硫醇还原α,α,α-三溴甲基酮类化合物的研究

详细信息    查看全文 | 推荐本文 |

英文篇名：Reduction of α,α,α-Tribromomethylketones by Mercaptan 作者：王慧 ; 杨莹 ; 阿布都热西提·阿布力克木 英文作者：WANG Hui;YANG Ying;ABULIKEMU Abudu Rexit;Department of Chemistry,Xinjiang Normal University; 关键词：2-苯硫代乙醇 ; α ; α-二溴甲基酮 ; 还原反应 ; α ; α ; α-三溴甲基酮 英文关键词：2-phenylthioethanol;;α,α-dibromomethylketones;;reduction;;α,α,α-tribromomethylketones 中文刊名：化学试剂 英文刊名：Chemical Reagents 机构：新疆师范大学化学系; 出版日期：2019-03-28 16:58 出版单位：化学试剂 年：2019 期：05 基金：π-Lewis酸/手性Br■nsted酸联合催化的不对称串联反应研究资助项目(21662035) 语种：中文; 页：91-95 页数：5 CN：11-2135/TQ ISSN：0258-3283 分类号：TQ224.5

摘要

报道了一种合成α,α-二溴甲基酮类化合物的新方法,该反应以硫醇作为还原剂,高效还原α,α,α-三溴甲基酮类化合物为目标化合物,合成了12种α,α-二溴甲基酮类化合物,该方法适用于脂肪族、芳香族和杂环类α,α,α-三溴甲基酮类化合物。最佳的反应条件是n(α,α,α-三溴甲基酮)∶n(还原剂)∶n(碳酸钾)=1∶2∶1. 2,二氯甲烷中0℃反应1 h,α,α-二溴甲基酮类化合物收率达81%～96%。其结构通过~1HNMR、~(13)CNMR、ESI-HRMS进行了表征和确认。该反应条件温和、操作简单、效率高,为α,α-二溴甲基酮类化合物的合成提供了新途径。
        A new method for synthesizing α,α-dibromomethylketones is reported.This reaction uses thiol as a reducing agent to efficiently reduce α,α,α-tribromomethylketones to target compounds.12 Kinds of α,α-dibromomethyl ketone compounds were suitable for aliphatic,aromatic and heterocyclic α,α,α-tribromomethyl ketones.The optimum reaction conditions are n( α,α,α-tribromomethylketone) ∶n( reducing agent) ∶n( potassium carbonate) = 1 ∶ 2 ∶ 1. 2,and reacted in dichloromethane at 0 ℃ for 1 h,The yield of α,α-dibromomethyl ketone compounds is 81% ～ 96%.The structure was confirmed by ~1HNMR,~(13)CNMR,ESI-HRMS.The protocol features mild conditions,simple operation and high efficiency,providing a new approach for synthesizing α,α-dibromomethylketones.

引文

[1]MAGLIOLI P,LUCCHI O D.Highly diastereoselective reduction and addition of nucleophiles to binaphthol-protected arylglyoxalsl[J]. Tetrahedron:Asymmetry,1992,3(3):365-366.
    [2]NEMERYUK M P,LIKHOVIDOVA M M,MITSEV I D,et al.Reaction of 4-methoxy(methylthio)-5-amino-6-mercaptopyrimidines withω,ω-dibromoacetophenone[J].Chem. Heterocycl. Compd.(Engl. Transl.),1986,22(4):468-469.
    [3]ARAK S,HIRASHITA T,SHIMIZU K,et al.Reaction ofα-halo organoindium reagents with carbonyl compounds and electron-deficient alkenes[J]. Tetrahedron,1996,52(8):2 803-2 816.
    [4]FURUKAWA J,MATSUMURA A,MATSUOKA Y,et al.The reaction of organic gem-dihalides with zerovalent transition metal complexes. An approach to organic synthesis[J].Bull.Chem.Soc.Jpn.,1976,49(3):829-830.
    [5]KAWABATA N,FUJII T,NAKA M,et al. Generation of ketocarbenoid byα-elimination ofω,ω-dibromoacetophenone with copper,and trapping by cycloaddition to olefins[J].Bull.Chem.Soc.Jpn.,1977,50(4):1 005-1 006.
    [6]KOWALSKI C J,REDDY R E.Ester homologation revisited:a reliable,higher yielding and better understood procedure[J].J.Org.Chem.,1992,57(26):7 194-7 208.
    [7]ZHDANKIN V V,STANG P J.Reaction of lithium alkynolates with acid chlorides:a conventional approach to the preparation of ynol esters[J]. Tetrahedron Lett.,1993,34(9):1 461-1 462.
    [8]DING Y X,HUANG X G.The design and synthesis ofβ-trifluoromethylenol phosphates as potential insecticides[J].Heteroat.Chem.,2003,14(4):304-308.
    [9]BOEYKENS M,KIMPE N. Selective transformation ofα,α-dibromomethyl ketones into a-monosulfenylated ketones[J].Tetrahedron,1994,50(43):12 349-12 360.
    [10]AHLUWALIA V K,MEHTA B,RAWAT M.An expeditious study of the nature of halogen(S)atγ-positions in carbonyl compounds[J]. Synth. Commun.,1992,22(18):2 697-2 701.
    [11]KOWALSKI C J,FIELDS K W.Alkynolate anions via a new rearrangement:the carbon analogue of the hofmann reaction[J].J.Am.Chem.Soc.,1982,104(5):321-323.
    [12]GHIACI M,ASGSARL J. Increasing the selectivity of bromination of aromatic compounds using Br2/Si O2[J].Bull.Chem.Soc.Jpn.,2001,74(6):1 151-1 152.
    [13]PRAVST I,ZUPAN M,STAVBER S.Halogenation of ketones with N-halosuccinimides under solvent-free reaction conditions[J]. Tetrahedron,2008,64(22):5 191-5 199.
    [14]LIU J H,LI W J,WANG C,et al.Selective 1,2-dihalogenation and oxy-1,1-dihalogenation of alkynes by Nhalosuccinimides[J].Tetrahedron,2011,52(33):4 320-4 323.
    [15]MAGEN S,OREN J,FUCHS B.Novel bromination reagents hexabromocyclopentadiene:bromination of activated saturated sites[J].Tetrahedron Lett.,1984,25(31):3 369-3 372.
    [16]TERENT'EV A O,KRYLOV I B,VIL V A,et al.Synthesis of dibromo ketones by the reaction of the environmentally benign H2O2-HBr system with oximes[J].Cent.Eur.J.Chem.,2012,10(2):360-367.
    [17]MADABHUSH S,JILLELLA R,MALLU K K R,et al.Vangipuram,V. S. A new and efficient method for the synthesis ofα,α-dihaloketones by oxyhalogenation of alkynes using oxone-KX(X=Cl,Br,or I)[J].Tetrahedron Lett.,2013,54(30):3 993-3 996.
    [18]YE C F,SHREEVE J M. Structure-dependent oxidative bromination of unsaturated C—C bonds mediated by selectfluor[J].J.Org.Chem.,2004,69(24):8 561-8 563.
    [19]NOBUTA T,HIRASHIMA S,TADA N,et al.Facile aerobic photo-oxidative syntheses of a,a-dibromoacetophenones from aromatic alkyneswith 48%aq HBr[J].Tetrahedron Lett.,2010,51(34):45 76-4 578.
    [20]TADA N,BAN K,ISHIGAMI T,et al.Tandem oxidation/bromination of ethyl aromatics toα,α-dibromoacetophenones with molecular oxygen under visible light irradiation[J].Tetrahedron Lett.,2011,52(29):3 821-3 824.
    [21]WU P,XU S H,XU H,et al.One-pot syntheses ofα,α-dibromoacetophenones from aromatic alkenes with 1,3-dibromo-5,5-dimethylhydantoin[J]. Tetrahedron Lett.,2017,58(7):618-621.
    [22]郭瑞霞,张宝华,史兰香,等.新方法合成α-溴代苯乙酮类化合物[J].化学试剂,2010,32(11):1 035-1 036.