乙醇中烯丙基胺的合成

第56卷第10期化工学报 Vol. 56 No. 102005年10月 Journal of Chemical Industry and Engineering (China) October 2005研究简报 Synthesis of allylamine in ethanol222222 TANG Bingtao(唐炳涛), ZHANG Shufen(张淑芬, YANG Jinzong(杨锦宗) (State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, Liaoning, China) Abstract: Allylamine was prepared from the ammonolysis of allyl chloride or the reaction of allyl chloride with hexamethylenetetramine in ethanol. The selectivity of allylamine was improved from 21. 4% to 67.6% when the reaction was carried out in ethanol instead of liquid ammonia. At the same time, the selectivity of allylamine was increased from 13. 3% to 67.6% when the molar ratio of NH, to allyl chloride was increased from 4.5: 1 to 25: 1. However, the reaction of allyl chloride and hexamethylenetetramine in ethanol produced allylamine with high selectivity(100%) and high yield(87%). The synthesis of allylamine from the reaction of allyl chloride and hexamethylenetetramine in ethanol was more straightforward and convenient. Key words: allyl chloride; allylamine; synthesis; hexamethylenetetramine CLC number: TQ 612.9 Document code: A Article ID:0438-1157(2005)10-1897-04 Introduction Moreover, allyl alcohol was formed as a by-product when aqueous ammonia was used for the Allylamine is a versatile organic intermediate. amination. Although the selectivity of allylamine It is useful as a corrosion inhibitor for steel11, and by the ammonolysis of allyl alcohol could reach is also used for the synthesis of quinolines[]. The 90%[8], the conversion of allyl alcohol was very polymer of allylamine can also be molded into low and the reaction conditions were quite severe. microcapsules3], polymeric fluorescence probes4] In this paper, two more straightforward and and polymeric catalytic carrier5. Allylamine is convenient methods of synthesis of allylamine by commonly prepared from ammonolysis of allyl (1) ammonolysis of allyl chloride in ethanol, and chloride6]. The process proceeds with low (2) reaction of allyl chloride and hexamethylene- selectivity of allylamine, and the selectivity of the tetramine in ethanol are reported. The results of transformation to allylamine, diallylamine and experiments showed that the selectivity of allylamine triallylamine depends on reaction temperature, reached 78. 8% and 100% respectively when NH3 and reaction time, molar ratio of NH3 /allyl chloride hexamethylenetetramine were used. and molar ratio of CuCl /allyl chloride. 1 Experimental 1. 1 Reagents and instruments Received date: 2004-10-12. Ethanol, NH. OH, potassium iodide and First author: TANG Bingtao, male, born in 1976, PhD hexamethylenetetramine were analytically pure candidate Corresponding author: Prof. ZHANG Shufen.- mail: reagents. CuCl was prepared according to the zhangshf@chem.dlut.edu.cn method described by Han, et al.The Foundation item: supported by Trans century Training determination of the ratio of allylamine, Program Foundation for the Talents by the State Education methylamine, diallylamine and triallylamine in the Commission and the National Natural Science Foundation of China11111111898·化工学报第56卷 1.2 Ammonolysis of allyl chloride in ethanol GC-MS showed that the product was pure The ethanol solution saturated with NH: allylamine (M+=57).(11.6%,mass,20c)o,CuCl(34mg,0.36 2 Results and discussion mmol) and allyl chloride (0. 7 g, 12 mmol) was added into a stainless steel autoclave reactor 2. 1 Ammonolysis of allyl chloride in ethanol equipped with a magnetic stirrer, and the reactor The reaction of allyl chloride(ac)and was kept at the designated temperature, under the ammonia proceeded in series, and the product was pressure of 0.6 MPa. After 8 h, the reactor was a mixture of monoallylamine (MAA),diallylamine allowed to cool down to room temperature and the (DAA)and triallylamine (TAA). When NH,OH pressure was released slowly. Analysis of the was used, allyl alcohol was formed as a by- product by GC-MS showed that the conversion of product. The process of the reaction is shown as allyl chloride was 100%, and the selectivity of the follows and the results are listed in Table 1. products was as follows: allylamine (M*=57) CH2 -CHCH2+ NH: CH2 -CHCH: NH2 +HCI67.6%, diallylamine(m+=97)24.2% and CH2=chch2n2+ch2=CCH2Cl→ triallylamine (M*=137)8.2%. (CH2 -CHCH: )2NH+HCI 1.3 Preparation of allylamine from reaction of (CH2-CHCH2 )2NH+CH2-CHCH: Cl allyl chloride and hexamethylenetetramine in ethanol A 500 ml three-necked flask equipped with a The data in Table show that when ethanol mechanical stirrer, a reflux condenser and a was used as solvent, the selectivity of the reaction thermometer was charged with allyl chloride (11.6 to generate allylamine reached 67.6%, whereasg,0.15mol), hexamethylenetetramine(20g, when liquid ammonia was used, the selectivity was 0.14 mol), 0.6 g KI (as catalyst) and 300 ml only 21.4%, which might be caused by the ethanol. The mixture was stirred for 10 at 40 C, following two reasons: (1) the polarity of ethanol then 60 ml conc. hydrochloric acid was was useful for stabilizing the x-allyl complex of added. After another 10 h, the solvents were allyl chloride and CuCl, enhancing the reaction of removed under reduced pressure. Then a solution of allyl compounds with nucleophiles1, 12; ()the 25.3 g sodium hydroxide in 250 ml water was strong exothermic amination reaction could take slowly added to the reaction mixture, and the place in a mild condition where the concentration of fraction (52 60 C) was collected. The fraction the reactants was diluted by adding solvent3). The was dried with anhydrous sodium sulfate to give formation of by-product allyl alcohol was due to the 6. 7 g product (84%). Analysis of the product by hydrolysis of allyl chloride when NH, OH was Table 1 Results of ammonolysis of allyl chloride Composition of product Solvents FINH,AC nCuClnAc Tem. /C Time/h MAA/% DAA/% TAA/% NH325:13:10045821.461.017.6 ethanol25:13:10045867.624.28.2 NH,OH7.5:13:10045840.333.521.2 ethanol4.5:13:10045813.330.356.4 ethanol25:11:10045843.39.64.2 ethanol25:14:10045878.817.43.8m第10期 TANG Bingtao et al: Synthesis of allylamine in ethanol1899 used as solvent. The increase of the selectivity of recycling chloroform, reduced the steps of allylamine from 13.3% to 67. 6%, as the molar operation, and decreased the cost of production. ratio of NH: to allyl chloride increased from 4. 5: 1 Meanwhile the conversion of allyl chloride reached to 25: 1, might result from the reason that a 100% and the yield of the allylamine reached 87%. larger excess of NH: restrained the further reaction The process is shown as follows and the results are of allylamine with allyl chloride. Furthermore, the listed in Table 2. selectivity of allylamine was improved from 43. 3% to 78. 8% when the catalyst (CuC1) was increased KI from 1% to 4%. The catalysis was attributed to the formation of x-allyl complex of allyl chloride with CuC14]. The similar -allylpalladium complex which reacted with nucleophiles to give a①NH2∠N,CH3NH2 wide variety of allylic functionalized compounds can②OH CI be formed via palladium catalyzed reactions15. 167. Moreover, the hydrolysis of allyl chloride was prevented when ethanol was used as solvent. 2.2 Preparation of allylamine from reaction of hexamethylenetetramine and allyl chloride As shown in Table 2, the sole product was in ethanol allylamine when the molar ratio of allyl chloride to Alkyl halides react with hexamethylenetetramine hexamethylenetetramine was increased from in chloroform to give the quaternary salts. After 0.95 1 to 1. 05: 1; and the yield of allylamine chloroform is removed, the quaternary salts reached 87% and 82% respectively when the molar decompose to give primary amines in strongly acidic ratios of allyl chloride to hexamethylenetetramine media( usually ethanol/concentrated hydrochloric were0.95:and1.05:1, which was attributed acid). This reaction, known as the Delepine to the high conversion ratio of one reactant when the method 17), is useful for the conversion of alkyl other reactant was in excess. However, a larger excess halides to primary amines without concomitant of allyl chloride yielded diallylamine as a by-product as formation of secondary amines. In this paper, a result of the reaction of allyl chloride with allylamine. allylamine was straightforwardly synthesized by When hexamethylenetetramine was in larger excess, the reaction of allyl chloride with hexamethylenetetramine in ethanol rather than in methyl amine was formed as a by-product as a result of chloroform. This change resolved the problem of the Sommelet reaction7] of allylamine with hexamethylenetetramine. Table 2 Results of analysis of product by GC-MS nc H,: nC H12G MS Product Conte nt Yield residue time/min m/(M+)s structure%0.90:1.001.4031 CH: NH51.7957 CH2 -CHCH2 NH2 95810.95:1.001.7957100 CH2 -CHCH2 NH2 100871.00:1.001.7957 CH2 -CHCH2 NH2 100781.05:1.001.7957 CH2-CHCH2 NH2 100821.10:1.001.7957 CH2-CHCH2NH288741517 NH11900化工学报第56卷 its catalytic effect in the hydrolysis of phenyl esters. 3 Conclusions Makromol.hem1987188:20712082 [6] Jubaraj B B. Ashoka G S. Allylic amination promoted by In conclusion, allylamine was synthesized by copper. Tetrahedron, 1991, 47 (45): 9449-9454 the reaction of allyl chloride with NH3 in ethanol. [7] Waldemar P. Eugeniusz M. Ammonolysis of allyl chloride Meanwhile the selectivity of allylamine was by ammonia solution. Ind. Eng. Chem. Res., 2002,41(11):2602—2610 improved from 21. 4% to 67. 6% when the reaction [8] Carrol W, Jaughenbaugh. Allylamine from allyl alcohol. was carried out in ethanol instead of liquidJ.Mol. Catal...1988,44:213—215 ammonia. But the highest selectivity of allylamine[9]《TanGuangdianZhaoShuweii《(韩广甸),ZhaoShuwei(赵树纬),Li Shuwen(李树文). Chemistry Handbook of Organic was only 78. 8%, which caused problem of Preparation(有机制备化学手册) Beijing: Petrochemical product separation. However, the reaction of allyl Industry Press,1977.15 chloride and hexamethylenetetramine in ethanol [10] Gu Qingc[10][10GuQingchaooShucong《Dai(顾庆超),LouShucong(楼书聪),Dai Qingping(戴庆平), Chemical Tables(化学用表) produced allylamine in high selectivity (100%)and Nanjing: Jiangsu Science and Technology Press, 1979. high yield (87%). In addition, this improvement2,6 resolved the problem of recycling chloroform, [11] Ryo T. Naoki U. Keisuke T. Kengo Y. Norihito S. Iridium complex-catalyzed allylic amination of allylic esters. J. Am. reduced the steps of operation, and decreased theChemoc2001123(39):9525-9534 cost of production, providing a more straight-[12] Trost B M, Toste F D. Regio- and enantioselective al forward and convenient synthesis of allylamine. alkylation of an unsymmetrical substrate: a working model.J.Am.Chem.Soc.,1999,121(19):45454554 References13] Lin Jianying(林建英). Study on the synthesis of octadecyamine. Speciality Petrochemicals(精细石油化[1] Cui Xiaoming(崔小明). Development and utilization of allyl工),2000,4:45-47 chloride and its derivatives. Chlor- Alkali Industry [14] Jubaraj B B. Ashoka S. Copper () promoted C-Cbond业),20005:17-19 forming reactions: direct activation of allyl alcohols. J.[2] Cho CS, Kim,ohbh. Ruthenium-cata- synthesis Organomet.Chem.. 1989, 361:C57-60 of quinolimes from anilines and allylammonium chlorides. [15] Ridha B C. Refat C. Andre L. Pierre M. Abdelhafid N. Tetrahedron,2000,56(39):7747-7750 Syhthesis of primary allylic amines. Synthesis, 1983, 11: [3] Kidchob T, Kimura S, Imanishi Y. Thermoresposive release68370 from poly (glu (ome ))-biock-poly Sar) microcapsules [16] Katritzky A R. Yao J C. Qi M. 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