2-Bromoethanol → 2-Bromoethyl 2-carboxyphenylacetate

HRID 231305

反応式

HRID 231305 の反応式
[C:1]([OH:13])(=O)[CH2:2][C:3]1[C:4](=[CH:8][CH:9]=[CH:10][CH:11]=1)[C:5]([OH:7])=O.[Br:14][CH2:15][CH2:16]O.[C:18]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=1[CH2:27][C:28]([O:30][CH2:31][CH2:32][Br:33])=[O:29])([OH:20])=[O:19].P(Cl)(Cl)(Cl)(Cl)[Cl:35]>C1C=CC=CC=1.S(=O)(=O)(O)O>[C:18]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=1[CH2:27][C:28]([O:30][CH2:31][CH2:32][Br:33])=[O:29])([OH:20])=[O:19].[Br:14][CH2:15][CH2:16][C:1]1[O:13][C:5]([C:4]2[C:3]([C:2]=1[Cl:35])=[CH:11][CH:10]=[CH:9][CH:8]=2)=[O:7]

参加物

8

反応物 4

HCID 108982-BromoethanolHCID 24819Phosphorus pentachloride2 回HCID 66643Homophthalic acidHCID 150524262-Bromoethyl 2-carboxyphenylacetate2 回

生成物 2

HCID 150524262-Bromoethyl 2-carboxyphenylacetate収率 64%HCID 214711384-Chloro-3-[2-bromoethyl]-isocoumarin収率 46%

試薬・触媒・溶媒 2

HCID 1118Sulfuric Acid触媒HCID 241Benzene溶媒2 回

実験手順

2-Bromoethyl 2-carboxyphenylacetate was prepared from heating 10 g of homophthalic acid (56 mmole) and 21 g of 2-bromoethanol (167 mmole) in 175 ml of benzene with a few drops of conc. sulfuric acid at 90°-110° for two hours, yield 64%. TLC shows that it is a pure compound. The cyclization of 2-bromoethyl 2-carboxy-phenylacetate with PCl5 was performed by a previous method with modification (Tirodkar, and Usgaonkar, Indian. J. Chem. 7, pp 1114-1116 (1969)). 1.15 g of 2-bromoethyl 2-carboxyphenylacetate was heated with 2.1 g of PCl5 in 90 ml of benzene at 70° C. for 2 hrs. The benzene was removed and the residue triturated with petroleum ether. The crude product was purified by silica gel column chromatography with methylene chloride as an eluent to give 560 mg of 3-(bromoethyl)-4-chloroisocoumarin (yield, 46%). IR and NMR spectra show it was the desired product. 100 mg of 3-bromomethyl-4-chloroisocoumarin (0.3 mmole) was heated with 60 mg of thiourea (0.8 mmole) in 5 ml of THF at 70° C. for 2 days to give a yellow solid, 50 mg (yield, 40%), m.p. 167°-169° C. (dec); one spot on TLC, Rf =0.7 (Butanol:acetic acid:water=6:1:5); NMR spectrum (d6 -DMSO), δ 9.1 (2b, 4H), 7.5-8.1 (m, 4H), 4.6 (t, 2H), 3.6 (t, 2H); mass spectrum (FAB+), m/e=299 (M+ -Br). Anal. Calc. for C12H12N2O3Br1Cl1S1 : C, 37.96; H, 3.19; N, 7.38. Found: C, 37.81; H, 3.27; N, 7.71.

後処理

  1. customThe benzene was removed
  2. customthe residue triturated with petroleum ether
  3. customThe crude product was purified by silica gel column chromatography with methylene chloride as an eluent

出典と根拠

ORDレコード
ord-b1b4f5aca5c84ac5bd318a0983defccd
出典データセット
uspto-grants-1989_07
特許番号
US04845242

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