2,3,4,4’2四羟基二苯甲酮合成研究王振宇,谭卫宁,周志纯,唐　浩(湖南化工研究院,湖南长沙410007)摘　要:以焦性没食子酸和对羟基苯甲酸为原料合成2,3,4,4’2四羟基二苯甲酮,通过正交实验对影响反应的因素进行考察,确定了优惠反应工艺条件,结果表明反应收率为83%,产品纯度达98%以上。

关键词:2,3,4,4’2四羟基二苯甲酮;焦性没食子酸;对羟基苯甲酸中图分类号:TQ22412　文献标识码:A　文章编号:1009-9212(2002)01-0018-02 2,3,4,4’2四羟基二苯甲酮[1,2]是一种重要的有机中间体,可用于微电子集成电路工业的光致抗蚀剂、医药中间体、紫外线吸收剂、树脂稳定剂、染料等,它在微电子工业方面主要是用作紫外正性光刻胶的感光剂中间体[3～5],此种光刻胶微细加工的芯片线宽达013～018μm。

目前,我国是世界上集成电路产业主要生产国之一,1999年大规模集成电路产量为21亿块,占全球产量的1/8,需i线紫外正性光刻胶100t/a,相应需要2,3,4,4’2四羟基二苯甲酮约5t/a。

我国一些科研院所已开发出i线紫外正性光刻胶,其产业化技术已列入“九五”国家攻关。

2, 3,4,4’2四羟基二苯甲酮的开发生产具有良好的市场前景。

2,3,4,4’2四羟基二苯甲酮的合成是经典的Friedel2Crafts酰基化反应。

文献报道的2,3,4,4’2四羟基二苯甲酮合成方法主要有氯化锌催化酰化法[6,7]、树脂催化法[8]、三氟化硼催化法[1,9]等。

笔者考察研究了三氟化硼催化法。

1　实验部分111　实验主要原料及其规格焦性没食子酸、对羟基苯甲酸、三氟化硼乙醚溶液、1,1,2,22四氯乙烷均为化学纯。

112　实验方法将焦性没食子酸、对羟基苯甲酸与1,1,2,22四氯乙烷混合,缓慢滴加三氟化硼乙醚溶液,加料毕,升温反应一定时间,析出黄色结晶,冷却后,中和,结晶过滤,水洗后干燥,得黄色结晶产物,即为本产品。

113　产品分析仪器型号:美国SSI2P4000型(带可变波长检测器)二元高压梯度液相色谱仪,保留时间测量和峰面积计算均由American Hi2Tech色谱工作站完成。

色谱柱:PRODIGY ODS(3)Φ4.60×250mm (5μm);柱温:室温;流动相:甲醇∶水=60∶40(V/ V)(少量H3PO4,1%二甲基甲酰胺);流速:0.8ml/ min;检测波长:300nm2　实验结果及讨论211　探索实验按上述的实验方法,进行探索实验,实验结果如表1所示:表1　探索实验结果表编号产品含量(%)收率(%)TB2198108015TB2298148112TB2399108019TB2498128016从表1可知,该工艺路线技术上可行,产品收率可达80%以上。

212　正交实验及验证实验由探索实验发现,影响2,3,4,4’2四羟基二苯甲酮合成的主要因素包括原料配比、催化剂量、反应温度、反应时间等,按4因素3水平进行正交实验,考查上述反应因素对反应结果的影响,优化反应条件,实验结果见表2～表4。

由表4正交实验分析方法计算所得的极差值(R)可知,4种反应因素对反应收率的影响顺序为: A(原料配比)、B(催化剂量)、D(反应时间)、C(反应温度),其中A(原料配比)的极差最大,表明其对反第32卷第1期2002年2月 精细化工中间体FIN E CHEM ICAL IN TERM EDIA TS Vol.32No.1February2002作者简介:王振宇(1970～),女,湖南长沙人,助理研究员,主要从事精细化工中间体开发研究。

收稿日期:2001-11-20应影响最大,对羟基苯甲酸量越大,焦性没食子酸的转化率越高,因而收率越高,再增加对羟基苯甲酸量,收率增加有限,从经济角度综合考虑选择A3作为最佳反应条件。

表2　正交实验因素水平表水平因 素A对羟基苯甲酸(g)B催化剂量(ml)C反应温度(℃)D反应时间(h)11214701001221318601101031512501208　注:焦性没食子酸加入量为1216g(0.10mol)表3　正交实验条件和结果表L9(34)编号正交条件产品含量(%)收率(%)TB28A1B1C1D197137616TB29A1B2C2D297187812TB210A1B3C3D398148010TB211A2B1C2D398167818TB212A2B2C3D199128015TB213A2B3C1D299108219TB214A3B1C3D298188215TB215A3B2C1D397178217TB216A3B3C2D198198219表4　正交实验数据处理结果分析水平收 率(%)A对羟基苯甲酸(g)B催化剂量(ml)C反应温度(℃)D反应时间(h)178137913801780112801780158010811238218821081108015极差值(R)415217110111从其它3个反应因素看,反应温度和反应时间这两个因素的极差值较小,说明这2个因素对反应的影响不大,因此从节省时间、节约能源和操作控制方便的角度考虑,选择催化剂量B3、反应温度C3、反应时间D2,即A3、B3、C3、D2为优惠反应条件。

以A3、B3、C3、D2优惠最佳反应条件进行验证实验,实验结果列于表5。

表5　优惠反应条件验证实验数据表编号正交条件产品含量(%)收率(%)TB220A3B3C3D299108312TB221A3B3C3D298188310TB222A3B3C3D298128219TB223A3B3C3D298178311TB224A3B3C3D299128314由表5可知,实验重复性很好,收率都达到83%以上,与文献报道值接近。

3　实验结论以三氟化硼为催化剂合成2,3,4,4’2四羟基二苯甲酮的反应条件温和,工艺简单易行,通过正交实验对影响反应收率的各种因素研究发现,原料配比对反应收率的影响最大,优惠反应条件为:焦性没食子酸与对羟基苯甲酸的摩尔比为1∶111,催化剂量为500ml(相对于1mol焦性没食子酸),反应温度为120℃,反应时间为10h,在此条件下产品收率达83%以上,产品纯度可达98%以上。

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[6]　小山慎一1ぺ 类の制造方法[P]1日本,特公开平62172252,1992-12-09.[7]　阿部善夫1 类の制造方法[P]1日本,特开平32167151,1988-11-27.[8]　安部卓1 ≠ 类の制造方法[P]1日本,昭612282235,1983-06-06.[9]　山田速生1 の制造法[P]1日本,昭61297240,1984-10-16.91第1期 王振宇,等:2,3,4,4’2四羟基二苯甲酮合成研究 The Analysis of the Market and Development of Organic Inter 2mediates in Asia.ZHA N G Xiao 2Qin ,et al.(S hanghaiDyestuf f s and Pesticide Indust ry Association ,S hanghai 200085)Chin.J.Fine chem.Intermediates ,32(1),2002,pp :3～7The current situation of the market of the organic intermedi 2ates used for manufacturing the fine chemicals in Asia was anal 2ysed in this paper ,and the recent development of the intermedi 2ate 2industry in China and India were reviewed and the key of de 2veloping intermediate 2market in Asia was pointed out.K ey w ords :Asia ;organic intermediates ;current situation of market ;developmental keyA R eview on the Synthesis and R esolution of DL -p 2hydrox 2yphenylglycine.Ren Guo 2bin ,et al.(Depart ment of Chemical Engineering ,Zheng Zhou U niversity ,Zhengahou 450002)Chin.J.Fine chem.Intermediates ,32(1),2002,pp :8～11A review is presented on the synthesis and resolution of DL 2p 2hydroxyphenylglycine.Five methods of synthesis and four methods of resolution are involved.K ey w ords :DL 2p 2hydroxyphenylglycine ;synthesis ;resolution The C atalytic Synthesis and Colour R eaction with Thorium of 1,2,3-tri (carboxylmethoxyl)benzene.ZHA N G Jian 2f eng ,et al.(Academy of Chemist ry and Chemical Engineering ,Cent ral South U niversity ,Changsha ,410083)Chin.J.Fine chem.Intermediates ,32(1),2002,pp :12～13A new reagent ,1,2,32tri (carboxylmethoxyl )benzene (TC 2MOB ),which is highly sensitive and selective chromogenic to the determination of thorium ,was catalytically synthesized from py 2rogallol ,chloroacetic acid and sodium hydroxide in a chloroform solvent.In a 2.5ml 4mol/L perchloric acid medium ,thorium reacts with TCMOB to form a stable 1∶1chelate ,which has a maximum absorption at 325nm.Beer ’s law is obeyed over the range of 0～30μg/25ml ,whereas the apparent molar absorptivi 2ty is 8.86×104L ・mol -1・cm -1.K eyw ords 1,2,32tri (carboxylmethoxyl )benzene ;synthe 2sis ;thoriumStudy on Synthesis of 1,2,32triazole.XIA O Guo 2min ,et al.(Depart ment of Chemist ry and Chemical Engineering ,South 2east U niversity ,N anjing ,210096)Chin.J.Fine chem.Inter 2mediates ,32(1),2002,pp :14～15S ome synthetic methods of 1,2,32triazole were introduced in this article.The process of preparation from p 2toluene sulfonyl hydrazine was selected for its advantages.Experiments were done to compare the different conditions of reaction ,and the o ptimal condition to synthesis of 1,2,32triazole was obtained as follows :p 2toluene sulfonyl hydrazine was prepared by reaction ofMeC 6H 4SO 2Cl (a )with H 2NNH 2・H 2O (b )in presence of ben 2zene as solvent and M ratio of a ∶b =1∶2at 60～70℃.Then high purity 1,2,32triazole was obtained by the reaction of p 2toluene sulfonyl hydrazide and glyoxal at M ratio 1∶2.7followed by the treatment of the intermediate with ammonia ,the yield over 66.8%.K ey w ords :1,2,32triazole ;p 2toluene sulfonyl hydrazine ;syn 2thesis ;β2lactam antibioticsA provement on the synthesis of methylene dinitrosamnc.L I S i 2nan ,et al.(Colloge of Chemical engineering ,Science and Technology U niversity of nanjing N anjing 210094)Chin.J.Fine chem.Intermediates ,32(1),2002,pp :16～17A new method for the synthesis of Methlene dinitrosaminc was presented from the hydrolysis of 2,4,62trinitro 22,4,62triaz 2cyclohexanone and purifying in chloroform.The yield was inereased to 60.8%.K ey w ords :methylene dinitrosaminc ;2,4,62trinitro 22,4,62triazcyclohexanone ;synthesisSynthesis Of 2,3,4,4’2T etrahydroxybenzophenone.W A N GZhen 2yu ,et al.(Hunan Research Institute of Chemical Indus 2t ry ,Changsha 410007)Chin.J.Fine chem.intermediates ,32(1),2002,pp :18～192,3,4,4’2tetrahydroxybenzophenone was synthesized with pyrogallol and p 2hydroxybenzoic acid ,and various factors of the reaction were investigated by the orthogonal experiment ,and the optimal reaction condition was described.The reaction yield and purity of 2,3,4,4’2tetrahydroxybenzophenone were above 83%and 98%.K ey w ords :2,3,4,4’2tetrahydroxybenzophenone ;synthesis Synthesis of 22methoxypropene.YA N G S hu 2min ,et al.(Xi ’an Modern Chemist ry Research Insitute ,Xi ’an 710065)Chin.J.Fine chem.intermediates ,32(1),2002,pp :20～2122Methoxypropene was obtained by the elimination of methanol from 2,22dimethoxypropane at 115℃gave the final compound.The distillation was 80.6%with the purity of 98%.The structure was confirmed by IR and 1HNMR.K ey w ords :22methoxypropene ;222methoxypropane ;prepa 2rationSynthesis of 3,42Dihydroxyl 252Nitrovanillic Acid.CHEN Yi 2ping,et al.(Dept.of Pharm aceutical chemist ry ,GuangxiCollege of T raditional Chinese Medicine ,N anning 530001)Chin.J.Fine chem.intermediates ,32(1),2002,pp :22～233,4-Dihydroxyl -5-nitrobenzoic acid was synthesizedVol.32No.1 FIN E CHEM ICAL IN TERM EDIA TS(Series No.136) February 2002。