反应 #2358500

ord-b95f062e2cf34926ab6257d876e644d7

反应方程式

O=C(Cl)OCc1ccccc1
benzyl chloroformate
NC1(C(=O)O)CCCC1
1-aminocyclopentanecarboxylic acid
O=C([O-])[O-].[Na+].[Na+]
sodium carbonate
O=C(NC1(C(=O)O)CCCC1)OCc1ccccc1
carbamate
收率 87.4%
O=C(NC1(C(=O)O)CCCC1)OCc1ccccc1
N-Benzyloxycarbonyl-1-aminocyclopentane-1-carboxylic acid
收率 87.4%

反应条件

详细条件
See reaction.notes.procedure_details.

后处理

  1. 1
    洗涤the reaction mixture washed with ether
  2. 2
    萃取extracted with ethyl acetate
  3. 3
    干燥dried (Na2SO4)
  4. 4
    过滤filtered
  5. 5
    其他the solvent removed

实验过程

A solution of benzyl chloroformate (0.290 g, 1.1 mmol) in dioxane (2.5 cm3) was added dropwise to a solution of 1-aminocyclopentanecarboxylic acid (Fluka) (0.2 g, 1.54 mmol) and sodium carbonate (0.490 g, 4.64 mmol) in water (5 cm3) at 0° C. Stirring was continued at room temperature overnight and the reaction mixture washed with ether. The aqueous layer was acidified with 2M hydrochloric acid, extracted with ethyl acetate, dried (Na2SO4), filtered and the solvent removed to afford carbamate 21 (0.253 g, 62%) as an oil which solidified on standing. Carbamate 21 was shown to be a 70:30 mixture of conformers by 1H NMR analysis (the ratio was estimated from the integration of the resonances at δ 5.31 and 7.29-7.40, assigned to the N—H protons of the major and minor conformers, respectively): mp 70-80° C. (lit.1 82-86° C., ethyl acetate, petroleum ether); δH (400 MHz; CDCl3; Me4Si) 1.83 (4H, br s, 2× cyclopentyl-H2), 2.04 (2H, br s, cyclopentyl-H2), 2.20-2.40 (2H, m, cyclopentyl-H2), 5.13 (2H, br s, OCH2Ph), 5.31 (0.7H, br s, N—H) and 7.29-7.40 (5.3H, m, Ph and N—H*); δC (100 MHz; CDCl3) 24.6 (CH2, cyclopentyl-C), 37.5 (CH2, cyclopentyl-C), 66.0 (quat., cyclopentyl-C), 66.8 (CH2, OCH2Ph), 128.0 (CH, Ph), 128.1 (CH, Ph), 128.4 (CH, Ph), 136.1 (quat, Ph), 155.8 (quat., NCO2) and 179.5 (quat., CO2H). * denotes resonance assigned to minor conformer.

来源

DOI: 10.6084/m9.figshare.5104873.v1专利: US09119851B2uspto-grants-2015_09