反応 #2358500

ord-b95f062e2cf34926ab6257d876e644d7

反応方程式

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
収率 87.4%
O=C(NC1(C(=O)O)CCCC1)OCc1ccccc1
N-Benzyloxycarbonyl-1-aminocyclopentane-1-carboxylic acid
収率 87.4%

反応条件

詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    洗浄the reaction mixture washed with ether
  2. 2
    抽出extracted with ethyl acetate
  3. 3
    乾燥dried (Na2SO4)
  4. 4
    ろ過filtered
  5. 5
    その他the solvent removed

実験手順

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.

出典

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