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 1995175Notes

Reaction equation

HRID 1995175 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]-cyclopropane-carboxylate 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-5adb3027aeeb452386418337147c4686
Source dataset
uspto-grants-1983_09
Patent number
US04402972

Reaction notes

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