Triphenylphosphine → Ethyl 3-{2-fluoro-4-[[(2-nitrophenyl)sulfonyl](4-{1-[(4-phenyl-1,3-thiazol-2-yl)methyl]butyl}benzyl)amino]phenyl}propanoate

HRID 508093ノート

反応式

HRID 508093 の反応式
[F:1][C:2]1[CH:7]=[C:6]([NH:8][S:9]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[N+:18]([O-:20])=[O:19])(=[O:11])=[O:10])[CH:5]=[CH:4][C:3]=1[CH2:21][CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24].[C:28]1([C:34]2[N:35]=[C:36]([CH2:39][CH:40]([C:44]3[CH:49]=[CH:48][C:47]([CH2:50]O)=[CH:46][CH:45]=3)[CH2:41][CH2:42][CH3:43])[S:37][CH:38]=2)[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[F:1][C:2]1[CH:7]=[C:6]([N:8]([S:9]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[N+:18]([O-:20])=[O:19])(=[O:10])=[O:11])[CH2:50][C:47]2[CH:48]=[CH:49][C:44]([CH:40]([CH2:39][C:36]3[S:37][CH:38]=[C:34]([C:28]4[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=4)[N:35]=3)[CH2:41][CH2:42][CH3:43])=[CH:45][CH:46]=2)[CH:5]=[CH:4][C:3]=1[CH2:21][CH2:22][C:23]([O:25][CH2:26][CH3:27])=[O:24]

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 23143323(4-{1-[(4-Phenyl-1,3-thiazol-2-yl)methyl]butyl}phenyl)methanolHCID 23157368Ethyl 3-(2-fluoro-4-{[(2-nitrophenyl)sulfonyl]amino}phenyl)propanoate

生成物 1

HCID 23157210Ethyl 3-{2-fluoro-4-[[(2-nitrophenyl)sulfonyl](4-{1-[(4-phenyl-1,3-thiazol-2-yl)methyl]butyl}benzyl)amino]phenyl}propanoate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of ethyl 3-(2-fluoro-4-{[(2-nitrophenyl)sulfonyl]amino}phenyl)propanoate (0.686 g, 1.73 mmol), (4-{1-[(4-phenyl-1,3-thiazol-2-yl)methyl]butyl}phenyl)methanol (0.389 g, 1.15 mmol) and triphenylphosphine (0.603 g, 2.30 mmol) in tetrahydrofuran (15 mL) was stirred under ice-cooling, and diethyl azodicarboxylate (40% toluene solution, 1.05 mL, 2.3 mmol) was added. The mixture was allowed to warm to room temperature and stirred for 16 hr. The reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (10%-80% ethyl acetate/hexane) to give ethyl 3-{2-fluoro-4-[[(2-nitrophenyl)sulfonyl](4-{1-[(4-phenyl-1,3-thiazol-2-yl)methyl]butyl}benzyl)amino]phenyl}propanoate as a yellow oil. To a solution of the obtained oil and mercaptoacetic acid (0.291 g, 3.16 mmol) in N,N-dimethylformamide (15 mL) was added lithium hydroxide monohydrate (0.265 g, 6.32 mmol), and the mixture was stirred at room temperature for 2 hr. Ethyl acetate was added to the reaction mixture, and the mixture was washed with saturated aqueous sodium hydrogencarbonate and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (5%-40% ethyl acetate/hexane) to give the title compound (0.420 g, yield 69%, 2 steps) as a colorless oil.

後処理

  1. temperaturecooling
  2. concentrationThe reaction mixture was concentrated under reduced pressure
  3. customthe residue was purified by silica gel column chromatography (10%-80% ethyl acetate/hexane)

出典と根拠

ORDレコード
ord-d22e85ce7eb3459ca87f2effc9a675a7
出典データセット
uspto-grants-2010_08
特許番号
US07786165B2

反応ノート

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