Benziodoxole的合成

第24卷第1期苏州大学学报(自然科学版)Vol.24 No.12008年1月JOURNAL of SUZHOU UNIVERSITY( NATURAL SCIENCE EDITION)Jan. 2008Benziodoxole的合成*张丽,曾润生(苏州大学化学化工学院,江苏省有机合成重点实验室,江苏苏州215123) .摘要:以邻碘苯甲酸为原料制得邻碘苯甲酰氯,邻碘苯甲酰氯再和N-甲基苯胺反应得到N-甲基~N-苯基-(2-碘)苯甲酰胺,进一步氧化得到Benziodoxole.关键词: N-甲基~N-苯基-(2.碘)苯甲酰胺;Benziodoxole;合成中图分类号: 0627文献标识码: A文章编号:1000 - 2073(2008)01 -0068 -020引言自1885年著名化学家Willgerodt合成第一个有机高价碘化合物二氯碘苯(PhICl,)以来,多种类型的有机高价碘化合物相继诞生.有机高价碘化合物具有稳定性好、制备容易、多种反应活性及环境友好等特点,在近二十年得到了迅速的发展“,2),广泛应用于有机合成.在过去十年里,人们对三价碘杂环化合物”进行了广泛的研究,其中研究最多的就是Benziodoxole,由于其碘上的基团可以被其它各种各样的基团所取代-4e),从而形成一系列Benziodoxole的衍生物.文献报道的Benziodoxole的合成方法主要有以下四种:由邻碘甲苯60C时在硝酸银和过硫酸钠的混合溶液中氧化而成[);由邻碘苯甲酸和氯气反应,三氯甲烷做溶剂，首先得到二氯碘化物,然后酸化得到产物'0;由邻碘苯甲酸酯在0C ~5C条件下，四氯化碳做溶剂,与氯气反应,最后加入碳酸氢钠水溶液制得[”;由复杂化合物断裂而成[8].本文以邻碘苯甲酸为原料制得邻碘苯甲酰氯,邻碘苯甲酰氯再和N-甲基苯胺反应得到N-甲基-N苯基-(2-碘)苯甲酰胺,进一步氧化得到Benziodoxole. 该反应条件温和、所用试剂毒性较低、方法简便.反应方程式如下:SOCl2)H60°CCIOH.cl + HNCH2Cb_AcOOH +0C01实验部分1.1仪器熔点(m. p. )用四川大学科仪厂的显微熔点测定仪测定,熔点未校正.核磁由Varian UNITY INOVA 400MHz核磁共振仪测试(溶剂用DMSO-d。,内标物用TMS).元素分析用CarloErba110型元素分析仪测定.中国煤化工MHCNMHG*收稿日期: 2007-10-14基金项目:国家自然科学基金资助项目(20772088)作者简介:张丽(1981-),女(汉族) ,山东临沂人,苏州大学化学系有机专业研究生,主要从事有机合成研究.第1期张丽,曾润生:Benziodoxole 的合成61.2邻碘苯甲 酰氯的制备在三颈烧瓶中加人(2.48g,10mmol)的邻碘苯甲酸,滴加几滴N,N-二甲基甲酰胺作为催化剂,用恒压滴液漏斗滴加5mL二氣亚砜,油浴60C反应3h.反应结束后,水泵减压蒸馏除去过量的二氯亚砜,然后油泵减压蒸馏得邻碘苯甲酰氯,产率90%.1.3 N甲基-N-苯基-(2-碘)苯甲酰胺的合成冰浴条件下,在反应瓶中加人N-甲基苯胺(1.07g, 10mmol). CH2C2 (50mL)、三乙胺(2. 78ml,20. 0mmol) ,搅拌条件下缓慢滴加2-碘苯酰氯(2.67g, 10mmol).冰浴反应2h,反应结束后加人40mL水.分层,用10%的盐酸溶液(50mL)洗涤有机层,再用5%的氢氧化钠水溶液(2x25mL)洗涤有机层.然后用无水硫酸镁干燥、真空浓缩得粗产品.经重结晶得产物2.79g,产率83%.1.4 Benziodoxole 的合成^向N-甲基-N苯基-<2-碘)苯甲酰胺(1.81g,5: 4mmol)中滴加过量过氧乙酸溶液,反应2h,加入冷水,有白色沉淀生成,过滤、水洗.干燥,得产物0.98g,产率69% ,m. p.219C ~2219C.'H NMR( 400 MHz, DMSO -d;):87.96 ~8. 09( m,2H,ArH),7. 85~ 7.87(d,1H,J = 8Hz, ArH),7.72(t,1H,J =7.2Hz, ArH),"C NMR( 100 MHz, DMSO - d。) :8120. 5,126. 3,130.4,131.3,131.5,134.5,167. 8. A-nal. Calced for C,H,O31:C,31. 84% ;H,1. 91% . Found:C,31.34% ;H,1. 91%.2结果与讨论制备邻碘苯甲酰氯的仪器应保证干燥,滴加DMF作为催化剂可使产率大大提高原料N-甲基=N~苯基-(2-碘)苯甲酰胺的制备采用新的合成方法,用二氯甲烷代替苯做溶剂,采用低温反应,产率较为理想. Benziod-oxole的制备,反应条件温和,所用试剂毒性较低,操作简便..参考文献:[1 ] Mico D A, Margaria R, Parlanti L. A Versatile and highly selective hypervalent lodine( 1)/2 ,2 ,6 ,6-tetramethyl-1 -piperidinylox.-yl-mediated oxidation of alcohols to carbonyl compounds[J].J Org Chem, 1997 ,62 :6974 - 6977.[2] Stang P J,Zhdankin v V. 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Tetrahedron Lett ,2007 ,48 :4297 - 4300Sulfamic acid-catalyzed direct amidation of benzhydryl alcoholZhang Lli , An Litao , Ding Feiqing , Zou Jianping(School of Chemistry and Chemical Engineering,Key Labortory of Oranie Synbeis of Jiangu Province ,Suzhou University ,Suzhou 215123 ,China)Abstract: SA ( sulfamic acid) catalyzed the amidation of benzhydryl alcohol in good to excellent yields under sol-vent-free condition. SA is cheaper，more stable and more environment benign than those previously used catalysts forthe similar reactions.Key words: benzhydryl alcohol ;sulfamic acid;environmentally benign;solvent fre(责任编辑:耳东)(上接第69页)Synthesis of benziodoxoleZhang Li,Zeng Runsheng(School of Chermistry and Chemical Engineering, Key Laboratory of Organic Syithesis of Jiangu Province ,Suzhou University ,Suzhou 215123 ,China)Abstract: 2-lodobenzoic acid reacted with thionyl chloride to give 2-iodobenzoyl chloride , which reacted with N-methybenzenamine to afford 2-iodo-N -methyI-N- phenylbenzamide. The latter was oxidated by peracetic acid to formtitle compound.Key words: 2-iodo-N-methyl-N-phenylbenzamide ;synthesis ;benziodoxole中国煤化工MYHCNMHG