乙醇中烯丙基胺的合成

第56卷第10期化工学报2005年10月Journal of Chemical Industry and Engineering ( China)October 2005研究简报Synthesis of ally lamine in ethanolBingtao(唐炳涛), ZHANG Shufen(张淑芬),YANG(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 chloridewith 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 ofallylamine was increased from 13. 3% to 67. 6% when the molar ratio of NH to allyl chloride was increasedfrom 4.5: 1 to 25: 1. However, the reaction of allyl chloride and hexamethylenetetramine in ethanolproduced allylamine with high selectivity(100%)and high yield(87%). The synthesis of allylamine fromthe reaction of allyl chloride and hexamethylenetetramine in ethanol was more straightforward andconvenientKey words: allyl chloride; allylamine; synthesis; hexamethylenetetramineCLC number: TQ. 9Document code: AArticle|D:0438-1157(2005)10-1897-04Moreover, allyl alcohol was formed as a by-productIntroductionwhen aqueous ammonia was used for theAllylamine is a versatile organic intermediateamination. Although the selectivity of allylamineIt is useful as a corrosion inhibitor for steel, and by the ammonolysis of allyl alcohol could reachis also used for the synthesis of quinolines[21. The 90%8J, the conversion of allyl alcohol was verypolymer of allylamine can also be molded into low and the reaction conditions were quite severe.microcapsulesl33, polymeric fluorescence probes 4JIn this paper, two more straightforward andand polymeric catalytic carrier[5]. Allylamine is convenient methods of synthesis of allylcommonly prepared from ammonolysis of allyl (1) ammonolysis of allyl chloride in ethanol, andchloride. The process proceeds with low(2)reaction of allyl chloride and hexamethylene-selectivity of allylamine, and the selectivity of thetetramine in ethanol are reported. The results oftransformation to allylamine, diallylamine andexperiments showed that the selectivity of allylamirtriallylamine depends on reaction temperature, reached 78.8% and 100% respectively when NH, andreaction time, molar ratio of NH3/allyl chloridehexamethylenetetramine were usedand molar ratio of CuCl /allyl chlorideExperimentalEthanol, NH.OHFirst author TANG Bingtao, male, born in 1976, PhDnetetramine were analytically pureCorresponding author: Prof. ZHANG Shufen,中国煤化工 d according to thehangshf( chem. dlut, edu. cnmetCNMHGTheFoundation item: supported by Trans-century Training determination of the ratio of allylamineProgram Foundation for the Talents by the State Education methylamine, diallylamine and triallylamine in theCommission and the National Natural Science Foundation of Chinaon of allyl chloride wa(20276009)performed on a HP6890GC/5973MSD·1898化工报第56卷1.2 Ammonolysis of allyl chloride in ethanolGC-MS showed that the product was pureThe ethanol solution saturated with NH3 allylamine(M=57)(11.6%,mass,20C)10,CuCl1(34mg,0.362 Results and discussionmmol) and allyl chloride(0.7 g, 12 mmol)waadded into a stainless steel autoclave reactor 2. 1 Ammonolysis of allyl chloride in ethanolequipped withThe reaction of allyl chloride (AC) andwas kept at the designated temperature, under the ammonia proceeded in series, and the product waspressure of 0.6 MPa. After 8 h, the reactor was a mixture of monoallylamine (MAA), diallylamineallowed to cool down to room temperature and the (DAA)and triallylamine(TAA). When NH, Opressure 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 asllyl chloride was 100 %, and the selectivity of the follows and the results are listed in Table 1products was as follows: allylamine (M= 57) CH2=CHCH, CI+NH,+,,=CHCH, NH,+HCl67.6%. diallylamine (M+=97)24.2%andCH=CHCH NH,+CH,=CHCH CItriallylamine (M+=137)8.2%(CH2=CHCH2)2 NH+HCI1.3 Preparation of allylamine from reaction of(CH,-CHCH,),NH+CH,-CHCH, C(CH,=CHCH)3N+HCIin ethanolCH,- CHCH, CI+OHCH,-CHCH, OH+ CIA 500 ml three-necked flask equipped with aThe data in Table 1 show that when ethanolmechanical stirrer, a reflux condenser andwas used as solvent, the selectivity of the reactionthermometer was charged with allyl chloride(11.6 to generate allylamine reached 67.6%,whereasg, 0.15 mol), hexamethylenetetramine (20when liquid ammonia was used, the selectivity was0. 14 mol),0.6 g KI (as catalyst) and 300 ml only 21. 4%, which might be caused by theethanol. The mixture was stirred for 1o h at 40 cfollowing two reasons:(1) the polarity of ethanol60 mlhydrochloric acid waswas useful for stabilizing the -allyl complex ofadded. After another 10 h. the solvents were allyl chloride and CuCl, enhancing the reaction ofremoved under reduced pressure. Then a solution of allyl compounds with nucleophiles[Il(2)th25.3 g sodium hydroxide in 250 ml water was strong exothermic amination reaction could takeslowly added to the reaction mixture, and the place in a mild condition where the concentration offraction (52)was collected. The fraction the reactants was diluted by adding solvent 133. Thewas dried with anhydrous sodium sulfate to give formation of by-product allyl alcohol was due to the6. 7 g product (84%). Analysis of the product by hydrolysis of allyl chloride when NH, OH wasTable 1 Results of ammonolysis of allyl chlorideTem/CTime/hMAA/%DAA/%DTAA/%NHs25:161.017.625:1中国煤化工2.2CNMHG33. 513.356.4ethanol1:10025:178.817.4O Content of allyl alcohol was 1.9 %; @ Conversion of allyl chloride was 57. 1%: Yield of allylamine was 50. 7% when amount of allylincreased from 0.9 g to 9 g: Mass percent, determined by GC-MS analysis of product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 ofallylamine from 13. 3% to 67.6%, as the molar operation, and decreased the cost of productiratio of nh to allyl chloride increased from 4.5: 1Meanwhile the conversion of allyl chloride reachedto 25: 1. might result from the rea100% and the yield of the allylamine reached 87%larger excess of NH restrained the further reactionThe process is shown as follows and the results areof allylamine with allyl chloride. Furthermore, the listed in Table 2selectivity of allylamine was improved from 43. 3%to 78.8% when the catalyst(CuCl)was increasedfrom 1% to 4%. The catalysis was attributed tothe formation of r-allyl complex of allyl chlorideThe similar t-allylpalladiumcomplex which reacted with nucleophiles to give a一CHNH②wide variety of allylic functionalized compounds canbe formed via palladium catalyzed reactions15,16Moreover, the hydrolysis of allyl chloride wasprevented when ethanol was used as solvent.2. 2 Preparation of allylamine from reaction ofhexamethylenetetramine and allyl chlorideAs shown in Table 2, the sole product wasn ethanolallylamine when the molar ratio of allyl chloride toAlkyl halides react with hexamethylenetetramine hexamethylenetetramine was increased froin chloroform to give the quaternary salts. After 0. 95:1 to 1.05: 1; and the yield of allylaminehloroform is removed, the quaternary salts reached 87% and 82% respectively when the molardecompose to give primary amines in strongly acidic ratios of allyl chloride to hexamethylenetetraminemedia ( usually ethanol/ concentrated hydrochloric were 0.95:1 and 1.05:1. which was attributThis reaction, known as the Delepine to the high conversion ratio of one reactant when themethod 17, is useful for the conversion of alkylother reactant was in excess. However, a larger excesshalides to primary amines without concomitantof allyl chloride yielded diallylamine as a by-product asformation of secondary amines. In this papera result of the reaction of allyl chloride with allylamine.llylamine was straightforwardly synthesized byWhen hexamethylenetetramine was in a larger excesswithhexamethylenetetramine in ethanol rather than inmethyl amine was formed as a by-product as a result ofhis change resolved the problem ofthe Sommelet reaction 7 of allylamine withchloroformTable 2 Results of analysis of product by GC-MsMSContent0.90:1.00中国煤化工CNMHGCH2-CHCH2 NH2 1001.05:1.00CH,-CHCh, NH10:1,00CH,-ChChzNH(CH,=CHCH),NH·1900·化工报第56卷3 ConclusionsMakromol.Chem.,1987,188:2071-2082S. Allylic amination promoted bIn conclusion, allylamine was synthesized bcopper. Tetrahedron, 1991. 47(45):9449-9454the reaction of allyl chloride with NH3 in ethanol. [7J Waldemar P, Eugeniusz M. Ammonolysis of allyl chlorideMeanwhile the selectivity of allylamine wasby ammonia solution. Ind. Eng. Chem. Res, 2002, 41(11):2602-2610improved from 21. 4% to 67. 6% when the reaction[8 Carrol W, Jaughenbaugh R, Allylamine from allyl alcohol.was carried out in ethanol instead of liquidammonia. But the highest selectivity of allylamine[ Han guangdian(韩厂甸),2 Zhao shuwei(赵树纬),Shuwen(李树文). Chemistry Handbook of Organicwas only 78.8%, which caused a problem ofPreparation(有机制备化学手册). Beijing: Petrochemicalproduct separation. However, the reaction of allylIndustry Press, 1977.chloride and hexamethylenetetramine in ethanol10 Gu Qingchao(顾庆超). Lou Shutong(楼书聪).DiQingping(戴庆平). Chemical tables(化学用表)produced allylamine in high selectivity (100 %)andNanjing Jiangsu Science and Technology Press, 1979.high yield(87%). In addition, this improvementresolved the problem of recycling chloroform[11 Ryo T. Naoki U. Keisuke T, Kengo Y, Norihito S. Iridiumcomplex-catalyzed allylic amination of allylic esters. J. Amreduced the steps of operation, and decreased theChem,Soc,,2001,123(39):9525-953cost of production, providing a more straight- [12] Trost B M, Toste F D. Regio- and enantioselective allyicforward and convenient synthesis of allylaminealkylation of an unsymmetrical substrate a working modeJ.Am.Chem.Soc.,1999,121(19):4545-4554References[13] Lin jianying(林建英). Studyoctadecylamine. Speciality Petrochemicals(精细石油[1] Cui xiaoming(崔小明). Development and utilization of allyl工)chloride and its derivatives. Chlor- Alkali Industry (RWI [14] Jubaraj B B. Ashoka GS. Copper(I) promoted C-Cbond业),2000,5:17—1forming reactions: direct activation of allyl alcohols[2] Cho C S, Kim J S, Oh B H. Ruthenium-catalyzed synthesisof quinolines from anilines and alkylammonium chlorid[15 Ridha B C, Refaat C, Andre L, Pierre M, Abdelhafid N.Tetrahedron,2000,56(39):7747-7750Syhthesis of primary allylic amines. S1983,11[3 Kidchob T. 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