(S)alpha-cyano-3-phenoxy-4-fluoro-benzyl(1R,cis,Z)2,2-dimethyl-3-[3-oxo-3-tert.-butoxy-1-propenyl]-cyclopropanecarboxylate → (S)alpha-cyano-3-phenoxy-4-fluoro-benzyl(1R,cis,Z)2,2-dimethyl-3-[3-oxo-3-hydroxy-1-propenyl]-cyclopropane-carboxylate

HRID 1719777Notes

Reaction equation

[CH3:1][C:2]1([CH3:34])[C@@H:4](/[CH:5]=[CH:6]\[C:7](=[O:13])[O:8]C(C)(C)C)[C@H:3]1[C:14]([O:16][C@H:17]([C:32]#[N:33])[C:18]1[CH:23]=[CH:22][C:21]([F:24])=[C:20]([O:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:19]=1)=[O:15]>C1(C)C=CC=CC=1>[CH3:1][C:2]1([CH3:34])[C@@H:4](/[CH:5]=[CH:6]\[C:7](=[O:8])[OH:13])[C@H:3]1[C:14]([O:16][C@H:17]([C:32]#[N:33])[C:18]1[CH:23]=[CH:22][C:21]([F:24])=[C:20]([O:25][C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[CH:19]=1)=[O:15]

Participants

Conditions

Temperature: 0 °C

Procedure

1.6 g of p-toluene sulonic acid monohydrate were added to a solution of 16.4 g of the product of Step B in 160 ml of toluene and the mixture was refluxed until gas evolution ceased (about 30 minutes) and was cooled to 0° C. and filtered The filtrate was evaporated to dryness under reduced pressure and the residue was chromatographed over silica gel. Elution with a 70-30-1 n-hexane-ethyl acetate-acetic acid mixture yielded 13.3 g of (S)α-cyano-3-phenoxy-4-fluoro-benzyl (1R,cis,Z) 2,2-dimethyl-3-[3-oxo-3-hydroxy-1-propenyl]-cyclopropane-carboxylate melting at 99° C. and having a specific rotation of [α]D20 =+52.5° ±2.5° (c=0.5% in chloroform).

Workup

temperaturethe mixture was refluxed until gas evolution
custom(about 30 minutes)
filtrationfiltered The filtrate
customwas evaporated to dryness under reduced pressure
customthe residue was chromatographed over silica gel
washElution with a 70-30-1 n-hexane-ethyl acetate-acetic acid mixture

Sources & evidence

ORD record: ord-3afe1591f18e4369809002324169d6ae
Source dataset: uspto-grants-1985_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04542142

Reaction notes

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