HRID6368

反应详情

EQUATION

反应方程式

REACTANTS

反应物

HCID8471

Triethylamine

C6H15N

HCID76704

4-Ethylpiperidine

C7H15N

HCID199401

Phosphinic azide, diphenyl-

C12H10N3OP

结构：CN(C)c1cccc2c(S(=O)(=O)NC(CCCNC(=O)OCc3ccccc3)C(=O)O)cccc12

HCID19793149

未命名化合物

PRODUCTS

生成物

结构：CCC1CCN(C(=O)C(CCCNC(=O)OCc2ccccc2)NS(=O)(=O)c2cccc3c(N(C)C)cccc23)CC1

HCID54192395

未命名化合物

收率 91.1%

AUXILIARIES

试剂、催化剂与溶剂

溶剂HCID6228

N,N-Dimethylformamide

C3H7NO

CONDITIONS

反应条件

温度: 0 °C

PROCEDURE

实验过程

To a cold (0° C.), nitrogen-blanketed mixture of 2d (48.90 g, 0.098 mol), triethylamine (25.0 mL, 0.18 mol) and 4-ethylpiperidine (20.0 g, 0.18 mol) in anhydrous dimethylformamide (160 mL) was added dropwise diphenylphosphoryl azide (21.1 mL, 0.098 mol). The mixture was stirred at about 0° C. for about 1 hour and at ambient temperature for about 2 hours before it was partitioned between ether (150 mL) and water (80 mL). The ethereal layer was separated and the aqueous layer was extracted four additional times with ether (80 mL). The combined ethereal extracts were then washed with saturated sodium bicarbonate solution and brine prior to drying (Na2SO4) and solvent concentration. Two identical reactions were performed in tandem. Purification of the combined residues by HPLC on silica gel (elution with 50% ethyl acetate in hexane) furnished 53.09 g (45%) of 3d as a yellow foam, m.p. 56°-62° C. (dec.); 1H NMR (CDCl3) δ 8.47 (d, 1H), 8.30 (t, 1H), 8.16 (d, 1H), 7.58 (m, 1H), 7.56-7.36 (m, 6H), 7.15 (d, 1H), 6.17-5.96 (dd, 1H), 5.10 (s, 2H), 4.75-4.62 (bm, 1H), 4.10-3.91 (bm, 2H), 3.42-3.30 (bm, 1H), 3.16-2.92 (bm, 2H), 2.85-2.83 (d, 6H), 2.68-2.41 (dt, 1H), 2.24-1.97 (m, 1H), 1.57-0.76 (m, 3 H), 0.16-0.08 (m, 1H); 13C NMR (CDCl3) ppm 168.50, 156.40, 151.62, 136.50, 135.00, 134.70, 130.56, 130.44, 129.80, 129.35, 129.18, 128.50, 128.41, 128.07, 128.00, 123.01, 122.93, 119.33, 115.58, 115.47, 66.60, 52.29, 52.19, 45.70, 45.43, 45.37, 45.13, 42.02, 42.21, 40.35, 40.18, 37.48, 37.34, 32.17, 31.92, 31.06, 30.79, 30.65, 29.67, 28.77, 28.58, 25.12, 11.08; IR (KBR, cm-1) 33,50 2975, 2975, 2950, 1725, 1650, 1550, 1475, 1350, 1275, 1180, 1160; MS m/z (MH+) 595.

WORKUP

后处理

customwas partitioned between ether (150 mL) and water (80 mL)
customThe ethereal layer was separated
extractionthe aqueous layer was extracted four additional times with ether (80 mL)
washThe combined ethereal extracts were then washed with saturated sodium bicarbonate solution and brine
customto drying
concentration(Na2SO4) and solvent concentration
customPurification of the combined residues by HPLC on silica gel (elution with 50% ethyl acetate in hexane)

来源与证据

来源类型: Open Reaction Database
ORD 记录: ord-2d1677a7d55446d6936250ae86c5bfcb
来源数据集: uspto-grants-1993_09
DOI: 10.6084/m9.figshare.5104873.v1
专利: US05248673
来源说明: uspto-grants-1993_09

反应 SMILES

[CH3:1][N:2]([CH3:35])[C:3]1[CH:12]=[CH:11][CH:10]=[C:9]2[C:4]=1[CH:5]=[CH:6][CH:7]=[C:8]2[S:13]([NH:16][CH:17]([CH2:21][CH2:22][CH2:23][NH:24][C:25]([O:27][CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)=[O:26])[C:18](O)=[O:19])(=[O:15])=[O:14].C(N(CC)CC)C.[CH2:43]([CH:45]1[CH2:50][CH2:49][NH:48][CH2:47][CH2:46]1)[CH3:44].C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1>CN(C)C=O>[CH3:35][N:2]([CH3:1])[C:3]1[CH:12]=[CH:11][CH:10]=[C:9]2[C:4]=1[CH:5]=[CH:6][CH:7]=[C:8]2[S:13]([NH:16][CH:17]([C:18]([N:48]1[CH2:49][CH2:50][CH:45]([CH2:43][CH3:44])[CH2:46][CH2:47]1)=[O:19])[CH2:21][CH2:22][CH2:23][NH:24][C:25](=[O:26])[O:27][CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)(=[O:15])=[O:14]