2007年第15卷合成化學(xué)第5期,595~596Chinese Joumal of Synthetic ChemistryNo.5,595-596快遞論文·4氯苯乙醇的合成徐建平,徐剛,吳堅(jiān)平,楊立榮(漸江大學(xué)材料與化學(xué)工程學(xué)院浙江杭州310027)摘要:以4氯苯乙酸為起始原料耦合酯化和還原反應(yīng)合成了4氯苯乙醇(1),其結(jié)構(gòu)經(jīng)HNMR和MS表征較適宜的反應(yīng)條件為4氯苯乙酸30mml,無水乙醇120mml,n(4氯苯乙酸):n(SOC2):n(NaBH1.0:0.5:16,于室溫反應(yīng)3b完成酯化反應(yīng),產(chǎn)物不經(jīng)分離直接于75℃反應(yīng)5h完成還原反應(yīng)收率高于95%,含量大于9%關(guān)詞:氯苯乙酸;氯苯乙醇;酯化反應(yīng);還原反應(yīng);合成中圖分類號(hào):TQ225.1;06213文獻(xiàn)標(biāo)識(shí)碼:A文章編號(hào):1005-1511(2007)0509502Synthesis of 2(4-Chlorophenyl)ethanolXU Jian-ping, XU Gang, WU Jian-ping, YANG Li-rongDepartment of Materials Science and Chemical Engineering, Zhejiang University, Hangzbou 310027, China)Abstract: 2-(4-Chlorophenyl)ethanol(1)was synthesized by esterification and reduction from 2(4chlorophenyl)acetic acid(3). The structure was characterized by H NMR and MS. The appropriatereaction conditions were as follows: 3 was 30 mmol, ethanol was 120 mmol, n(3):n(SOCl,): n( NaBH )was 1.0: 0.5: 1.6. The yield of I was ower 95% by esterification at room temperature for3 h and reduction at 75C for 5 hKeywords: chlorophenyl-acetic acid; chlorophenyl-ethanol; esterification; reduction; synthesis腈苯唑是一種高效、低毒的三唑類殺菌劑。Avance DMX400型核磁共振儀(CDCl2為溶合成腈苯唑一般以4氯苯乙醇(1)為原料但是1劑TMS為內(nèi)標(biāo));島津CC14C,HPCS6890,的合成方法在國內(nèi)還鮮見報(bào)道,沒有成熟的工藝,Ms93氣相色譜質(zhì)譜聯(lián)用儀。相關(guān)的文獻(xiàn)也較少。我們參考合成類似化合物的3,工業(yè)品;硼氫化鈉,含量9%;其余所用試文獻(xiàn){4方法提出了一條新的簡潔、環(huán)保、高效的合成1的路線劑均為分析純。本文以4氯苯乙酸(3)為起始原料耦合酯化和還原反應(yīng)合成了1( Scheme1),其結(jié)構(gòu)經(jīng)1.21的合成HNMR和M表征。在三口反應(yīng)瓶中加人317.23g(100mmo)和無水乙醇1843g(400mml),攪拌下在30min實(shí)驗(yàn)部分內(nèi)滴加氯化亞砜(SOc2)599g(50mmol),滴畢,1.1儀器與試劑反應(yīng)3h(酯化反應(yīng)結(jié)束)。冰浴下用30%NaOH收稿日期:20070516中國煤化工基金項(xiàng)目:國家自然科學(xué)基金資助項(xiàng)目(20606030)CNMHG作者簡介:徐建平(1982-),男漢族上海人在讀碩士,主要從事有口H通訊聯(lián)系人:楊立榮教授博士生導(dǎo)師,T.057187952363, E-mail: Ryang如,dum合成化學(xué)vdL.15,2007OH SOCL, EtOHOEt NaBh, EtoHH20℃,3.5h75℃,5hC溶液調(diào)節(jié)pH值至弱堿性。室溫下在1h內(nèi)滴加330mmol,無水乙醇120mmol,s0cl215硼氫化鈉(NaBH4)6.31g(160mmo)的水(10mmod,其余反應(yīng)條件同1.2,考察NaBH用量對合mL)溶液滴畢,回流反應(yīng)4h(還原反應(yīng)結(jié)束)。成1的影響結(jié)果見表2。由表2可知,NaBH4用量冰浴下用10%鹽酸調(diào)節(jié)pH值至弱酸性用乙酸為48mmol時(shí)[n(3):n(NBH)=1.0:1.6],1收乙酯(3×30m)萃取合并有機(jī)層,經(jīng)脫溶、干燥率高于95%,含量接近9%得無色液體115.03g,收率95.1%,含量99.1%;HNMR8:7.27(d,J=84H,2H,ArH),2.3還原反應(yīng)溫度與時(shí)間的對應(yīng)關(guān)系7.14(d,J=8.4Hz,2H,ArH),3.79(t,J330mmol,無水乙醇120mmol,socl215136H,16.8H,2H,CH1OH),27(t,J=mm,№BH48mo,其余反應(yīng)條件同2,166出,132H,2H,ACH2),235(b,1H,收率高于95%,含量大于99%時(shí)結(jié)束反應(yīng),反應(yīng)OH);EMSm/z(%):156(M’,32),125溫度與反應(yīng)時(shí)間的對應(yīng)關(guān)系見表3。由表3可(100),99(8),91(37),63(12)。知當(dāng)還原反應(yīng)溫度為75℃時(shí),反應(yīng)僅需5h2結(jié)果與討論3還原反應(yīng)溫度對合成1的影響Table 3 Eect of reduction temperature on yield of 12.1SoCl2用量對合成1的影響反應(yīng)溫度/2040607075330mmol,無水乙醇120mml,NaBH460反應(yīng)時(shí)間h4820137mmol,其余反應(yīng)條件同1.2,考察Socl2用量對合s0215mmol,NaBH48mmol,其余反應(yīng)條件同成1的影響結(jié)果見表1。由表1可知,Socl2用表1,1收率高于95%,含量大于99%時(shí)結(jié)束反應(yīng)量為15mmol時(shí)[n(3):a(Socl2)=1.0:0.5],1收率高于95%,含量接近99%。綜上所述合成1的較適宜反應(yīng)條件為330mmd,無水乙醇120mmol,n(3):n(SoCl2):n1S0C2用量對合成1的影響(NaBH4)=1.0:05:1.6,于室溫反應(yīng)3h完成Table 1 Eect of soCl amount on yield of 1酯化反應(yīng),產(chǎn)物不經(jīng)分離直接于75℃反應(yīng)5h完101520353成還原反應(yīng)1收率高于9%含量大于99%含量/%95.498.599.299.199.5收率%928954參考文獻(xiàn)395.796.1330mml,無水乙醇120mml,NaB460mmol,其1 I Rohm and Haas Company.,1-and4 arylcyano-alkyl-1余反應(yīng)條件同122, 4-triazoles and fungicidal useIP]表2·NBH用量對合成1的影響[2]Table 2 .Eect of Nabh, amount on yield of 1yl-lH-1, 2, 4-trinazole-l-propanenitriles[P].EP 0251NaBh/mmol 30 45.48 60 90775,1988含量/%75.696298.599.499.3[3] Rohm and Haas Compamy. Process for alkylation withtriazoles[P].US5510493,1996收率%70.193.8%5295.5964[4]中國煤化工)M.北京化socl215mmol,其余反應(yīng)條件同表1HCNMHG生有機(jī)合成中的2.2NaBH4用量對合成1的彩響研究進(jìn)展[J]應(yīng)用化學(xué),2002,19(5):409-415