Aniline → Ethyl 3-allyl-5-nitrobenzoate

HRID 1595012

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HRID 1595012 반응식
[C:1](ON=O)(C)([CH3:3])[CH3:2].C(Br)C=C.N[C:13]1[CH:14]=[C:15]([CH:21]=[C:22]([N+:24]([O-:26])=[O:25])[CH:23]=1)[C:16]([O:18][CH2:19][CH3:20])=[O:17].NC1C=CC=CC=1>CC#N>[CH2:3]([C:13]1[CH:14]=[C:15]([CH:21]=[C:22]([N+:24]([O-:26])=[O:25])[CH:23]=1)[C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH:1]=[CH2:2]

참가 물질

6

반응물 4

HCID 6115AnilineHCID 7841Allyl bromideHCID 10906Tert-Butyl nitrite2회HCID 826201Benzoic acid, 3-amino-5-nitro-, ethyl ester

생성물 1

HCID 9816095Ethyl 3-allyl-5-nitrobenzoate수율 67%

시약·촉매·용매 1

HCID 6342Acetonitrile용매

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온도
11 °C

실험 절차

To a solution of t-butylnitrite (535 μl, 4.5 mmol) and allyl bromide (3.9 ml, 45.0 mmol) in CH3CN (3 ml), ethyl 3-amino-5-nitrobenzoate (631 mg, 3.0 mmol) was added during 20 minutes while maintaining the temperature of the reaction mixture at 10-12° C. At the end of the addition of the aniline, extra t-butylnitrite (180 μl, 1.5 mmol) was added to the reaction mixture which then was stirred at 25° C. for one hour. The volatile material in the reaction mixture was removed at reduced pressure. Column chromatography (heptane-ethyl acetate 47:3) gave 470 mg (67%) of ethyl 3-allyl-5-nitrobenzoate as a light yellow oil, which crystallized upon standing overnight in the refrigerator. 1H NMR (CDCl3, 400 MHz) δ 8.70, (m, 1H), 8.24, (m, 1H), 8.20, (m, 1H), 6.03-5.91, (m, 1H), 5.24-5.13, (m, 2H), 4.44, (q, 2H, J=7.1 Hz), 3.56, (d, 2H, J=6.5 Hz), 1.44, (t, 3H, J=7.1 Hz); 13C NMR (CDCl3, 100 MHz) δ 165.0, 148.8, 143.1, 135.9, 135.5, 132.6, 127.7, 122.9, 118.4, 62.3, 39.9, 14.7; Anal HRMS Calcd. for C12H13NO4 (M): 235.0845. Found: 235.0846.

후처리

  1. additionwas added to the reaction mixture which
  2. customThe volatile material in the reaction mixture was removed at reduced pressure

출처 및 근거

ORD 기록
ord-9d7f0f9841f94b4786d62455b4fa6889
출처 데이터셋
uspto-grants-2001_09
특허 번호
US06284894B1

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