Triphenylphosphine → (R)-2-[2,6-Dibromo-4-(6-bromo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenoxy]-3-phenyl-propionic acid, methyl ester

HRID 1873158노트

반응식

HRID 1873158 반응식
CCOC(/N=N/C(OCC)=O)=O.[Br:13][C:14]1[CH:19]=[C:18]([C:20]2[C:29]3[C:30]4[CH:36]=[CH:35][CH:34]=[CH:33][C:31]=4[S:32][C:28]=3[C:27]([Br:37])=[C:26]3[C:21]=2[CH:22]=[CH:23][CH:24]=[CH:25]3)[CH:17]=[C:16]([Br:38])[C:15]=1[OH:39].O[C@@H:41]([CH2:46][C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)[C:42]([O:44][CH3:45])=[O:43].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl.C1C=CC=CC=1>[Br:38][C:16]1[CH:17]=[C:18]([C:20]2[C:29]3[C:30]4[CH:36]=[CH:35][CH:34]=[CH:33][C:31]=4[S:32][C:28]=3[C:27]([Br:37])=[C:26]3[C:21]=2[CH:22]=[CH:23][CH:24]=[CH:25]3)[CH:19]=[C:14]([Br:13])[C:15]=1[O:39][C@H:41]([CH2:46][C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)[C:42]([O:44][CH3:45])=[O:43]

참가 물질

7

반응물 4

HCID 11776TriphenylphosphineHCID 5289077(S)-methyl 2-hydroxy-3-phenylpropanoateHCID 5462977Diethyl azodicarboxylateHCID 108406542,6-Dibromo-4-(6-bromo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenol

생성물 1

HCID 11803003(R)-2-[2,6-Dibromo-4-(6-bromo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenoxy]-3-phenyl-propionic acid, methyl ester수율 90.4%

시약·촉매·용매 2

HCID 241Benzene용매HCID 6344Dichloromethane용매

반응 조건

온도
80 °C

실험 절차

Diethylazodicarboxylate (0.437 mL, 2.74 mmol) was added dropwise to a stirred, room temperature suspension of 2,6-dibromo-4-(6-bromo-benzo [b]naphtho[2,3-d]thiophen-11-yl)-phenol (1.00 g, 1.83 mmol), (S)-2-hydroxy-3-phenylpropionic acid, methyl ester (0.494 g, 2.74 mmol), triphenylphosphine (0.72 g, 2.74 mmol) and benzene (12 mL) under a dry nitrogen atmosphere. Dissolution occurred and the solution was heated in an 80° C. oil bath for 3.5 h. Upon cooling to room temperature, the reaction mixture was diluted with dichloromethane and silica gel (30 mL) was added. The reaction mixture was concentrated and the silica adsorbate was flash chromatographed (96:4 petroleum ether:ethyl acetate) to provide the title compound as a white solid (1.20 g, 90%): mp 138-139.5° C.: NMR (CDCl3); δ8.36 (ddd, J=8, 1, 1 Hz, 1 H), 7.83 (ddd., J=8, 1, 1 Hz, 1 H), 7.68 (ddd, J =8, 7, 1 Hz, 1 H), 7.60 (dd, J=5, 2 Hz, 2 H), 7.60-7.48 (m, 2 H), 7.46-7.28 (m, 6 H), 7.18 (ddd, J=8, 7, 1 Hz, 1 H), 6.74 (ddd, J=8, 1, 1 Hz, 1 H), 5.26 (t, J=8 Hz, 1 H), 3.76 (s, 3 H), 3.59 (dd, J=8, 5 Hz, 2 H); MS (FAB+): [M+], 3 bromine isotope pattern, 722 (30%), 724 (70%) 726 (100%) 728 (35%); Anal. Calc. for C32H21Br3O3S: C, 52.99, H, 2.99, N, 0.00. Found: C, 52.60, H, 2.68, N, 0.07.

후처리

  1. dissolutionDissolution
  2. temperatureUpon cooling to room temperature
  3. additionwas added
  4. concentrationThe reaction mixture was concentrated
  5. customchromatographed (96:4 petroleum ether:ethyl acetate)

출처 및 근거

ORD 기록
ord-ce08e168309746c9901ba4559a9e68ad
출처 데이터셋
uspto-grants-2000_08
특허 번호
US06110962

반응 노트

불러오는 중…