4-cyano-3-trifluoromethyl-N-(2-hydroxy-3-phenylthio-2-trifluoromethylpropionyl)aniline → 4-cyano-3-trifluoromethyl-N-[2-(-)-camphanoyloxy-3-phenylthio-2-trifluoromethylpropionyl)aniline

HRID 980158Notes

Reaction equation

[C:1]12([CH3:13])[C:7]([CH3:9])([CH3:8])[CH:4]([CH2:5][CH2:6]1)[CH2:3][CH:2]2[C:10](Cl)=[O:11].[C:14]([C:16]1[CH:38]=[CH:37][C:19]([NH:20][C:21](=[O:36])[C:22]([OH:35])([C:31]([F:34])([F:33])[F:32])[CH2:23][S:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[CH:18][C:17]=1[C:39]([F:42])([F:41])[F:40])#[N:15]>N1C=CC=CC=1>[C:14]([C:16]1[CH:38]=[CH:37][C:19]([NH:20][C:21](=[O:36])[C:22]([O:35][C:10]([CH:2]2[CH2:3][CH:4]3[C:7]([CH3:9])([CH3:8])[C:1]2([CH3:13])[CH2:6][CH2:5]3)=[O:11])([C:31]([F:32])([F:33])[F:34])[CH2:23][S:24][C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)=[CH:18][C:17]=1[C:39]([F:41])([F:42])[F:40])#[N:15]

Participants

Conditions

Temperature: 95 °C

Procedure

(-)-Camphanoyl chloride (4.33 g.) was added portionwise during 5 minutes to a solution of 4-cyano-3-trifluoromethyl-N-(2-hydroxy-3-phenylthio-2-trifluoromethylpropionyl)aniline (5.8 g.) in pyridine (35 ml.) and the mixture was heated at 95° C. for 150 minutes and then evaporated to dryness. Toluene (50 ml.) was added and the mixture was again evaporated to dryness. The residue was dissolved in ethyl acetate (200 ml.) and the solution was washed with water (30 ml.) and then twice with saturated aqueous sodium chloride solution (20 ml. each time), dried over magnesium sulphate and evaporated to dryness under reduced pressure. The residue was dissolved in methylene chloride (10 ml.) and the solution was flash chromatographed on silica gel (Merck 9385) using methylene chloride as eluant. There were thus obtained the two disastereoisomers of 4-cyano-3-trifluoromethyl-N-[2-(-)-camphanoyloxy-3-phenylthio-2-trifluoromethylpropionyl)aniline, the less polar isomer having m.p. 121°-123° C. and the more polar isomer having m.p. 140°-143° C.

Workup

customevaporated to dryness
additionToluene (50 ml.) was added
customthe mixture was again evaporated to dryness
dissolutionThe residue was dissolved in ethyl acetate (200 ml.)
washthe solution was washed with water (30 ml.)
dry with materialeach time), dried over magnesium sulphate
customevaporated to dryness under reduced pressure
dissolutionThe residue was dissolved in methylene chloride (10 ml.)
customchromatographed on silica gel (Merck 9385)

Sources & evidence

ORD record: ord-5d94e0c5298a46e2b7172da9459d8773
Source dataset: uspto-grants-1987_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04636505

Reaction notes

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