第38卷第6期太原理工大學(xué)學(xué)報(bào)Vol 38 No 62007年11月OURNAL OF TAIYUAN UNIVERSITY OF TECHNOLOGYNov.2007文章編號(hào):1007-9432(2007060507-02N,N-二乙氨基乙醇己酸酯的合成魏文瓏,侯忠德,常宏宏,王靜,王志忠(太原理工大學(xué)化學(xué)與化工學(xué)院,山西太原030024)摘要:以NN-二乙氛基乙醇和己酸為原料,在氯化鈣催化劑的存在下合成了N,N-二乙氯基乙醇己酸酯?？疾炝朔磻?yīng)瞎劑及用量、反應(yīng)時(shí)間、催化劑用量及重復(fù)利用次數(shù)、原料摩爾比等對(duì)反應(yīng)的影響,得到了最佳工藝親件,即溶劑為環(huán)已烷且為80mL,反應(yīng)時(shí)間6h,氧化鈣1.0gNN-二乙氯基乙醇與己酸的摩爾比為1:1。此條件下的最高收率為85.96%,產(chǎn)物經(jīng)紅外光譜和氣相色譜分析,純度達(dá)98.76%關(guān)攏詞:N,N-二乙敷基乙醇己酸酯;合成;氧化鈣;環(huán)己烷中圖分類號(hào):TQ463文獻(xiàn)標(biāo)識(shí)碼:A乙氨基乙基羧酸酯是近年來開發(fā)應(yīng)用的一類FTIR-8400S型紅外光譜儀,日本島津公司;高效植物生長(zhǎng)調(diào)節(jié)劑口。該類化合物具有生長(zhǎng)素、DRⅹ3000核磁共振儀,瑞士布魯克公司;LC赤霉素及細(xì)胞分裂素的多種功能通過增強(qiáng)植物光10ATVP型高效液相色譜儀,日本島津公司;SP合作用和植物酶活性,促進(jìn)細(xì)胞分裂、伸長(zhǎng)和植株碳2100型氣相色譜儀,北京北分瑞利分析儀器公司。氮代謝等,具有增產(chǎn)、早熟改善品質(zhì)及抗病、抗逆功1.2合成路線效。其中N,N-二乙氨基乙醇己酸酯(俗稱DA是該類化合物的典型代表,它能誘導(dǎo)植物體內(nèi)P胡CH,(CH,). COOH+HOCH, CH,N(C2 Hs )2蘿卜素的合成,提高P胡蘿卜素的含量;還可大幅CH,(CH, ) COOCH, CH,N(C Hs)2+H,O.度提高作物的產(chǎn)量,顯著改善產(chǎn)品的品質(zhì)4;并以13實(shí)驗(yàn)步驟其高效、低毒、使用安全、生產(chǎn)使用成本低等特點(diǎn)而在裝有機(jī)械攪拌、溫度計(jì)、分水器和回流冷凝管倍受青睞,早已在日本等國(guó)家被廣泛應(yīng)用于蔬菜油的250mL三口燒瓶中加入117g(0.1mol)N,N料、糧食等作物,目前國(guó)內(nèi)正在大面積推廣使用中二乙氨基乙醇、11.6g(0.lmol)己酸、適量環(huán)己烷目前,DA6的合成方法主要有固體酸催化和氯化鈣,加熱回流分水反應(yīng)3~9b,反應(yīng)溫度維法酰氯法、有機(jī)酸催化法和非酸催化劑催化持在80℃.反應(yīng)完成后抽濾除去氯化鈣,濾液先常法1四種。其中固體酸催化法收率較高,但催化壓蒸餾除去環(huán)己烷再減壓蒸餾收集146~150℃/劑制備繁瑣,生產(chǎn)工藝復(fù)雜;酰氯法所使用的二氯亞0.0875MPa下的餾分,得淺黃色透明液體,收率為砜極易水解,運(yùn)輸貯存都不方便,且對(duì)設(shè)備的腐蝕85.96%。經(jīng)氣相色譜分析純度為98.76%。IR性較強(qiáng)不易實(shí)現(xiàn)工業(yè)化;有機(jī)酸催化收率不是很(mx,cm1):1737(C=0),1244,1099(C-N),高,且催化劑與二乙氨基乙醇成鹽與反應(yīng)體系互溶,1171(00C),1068(0-C-C),1466,1294(C后處理難度較大;非酸催化劑催化法報(bào)道中用到的H)。HNMR(,CDCl/TMS):4.13(2H,t酞酸四丁酯價(jià)格較貴,成本較高。本實(shí)驗(yàn)嘗試了未 COO--CH2-),2.70(2H,t,O-C-CH2-N)見文獻(xiàn)報(bào)道的氯化鈣作催化劑和環(huán)已烷作帶水劑,2.53(4H,t,2x-NCH2),2.30(2H,t探索了合成N,N二乙氨基乙醇己酸酯的方法。該CH2-CO-),1.59(2H,m,C-C-C—CH2-)方法操作簡(jiǎn)單、能耗低、易于工業(yè)化1.32(2H,m,C-C-CH2-),1.05(6H,t2x-N一C—CH3),0.90(3H,t,CH3)。1實(shí)驗(yàn)部分1.I試劑與儀器己酸、二乙氨基乙醇、環(huán)已烷氯化鈣為分析純收稿日期:2006-0522作者簡(jiǎn)介:魏文黨(1959-),男,山西陽(yáng)泉人,教授,主要從事藥物中間體及有機(jī)合成方面的研究,(Tel)0351-6l116508太原理工大學(xué)學(xué)報(bào)第38卷隨氯化鈣利用次數(shù)的增加而降低,這與在抽濾等操2結(jié)果與討論作中催化劑的部分損耗有一定的關(guān)系。若實(shí)驗(yàn)中能2.1反應(yīng)溶劑及其用量的影響設(shè)法降低其損耗,則重復(fù)利用催化劑三次的收率基考察了四種溶劑對(duì)酯化反應(yīng)的影響用量均取本是一樣的。80mL,其中以環(huán)已烷作溶劑收率最高(見表1)。進(jìn)一步考察了環(huán)己烷用量對(duì)酯化反應(yīng)的影響,發(fā)現(xiàn)當(dāng)80環(huán)己烷用量超過80mL后,收率增加不顯著(見圖1),因此環(huán)己烷適宜用量為80mL。表1不同溶劑對(duì)產(chǎn)物收率的影響匚幣劑「環(huán)已烷苯甲革二收事/%78571.7357.826285氯化鈣用量/g化劑用量對(duì)產(chǎn)物收率的影陪衰3催化劑重復(fù)利用次數(shù)對(duì)產(chǎn)物收率的影響數(shù)收率/%85968123768164.06508739.32.4物料配比的影響由于N,N二乙氨基乙醇價(jià)格高,為提高其轉(zhuǎn)環(huán)己烷用量/mL化率,考察了物料配比對(duì)酯化收率的影響,結(jié)果發(fā)現(xiàn)圖1環(huán)已烷用量對(duì)產(chǎn)物收率的影響2.2反應(yīng)時(shí)間的影響收率并不隨己酸用量的增加而增加(見表4),因此考察了反應(yīng)時(shí)間對(duì)酯化反應(yīng)的影響(見表2),N,N二乙氨基乙醇與已酸的摩爾比以1:1為宜表4不同物料配比下的收率結(jié)果表明隨反應(yīng)時(shí)間增加收率隨之提高,6h時(shí)達(dá)n(A)/m(B)1:091:u1:t.1|1:1.21:1.3到最高,再延長(zhǎng)反應(yīng)時(shí)間收率不升反降。因此最佳收率/%7.817.8569.96648960.56反應(yīng)時(shí)間為6h。注:A為N,N二乙氨基乙醇B為己表2反應(yīng)時(shí)間對(duì)產(chǎn)物收率的影響3結(jié)論收率/%964233723.27383845005443時(shí)間/h6.06.57.07.58.08.5用己酸和N,N二乙氨基乙醇為原料,氯化鈣收率/%7821726727634156.355591為催化劑合成N,N二乙氨基乙醇己酸酯的最佳工2.3催化劑用量及其重復(fù)利用次數(shù)的影響藝條件為:溶劑為環(huán)己烷且為80mL;反應(yīng)時(shí)間6h;氯化鈣有一定的吸水性,將其用于酯化反應(yīng)中氯化鈣1.0g;N,N二乙氨基乙醇與已酸的摩爾比可在反應(yīng)體系內(nèi)部吸附部分反應(yīng)生成的水這與外為1:1。此條件下的最高收率為8596%部的分水器形成內(nèi)外脫水能力,共同促使反應(yīng)向右進(jìn)行。氯化鈣對(duì)酯化反應(yīng)的影響見圖2,結(jié)果表明問題,具有價(jià)格低廉、重復(fù)性好、反應(yīng)條件溫和、生產(chǎn)隨氯化鈣用量的增加收率隨之提高,1.0g時(shí)達(dá)到能耗低且過程無污染、易于工業(yè)化等優(yōu)點(diǎn)。這不僅最高,再增加氯化鈣用量收率也是不升反降。因此為工業(yè)生產(chǎn)DA6提供了合理的生產(chǎn)工藝,更為其最佳催化劑用量為1.0g。進(jìn)一步考察了催化劑重在農(nóng)業(yè)上的廣泛應(yīng)用創(chuàng)造了條件復(fù)利用次數(shù)對(duì)酯化反應(yīng)的影響(見表3),發(fā)現(xiàn)收率參考文獻(xiàn):[1] Yamaguchi Kyoichi, Hayashi Ayako. Preparation of diethylamino)ethyl alkanoate as plant growth promoters[P]. JP01290606,1988-05-17[2] Poling Stephen M, Hsu Wan-Jean, Koehrm Fred J. Chemical regulation of carotenoid biosynthesis, Part 10. Chemical induc-tion of A-carotene biosynthesis[J]. Phytochenistry, 1977, 16(5): 551-555下轉(zhuǎn)第513頁(yè))袁淑霞等:活性炭改性對(duì)濾嘴吸附性能的影響513Effect of the Modification of ActivatedCarbon on Adsorptive Performance of Activated Carbon FiltersYUAN Shu-xia., LU Chun-xiang, LI Yong-hong', LIANG Dong(L Key Laboratory of Carbon Material, Institute of Coal Chemistry,Chinese Academy of Sciences, Taiyuan 030001, China2. Graduate School of the Chinese Academy of sciences, Beijing 100039, China)Abstract: Pore texture and specific surface area of activated carbon were analyzed bysorptomatic instrument, Surface acidity and acidity distribution measured by Boehm titration andoxygen content of the activated carbon before and after modification analyzed semi-quantitativelyby EDS were used to characterize the influence of physical and chemical properties of activatedcarbon on adsorption performance of filter. The results indicate that adsorption capacity of filterto smoking became high with increasing of the content of activated carbon in filter, and if the internal resistance of cigarette was maintained constant, the best content of activated carbon in fil-ter was 30 mg/g. High specific surface area, larger pore volume and acidity ofcould contribute to the excellent adsorption performance of filter to mainstream smoking of ciga-rette. The adsorption capacity of the filter to nicotin and tar were about 25. 6% and 8.8% highethan that of filter containing common cellulose acetateKey words: activated carbon; composite filter; adsorption(編輯:張紅霞)上接第508頁(yè))[3]徐秋曼程景勝高虹DA6浸種對(duì)水稻幼苗的生理效應(yīng)初探[.天津師范大學(xué)學(xué)報(bào),2001,21(2);57-60.[4]目建洲,張琴,李桂琴,等二烷氨基乙醇已酸酯對(duì)瓜葉菊生長(zhǎng)及生理活性的影響[.遼寧師范大學(xué)學(xué)報(bào)〔自然科學(xué)版1999,22(2):153-1[5]夏門大學(xué).二烷氨基乙醇羧酸南的制備方法[P]中國(guó)專利:1073429,1993-06-23[6] Zhang H K, Chen M D, Guo Q Z Synthesis of (N, N-Diethylamino)ethyl caproate by using solid superacid catalyst SO42-/TO2[]合成化學(xué),1995,3(3):250-252[7] Yamaguchi K, Hayashi A, Plant Growth Promoter and Production Thereof[P]. JP, 1290606,1989-11-22[8]李惠靜,許良忠張樹圣用鈦酸四丁酯催化合成NN二乙氨基乙醇己酸酯].青島化工學(xué)院學(xué)報(bào),2001,22(2):147-148[]張洪查李娟陳明德,等.氧化亞錫催化己酸與憨船化的研究[.廈門大學(xué)學(xué)報(bào)(自然科學(xué)報(bào)),199837(1):64-69[10]珠海真綠色技術(shù)有限公司.二烷氨基乙醇羧酸豳及其鹽的制備方祛[P]中國(guó)專利:1305987,2001-08-01Synthesis of N, N-diethylaminoethyl CaproateWEI Wen-long, HOU Zhong-de, CHANG Hong-hong, WANG Jing, WANG Zhi-zhong(College of Chemistry and Chemical Engineering of TuT, Taiyuan 030024, China)Abstract:(N, N-diethylamino)ethyl caproate is prepared from N, N-diethylamino ethanol andcaproic acid by using calcium chIoride as catalyt. The effects of solvents and the dosage of thesolvents, reaction time, the dosage of the catalyst, mole ratio of reactants, etc. are investigated.The optimal conditions are as follows: the solvent is cyclohexane and its dosage is 80mL, reactiontime is 6 h, the dosage of calcium chloride is 1.0 g, the mole ratio of N, N-diethylamino ethanoland caproic acid is 1 1. Under this condition, the highest yield of the product can be 85.96%The product is characterized by IR and GC/FID, and the purity of the product is 98. 76%Key words: N, N-diethylaminoethyl caproate; synthesis; calcium chloride; cyclohexar(編輯:張紅霞)