tert-Butanol → 3-Nitro-5-(octadecyloxy)phenylcarbamic acid dimethylethyl ester

反応式

[N+:1]([C:4]1[CH:5]=[C:6]([CH:10]=[C:11]([O:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])[CH:12]=1)C(O)=O)([O-:3])=[O:2].C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:39])C=CC=CC=1.C([N:51]([CH2:54]C)CC)C.[C:56]([OH:60])([CH3:59])([CH3:58])[CH3:57]>>[CH3:57][C:56]([O:60][C:54](=[O:39])[NH:51][C:6]1[CH:10]=[C:11]([O:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])[CH:12]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1)([CH3:59])[CH3:58]

参加物

反応物 4

HCID 6386tert-Butanol

HCID 8471Triethylamine

HCID 199401P,P-Diphenylphosphinic azide

HCID 193889433-Nitro-5-(octadecyloxy)benzoic acid

生成物 1

HCID 542156373-Nitro-5-(octadecyloxy)phenylcarbamic acid dimethylethyl ester収率 79%

実験手順

A mixture of 5.0 g (11.5 mmol) of 3-nitro-5-(octadecyloxy)benzoic acid, 3.0ml (13.8 mmol) of diphenylphosphoryl azide and 2.0 ml (13.8 mmol) of triethylamine in 45 ml of t-butylalcohol (freshly distilled from sodium) was stirred at reflux under argon for 20 hours. The excess t-butylalcohol was removed at reduced pressure and methylene chloride was added to the residue. The extract was washed with NaHCO3 solution, dried and concentrated at reduced pressure to an oil which was purified by HPLC using 5% ethyl acetate-hexane to give 4.6 g (79% yield, mp 70°-72°) of 3-nitro-5-(octadecyloxy)phenylcarbamic acid dimethylethyl ester. The structure was confirmed by nmr and mass spectra.