反応 #439742

反応方程式

compounds 1

1-(2-Bromo-4,5-dichloro-thiophen-3-yl)-2-chloro-ethanone

chloroacetyl chloride

Compound 16

2-Chloro-1-[5-(2-chloro-acetyl)-4-methyl-thiophen-3-yl]-ethanone

Compound 17

2-Chloro-1-(4-methyl-thiophen-2-yl)-ethanone

3-methylthiophene

→

Compound 18

収率 5.0%

2-chloro-1-(3-methyl-thiophen-2-yl)-ethanone

収率 5.0%

溶媒

hexane ethyl acetate

acetonitrile H2O

Acetonitrile H2O

反応条件

実験手順

General procedure described for compounds 1 and 2 starting from 3-methylthiophene and chloroacetyl chloride. Three products were isolated by column chromatography column (hexane:ethyl acetate 3:1). Compound 16: yield 69%, m.p.: 155-156° C., 1H-NMR (CDCl3): δ8.2 (s, 1H, Ar), 4.54 (s, 2H, CH2), 4.52 (s, 2H, CH2), 2.8 (s , 3H, CH3); 13C-NMR (CDCl3): δ187.2 (CO), 185.1 (CO), 148.2 (C—CO), 139.1 (C—CO), 137.9 (CH), 48.1 (CH2), 47.3 (CH2), 16.0 (CH3); M/z (EI): 254, 252, 250 (M+, 1, 6, 9%), 203, 201 (M-CH2Cl, 47, 100%); HPLC: Column μ Bondapack C18, 5 μm, 300 A, (300×3.9 mm), Purity 99%, r.t.=4.73 min, acetonitrile/H2O (0.05% H3PO4+0.04% Et3N) 50/50. Compound 17: yield 8%, m.p.; 76-77° C., 1H-NMR (CDCl3): δ7.6 (s, 1H, Ar), 7.1 (s, 1H, Ar), 4.55 (s, 2H, CH2), 2.3 (s , 3H, CH3); 13C-NMR (CDCl3): δ188.1 (CO), 144.2 (C—CO), 143.2 (C—CH3), 138.9 (CH), 134.9 (CH), 49.4 (CH2), 19.5 (CH3); M/z (EI): 176, 174 (M+, 9, 23%), 125 (M-CH2Cl, 100%); HPLC: Column μ Bondapack C18, 5 μm, 300 A, (300×3.9 mm), Purity 98%, r.t.=4.56 min, Conditions Acetonitrile/H2O [(0.05% H3PO4+0.04% Et3N)] 50/50. Compound 18 yield 5%, yellow oil, 1H-NMR (CDCl3): δ7.44 (d, J=4.9 Hz, 1H, Ar), 7.0 (d, J=4.9 Hz, 1H, Ar), 4.55 (s, 2H, CH2), 2.3 (s ,3H, CH3); 13C-NMR (CDCl3): δ188.2 (CO), 151.3 (C—CH3), 136.8 (CH), 136.2 (C—CO), 135.0 (CH), 51.5 (CH2), 20.9 (CH3); M/z (EI): 176, 174 (M+, 6, 16%), 125 (M-CH2Cl, 100%); HPLC: Column μ Bondapack C18, 5 μm, 300 A, (300×3.9 mm), Purity 99%, r.t.=3.65 min, acetonitrile/H2O (0.05% H3PO4+0.04% Et3N) 50/50.

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