2-Bromoethanol → 2-Bromoethyl 2-carboxyphenylacetate

HRID 231305

반응식

HRID 231305 반응식
[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]

참가 물질

8

반응물 4

HCID 108982-BromoethanolHCID 24819Phosphorus pentachloride2회HCID 66643Homophthalic acidHCID 150524262-Bromoethyl 2-carboxyphenylacetate2회

생성물 2

HCID 150524262-Bromoethyl 2-carboxyphenylacetate수율 64%HCID 21471138HCID 21471138, 화합물수율 46%

시약·촉매·용매 2

HCID 1118Sulfuric Acid촉매HCID 241Benzene용매2회

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-b1b4f5aca5c84ac5bd318a0983defccd
출처 데이터셋
uspto-grants-1989_07
특허 번호
US04845242

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