松油醇副产物合成农药增效剂N-取代基单萜烯基酰亚胺
|
摘要
为了开发利用广西丰富的可再生资源松节油生产松油醇过程中产生的副产物萜烯,本文研究以松油醇副产物为原料首先与马来酸酐合成中间体萜烯-马来加成物,再利用乙酐法和共沸法与相应的伯胺反应,从而合成出农药增效剂N-取代基单萜烯基酰亚胺。
本文主要研究的内容有:
(1)在无溶剂条件下,松油醇副产物在催化剂和助催化剂作用下发生异构,同时与马来酸酐发生Diels-Alder反应,并生成1-异丙基-4-甲基二环[2,2,2]-5-辛烯-2,3-二酸酐(简称TMA)。实验过程中对催化剂磷酸、对甲苯磺酸、氯化铝、四氯化钛、树脂进行了筛选,实验证明磷酸作为催化剂效果最好。然后实验以磷酸为催化剂,再添加助催化剂碘,效果更好的进行了TMA的合成,并运用正交实验确定了合成TMA的最佳合成条件:反应温度155℃,催化剂质量分数为1.5%,助催化剂质量分数为0.05%,n(副产物主成分):n(马来酸酐)=2.2:1,反应时间为2h,TMA的收率为86.2%,纯度为99.2%,并利用红外光谱、核磁共振、质谱等方法对TMA结构进行分析和表征。
(2)以TMA和相应的伯胺为原料,分别采用乙酐法和共沸法合成了N-苯基单萜烯基酰亚胺、N-环己基单萜烯基酰亚胺、N-十二烷基单萜烯基酰亚胺。实验结果表明,乙酐法制备N-取代基单萜烯基酰亚胺的收率比共沸法稍好。通过气相色谱、IR和1H-NMR对产品结构进行分析和表征。
In order to explore the use of turpentine, a by-product in the production of terpineol from turpentine oil, which is a renewable resources abundant in Guangxi , the chemicall characteristics of turpentine was studied as following, turpentine reacted with maleic anhydride, and produced terpinene-maleic anhydride adduct. The anhydrid adduct reacted with related primary amine and obtained pesticide synergist N-substituted base monoterpenes imide by acetic anhydride method and azeotropic method
The research work in the paper was proposed as follows:
(1)1-lsopropyl-4-methylbicyclo[2,2,2]oct-5-ene-2,3-dicarboxylic anhydride (TMA) was prepared via isomerization of by-products of terpineol in the presence of phosphate catalyst and the co-catalyst ,and by Diels-Alder reaction with maleic anhydride. The catalytic activity of phosphoric acid,ρ-toulenesulfonic acid, aluminium chloride, titanic chloride and resin were respectively explored, phosphoric acid was proved to be of the highest catalytic activity. The optimum reactional conditions in the synthesis of TMA on the basis of phosphoric acid as catalyst and iodine as co-catalyst were obtained by orthogonal test as follows: reaction temperature at 155℃, catalyst at concentration of 1.5% (mass fraction), co-catalysts at concentration of 0.05%(mass fraction). The molar ratio between by-product of principal component and maleic anhydride is 2.2:1, and reaction time of 2 hours.The yield of TMA amounted to 86.2% and the purity to 99.2%. The structure of the TMA was analyzed and characterized by IR, NMR and MS.
(2) N-phenyl base monoterpenes imide, N-cyclohexyl based monoterpenes imide, and N-dodecyl base monoterpenes imide were synthesized by TMA and the corresponding primary amines on acetic anhydride method and azeotropic method . The results showed that acetic anhydride method was slightly better than the azeotropic method in preparation of N-substituted base monoterpenes imide . The products were analyzed and characterized by GC, IR and HNMR .
本文主要研究的内容有:
(1)在无溶剂条件下,松油醇副产物在催化剂和助催化剂作用下发生异构,同时与马来酸酐发生Diels-Alder反应,并生成1-异丙基-4-甲基二环[2,2,2]-5-辛烯-2,3-二酸酐(简称TMA)。实验过程中对催化剂磷酸、对甲苯磺酸、氯化铝、四氯化钛、树脂进行了筛选,实验证明磷酸作为催化剂效果最好。然后实验以磷酸为催化剂,再添加助催化剂碘,效果更好的进行了TMA的合成,并运用正交实验确定了合成TMA的最佳合成条件:反应温度155℃,催化剂质量分数为1.5%,助催化剂质量分数为0.05%,n(副产物主成分):n(马来酸酐)=2.2:1,反应时间为2h,TMA的收率为86.2%,纯度为99.2%,并利用红外光谱、核磁共振、质谱等方法对TMA结构进行分析和表征。
(2)以TMA和相应的伯胺为原料,分别采用乙酐法和共沸法合成了N-苯基单萜烯基酰亚胺、N-环己基单萜烯基酰亚胺、N-十二烷基单萜烯基酰亚胺。实验结果表明,乙酐法制备N-取代基单萜烯基酰亚胺的收率比共沸法稍好。通过气相色谱、IR和1H-NMR对产品结构进行分析和表征。
In order to explore the use of turpentine, a by-product in the production of terpineol from turpentine oil, which is a renewable resources abundant in Guangxi , the chemicall characteristics of turpentine was studied as following, turpentine reacted with maleic anhydride, and produced terpinene-maleic anhydride adduct. The anhydrid adduct reacted with related primary amine and obtained pesticide synergist N-substituted base monoterpenes imide by acetic anhydride method and azeotropic method
The research work in the paper was proposed as follows:
(1)1-lsopropyl-4-methylbicyclo[2,2,2]oct-5-ene-2,3-dicarboxylic anhydride (TMA) was prepared via isomerization of by-products of terpineol in the presence of phosphate catalyst and the co-catalyst ,and by Diels-Alder reaction with maleic anhydride. The catalytic activity of phosphoric acid,ρ-toulenesulfonic acid, aluminium chloride, titanic chloride and resin were respectively explored, phosphoric acid was proved to be of the highest catalytic activity. The optimum reactional conditions in the synthesis of TMA on the basis of phosphoric acid as catalyst and iodine as co-catalyst were obtained by orthogonal test as follows: reaction temperature at 155℃, catalyst at concentration of 1.5% (mass fraction), co-catalysts at concentration of 0.05%(mass fraction). The molar ratio between by-product of principal component and maleic anhydride is 2.2:1, and reaction time of 2 hours.The yield of TMA amounted to 86.2% and the purity to 99.2%. The structure of the TMA was analyzed and characterized by IR, NMR and MS.
(2) N-phenyl base monoterpenes imide, N-cyclohexyl based monoterpenes imide, and N-dodecyl base monoterpenes imide were synthesized by TMA and the corresponding primary amines on acetic anhydride method and azeotropic method . The results showed that acetic anhydride method was slightly better than the azeotropic method in preparation of N-substituted base monoterpenes imide . The products were analyzed and characterized by GC, IR and HNMR .
引文
[1]林业部林产工业公司松香、松节油再加工产品市场调查组.松香、松节油再加工产品市场调查报告[J].林产化工通讯,1990,24(4):5-11.
[2]南京林产工业学院.林产化学工业手册[M].中国林业出版社,1980:390-397.
[3]程芝.天然树脂生产工艺学[M].中国林业出版社,l996:305-307
[4]朱凯,朱新宝,毛连山.松油醇制备中副产物红油化学组成的研究[J].现代化工,2004,24(11):33-35.
[5]吴文通,谢献征.混酸一步法合成松油醇小试报告[J].林化科技通讯,1986, 5(6):24-26.
[6]郭中荃,吴文通,揭秉泉.混酸一步法合成桧油醇生产性试验报告[J].林化科技通讯,1986,(7):1-5.
[7]荣德美,蒋爱平.相转移催化剂在合成松油醇中的应用[J].林产化工通讯,1996,3O(2):15-19.
[8]梁鸣,周永芳,祝明松等.出口松油及松油醇的主要组分分析[J].香料香精化妆品,1994,(1):2932.
[9]胡贵贤,赵振东,李冬梅等.松油醇生产中副产物化学组成及分离利用的研究[J].林产化学与工业,2000,20(1):1-5.
[10]安鑫南,罗金岳.松油醇生产中副产物化学组成分析及利用[J].南京林业大学学报,2008,32(5):32-36.
[11]陈正桂.松油醇副产物——红油制萜烯树脂研究[J].浙江化工,2001,3 (28):30.
[12]李桂珍,梁忠云,刘虹,文彩琳.松油醇副产物红油中异松油烯的精馏工艺研究[J].应用化工,2009,(38):1078-1079.
[13] Albert A.Schreiber,Salem,N.Y.,N-2-ETHYL HEXYLα,α’-DI-KETOβ,β’-(1,4 -△2- CYCLOPENTENYLENE)-PYRROLIDINE AND SYNTHESIS THEREOF [P] 2,476,512.1949,07,19.
[14] Gwyneth M.Roberts.BICYCLO(2,2,2)OCT-5-ENE-2,3-DICARBOXYLIC ANHYDRIDES AS HERBICIDES. [P]3,476,546.1969,11,4.
[15]MatyniaTadeuszDiels-Alderadduetsofterpenehydroearbonsasliquidanhydrideeuringagentsforepoxyresins[J].Part1.Studiesofpropertiesofdianepoxyresins.Polymery(Warsaw)1976,21(9):404-408.
[16]MatyniaTadeusz.Diels-Alderadduetsofterpeniehydroeabonsasproduetsfor synthesisofeuringagentsandexpoxyresins[J].Polymery(Warsaw)1980,25(6-7):227-30.
[17]MatyniaTadeusz,BartrikTeresa.Hardeningepoxyresins[P].Pol.108656,1980-11- 31.
[18] MatyniaTadeusz.Epoxyresinsbasedonglyeidylesters[P].Pol.PLll079,1981-9-30.
[19]BartrikTeresa,MatyniaTadeusz,KISielLeszek[P].Curingagentforepoxyresins.Po1.PL123360,1984-3-31.
[20]FurmaniakMaria,MatyniaTadeusz,UrbanJerzy,GorniakElzbieta,Epoxyeompositionforpressure injeetionmolding[P].Pol.PL120951,1984-l-10. [21MatyniaTadeuszHardenerforepoxyresins[P].Pol.PL129726,1985-8-30.
[22]MatyniaTadeusz.Hardeningofepoxyresineompositions[P].Pol.PL129725,1985-11-15.
[23]MatvniaTadeusz.Removalofaeideatalyst,inpartieularphosphorieaeid,fromareaetionProduetofeomPoundseontainingeonjugatedsystemofdoublebondswithmaleieanhydride[P].Pol.PL139443,1987-8-31.
[24]MatyniaTadeuszManufatureofmaleatedturpentineesterhardenerforepoxyresins[P].Pol.PL142389,1988-3-15.
[25]Ewa.A.Bardasz,Mentor,Ohio.TERPINENE-MALEIC ANHYDRIDE ADDUCT DERIVAVTIVES AS CORRO -SION INHIBITORS.[P]5,006,461.Nov.19,1991.
[26]Degtyarenko Anna S,AntonoviehIgorV,BitkinsTatyana A, Vyrodova ValentinaV.P- reparation of awater-solubleantiseptie[P].U.5.5.R. SU1759830, 1992-9-7.
[27]DegtyarenkoAnnaS,KaeherovskayaFridaB,VorkovValerijG.MethodformanufaetureofmaleatedterPeniehydroearbonastartingmaterialforPreParationofawater-solubleantiseptie[P].U.5.5.R.SU1768577,1992-10-15.
[28]Ak1yamaTakeshi,ChihoSatoshi.Pestieidesforeontrollinghousefleas[P].Jnn.Kokai TokkyoKohoJP2002193803A2,2002-7-10.
[29]LwakawaToru,KobayashiTomonori,MorikawaToshiyuki.WoodpresservativeseontainingterPene-maleieanhydrideadduetsandnaturalfungieidalandinseetieidaleomponents[P].Jpn.KokaiTokkyoKohoJP2002363006AZ,2002-12-18.
[30] NakahashiManabu, ShimokadoRyuiehiro.Diimideeompoundsformodifiersof enginee -ringplasties, generalpurposereings,andbiodegradableplasties[P].Jpn. KokaiTokkyo Koho [P]2003212849AZ,2003-7-30.
[31] AMLNO-CYCLIC-DICARBOXYLIC ACID IMIDES Jap.17580/65,clg.(Non-C on) 15.12.62(Jap) as 57228/62.
[32]高南,孟佳伦,王秋萍等.α-蒎烯一马来酸酐加成物及其应用的研究[J].林产化学与工业,1986,6(2):9-18.
[33]高南,王明谓,朱克奇等.萜烯双马来酞亚胺T(BM)I的研究[J].林产化学工业,1992,12(2):121-126.
[34]高南,潘鹏程,郁文.α-蒎烯一马来酸酐加成物同分异构体的研究-分离与性能[J].应用科学学报,1994,12(1):61-66.
[35]林中祥,程康华.萜烯马来酐加合物固化环氧树脂的性能研究[J].林产化工通讯,1997,2:18-19.
[36]周永红,王延,宋湛谦.α-蒎烯合成杀虫增效剂的研究[J].林产化学与工业,1998,18(3):1-11.
[37]周永红,谢晖,宋湛谦.松节油酰亚胺的合成、鉴定及杀虫增效活性[J].林产化学与工业,2001,21(3):6-10.
[38]周文富,贾德民.油酸接枝TMA多嵌段聚醋树脂[J].涂料工业,2000(8):8-11
[39]赖文忠,肖旺钏,周文富.新型紫外光固化TMA环氧丙烯酸醋树脂性能研究[J].三明高等专科学校学报,2001,18(2):44-48.
[40]段文贵,罗常泉,岑波,耿哲. N-(1-异丙基-2-羧基-4-甲基二环[2,2,2]-5-辛烯-3-羰基)-N`-芳基(硫)脲的合成[J].化学通报,2007,(9):695-698.
[41]张晋康王文龙俞雪英谭家勇.α-松油烯的研制[J],南京林业大学学报,1990.9.14(3):26～30
[42]陆占国,李健.1-甲基-4-异丙基-二环[2,2,2]辛烯-2,3-二酸酐制法[P].CN:1562990A,2005,1,12.
[43]李健,陆占国,刘宁,吉村吉博.松油烯与马来酸酐的环加成反应的条件研究.林产化学与工业,2006,26(3):93-96.
[44]于世涛,宋湛谦.固体超强酸SO42-/TiO2催化合成萜烯-马来酸酐加成物的研究[J].精细化工,1999,16(1):34-37.
[45]罗常泉,段文贵,岑波,班丽娜.α-蒎烯-马来酸酐加成物的合成.生物质化学工程,2006,40(3):25-28.
[46]哈成勇,肖永华,何云莲,黄伟雄.双戊烯合成萜马加成物的研究[J].广州化学,1995(1),31.
[47]哈成勇,胡建中.稀土金属衍生物催化合成萜马加成物反应的研究[J].化学工程师,1996,(3):54.
[48]哈成勇,金建忠.双戊烯合成萜马加成物反应的研究[J].天然产物的研究与开发,1997,9(1):19-23.
[49]林中祥,王阿法,马吉玲.碘催化双戊烯合成萜烯马来酸酐加合物[J].林产化工通讯,1996,4,11-12.
[50]林中祥.磷酸催化工业双戊烯与顺丁烯二酸酐加成反应[J].广西化工.1997,3(26):16-17.
[51]衣志伟,赵文浩,赖刚,等.氨水循环法制备邻苯二甲酰亚胺[J].化工技术与开发,2006,35(4):4-5.
[52] Kobayashi S,Ishitani H.Catalytic enantioselective ad.dition to imines[J].Chem Rev,1999,99(5):1069-1094.
[53]黄明智,李宏伟,庞怀林,张泉,任叶果,尹笃林.N-[2,4.二取代-5-(3-甲基-2,6-二氧-4-三氟甲基-1,2,3,6-四氢嘧啶-1-基)苯基]酰亚胺类化合物的合成及除草活性[J].有机化学,2008,28(8):1433-1438.
[54]钱旭红,唐军,陈卫东.四甲基萘并二呋喃的合成和DNA嵌入性能及其结构的分子模拟研究[J].高等学校化学学报,1996,9:1399-1403.
[55]徐晓勇,陈刚,钱晓红.吡啶甲基亚氨基噻_噁_唑烷的合成及生物活性[J],农药学学报,2003,5(1):27-33.
[56]慕长炜,覃兆海.吡啶类农药的研究进展[J].现代农药,2003,2(2):1-6.
[57]陈景文,陆国元等.取代氮杂环类化合物对大型蚤(Daphnia magna Straus)的定量结构-活性关系研究[J].农药,1996,35(5):21-24.
[58]吕兆萍张晓燕杨红.微波辐射合成N-(2-氯-1-氧-5-吡啶甲基)二甲酰亚胺类化合物和生物活性研究[J].有机化学,2008,28(1),89-93.
[59] Sena V M,Srivastava R M,Silva R 0,et .Synthesisand hypolipidemie activity of N-substituted phthalimidesPart V[J].IL Farmaco,2003,58(12):1283-1288.
[60] Katayama H,Greef F A,Kooiiman H,eta1.Towardpoly(aminophthalimide), structure of dimers and tri-mers[J].Tetrahedron,2007,63(28):6642-6653.
[61] Capitosti S M,Hansen T P,Brown M L.Thalidomideanalogues demonstrate dual inhabition of both anSiogenesisand prostste[J].Bioorg&Med Chem,2004,12(2):327-336.
[62] Shinji C,Nakamura T,Maseda S,et a1.Design andsynthesis of phthalimide·-type histone deaeetylase in·-habitors[J].Bioorg& Med Chem Lett,2005,15(20):4427-4431.
[63] Matsubayashi M,Kubo Y.Control of photophysicalproperties and photoreactions of aromatic imides byuse of intermoleeular hydrogen bonding[J]. OrgChem,2008,73 (13):4915-4919.
[64]郑凯,姚成.4-硝基-N-甲基-邻苯二甲酰亚胺合成新工艺[J].石油化工, 2004,33(2):145-148 .
[65]管冲,吕亮,王晓东,黄培.N-甲基邻苯二甲酰亚胺的新合成方法[J].南京工业大学学报, 2007,29(4):77-79.
[66]陈平,张士娥,黄朋勉,颜少慰,辛玉兵,李锦锦.微波催化合成Ⅳ_(2-吡啶基)邻苯二甲酰亚胺的研究[J].精细化工中间体,2008,38(6):29-31.
[67] Ryota H,Hiiroto W,Mamoru S.A solvent.free organicsynthesis from solid-state reactants through au-togenous fusion due to formation of molecular comple- and increasing alcohol nueleophilieity[J]. TetrahedronLett,2006,47(18):3111-3114.
[68]臧洪俊,李正名,王宝雷.固态有机合成反应进展[J].有机化学, 2003,23 (10):1058-1063.
[69] Tanaka K,Toda F.Solvent-free organic synthesis[J].Chem Rev,2000,100(3):1025-1074.
[70]唐林生,冯柏成.无溶剂有机合成的促进方法及前景[J].精细石油化工进展,2008,9(3):19-22.
[71]金锋,刘建军,陈海平,左胜利.新型N-氨基取代的1,6-亚甲基桥[1O]轮烯-3,4-二甲酰亚胺的无溶剂合成[J].合成化学,2009,17(5):606-608.
[72] Vogel E,Roth H D.The cyclodecapentaene system [J].Angew Chem Int Ed Engl,1964,3:228-229.
[73] Peart P A,Tovar J D.Me-ano[10]annulene revisited:extended delocalization through conjugated polymer bear-ing larger hllckel aromatics [J]. Org Lett, 2007, 9(16):3041-3044.
[74] Kajioka T,Ikai M,Fujikawa H,et a1.Disubstituted 1,6-methano[10]annulene derivatives for use in organiclight-emitting diodes[J].Tetrahedron,2004,60:6183- 6187.
[75] Kuroda S,Kajioka T,Fukuta A,et a1.Revisitation ofcycloheptatriene derivatives as abuilding block for varioussubstituted and fused 1,6-methano[10]annulenes and substituted 4,9-methano annulenes[J].Mini-Re-views in Organic Chemistry, 2007, 4: 31-49.
[76]金锋,刘建军,陈海平,左胜利.新型N-取代-1,6-亚甲基桥[10]轮烯-3,4-二甲酰亚胺的合成[J].北京化工大学学报(自然科学版),2010,37(1):28-30.
[77] WADA K.GOMIBuCHl T,Y0NETA Y,et a1.Preparation of Isoindolinone Derivative Insecticides:WO 2004l10149.2oo4.12-23.
[78]柳明,崔永亮,芮昌辉,王敏,王毅,段又生,刘尚钟.N-苯基氨基邻苯二甲酰亚胺衍生物的合成及初步杀虫活性[J].农药学学报,2009,11(1):51-54.
[79]赵新刚,于振环,李树丰等.耐热型ABS共聚物的研制[J].化工新型材料,2004,32(5):33-35.
[80]陶然,陶果.4-硝基苯基马来酰亚胺的合成研究[J].塑料工业, 2009,37(3):34-36.
[81]王国祥,刘华伟.N-(1-萘基)马来酰亚胺合成研究[J].绝缘材料,2007,40(5):10-14.
[82]曾玉香,卑凤利.N-(4-磺酸苯基)马来酰亚胺及其聚合物的合成与量子化学计算[J].天津化工,2008,22(6):35-37.
[83]史东明,钱捷.N-邻位取代苯基马来酰亚胺的研究概述[J].浙江化工,2009, 4O(2):20-23.
[84]钟红梅,侯德顺.N-异丙酸基马来酰亚胺的合成[J].化学工程师,2009,(3): 60-61.
[85]邢锦娟,钱建华,李国浩,王道林,谷坛.SO42-/ZrO2-MoO3复合固体酸催化合成N-环己基马来酰亚胺[J].石油与天然气化工,2008,37(4):337-339.
[86]李梅,仝春晖.微波促进N-嗯唑啉苯基马来酰亚胺的合成[J].河北化工,2008, (31)6:50-52.
[87]徐桂清,胡永洲,张冲,何俏军,杨波.吲哚马来酰亚胺类化合物的合成及其抗肿瘤活性[J].有机化学,2009,29(6):916-923.
[88]王彦林,赵忠波.阻燃剂N-(2,4,6-三溴苯基)马来酰亚胺的合成研究[J].盐业与化工,2007,37(l):9-11.
[89]匡永清,张生勇,姚素辰.合成N-甲基-4-氨基邻苯二甲酰亚胺的新路线[J].化学试剂,1992,14(5):301,31.
[90]Rafaella F, Davide C ,Elena M , et a1. A Simple CatalyticSynthesis of Condensed Pyridones from 0-Bromoarylcar-box-amides Involving Ipso Subsitution via Pa11adacyc1es[J].J AmChem Soc,2006,128:722-723.
[91] Jasztold-Howorko R,Pelczynska M ,et a1.The Synthesis andBiological Properties of a 1-(2-methylpyrid-in-4-y1)olivacine Derivative[J].Scientia Pharmaceutica, 2005, 73(3): 101-112.
[92]Tundo Pietro, Bressanello Salima,Loris Alessandro, et a1.Direct Synthesis of N -methylurethanes from Primary Amineswith Dimethyl Carbonate EJ].Pure and Applied Chemistry,2005,77(10):1719-1725.
[93]江琦.碳酸二甲酯在化工领域中的应用EJ].石油化工,2000,29(2):144-147.
[94]周远明,史美丽,王辉. N-甲基邻苯二甲酰亚胺的合成新工艺[J].精细石油化工,2008,25(4):4-6.
[95] Brana M F,Anorhe L,Tarrason G,et a1.Synthesisand biological evaluation of novel bisindolymaleimides that inhibit vascular endothelial cell proliferation[J]. Bioorg Med Chem Lett,2001,11:2701-2703.
[96] Mahboobi S,Eichhom E,Popp A,eta1.3-Bromo-4-(1H-3-indoly1)-2,5-dihydm -1H-2,5–pyrroledione de-rivatives as new lead compounds for antibacterially ac-tire substances [J]. Eur J Med Chem,2006,41:176-191.
[97] Katoh M,Dodo K,Fujita M,et a1.Structure-activityrelationship of N-methyl- bisindolylm aleimide derivatives as cell death inhibitors[J].Bioorg Med chemistry, 2005,15:3109-3113.
[98] Dodo K,Katoh M,Shimizu T,et a1.Inhibition of hy.drogen peroxide induced necrotic cell death with 3-ami-no-2-indolylmaleimide derivatives[J].Bioorg MedChem Lett, 2005, 15: 3114 -3118.
[99] Brenner M,Rexhausen H,Stefan B,et a1.Synthesisof amyriarubin B and related bisindolylmaleimides[J].Tetrahedron,1988,44:2887-2892.
[100]张海泉,贾红圣,赵圣印. 2-溴-3-(1-吲哚-3)-N-甲基马来酰亚胺的合成[J].合成化学,2008,16(1):105-106.
[101]魏清,李建生.N-氯代邻苯二甲酰亚胺的合成研究[J].化工科技市场, 2008,31(8):15-16.
[2]南京林产工业学院.林产化学工业手册[M].中国林业出版社,1980:390-397.
[3]程芝.天然树脂生产工艺学[M].中国林业出版社,l996:305-307
[4]朱凯,朱新宝,毛连山.松油醇制备中副产物红油化学组成的研究[J].现代化工,2004,24(11):33-35.
[5]吴文通,谢献征.混酸一步法合成松油醇小试报告[J].林化科技通讯,1986, 5(6):24-26.
[6]郭中荃,吴文通,揭秉泉.混酸一步法合成桧油醇生产性试验报告[J].林化科技通讯,1986,(7):1-5.
[7]荣德美,蒋爱平.相转移催化剂在合成松油醇中的应用[J].林产化工通讯,1996,3O(2):15-19.
[8]梁鸣,周永芳,祝明松等.出口松油及松油醇的主要组分分析[J].香料香精化妆品,1994,(1):2932.
[9]胡贵贤,赵振东,李冬梅等.松油醇生产中副产物化学组成及分离利用的研究[J].林产化学与工业,2000,20(1):1-5.
[10]安鑫南,罗金岳.松油醇生产中副产物化学组成分析及利用[J].南京林业大学学报,2008,32(5):32-36.
[11]陈正桂.松油醇副产物——红油制萜烯树脂研究[J].浙江化工,2001,3 (28):30.
[12]李桂珍,梁忠云,刘虹,文彩琳.松油醇副产物红油中异松油烯的精馏工艺研究[J].应用化工,2009,(38):1078-1079.
[13] Albert A.Schreiber,Salem,N.Y.,N-2-ETHYL HEXYLα,α’-DI-KETOβ,β’-(1,4 -△2- CYCLOPENTENYLENE)-PYRROLIDINE AND SYNTHESIS THEREOF [P] 2,476,512.1949,07,19.
[14] Gwyneth M.Roberts.BICYCLO(2,2,2)OCT-5-ENE-2,3-DICARBOXYLIC ANHYDRIDES AS HERBICIDES. [P]3,476,546.1969,11,4.
[15]MatyniaTadeuszDiels-Alderadduetsofterpenehydroearbonsasliquidanhydrideeuringagentsforepoxyresins[J].Part1.Studiesofpropertiesofdianepoxyresins.Polymery(Warsaw)1976,21(9):404-408.
[16]MatyniaTadeusz.Diels-Alderadduetsofterpeniehydroeabonsasproduetsfor synthesisofeuringagentsandexpoxyresins[J].Polymery(Warsaw)1980,25(6-7):227-30.
[17]MatyniaTadeusz,BartrikTeresa.Hardeningepoxyresins[P].Pol.108656,1980-11- 31.
[18] MatyniaTadeusz.Epoxyresinsbasedonglyeidylesters[P].Pol.PLll079,1981-9-30.
[19]BartrikTeresa,MatyniaTadeusz,KISielLeszek[P].Curingagentforepoxyresins.Po1.PL123360,1984-3-31.
[20]FurmaniakMaria,MatyniaTadeusz,UrbanJerzy,GorniakElzbieta,Epoxyeompositionforpressure injeetionmolding[P].Pol.PL120951,1984-l-10. [21MatyniaTadeuszHardenerforepoxyresins[P].Pol.PL129726,1985-8-30.
[22]MatyniaTadeusz.Hardeningofepoxyresineompositions[P].Pol.PL129725,1985-11-15.
[23]MatvniaTadeusz.Removalofaeideatalyst,inpartieularphosphorieaeid,fromareaetionProduetofeomPoundseontainingeonjugatedsystemofdoublebondswithmaleieanhydride[P].Pol.PL139443,1987-8-31.
[24]MatyniaTadeuszManufatureofmaleatedturpentineesterhardenerforepoxyresins[P].Pol.PL142389,1988-3-15.
[25]Ewa.A.Bardasz,Mentor,Ohio.TERPINENE-MALEIC ANHYDRIDE ADDUCT DERIVAVTIVES AS CORRO -SION INHIBITORS.[P]5,006,461.Nov.19,1991.
[26]Degtyarenko Anna S,AntonoviehIgorV,BitkinsTatyana A, Vyrodova ValentinaV.P- reparation of awater-solubleantiseptie[P].U.5.5.R. SU1759830, 1992-9-7.
[27]DegtyarenkoAnnaS,KaeherovskayaFridaB,VorkovValerijG.MethodformanufaetureofmaleatedterPeniehydroearbonastartingmaterialforPreParationofawater-solubleantiseptie[P].U.5.5.R.SU1768577,1992-10-15.
[28]Ak1yamaTakeshi,ChihoSatoshi.Pestieidesforeontrollinghousefleas[P].Jnn.Kokai TokkyoKohoJP2002193803A2,2002-7-10.
[29]LwakawaToru,KobayashiTomonori,MorikawaToshiyuki.WoodpresservativeseontainingterPene-maleieanhydrideadduetsandnaturalfungieidalandinseetieidaleomponents[P].Jpn.KokaiTokkyoKohoJP2002363006AZ,2002-12-18.
[30] NakahashiManabu, ShimokadoRyuiehiro.Diimideeompoundsformodifiersof enginee -ringplasties, generalpurposereings,andbiodegradableplasties[P].Jpn. KokaiTokkyo Koho [P]2003212849AZ,2003-7-30.
[31] AMLNO-CYCLIC-DICARBOXYLIC ACID IMIDES Jap.17580/65,clg.(Non-C on) 15.12.62(Jap) as 57228/62.
[32]高南,孟佳伦,王秋萍等.α-蒎烯一马来酸酐加成物及其应用的研究[J].林产化学与工业,1986,6(2):9-18.
[33]高南,王明谓,朱克奇等.萜烯双马来酞亚胺T(BM)I的研究[J].林产化学工业,1992,12(2):121-126.
[34]高南,潘鹏程,郁文.α-蒎烯一马来酸酐加成物同分异构体的研究-分离与性能[J].应用科学学报,1994,12(1):61-66.
[35]林中祥,程康华.萜烯马来酐加合物固化环氧树脂的性能研究[J].林产化工通讯,1997,2:18-19.
[36]周永红,王延,宋湛谦.α-蒎烯合成杀虫增效剂的研究[J].林产化学与工业,1998,18(3):1-11.
[37]周永红,谢晖,宋湛谦.松节油酰亚胺的合成、鉴定及杀虫增效活性[J].林产化学与工业,2001,21(3):6-10.
[38]周文富,贾德民.油酸接枝TMA多嵌段聚醋树脂[J].涂料工业,2000(8):8-11
[39]赖文忠,肖旺钏,周文富.新型紫外光固化TMA环氧丙烯酸醋树脂性能研究[J].三明高等专科学校学报,2001,18(2):44-48.
[40]段文贵,罗常泉,岑波,耿哲. N-(1-异丙基-2-羧基-4-甲基二环[2,2,2]-5-辛烯-3-羰基)-N`-芳基(硫)脲的合成[J].化学通报,2007,(9):695-698.
[41]张晋康王文龙俞雪英谭家勇.α-松油烯的研制[J],南京林业大学学报,1990.9.14(3):26～30
[42]陆占国,李健.1-甲基-4-异丙基-二环[2,2,2]辛烯-2,3-二酸酐制法[P].CN:1562990A,2005,1,12.
[43]李健,陆占国,刘宁,吉村吉博.松油烯与马来酸酐的环加成反应的条件研究.林产化学与工业,2006,26(3):93-96.
[44]于世涛,宋湛谦.固体超强酸SO42-/TiO2催化合成萜烯-马来酸酐加成物的研究[J].精细化工,1999,16(1):34-37.
[45]罗常泉,段文贵,岑波,班丽娜.α-蒎烯-马来酸酐加成物的合成.生物质化学工程,2006,40(3):25-28.
[46]哈成勇,肖永华,何云莲,黄伟雄.双戊烯合成萜马加成物的研究[J].广州化学,1995(1),31.
[47]哈成勇,胡建中.稀土金属衍生物催化合成萜马加成物反应的研究[J].化学工程师,1996,(3):54.
[48]哈成勇,金建忠.双戊烯合成萜马加成物反应的研究[J].天然产物的研究与开发,1997,9(1):19-23.
[49]林中祥,王阿法,马吉玲.碘催化双戊烯合成萜烯马来酸酐加合物[J].林产化工通讯,1996,4,11-12.
[50]林中祥.磷酸催化工业双戊烯与顺丁烯二酸酐加成反应[J].广西化工.1997,3(26):16-17.
[51]衣志伟,赵文浩,赖刚,等.氨水循环法制备邻苯二甲酰亚胺[J].化工技术与开发,2006,35(4):4-5.
[52] Kobayashi S,Ishitani H.Catalytic enantioselective ad.dition to imines[J].Chem Rev,1999,99(5):1069-1094.
[53]黄明智,李宏伟,庞怀林,张泉,任叶果,尹笃林.N-[2,4.二取代-5-(3-甲基-2,6-二氧-4-三氟甲基-1,2,3,6-四氢嘧啶-1-基)苯基]酰亚胺类化合物的合成及除草活性[J].有机化学,2008,28(8):1433-1438.
[54]钱旭红,唐军,陈卫东.四甲基萘并二呋喃的合成和DNA嵌入性能及其结构的分子模拟研究[J].高等学校化学学报,1996,9:1399-1403.
[55]徐晓勇,陈刚,钱晓红.吡啶甲基亚氨基噻_噁_唑烷的合成及生物活性[J],农药学学报,2003,5(1):27-33.
[56]慕长炜,覃兆海.吡啶类农药的研究进展[J].现代农药,2003,2(2):1-6.
[57]陈景文,陆国元等.取代氮杂环类化合物对大型蚤(Daphnia magna Straus)的定量结构-活性关系研究[J].农药,1996,35(5):21-24.
[58]吕兆萍张晓燕杨红.微波辐射合成N-(2-氯-1-氧-5-吡啶甲基)二甲酰亚胺类化合物和生物活性研究[J].有机化学,2008,28(1),89-93.
[59] Sena V M,Srivastava R M,Silva R 0,et .Synthesisand hypolipidemie activity of N-substituted phthalimidesPart V[J].IL Farmaco,2003,58(12):1283-1288.
[60] Katayama H,Greef F A,Kooiiman H,eta1.Towardpoly(aminophthalimide), structure of dimers and tri-mers[J].Tetrahedron,2007,63(28):6642-6653.
[61] Capitosti S M,Hansen T P,Brown M L.Thalidomideanalogues demonstrate dual inhabition of both anSiogenesisand prostste[J].Bioorg&Med Chem,2004,12(2):327-336.
[62] Shinji C,Nakamura T,Maseda S,et a1.Design andsynthesis of phthalimide·-type histone deaeetylase in·-habitors[J].Bioorg& Med Chem Lett,2005,15(20):4427-4431.
[63] Matsubayashi M,Kubo Y.Control of photophysicalproperties and photoreactions of aromatic imides byuse of intermoleeular hydrogen bonding[J]. OrgChem,2008,73 (13):4915-4919.
[64]郑凯,姚成.4-硝基-N-甲基-邻苯二甲酰亚胺合成新工艺[J].石油化工, 2004,33(2):145-148 .
[65]管冲,吕亮,王晓东,黄培.N-甲基邻苯二甲酰亚胺的新合成方法[J].南京工业大学学报, 2007,29(4):77-79.
[66]陈平,张士娥,黄朋勉,颜少慰,辛玉兵,李锦锦.微波催化合成Ⅳ_(2-吡啶基)邻苯二甲酰亚胺的研究[J].精细化工中间体,2008,38(6):29-31.
[67] Ryota H,Hiiroto W,Mamoru S.A solvent.free organicsynthesis from solid-state reactants through au-togenous fusion due to formation of molecular comple- and increasing alcohol nueleophilieity[J]. TetrahedronLett,2006,47(18):3111-3114.
[68]臧洪俊,李正名,王宝雷.固态有机合成反应进展[J].有机化学, 2003,23 (10):1058-1063.
[69] Tanaka K,Toda F.Solvent-free organic synthesis[J].Chem Rev,2000,100(3):1025-1074.
[70]唐林生,冯柏成.无溶剂有机合成的促进方法及前景[J].精细石油化工进展,2008,9(3):19-22.
[71]金锋,刘建军,陈海平,左胜利.新型N-氨基取代的1,6-亚甲基桥[1O]轮烯-3,4-二甲酰亚胺的无溶剂合成[J].合成化学,2009,17(5):606-608.
[72] Vogel E,Roth H D.The cyclodecapentaene system [J].Angew Chem Int Ed Engl,1964,3:228-229.
[73] Peart P A,Tovar J D.Me-ano[10]annulene revisited:extended delocalization through conjugated polymer bear-ing larger hllckel aromatics [J]. Org Lett, 2007, 9(16):3041-3044.
[74] Kajioka T,Ikai M,Fujikawa H,et a1.Disubstituted 1,6-methano[10]annulene derivatives for use in organiclight-emitting diodes[J].Tetrahedron,2004,60:6183- 6187.
[75] Kuroda S,Kajioka T,Fukuta A,et a1.Revisitation ofcycloheptatriene derivatives as abuilding block for varioussubstituted and fused 1,6-methano[10]annulenes and substituted 4,9-methano annulenes[J].Mini-Re-views in Organic Chemistry, 2007, 4: 31-49.
[76]金锋,刘建军,陈海平,左胜利.新型N-取代-1,6-亚甲基桥[10]轮烯-3,4-二甲酰亚胺的合成[J].北京化工大学学报(自然科学版),2010,37(1):28-30.
[77] WADA K.GOMIBuCHl T,Y0NETA Y,et a1.Preparation of Isoindolinone Derivative Insecticides:WO 2004l10149.2oo4.12-23.
[78]柳明,崔永亮,芮昌辉,王敏,王毅,段又生,刘尚钟.N-苯基氨基邻苯二甲酰亚胺衍生物的合成及初步杀虫活性[J].农药学学报,2009,11(1):51-54.
[79]赵新刚,于振环,李树丰等.耐热型ABS共聚物的研制[J].化工新型材料,2004,32(5):33-35.
[80]陶然,陶果.4-硝基苯基马来酰亚胺的合成研究[J].塑料工业, 2009,37(3):34-36.
[81]王国祥,刘华伟.N-(1-萘基)马来酰亚胺合成研究[J].绝缘材料,2007,40(5):10-14.
[82]曾玉香,卑凤利.N-(4-磺酸苯基)马来酰亚胺及其聚合物的合成与量子化学计算[J].天津化工,2008,22(6):35-37.
[83]史东明,钱捷.N-邻位取代苯基马来酰亚胺的研究概述[J].浙江化工,2009, 4O(2):20-23.
[84]钟红梅,侯德顺.N-异丙酸基马来酰亚胺的合成[J].化学工程师,2009,(3): 60-61.
[85]邢锦娟,钱建华,李国浩,王道林,谷坛.SO42-/ZrO2-MoO3复合固体酸催化合成N-环己基马来酰亚胺[J].石油与天然气化工,2008,37(4):337-339.
[86]李梅,仝春晖.微波促进N-嗯唑啉苯基马来酰亚胺的合成[J].河北化工,2008, (31)6:50-52.
[87]徐桂清,胡永洲,张冲,何俏军,杨波.吲哚马来酰亚胺类化合物的合成及其抗肿瘤活性[J].有机化学,2009,29(6):916-923.
[88]王彦林,赵忠波.阻燃剂N-(2,4,6-三溴苯基)马来酰亚胺的合成研究[J].盐业与化工,2007,37(l):9-11.
[89]匡永清,张生勇,姚素辰.合成N-甲基-4-氨基邻苯二甲酰亚胺的新路线[J].化学试剂,1992,14(5):301,31.
[90]Rafaella F, Davide C ,Elena M , et a1. A Simple CatalyticSynthesis of Condensed Pyridones from 0-Bromoarylcar-box-amides Involving Ipso Subsitution via Pa11adacyc1es[J].J AmChem Soc,2006,128:722-723.
[91] Jasztold-Howorko R,Pelczynska M ,et a1.The Synthesis andBiological Properties of a 1-(2-methylpyrid-in-4-y1)olivacine Derivative[J].Scientia Pharmaceutica, 2005, 73(3): 101-112.
[92]Tundo Pietro, Bressanello Salima,Loris Alessandro, et a1.Direct Synthesis of N -methylurethanes from Primary Amineswith Dimethyl Carbonate EJ].Pure and Applied Chemistry,2005,77(10):1719-1725.
[93]江琦.碳酸二甲酯在化工领域中的应用EJ].石油化工,2000,29(2):144-147.
[94]周远明,史美丽,王辉. N-甲基邻苯二甲酰亚胺的合成新工艺[J].精细石油化工,2008,25(4):4-6.
[95] Brana M F,Anorhe L,Tarrason G,et a1.Synthesisand biological evaluation of novel bisindolymaleimides that inhibit vascular endothelial cell proliferation[J]. Bioorg Med Chem Lett,2001,11:2701-2703.
[96] Mahboobi S,Eichhom E,Popp A,eta1.3-Bromo-4-(1H-3-indoly1)-2,5-dihydm -1H-2,5–pyrroledione de-rivatives as new lead compounds for antibacterially ac-tire substances [J]. Eur J Med Chem,2006,41:176-191.
[97] Katoh M,Dodo K,Fujita M,et a1.Structure-activityrelationship of N-methyl- bisindolylm aleimide derivatives as cell death inhibitors[J].Bioorg Med chemistry, 2005,15:3109-3113.
[98] Dodo K,Katoh M,Shimizu T,et a1.Inhibition of hy.drogen peroxide induced necrotic cell death with 3-ami-no-2-indolylmaleimide derivatives[J].Bioorg MedChem Lett, 2005, 15: 3114 -3118.
[99] Brenner M,Rexhausen H,Stefan B,et a1.Synthesisof amyriarubin B and related bisindolylmaleimides[J].Tetrahedron,1988,44:2887-2892.
[100]张海泉,贾红圣,赵圣印. 2-溴-3-(1-吲哚-3)-N-甲基马来酰亚胺的合成[J].合成化学,2008,16(1):105-106.
[101]魏清,李建生.N-氯代邻苯二甲酰亚胺的合成研究[J].化工科技市场, 2008,31(8):15-16.