第28卷第2期凌瑩等:用Witting反應(yīng)合成三苯甲基取代烯烴111化學(xué)試劑,2006,28(2),111~112用Witting反應(yīng)合成三苯甲基取代烯烴凌瑩,陽年發(fā)" ,楊利文,肖亮(湘潭大學(xué)化學(xué)學(xué)院,湖南湘潭411105)摘要:利用Wittig 反應(yīng),合成了(E)-5,5,5-三苯基-2-戊烯和2-甲基-5,5 ,5-三苯基-2-戊烯兩種三苯甲基取代的烯烴。探討了影響反應(yīng)的各種因素,并找到了較好的合成條件。關(guān)鍵詞:Wittig反應(yīng);三苯甲基;非官能團(tuán)烯烴;制備中圖分類號(hào):0625. 12文獻(xiàn)標(biāo)識(shí)碼:A文章編號(hào):28328320020111-02含有大體積基團(tuán)的烯烴是合成螺旋型手性聚產(chǎn)率63.1%。m.p.115~ 116C。'HNMR(CDClz),8:合物的重要單體[1],因?yàn)榇篌w積基團(tuán)的位阻作用1.49(d,3H,J = 6.3Hz);3.36(d,2H, J= 5.7Hz);可以使烯烴在其聚合過程中形成螺旋結(jié)構(gòu),因此5.28(m, 1H) ;5.36(m, 1H) ;7.18 ~ 7.32(m,15H)。近幾年來這類化合物的合成引起了人們的關(guān)注。1.2.22-甲基-5,5,5-三苯基-2-戊烯 的合成，Okamoto2l在1990年用Wittig 反應(yīng)制備了3,3,3-其合成方法與1.2.1合成方法相同。氮?dú)獗Ｈ交?然后用相似的方法又相繼合成了4,護(hù)下將4.0g( 10mmol)異丙基三苯基溴化鏻懸浮于4,4三苯基-2-丁烯和1,1,1-三苯基2-戊烯兩種三40mL無水四氫呋喃中，在-78C下緩慢滴加.苯甲基取代烯烴。我們利用Wittig 反應(yīng),合成了7.6mL 1.3mol/L的正丁基鋰。滴畢，將反應(yīng)混合兩種新的三苯甲基取代烯烴(E)-5,5,5-三苯基-2-物置于室溫下攪拌1h, 再將反應(yīng)混合物冷至戊烯和2-甲基-5,5,5-三苯基-2-戊烯。- 78C,緩慢滴加20mL溶有2.0g(7mmol) 3,3,3-三苯基丙醛的四氫呋喃溶液。滴畢,在室溫下繼1實(shí)驗(yàn)部分續(xù)攪拌12h。后處理同1.2.1 ,得1.6g白色針狀晶1.1主要儀器與試劑體,產(chǎn)率73.3%。m.p.80 ~ 82C。'HMR(CDClz),BrukerAV400核磁共振儀;X4型數(shù)字顯示顯8:1.39(s, 3H); 1.55(s, 3H);3.31(d,2H,J =微熔點(diǎn)測定儀(北京泰克儀器有限公司)。6.7Hz);5.02(t,1H,J = 6.7Hz);7.17 ~ 7.27(m,乙基三苯基溴化轔、異丙基三苯基溴化轔參15H)。照文獻(xiàn)[3]自制;正丁基鋰參照文獻(xiàn)[4]自制;3,3,3-三苯基丙醛參照文獻(xiàn)[5]自制;四氫呋喃(氮?dú)?結(jié)果與討論.保護(hù)下加金屬鈉回流,二苯甲酮為指示劑,蒸出后我們通過Wittig 反應(yīng)合成了(E)-5,5,5-三苯備用);正己烷、正丙醇均為分析純?cè)噭?。?2-戊烯和2-甲基-5,5,5-三苯基-2-戊烯,反應(yīng)式1.2合成方法如下。1.2.1 (E)-5,5,5-三苯基-2-戊烯 的合成CnHCHj(CH,),Br ncmhyu-CH,CH-iP(CH)s將3.9g( 10mmol)乙基三苯基溴化鏷加人到THF100mL三口瓶中,氮?dú)獗Ｗo(hù)下加人40mL無水四氫PhyCCH2CHOhsCCH2呋喃,開動(dòng)電磁攪拌使之溶解,在- 78C下緩慢滴CH,加7.6mL 1.3mol/L的正丁基鋰,溶液逐漸變?yōu)榻?CH)2CHP(CH)Brn-CyHgLi-(CH)2C- -P(G&H),紅色。滴畢,將反應(yīng)混合物置于室溫下攪拌1h,溶液變成暗紅色。此時(shí)再將反應(yīng)混合物冷至PhyCCH,HC- -C(CH)2- 78C ,緩慢滴加20ml溶有2.0g(7mmol) 3,3,3-三苯基丙醛的四氫呋喃溶液。滴畢,在室溫下繼.收稿日期:2005-06-11續(xù)攪拌12h。將反應(yīng)液倒人40mL正己烷中,靜置基金項(xiàng)目:國家自然科學(xué)基金(20472069)資助項(xiàng)目。2h,過濾除去沉淀,旋干濾液,剩余的油狀物經(jīng)冷作者簡介:凌瑩(1980-),女,浙江湖州人,碩士生,主要研究凍固化后用正丙醇重結(jié)晶,得1.3g白色粒狀晶體，方向?yàn)橛袡C(jī)合成。112化學(xué)試劑2006年2.1正丁基鋰的用量對(duì)產(chǎn)率的影響[1]Nakano T,0kamoto Y . Synthetic helical polymers: Conforma-在合成這兩種烯烴的過程中，發(fā)現(xiàn)正丁基鋰tion and function[J]. Chem. Rev. , 2001 , 101 (12): 4013-的用量對(duì)產(chǎn)率是有影響的。當(dāng)正丁基鋰與季轔鹽4038.[2]Shi Min, Okamoto Y . Photolysis of 1,1, 1-rayalk 2-enes and(乙基三苯基溴化鏷或異丙基三苯基溴化轔)的物1,1, 1-tiaryhept-2-ynes. A novel generation of aryl( ak-1-質(zhì)的量比小于1時(shí),產(chǎn)率隨正丁基鋰用量的增加enyI) cearbenes and arl(alk-1-ymy1) carbenes[J]. J. Chem.而增加;反之,當(dāng)正J基鋰與季轔鹽的物質(zhì)的量比Soc. Perkin Trans. 1 , 1990:2443-2450.大于1時(shí),產(chǎn)率隨正丁基鋰用量的增加而減少。[3]Fagerlund U H M, ldler D R. Marine sterols. IV .24-Dehydro-這可能是過量的正丁基鋰使醛發(fā)生羥醛縮合副反cholesterol :Isolation from a barmacle and synthesis by the wit-應(yīng)而導(dǎo)致產(chǎn)率下降。實(shí)驗(yàn)結(jié)果表明,正丁基鋰與tig reaction[]. J. Am. Chem. Soc. , 1957 , 79(24):6473-季轔鹽的最佳物質(zhì)的量比為0.98。6475.2.2滴加3,3,3-三苯 基丙醛溶液的溫度對(duì)產(chǎn)率[4]謝如剛.有機(jī)合成試劑制備手冊(cè)[M].成都:四川大學(xué)出版社, 1988.7-78.的影響在10C滴加3,3,3-三苯基丙醛溶液時(shí),未得[5]Curtn D Y, Hurvitz M J. Free radical rearangements in thedecarbonyaion of aldehydes[J]. J. Am . Chem . Soc. , 1952,到(E)-5,5,5-三苯基-2-戊烯和2-甲基-5,5,5-三苯74(21) :5381-5387.基-2-戊烯。溫度在-90~-15C范圍內(nèi)變化時(shí),產(chǎn)率降低比較平緩,溫度高于- 15C后,產(chǎn)率降低The synthesis of tripbenylmethyl substituted olefn visa Witing較大。這可能是在較低的溫度下抑制了3,3,3-三.reaction LING Ying， YANG Nianfa" ，YANG Li-wen, XIAO苯基丙醛發(fā)生羥醛縮合等副反應(yīng)。iang ( Department of chemistry , Xiangtan University，Xiangtan反應(yīng)結(jié)束后將反應(yīng)混合物倒人正己烷中，411105 , China) , Huaxue Shji ,2006 ,28(2),111~ 112主要是為了使副產(chǎn)物三苯基氧化膦以沉淀的形式Abstract:( E)-5,5,5-triphenylpent-2-ene and 2-methy)-5,5,5-triphenylpent-2-ene were synthesized via Witig reaction.The fac-析出，以便通過過濾除去。靜置2h,三苯基氧化tors affecting reaction were discussed and the optimum reaction膦已析出完全。conition was found.Key words: Witig reaction; triphenylmethyl; simple olefin;參考文獻(xiàn):preparation(上接第70頁)Chemical Engineering, Anyan Institute of Technology ，Anyang[9]牛永生,邱明艷,李建平.芳?；蓟嫉衔锏暮?5000,0 China) , Huaxue Shiji , 2006 ,28(2) ,68 ~ 70;112成[J].應(yīng)用化學(xué),2005 , 22(1): 108-110.Abstrat:Thirteen acyldiazene compounds were synthesized. witha yield between 84% ~ 94% using sodium bromate as the oxida-Synthesis of acyldiazenes using NaBrO3/H,SO, as oxidationtion reagent in sulfuric acid . Their structures were confirmed byreagents NIU Yong sheng'.2 , U Jian-ping "' , ZHENG Peng- zhil'IR,' HNMR and elemental analysis . The reaction mechanism has(1. College of Chemistry and Environmental Science , Henan Nor-been discused.mal University , Key Laboratory of Environmental Pollution ContolKey words: acylhydrazines; acyldiazenes; NaBrOz/H2SO4; syn-of Henan Province , Xinxiang 453007, China; 2. Department ofthesis(上接第110頁)(State Key Laboratory of Fine Chemicals, Dalian University of[6]Olah G A,Parker D C, Yoneda N,et al. OxfuntionalizationTechnology , Dalian 116012 , China)，Huaxue Shiji,2006, 28(2), .109~ 110;112of hydrocarbons. 1. Protolytic cleavage- rearrangement reac-Abstract: 8-Amyl hydroperoxide (TAHP) was synthesized by antions of tertiary alkyI hydroperoxides with magie acid[J].J.improved method using t-amy! alcohol, hydrogen peroxide andAm. Chem . Soc. ,1976,98(8) :2245-2250.sulfurie acid. The optimal condition is: temperature 35C , time[7 ]Philpotts A R, Thain W . Infrared absorption spectra of teriary2h, mol ratio 1:1:1.The reaction time was reduced from 24h toperoxides[J] . Anal. Chem. , 1952 ,24(4) :638-643.2h and the yield improved from 38% to 68% . The structure ofTAHP was identifed by IR,' HNMR and BCNMR.Improvement in synthetic method of t-amyl hydroperoxideKey words: t-amyl hydroperoxide; 8-amyl alcohol; synthesis;ZHOU Xin-rui* , U Jian-yuan, ZHAO Defeng, WANG LinTAHP