氯化N-(3-长链烷氧-2-羟)丙基-N,N,N-三甲基铵的合成及性质

脂肪醇和环氧氯丙烷在相转移条件下反应得到长链烷基缩水甘油醚（收率97％），以此为原料和三甲胺盐酸盐反应得到氯化N－（3-长链烷氧-2-羟）丙基-N，N，N-三甲基铵（收率96％）．其结构通过红外光谱、核磁共振氢谱及元素分析结果得以证实。本文还测定了所合成产品的表面张力和临界胶束浓度．     

N-二甲氨基丙基-N-三乙氧基硅甲基全氟辛基磺酰胺的合成

全氟辛基磺酰氟与N,N-二甲基-1,3-丙二胺在甲苯中反应,得到N-3-二甲氨基丙基全氟辛基磺酰胺;再与氯甲基三乙氧基硅烷在乙醇中反应,制得N-二甲氨基丙基-N-三乙氧硅基甲基全氟辛基磺酰胺,产率达84%.通过红外光谱、核磁共振谱对目标产物进行了结构表征,测得该化合物在乙醇-水溶液中的表面张力为17.3 mN/m.     

N-长链烷基脒基碳酸氢盐表面活性的研究

以N-长链烷基脒为原料,在CO2氛围下制备得到N-长链烷基脒基碳酸氢盐。系统研究其表面活性发现：N-长链烷基脒基碳酸氢盐具有很好的表面活性,γcmc在20.5～32.3 mN/m之间;随着疏水链长的增加,N-长链烷基甲脒碳酸氢盐和N-长链烷基乙脒碳酸氢盐溶液的cmc和γcmc均逐渐降低,但N-长链烷基甲脒碳酸氢盐的cmc和γcmc均比N-长链烷基乙脒碳酸氢盐高;30～70℃时,N-长链烷基脒基碳酸氢盐溶液的表面张力均随温度的升高先降低后增大,热重分析表明这是由于在高温下脒盐会发生分解,溶液中的脒盐会部分转化成为中性脒,使得溶液中的脒盐浓度降低,表面张力变大。     

4-（4′，4′-二苯基-1′，3′-丁二烯基）-N，N-二（4″-甲基苯基）苯胺的合成及性能

该文通过V ilsm e ier反应,用4,4′-二甲基三苯胺制得了4-[N,N-二(4′-甲基苯基)]氨基苯甲醛(Ⅰ),收率85.4%;Ⅰ与1,1-二苯基-3-氯丙烯经W ittig反应合成了三苯胺衍生物4-(4,′4′-二苯基-1,′3′-丁二烯基)-N,N-二(4″-甲基苯基)苯胺(Ⅱ),收率43.0%,HPLC面积归一法测定目的产物为99.64%。通过紫外光谱、红外光谱、质谱和元素分析对产物的组成和结构进行了鉴定。用Ⅱ作空穴传输材料制成功能分离型有机光导体,测得其静电特性数据为V0=-580 V,VR=-20 V,E1/2=0.50 lx.s,表明Ⅱ具有优良的空穴传输特性。     

6-氟-3-(4-哌啶基)-1,2-苯并异噁唑盐酸盐的合成

4-哌啶甲酸(2)与乙酐反应制得N-乙酰基-4-哌啶甲酸(3),3经历酰氯化、与间二氟苯Friedel-Crafts反应得到N-乙酰基-4-(2,4-二氟苯甲酰基)哌啶(4).4脱保护产物5与盐酸羟胺进行缩合反应生成(2,4-二氟苯基)-(4-哌啶基)甲酮肟盐酸盐(6).最后,6经分子内环合、成盐反应得精神病治疗药的中...     

N,N-二(2-羟丙基)-2,4,6-三溴苯胺的合成

以苯胺、环氧丙烷和溴素为原料，合成了M，N-二(2-羟丙基)-2，4，6-三溴苯胺(BHTBA)。经红外光谱和元素分析等方法确认了BHTBA的化学结构。实验考察了物料配比、反应温度、反应时间、溶剂等条件对中间体N，N-二(2-羟丙基)苯胺及N，N-二(2-羟丙基)-2，4，6-三溴苯胺产率的影响。BHTBA可用作合成聚氨酯的阻燃型扩链剂。     

聚(3,3,3-三氟丙基)甲基/N-β-氨乙基-γ-氨丙基甲基硅氧烷

正陕西省石油化工研究设计院的王前进等人以KOH为催化剂,在110℃下反应,实现了1,35-三甲基-1,3,5-三(3,3,3氟丙基)环三硅氧烷和N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷的本体聚合,得到了侧链含(3,3,3-三氟丙基)和N-β-氨乙基-γ-氨丙基的聚甲基硅氧烷(FASO),其氨值为0.5702 mmol/g黏度为1200 mPa·s。将棉布样浸入固体质量分     

1-氨基-2-(N,N-二甲氨基)-4-羟基-蒽醌的合成新方法

以分散红60和DMF为原料,在碳酸钾作用下反应制备得到1-氨基-2-(N,N-二甲氨基)-4-羟基-蒽醌,产品收率92.8%。     

N-(6-氯-1-氧-3-吡啶甲基)邻苯二甲酰亚胺的合成

以邻苯二甲酰亚胺为起始原料,在常温条件下与氢氧化钾反应合成了邻苯二甲酰亚胺钾,其熔点352.8~353.4℃,收率95%。然后在70℃和微波辐射条件下,以邻苯二甲酰亚胺钾作为亲核试剂,与2-氯-5-氯甲基吡啶反应20 m in,制备了N-(6-氯-3-吡啶甲基)邻苯二甲酰亚胺,熔点140.3~140.5℃,收率98.5%。最后以双氧水为氧化剂,在75℃条件下,N原子氧化,合成了目标产物N-(6-氯-1-氧-3-吡啶甲基)邻苯二甲酰亚胺,熔点138.2~139.4℃,收率92%。利用红外光谱(FTIR)、核磁共振氢谱(1HNMR)、气-质联用仪(GC-MS)解析并确定了中间产物及目标化合物的结构。     

一种微波法制备N-((4-氨基-2-甲基嘧啶-5-基)甲基)甲酰胺

提供了一种微波法制备N-((4-氨基-2-甲基嘧啶-5-基)甲基)甲酰胺的新方法。在一定条件下,使用液体甲醇钠与盐酸乙脒进行游离反应,滤除氯化钠,蒸除甲醇得游离的乙脒,再与定量的N-(3-(2-氯苯基)-2氰基烯丙基)-甲酰胺和甲醇于微波中进行环合反应得目标产物并进行了数据表征。该工艺的最佳实验条件为0.13 moL盐酸乙脒与0.085 moL N-(3-(2-氯苯基)-2氰基烯丙基)-甲酰胺和10 mL甲醇在50℃条件下于微波中反应4.5 min得N-((4-氨基-2-甲基嘧啶-5-基)甲基)甲酰胺13.9 g,含量93.0%,收率90.4%。本方法具有反应时间短,收率高,易操作等特点,为工业化奠定了一定基础。     

甲基丙烯酸2-(二乙氧基硫代磷酰氧基)乙基酯的合成及应用

以甲基丙烯酸-β-羟乙酯(HEMA)与O,O-二乙基硫代磷酰氯为原料,在三乙胺作缚酸剂,氯化亚铜(CuCl)作催化剂的条件下,合成了甲基丙烯酸2-(二乙氧基硫代磷酰氧基)乙基酯(DPTEM)阻燃剂,再与丙烯腈共聚得到了阻燃聚丙烯腈共聚物。在n(HEMA)/n(三乙胺)=1,m(CuCl)/m(HEMA)=0.01~0.02,反应温度0~5℃条件下,DPTEM的产率达82%;通过FTIR、1HNMR、MS测试技术表征了DPTEM的结构,证明产品结构正确。丙烯腈共聚物中w(DPTEM)=25%时,极限氧指数(LOI)值可达27。该工艺已通过中试,正在进行扩大化生产。     

2-(N,N-二甲胺基)丙酸十二醇酯的合成研究

以 2 氯丙酸、正十二醇为原料 ,氯化铁催化 ,甲苯共沸回流带水酯化 ;再与二甲胺在三乙胺的作用下胺化 ,合成了透皮吸收促进剂 2 (N ,N 二甲胺基 )丙酸十二醇酯 (DDAIP) ,合成总收率达 72 5 %。考察了催化剂的用量、物质的量比及反应时间对反应的影响 ,确定出反应的最佳工艺条件为 :n(正十二醇 )∶n (2 氯丙酸 )∶n(FeCl3 ·6H2 O)∶n(甲苯 ) =1∶1 4∶0 0 4 5∶9 4 ,回流反应 4 5h制得 2 氯丙酸十二醇酯 ,收率为 83 8% ;n(2 氯丙酸十二醇酯 )∶n(二甲胺 )∶n(三乙胺 )∶n(氯仿 ) =1∶ 4∶1 5∶11,室温反应 16h制得DDAIP ,收率为 86 5 %。     

N，O，O′─三（对甲苯磺酰基）双（2─羟乙基）胺的合成

二乙醇胺和对甲苯磺酰氯在三乙胺存在下，反应生成Ｎ，０，Ｏ′－三（对甲苯磺酰基）双（２－羟乙基）胺，产率９３％。从反应混合物中分离得副产物Ｎ，Ｏ－二（对甲苯磺酰基）双（２－羟乙基）胺。     

植物生长调节剂2-(2,4-二氯苯氧基)三乙胺的合成新方法

以2,4 二氯苯酚为原料,采用相转移催化剂,经过醚化、胺化反应合成了2 (2,4 二氯苯氧基)三乙胺,总收率大于80%。研究了反应物的摩尔配比、反应时间及反应温度对2,4 二氯苯酚和二溴乙烷的醚化反应的影响,优惠工艺条件为:2,4 二氯苯酚与1,2 二溴乙烷配比为1∶30(mol/mol),反应温度80℃、反应时间10h。通过红外光谱、核磁共振氢谱和元素分析确定了目标化合物的结构。     

氯化N—（3—苯氧—2—羟）丙基—N，N，N—三烷基铵的合成及其相转移催化性能

苯酚和环氧氯丙烷在相转移催化条件下反应生成苯基缩水甘油醚，然后和三甲胺或三乙胺的盐酸盐反应得到氯化N-（3-苯氧-2-羟）丙基-N，N，N-三烷基铵，其结构通过红外光谱、核磁共振氢谱及元素分析得以证实。测定了其对氧烷基化反应、氮烷基化反应的相转移催化作用。     

Surface-Enhanced Raman Scattering from Polyimide Model Compounds on Functionalized Metal Surfaces. Part II: Phthalic Anhydride/meta-Aminothiophenol/Silver

The interphase between a polyimide and a metal substrate was modeled by depositing phthalic anhydride (PA) onto a silver substrate pretreated with meta-aminothiophenol (m-ATP) and then curing in a mixture of acetic anhydride and pyridine or triethylamine. Surface-enhanced Raman scattering (SERS) and reflection-absorption infrared spectroscopy (RAIR) were used to determine the molecular structure of the interphase. It was found that m-ATP was adsorbed dissociatively onto silver substrates through the thiol groups. The tilt angle for m-ATP molecules adsorbed on silver substrates was determined using RAIR to be approximately 39°. However, there was no preferred rotational angle of the adsorbed APDS molecules about the molecular axes. When PA was deposited onto m-ATP pretreated silver substrates, anhydride groups of PA reacted with amino groups of m-ATP to form amic acids. When PA/m-ATP/Ag samples were chemically cured in acetic anhydride and pyridine or triethylamine, isoimide was the predominant product regardless of the use of pyridine or triethylamine as catalyst. These results were different from those obtained from PA/APDS/Au systems in which imide was the major product in the presence of triethylamine. These differences in the relative composition of cured products between two model systems were explained by the effect of substituents attached to APDS and m-ATP benzene rings.     

SELF-ADHESION HYSTERESIS IN POLYDIMETHYLSILOXANE ELASTOMERS

The interphase between a polyimide and a metal substrate was modeled by depositing phthalic anhydride (PA) onto a silver substrate pretreated with meta-aminothiophenol (m-ATP) and then curing in a mixture of acetic anhydride and pyridine or triethylamine. Surface-enhanced Raman scattering (SERS) and reflection-absorption infrared spectroscopy (RAIR) were used to determine the molecular structure of the interphase. It was found that m-ATP was adsorbed dissociatively onto silver substrates through the thiol groups. The tilt angle for m-ATP molecules adsorbed on silver substrates was determined using RAIR to be approximately 39°. However, there was no preferred rotational angle of the adsorbed APDS molecules about the molecular axes. When PA was deposited onto m-ATP pretreated silver substrates, anhydride groups of PA reacted with amino groups of m-ATP to form amic acids. When PA/m-ATP/Ag samples were chemically cured in acetic anhydride and pyridine or triethylamine, isoimide was the predominant product regardless of the use of pyridine or triethylamine as catalyst. These results were different from those obtained from PA/APDS/Au systems in which imide was the major product in the presence of triethylamine. These differences in the relative composition of cured products between two model systems were explained by the effect of substituents attached to APDS and m-ATP benzene rings.     

头孢雷特中间体2-氨甲基苯乙酸的氨基保护

头孢雷特是临床中常用的第二代头孢类抗生素,其临床应用前景十分看好。2-氨甲基苯乙酸是生产头孢雷特的重要中间体,由于该化合物中同时存在氨基和羧基两个活性集团,因此,在生产中需要先将氨基进行保护,以便羧基进行下一步反应。     

Copper‐Catalyzed Highly Efficient Multicomponent Reactions of Terminal Alkynes,Acid Chlorides,and Carbodiimides: Synthesis of Functionalized Propiolamidine Derivatives

Functionalized propiolamidine derivatives were prepared in good to excellent yields under very mild conditions via a copper‐catalyzed multicomponent reaction (MCR) of readily available terminal alkynes, acid chlorides and carbodiimides with the assistance of triethylamine. The mechanism of this MCR is postulated.     

三光气合成N-硝基-N,N'-二苯基脲的“一锅法”工艺

以N-硝基-2,4,6-三氯苯胺为原料,三光气为酰化剂,一锅法合成N-硝基-N-(2,4,6-三氯苯基)-N′-3,5-二甲基苯基脲。并确定酰化反应的优惠条件为:甲苯作溶剂、三乙胺为催化剂、n(三光气)∶n(N-硝基-2,4,6-三氯苯胺,5)=0.36∶1,反相滴加,反应温度为20℃,反应时间2h,此条件下收率为80%左右。通过元素分析、红外光谱分析、核磁氢谱对产品进行了结构鉴定。