第24卷第1期蘇州大學(xué)學(xué)報(自然科學(xué)版)Vol.24 No.12008年1月JOURNAL of SUZHOU UNIVERSITY( NATURAL SCIENCE EDITION)Jan. 2008Benziodoxole的合成*張麗,曾潤生(蘇州大學(xué)化學(xué)化工學(xué)院,江蘇省有機合成重點實驗室,江蘇蘇州215123) .摘要:以鄰碘苯甲酸為原料制得鄰碘苯甲酰氯,鄰碘苯甲酰氯再和N-甲基苯胺反應(yīng)得到N-甲基~N-苯基-(2-碘)苯甲酰胺,進(jìn)一步氧化得到Benziodoxole.關(guān)鍵詞: N-甲基~N-苯基-(2.碘)苯甲酰胺;Benziodoxole;合成中圖分類號: 0627文獻(xiàn)標(biāo)識碼: A文章編號:1000 - 2073(2008)01 -0068 -020引言自1885年著名化學(xué)家Willgerodt合成第一個有機高價碘化合物二氯碘苯(PhICl,)以來,多種類型的有機高價碘化合物相繼誕生.有機高價碘化合物具有穩(wěn)定性好、制備容易、多種反應(yīng)活性及環(huán)境友好等特點,在近二十年得到了迅速的發(fā)展“,2),廣泛應(yīng)用于有機合成.在過去十年里,人們對三價碘雜環(huán)化合物”進(jìn)行了廣泛的研究,其中研究最多的就是Benziodoxole,由于其碘上的基團可以被其它各種各樣的基團所取代-4e),從而形成一系列Benziodoxole的衍生物.文獻(xiàn)報道的Benziodoxole的合成方法主要有以下四種:由鄰碘甲苯60C時在硝酸銀和過硫酸鈉的混合溶液中氧化而成[);由鄰碘苯甲酸和氯氣反應(yīng),三氯甲烷做溶劑，首先得到二氯碘化物,然后酸化得到產(chǎn)物'0;由鄰碘苯甲酸酯在0C ~5C條件下，四氯化碳做溶劑,與氯氣反應(yīng),最后加入碳酸氫鈉水溶液制得[”;由復(fù)雜化合物斷裂而成[8].本文以鄰碘苯甲酸為原料制得鄰碘苯甲酰氯,鄰碘苯甲酰氯再和N-甲基苯胺反應(yīng)得到N-甲基-N苯基-(2-碘)苯甲酰胺,進(jìn)一步氧化得到Benziodoxole. 該反應(yīng)條件溫和、所用試劑毒性較低、方法簡便.反應(yīng)方程式如下:SOCl2)H60°CCIOH.cl + HNCH2Cb_AcOOH +0C01實驗部分1.1儀器熔點(m. p. )用四川大學(xué)科儀廠的顯微熔點測定儀測定,熔點未校正.核磁由Varian UNITY INOVA 400MHz核磁共振儀測試(溶劑用DMSO-d。,內(nèi)標(biāo)物用TMS).元素分析用CarloErba110型元素分析儀測定.中國煤化工MHCNMHG*收稿日期: 2007-10-14基金項目:國家自然科學(xué)基金資助項目(20772088)作者簡介:張麗(1981-),女(漢族) ,山東臨沂人,蘇州大學(xué)化學(xué)系有機專業(yè)研究生,主要從事有機合成研究.第1期張麗,曾潤生:Benziodoxole 的合成61.2鄰碘苯甲 酰氯的制備在三頸燒瓶中加人(2.48g,10mmol)的鄰碘苯甲酸,滴加幾滴N,N-二甲基甲酰胺作為催化劑,用恒壓滴液漏斗滴加5mL二氣亞砜,油浴60C反應(yīng)3h.反應(yīng)結(jié)束后,水泵減壓蒸餾除去過量的二氯亞砜,然后油泵減壓蒸餾得鄰碘苯甲酰氯,產(chǎn)率90%.1.3 N甲基-N-苯基-(2-碘)苯甲酰胺的合成冰浴條件下,在反應(yīng)瓶中加人N-甲基苯胺(1.07g, 10mmol). CH2C2 (50mL)、三乙胺(2. 78ml,20. 0mmol) ,攪拌條件下緩慢滴加2-碘苯酰氯(2.67g, 10mmol).冰浴反應(yīng)2h,反應(yīng)結(jié)束后加人40mL水.分層,用10%的鹽酸溶液(50mL)洗滌有機層,再用5%的氫氧化鈉水溶液(2x25mL)洗滌有機層.然后用無水硫酸鎂干燥、真空濃縮得粗產(chǎn)品.經(jīng)重結(jié)晶得產(chǎn)物2.79g,產(chǎn)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)中滴加過量過氧乙酸溶液,反應(yīng)2h,加入冷水,有白色沉淀生成,過濾、水洗.干燥,得產(chǎn)物0.98g,產(chǎn)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結(jié)果與討論制備鄰碘苯甲酰氯的儀器應(yīng)保證干燥,滴加DMF作為催化劑可使產(chǎn)率大大提高原料N-甲基=N~苯基-(2-碘)苯甲酰胺的制備采用新的合成方法,用二氯甲烷代替苯做溶劑,采用低溫反應(yīng),產(chǎn)率較為理想. Benziod-oxole的制備,反應(yīng)條件溫和,所用試劑毒性較低,操作簡便..參考文獻(xiàn):[1 ] Mico D A, Margaria R, Parlanti L. 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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(責(zé)任編輯:耳東)(上接第69頁)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中國煤化工MYHCNMHG