合成5—氟尿嘧啶—N^1—甲酰基异亮氨酸的新方法

合成５－氟尿嘧啶－Ｎ~１－甲酰基异亮氨酸的新方法叶发青（咸宁医学院化教研室，咸宁４３７１００）５－氟尿嘧啶－Ｎ１－甲酰基异亮氨酸具有较高的抗肿瘤活性，并且毒副作用较低［１］。对此类药物的开发具有较广泛的应用前景。它也是合成含５－氟尿嘧啶的高分子抗癌药?..     

α-（5-氟尿嘧啶-1-基甲基甲酰基）氨基-2-甲基戊酸的合成

采用碳二亚胺法以5-氟尿嘧啶-1-基乙酸、二环已基碳二酰亚胺和L-亮氨酸为原料,1-羟基苯并三氮唑为辅助试剂,通过液相偶联法合成了-种新型的α-（5-氟尿嘧啶-1-基甲基甲酰基）氨基-2-甲基戊酸化合物。通过红外光谱、元素分析和核磁共振氢谱等确证了其结构。     

5-氟尿嘧啶-1-基乙酸合成方法的改进

以氯乙酸和5-氟尿嘧啶为原料合成了标题化合物,产率81％．产品纯度99．57％。     

5-氟尿嘧啶-1-基乙酸合成新方法

5-氟尿嘧啶与氢氧化钾作用得到5-氟尿嘧啶单钾盐,5-氟尿嘧啶单钾盐与氯乙酰乙酯得到N1-乙酸乙酯取代5-氟尿嘧啶,再经酸性条件下水解合成了5-氟尿嘧啶-1-基乙酸,产率85%,产品纯度99.52%,并采用红外、核磁、紫外的方法表征了产物的结构,确定了产品的最佳反应条件。采用此法制备5-氟尿嘧啶-1-基乙酸原料便宜易得,操作方法简单,产物具有较高的产率和纯度。     

5-甲酰基尿嘧啶合成工艺研究

本文研究了5-甲酰基尿嘧啶的合成新工艺.该工艺原料易得,反应条件温和,收率高.首先以尿嘧啶为底物,与多聚甲醛进行羟甲基化反应,制备得到5-羟甲基尿嘧啶中间体,进一步以该中间体为底物进行氧化反应,制备得到5-甲酰基尿嘧啶.重点考察了反应时间、溶剂、温度、催化剂等四类条件对氧化反应的影响.最终以尿嘧啶为起始原料制备5-甲酰...     

α-(5-氟尿嘧啶-1-基甲基甲酰基)氨基戊二酸的合成与表征

以5-氟尿嘧啶-1-基乙酸、二环己基碳二酰亚胺和L-谷氨酸为原料,用1-羟基苯并三氮唑(BtOH)作辅助试剂,采用碳二亚胺法并通过液相偶联合成了标题化合物,收率为81.5%。通过红外光谱、元素分析确证了该种“5-氟尿嘧啶短肽化合物”的结构。     

4-甲基-5-甲酰基噻唑的合成

以氯丙酮和硫脲为起始原料,经环合、Vilsmeier甲酰化、重氮化还原得到头孢托仑匹酯关键中间体4-甲基-5-甲酰基噻唑,反应总收率为42．8％。重点考察了Vilsmeier甲酰化反应中双（三氯甲基）碳酸酯（BTc）／DMF用量、反应温度和反应时间对中间体4收率的影响,得出了较佳的工艺条件,并对其反应机理进行了探讨。     

1-甲酰基苯并三唑席夫碱的合成及荧光性能

以苯并三唑、甲醛、伯胺为原料,合成了3种新的1-甲酰基苯并三唑席夫碱,分别简称为FBTTS、FBTSC和FBTAP。其最佳反应条件是以TBAB为相转移催化剂,三氯甲烷作溶剂,反应温度控制在50~55℃。通过IR、元素分析等检测手段,确证了3种新席夫碱的相应结构,并对其荧光性能进行了初步测试。     

用Curtius重排反应合成4-氯苯基异氰酸酯

按Curtius重排反应原理 ,采用叠氮化钠与4-氯苯甲酰氯反应合成4-氯苯基异氰酸酯。该法反应条件温和 ,操作简便 ,产率高     

α-(-5-氟尿嘧啶-1-基甲基甲酰基)氨基-3-羟基丙酸的合成及红外光谱研究

采用碳二亚胺法以5-氟尿嘧啶-1-基乙酸、二环己基碳二酰亚胺和L-丝氨酸为原料,1-羟基苯并三氮唑为辅助试剂,通过液相偶联法合成了一种新型的α-（5-氟尿嘧啶-1-基甲基甲酰基）氨基-3-羟基丙酸化合物。通过红外光谱、元素分析确证了该种“5-氟尿嘧啶短肽化合物”的结构。     

固-液相转移催化法合成对甲基苯异氰酸酯

讨论了在固－液相转移催化下，采用Curtius重排反应，合成对甲基苯基异氰酸酯的新方法，合成反应在非水溶液中进行，对最佳反应条件进行了探讨，该法具有反应条件温和，操作简便，产率高等优点。     

洋茉莉醛的合成新路线

以香兰素为原料经脱甲基得到3,4-二羟基苯甲醛,再与二氯甲烷环合得到3,4-亚甲二氧基苯甲醛,总收率为31.1%.产品结构经红外光谱(IR)及氢核磁共振谱确证.     

The study of oxazolidone formation from 9,10-epoxyoctadecane and phenylisocyanate

The formation of oxazolidone from 9,10-epoxyoctadecane and phenylisocyanate was studied. One branch of epoxidized vegetable oil with one epoxy group per chain corresponds to 9,10-epoxyoctadecane. This model could explain the probability of oxazolidone formation from natural oil-derived epoxides. Epoxidized natural oils are TG consisting of glycerin and three FA with or without one to three epoxy groups in the middle of the chain. To study oxazolidone formation from an internal epoxy group without possible interference from the side reactions on the ester group, 9,10-epoxyoctadecane was selected as the most appropriate model compound. Epoxy groups in the middle of allong aliphatic chain are of low reactivity toward isocyanates, and preparation of oxazolidones requires fairly harsh conditions such as high temperatures and catalysts, which also promote side reactions. The dominant side reaction is rearrangement of the epoxy groups. We found that the direction and magnitude of the rearrangement and the yield of any particular product depended on the catalyst used. Lithium chloride, aluminum trichloride, and zinc iodide catalyzed oxazolidone formation, along with the catalysis of side reactions such as ketone and carbonate formation. Aluminum trichloride showed the highest conversion of 9,10-epoxyoctadecane to oxazolidone. Aluminum triisopropoxide, triphenylantimony iodide, and imidazole did not catalyze the formation of oxazolidone. They were effective as catalysts of epoxy group rearrangement and promoted the formation of hydroxyl, ketone, and carbonate compounds. Hydroxyl groups reacted with isocyanate to produce urethane.     

Synthesis and characterization of new soluble and thermostable polyimides via novel diisocyanates

A facile synthesis of two novel diisocyanates containing methylene groups and preformed imide structure is described. Furthermore, six thermally stable and soluble polyimides were synthesized by polycondensation of these two diisocyanates with pyromellitic dianhydride (PMDA), 3, 3 ′,4, 4 ′‐benzophenonetetracarboxylic dianhydride (BTDA) and hexafluoroisopropylidene‐2,2‐bis‐(phthalic anhydride) (6FDA) in N,N ‐dimethyl acetamide. All monomers and polymers were characterized by conventional methods and their physical properties such as solution viscosity, solubility properties, thermal stability and thermal behaviour were studied. © 1999 Society of Chemical Industry     

O-正丙基硫代磷酰二氯重排反应研究

介绍了Ｏ 正丙基硫代磷酰二氯在常温范围内Ｐｉｓｔｓｃｈｉｍｌｃｋａ重排生成Ｓ 正丙基硫代磷酰二氯的反应,收率达８４９％。     

2-氯腺苷的合成路线研究

以2-氯腺嘌呤和1,2,3,5-四乙酰基核糖为原料,四氯化锡为催化剂,在130℃下反应15min,得到中间体2-氯腺嘌呤-2’,3’,5’-三乙酰基核苷。室温下用氨的甲醇饱和溶液脱酰基,在乙醇中进行结晶,得到白色2-氯腺苷粉状晶体,收率70.2%,纯度(HPLC)≥99.0?,155℃发生分解。     

绿色的Curtius重排及其新应用的研究

Curtius重排是众多重排反应中较为绿色的重排反应。它易反应,几乎无污染,产率高,因此其应用相当广泛,前景也很诱人。近年来,Curtius重排在精细有机合成中又有了令人注目的新应用。     

高效萃取剂LIX841的合成及应用

高效萃取剂LIX841是一种高效的铜萃取剂,结构为2-羟基-5-壬基苯乙酮肟,实验通过壬基酚与乙酸酐,80℃合成中间产物壬基酚乙酸酯,经分离提取,所得中间产物溶于四氯乙烯并在120℃下持续1.5h重排反应得壬基苯乙酮,所得产物在85℃与盐酸羟胺溶液混溶反应2h,得终产物2-羟基-5-壬基苯乙酮。     

唑啉草酯的合成路线评述

综述了除草剂唑啉草酯的合成路线,并对两条路线进行了比较和评价,以2,6-二乙基-4-甲基苯胺为原料,经重氮化、偶联和醇解反应合成唑啉草酯的路线为最佳路线。     

Direct synthesis of soluble and thermally stable poly(urethane-imide)s from a new triimide-dicarbonylazide

A new aromatic dicarbonylazide (3) bearing three preformed imide rings was synthesized by treating N-[3,5-bis(trimellitimido)phenyl]phthalimide (1) with thionyl chloride followed by a nucleophilic reaction with sodium azide. A novel family of fully aromatic poly(urethane-imide)s with inherent viscosities of 0.19-0.24 dl g⁻¹ were prepared from triimide-dicarbonylazide 3 and various aromatic diols. The polyaddition reactions readily proceeded in desirable yields as one-pot reactions starting from 3 without separately synthesis of the corresponding diisocyanate. All of the resulted polymers were thoroughly characterized by spectroscopic methods and elemental analyses. The poly(urethane-imide)s exhibited an excellent solubility in a variety of polar solvents. Crystallinity nature of the polymers was estimated by means of WXRD. The glass transition temperatures of the polymers determined by DSC method were in the range of 197-219 °C. The 10% weight loss temperatures of the poly(urethane-imide)s from their TGA/DTG curves were found to be in the range of 391-412 °C in nitrogen. The films of the polymers were also prepared by casting the solution.