N-苄基苦参醇桂皮酸酯的合成

目的：合成N-苄基苦参醇桂皮酸酯并优化其合成工艺。方法：以苦参碱为原料,通过碱水解开环,氯苄苄基化得到N-苄基苦参酸苄酯,再经四氢铝锂还原得到N-苄基苦参醇,最后在EDAC脱水剂作用下与桂皮酸缩合,得到目标物N-苄基苦参醇桂皮酸酯。结论：设计合成的N-苄基苦参醇桂皮酸酯收率达60.2%,产物的化学结构经TLC、IR、MS、1H-NMR等确证。     

N-苄基苦参醇阿魏酸酯的合成

目的:合成N-苄基苦参醇阿魏酸酯并优化其合成工艺。方法:以苦参碱为原料,通过碱水解开环,氯苄苄基化得到N-苄基苦参酸苄酯,再经四氢铝锂还原得到N-苄基苦参醇,与乙酰阿魏酸在EDAC作用下缩合,得到N-苄基苦参醇乙酰阿魏酸酯,最后水解得目标物N-苄基苦参醇阿魏酸酯。结果与结论:设计并合成了N-苄基苦参醇阿魏酸酯,IR、MS、1H-NMR等方法确证目标产物的化学结构正确。经优化的合成工艺更具可行性,反应条件温和,后处理简便。     

N-苄基苦参酸姜黄素酯的合成

目的:合成N-苄基苦参酸姜黄素酯并优化其合成工艺。方法:以苦参碱为原料,通过水解开环,苄基化得到N-苄基苦参酸苄酯,继而水解得到N-苄基苦参酸,最后在脱水剂作用下与姜黄素缩合,得到目标物N-苄基苦参酸姜黄素单酯。结果与结论:设计合成了N-苄基苦参酸姜黄素酯,收率达51.3%,产物的化学结构经IR、MS、1H-NMR等表征。     

N-苄基苦参酰甘氨酸的合成

目的:合成N-苄基苦参酰甘氨酸。方法:以苦参碱为原料,经水解、苄基化、水解等反应得到N-苄基苦参酸,然后利用其结构上的羧基,与甘氨酸甲酯盐酸盐缩合形成N-苄基苦参酰甘氨酸甲酯,再进一步水解生成N-苄基苦参酰甘氨酸。结果与结论:合成得到目标化合物,其结构经MS、IR、1H-NMR等方法确证,产物收率为74.4%(以N-苄基苦参酸计)。     

N-乙基苦参酸百里酚酯的合成

以苦参碱为原料,通过碱水解开环,溴乙烷乙基化得到N-乙基苦参酸乙酯,继而水解得到N-乙基苦参酸,最后在脱水剂作用下与百里酚缩合,得到N-乙基苦参酸百里酚酯。目标化合物的化学结构经红外光谱、核磁共振氢谱及质谱确证。考察了N-乙基苦参酸与百里酚缩合反应中脱水剂、反应物配比、温度等因素对产率及反应时间的影响,优选出最佳合成工艺。最佳合成工艺为:以1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDCI)为脱水剂,反应物配比为n(N-乙基苦参酸)∶n(百里酚)=1∶1.5,反应温度45~50℃,该条件下N-乙基苦参酸百里酚酯的收率达60.6%。     

一种紫外线吸收剂的合成新方法

采用新方法合成了紫外线吸收剂苯基-(3,5-二叔丁基-4-羟基苄基)丙二酸二(1,2,2,6,6-五甲基-4-哌啶)酯。苯基丙二酸二乙酯和N-甲基-2,2,6,6-四甲基-4-哌啶醇在甲苯中微纳米碳酸钾催化下反应,得到苯基丙二酸二(1,2,2,6,6-五甲基哌啶醇)酯,然后在乙醇中与 4-羟基-3,5-二叔丁基苄基氯反应,得到目标产物,总收率为80%。化合物的结构通过1H NMR和13C NMR进行了表征。     

2-氰基-2,2-二(4-溴苄基)乙酸乙酯的合成

室温下,在二氯甲烷溶剂中,用三溴化硼溴化4-溴甲苯甲基侧链,合成了4-溴溴苄,收率84.4%;无水乙醇回流条件下,物料比n(4-溴溴苄)∶n(吡啶)=1∶1时,合成溴化N-(4-溴苄基)吡啶,收率95.3%;物料比n(溴化N-(4-溴苄基)吡啶)∶n(丙二腈)=2∶1时,合成2,2-二(4-溴苄基)丙二腈,收率67.0%;二氯亚砜催化2,2-二(4-溴苄基)丙二腈在有水的条件下醇解合成2-氰基-2,2-二(4-溴苄基)乙酸乙酯,收率65.3%。     

4-((4-氯苄基)氧基)-N,N-二乙基丁-2-炔-1-胺的合成研究

以对氯苄醇、3-溴丙炔为起始原料,经过醚化反应合成中间产物1-氯-4-((丙-2-炔-1-基氧基)甲基)苯,再与多聚甲醛、三乙胺经曼尼希反应,合成具有抗心律不齐功能的化合物4-((4-氯苄基)氧基)-N,N-二乙基丁-2-炔-1-胺。通过GC-MS和1H NMR表征了产物结构。确定合成4-((4-氯苄基)氧基)-N,N-二乙基丁-2-炔-1-胺的较优条件为:1-氯-4-((丙-2-炔-1-基氧基)甲基)苯1 mmol,n(1-氯-4-((丙-2-炔-1-基氧基)甲基)苯)∶n(多聚甲醛)∶n(三乙胺)=1∶1∶2,溶剂为二氧六环,催化剂为氯化亚铜,其用量占原料质量的20%,反应温度90℃,反应时间6 h,在上述适宜条件下4-((4-氯苄基)氧基)-N,N-二乙基丁-2-炔-1-胺的得率为74.6%。     

4-((4-氯苄基)氧基)-N,N-二乙基丁-2-炔-1-胺的合成研究

以对氯苄醇、3-溴丙炔为起始原料,经过醚化反应合成中间产物1-氯-4-((丙-2-炔-1-基氧基)甲基)苯,再与多聚甲醛、三乙胺经曼尼希反应,合成具有抗心律不齐功能的化合物4-((4-氯苄基)氧基)-N,N-二乙基丁-2-炔-1-胺。通过GC-MS和1H NMR表征了产物结构。确定合成4-((4-氯苄基)氧基)-N,N-二乙基丁-2-炔-1-胺的较优条件为:1-氯-4-((丙-2-炔-1-基氧基)甲基)苯1 mmol,n(1-氯-4-((丙-2-炔-1-基氧基)甲基)苯)∶n(多聚甲醛)∶n(三乙胺)=1∶1∶2,溶剂为二氧六环,催化剂为氯化亚铜,其用量占原料质量的20%,反应温度90℃,反应时间6 h,在上述适宜条件下4-((4-氯苄基)氧基)-N,N-二乙基丁-2-炔-1-胺的得率为74.6%。     

在Br(o)nsted酸性功能化离子液体中室温无溶剂合成长链脂肪酸甲酯

该文以N-甲基咪唑、苄基氯、硫酸、氯磺酸为原料,经季铵化、离子交换、磺化3步反应合成了磺酸型Br(o)nsted 酸性离子液体:1-(4-磺酸基苄基)-3-甲基-咪唑硫酸氢根盐,通过FTIR、1HNMR对其结构进行了确证.以其作为反应介质与催化剂,考察了C4～C16的直链脂肪酸与甲醇的Fischer酯化反应,确定了最佳反应条件:n(酸):n(醇):n(离子液体)=1:1:0.1,反应温度25 ℃、反应时间3～4.5 h,产率84%～98%,产物气相色谱纯度≥96%.该法无需加热、分水,产物分离简便,离子液体经真空除水后可重复使用,循环使用3次,催化活性保持不变.     

新藤黄酸制备工艺优化

优化了新藤黄酸制备工艺。以制备藤黄酸吡啶盐的母液为原料,酸化后柱层析分离得到新藤黄酸。分离得到目标物,产率达20%。优化后的制备工艺简化了操作,降低了成本,利于新藤黄酸的大量制备。     

Neopentylbenzene的合成工艺研究

分别采用苯甲醇和氯苄为起始原料合成化合物Neopentylbenzene,并探讨了两条反应路线的条件、收率及工业生产的可行性,从而确定了以苯甲醇为起始原料的合成路线是一条较佳工业合成工艺路线,其总收率为30.1%。     

乙酸苄酯的合成

以氯化苄和无水乙酸钠为原料,三乙基苄基氯化铵(TEBAC)为催化剂合成乙酸苄酯。考察了水的加量、反应温度、原料配比、催化剂用量、反应时间等因素对反应收率的影响。结果表明:当n(氯化苄):n(无水乙酸钠):n(TEBAC):n(水)=1:1.25:0.02:0.45,反应温度110℃,反应时间4h,产物摩尔收率可达94.50%。     

水杨酸苄酯的合成工艺改进

介绍了以氯化苄和过量水杨酸在碳酸氢钠介质中利用相转移催化合成水杨酸苄酯的改进工艺,收率达８１ ％ ,香气良好。     

Cure behavior of epoxy resins with different kinds of onium salts as latent thermal catalysts

Two latent thermal catalysts, Dimethyl phenacylsulfonium hexafluoroantimonate, (Benzyl‐S), and triphenyl benzyl phosphonuim hexafluoroantimonate, (Benzyl‐P), were synthesized. Both these synthesized catalysts fulfill requirements for a rapid cure at a moderately elevated temperature in curing the epoxy resins of neat 3,4‐epoxycyclohexylmethyl‐3,4‐epoxycyclohexane‐carboxylate, (EPC), neat 2,2‐bis(4‐glycidyloxyphenyl)propane, (EPA), and their hybrid resin. The cure behavior of these resins cured individually with the synthesized catalysts was studied through correlation of the in situ FTIR (Fourier transform infrared) spectroscopy and DSC (differential scanning calorimetry) dynamic scanning results. Catalyst Benzyl‐S is more effective than Benzyl‐P. Resin EPC is significantly more sensitive to the latent thermal catalysts than the EPA resin. Activated chain‐end (ACE) and activated monomer (AM) mechanisms are basically adopted. Isomerization occurs in the neat EPA cure system, and transesterification takes place in all systems containing EPC species in the latter curing stage. Most importantly, ester linkages C?O in the hybrid systems have been destroyed at some time during the curing process, but some reformed at the latter curing stage. It is most likely that the C?O linkage in the EPC segments was attacked by the activated chain‐end of the epoxide group of EPA species to form a five‐membered cyclic acetal. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3539–3551, 2001     

顺酐一步法复合催化合成富马酸二苄酯

顺丁烯二酸酐和苄醇在复合催化剂对甲苯磺酸－硫脲的存在下以甲苯作带水剂一步合成富马酸二苄酯，收率在８０％以上。     

Electrochemical coupling reactions of benzyl halides on a powder cathode and cavity cell

Benzyl halides adsorbed on a cathode made of pure or silver-doped graphite powder were reduced in an undivided cell using an aqueous electrolyte and an inert anode, in the absence or presence of benzaldehyde. The product ratio is influenced by the applied potential, the leaving halide group and presence/absence of silver electrocatalyst. The highest yield of bibenzyl was obtained from the electrolysis of benzyl bromide on silver-doped graphite at a constant potential equal to −1.0 V vs Ag/AgCl (sat. KCl). Benzyl chloride is less prone to dimerization, but undergoes efficient carbonyl addition to benzaldehyde, especially in the presence of silver. The results can be interpreted as a competition of radical and anionic processes.     

Nonvolatilealpha-branched chain fatty esters. II

A group of nonvolatilealpha-branched esters was prepared by the di-tertiary butyl peroxide-promoted addition of normal esters to terminal olefins containing methyl branches or aryl groups. Methyl stearate was added to 3,7-dimethyl-1-octene, 3,5,5-trimethyl-1-hexene, and 4-phenyl-1-butene. The reaction with 2,4,4-trimethyl-1-pentene, a terminal alkene with a methyl branch at the internal ethylenic carbon, was not successful. Benzyl 2-(4-phenylbutyl) octadecanoate was prepared by transesterification of the corresponding methyl ester. Benzyl 2,2-dimethylpropanoate, which has no α-hydrogen in the acyl portion of the molecule, was added to 1-hexadecene to form α-hexadecylbenzyl 2,2-dimethylpropanoate. Lubricant evaluation data were obtained on the above compounds. Presented at the AOCS Meeting, New Orlenas, May 1967. E. Utiliz. Res. Dev. Div., ARS, USDA.     

苯甲酸苄酯合成工艺改进研究

研究了在有水存在下,利用相转移催化剂三乙胺催化苯甲酸钠和氯化苄的酯化反应。收率达８０％～９０％,酯含量在９８％以上。该工艺操作简单,是一种较为简便的适合于工业化生产的合成方法。     

邻苯二甲酸丁苄酯的相转移催化合成

本文研究了用相转移催化剂和三相催化剂合成BBP的工艺条件。当以新洁而灭为相转移催化剂时,最佳反应条件下产物收率达97％。当以PSTB为三相催化剂时,最佳反应条件下产物收率为86％。