Dichloromethane → (S)alpha-cyano-3-phenoxy-benzyl (1R,cis) 2,2-dimethyl-3-(2,2,2-trichloroethoxycarbonylethynyl)-cyclopropane-carboxylate

HRID 1719741Notes

Reaction equation

HRID 1719741 reaction equation
[CH3:1][C:2]1([CH3:18])[C@@H:4]([C:5]#[C:6][C:7]([O:9][CH2:10][C:11]([Cl:14])([Cl:13])[Cl:12])=[O:8])[C@H:3]1[C:15]([OH:17])=[O:16].C(Cl)Cl.[C:22]([C@@H:24](O)[C:25]1[CH:30]=[CH:29][CH:28]=[C:27]([O:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[CH:26]=1)#[N:23]>N1C=CC=CC=1>[CH3:1][C:2]1([CH3:18])[C@@H:4]([C:5]#[C:6][C:7]([O:9][CH2:10][C:11]([Cl:13])([Cl:14])[Cl:12])=[O:8])[C@H:3]1[C:15]([O:17][C@H:24]([C:22]#[N:23])[C:25]1[CH:30]=[CH:29][CH:28]=[C:27]([O:31][C:32]2[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=2)[CH:26]=1)=[O:16]

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 9837437(2S)-2-hydroxy-2-(3-phenoxyphenyl)acetonitrileHCID 13093792(1R,cis)2,2-dimethyl-3-(2,2,2-trichloroethoxycarbonylethynyl)-cyclopropane-carboxylic acid

Product 1

HCID 13093794(S)alpha-cyano-3-phenoxy-benzyl (1R,cis) 2,2-dimethyl-3-(2,2,2-trichloroethoxycarbonylethynyl)-cyclopropane-carboxylateYield 76.3%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

6.2 g of dicyclohexycarbodiimide were added to a solution of 9.5 g of the product of Step C, 30 ml of methylene chloride and 3 ml of pyridine and the reaction mixture was stirred for half an hour. 6.8 g of (S)α-cyano-3-phenoxy-benzyl alcohol were added thereto and the mixture was stirred for an hour and half and filtered. The filtrate was washed with N hydrochloric acid, then with water until neutral, dried, and evaporated to dryness. The 15.3 g of oil residue were chromatographed over silica gel and eluted with a 97-3 mixture of benzene-ethyl acetate to obtain 12 g of (S)α-cyano-3-phenoxy-benzyl (1R,cis) 2,2-dimethyl-3-(2,2,2-trichloroethoxycarbonylethynyl)-cyclopropane-carboxylate melting at 101° C.

Workup

  1. stirringthe mixture was stirred for an hour
  2. filtrationhalf and filtered
  3. washThe filtrate was washed with N hydrochloric acid
  4. dry with materialwith water until neutral, dried
  5. customevaporated to dryness
  6. customThe 15.3 g of oil residue were chromatographed over silica gel
  7. washeluted with a 97-3 mixture of benzene-ethyl acetate

Sources & evidence

ORD record
ord-6a240de6243f44c2b32fec98f0f45fd0
Source dataset
uspto-grants-1985_09
Patent number
US04542142

Reaction notes

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