2,3-Dimethylbutan-1-ol → (S)alpha-cyano-3-phenoxy-benzyl (1R,cis) 2,2-dimethyl-3-[Z-2-(2-isopropyl-propyloxycarbonyl)-ethenyl]-cyclopropane-carboxylate

HRID 464468Notes

Reaction equation

HRID 464468 reaction equation
[CH3:1][C:2]1([CH3:29])[C@@H:4](/[CH:5]=[CH:6]\[C:7]([OH:9])=[O:8])[C@H:3]1[C:10]([O:12][C@H:13]([C:27]#[N:28])[C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([O:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:15]=1)=[O:11].[CH:30]([CH:33]([CH3:36])[CH2:34]O)([CH3:32])[CH3:31]>C(Cl)Cl>[CH3:1][C:2]1([CH3:29])[C@@H:4](/[CH:5]=[CH:6]\[C:7]([O:9][CH2:31][CH:30]([CH:33]([CH3:36])[CH3:34])[CH3:32])=[O:8])[C@H:3]1[C:10]([O:12][C@H:13]([C:27]#[N:28])[C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([O:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH:15]=1)=[O:11]

Participants

4

Reactant 2

HCID 296562,3-Dimethylbutan-1-olHCID 13093798(S)alpha-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-[Z-2-carboxy-ethenyl]-cyclopropanecarboxylate

Product 1

HCID 86739011(S)alpha-cyano-3-phenoxy-benzyl (1R,cis) 2,2-dimethyl-3-[Z-2-(2-isopropyl-propyloxycarbonyl)-ethenyl]-cyclopropane-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A mixture of 3 g of (S)α-cyano-3-phenoxy-benzyl(1R,cis)2,2-dimethyl-3-[Z-2-carboxy-ethenyl]-cyclopropanecarboxylate in 30 ml of methylene chloride was added to a mixture of 3 ml of 1-dimethylamino-1-chloro-2-methyl-propen-1-yl [J. Org. Chem., Vol. 35 (1970), p. 3970] in 3 ml of methylene chloride and the mixture was stirred at room temperature for 15 minutes. After cooling the mixture to 5° C., 5 ml of 2-isopropyl-propanol were added thereto and the mixture was stirred at room temperature for 16 hours, was washed with water, with aqueous sodium chloride solution, was dried and evaporated to dryness under reduced pressure. The residue was chromatographed over silica gel and was eluted with a 9-1 cyclohexane-ethyl acetate mixture to obtain 2.25 g of (S)α-cyano-3-phenoxy-benzyl (1R,cis)2,2-dimethyl-3-[Z-2-(2-isopropyl-propyloxycarbonyl)-ethenyl]-cyclopropane-carboxylate with a specific rotation of [α]D20 =+61.5°±2.5° (c=0.5% in benzene).

Workup

  1. temperatureAfter cooling the mixture to 5° C.
  2. stirringthe mixture was stirred at room temperature for 16 hours
  3. washwas washed with water, with aqueous sodium chloride solution
  4. customwas dried
  5. customevaporated to dryness under reduced pressure
  6. customThe residue was chromatographed over silica gel
  7. washwas eluted with a 9-1 cyclohexane-ethyl acetate mixture

Sources & evidence

ORD record
ord-627436907a9948c7bf6e280c00a6194f
Source dataset
uspto-grants-1985_10
Patent number
US04547522

Reaction notes

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