tert-Butanol → Tert-butyl (4-chloro-2,6-difluorophenyl)carbamate

反応式

[Cl:1][C:2]1[CH:10]=[C:9]([F:11])[C:5](C(O)=O)=[C:4]([F:12])[CH:3]=1.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:20])C=CC=CC=1.C([N:32]([CH2:35]C)CC)C.[C:37]([OH:41])([CH3:40])([CH3:39])[CH3:38]>>[C:37]([O:41][C:35]([NH:32][C:5]1[C:4]([F:12])=[CH:3][C:2]([Cl:1])=[CH:10][C:9]=1[F:11])=[O:20])([CH3:40])([CH3:39])[CH3:38]

参加物

反応物 4

HCID 6386tert-Butanol

HCID 8471Triethylamine

HCID 199401P,P-Diphenylphosphinic azide

HCID 177506844-Chloro-2,6-difluorobenzoic acid

生成物 1

HCID 21260314Tert-butyl (4-chloro-2,6-difluorophenyl)carbamate収率 25%

実験手順

4-Chloro-2,6-difluorobenzoic acid (500 mg, 2.6 mmol) was added to a solution of diphenylphosphoryl azide (737 mg, 3 mmol) in t-butanol (8 ml) followed by triethylamine (477 ml, 6 mmol) and the mixture heated at reflux for 2 hours. The reaction mixture was allowed to cool and the solvent removed by evaporation. The residue was dissolved in ethyl acetate, washed with water, dried (MgSO4) and purified by column chromatography eluting with increasingly polar mixtures of methylene chloride, hexane and methanol (/1/1/0 to 95/0/5) to give N-t-butoxycarbonyl-4-chloro-2,6-difluoroaniline (170 mg, 25%).