (interm. 13).

Workup

  1. temperaturecooled
  2. customat a temperature below 5° C
  3. stirringThe whole was stirred for 2 hours in an ice bath
  4. customwas kept below 10° C
  5. stirringStirring
  6. customovernight
  7. customat room temperature
  8. washThe mixture was washed successively once with water, twice with a sodium hydroxide solution 5% and three times with water
  9. customdried
  10. filtrationfiltered
  11. customevaporated
  12. customThe residue was crystallized from acetonitrile
  13. filtrationThe product was filtered off
  14. customdried

Sources & evidence

ORD record
ord-94926f32bb7f46e7af0d6479143e8f73
Source dataset
uspto-grants-1991_02
Patent number
US04990521

Reaction notes

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