单烷基取代苯基哌嗪衍生物的合成

单烷基取代苯基哌嗪衍生物是合成苯基哌嗪类化合物的重要中间体。以二乙醇胺为起始原料,在10℃滴加氯化亚砜,室温反应1 h,再于60℃反应5 h,经氯代反应制得β,β′-二氯代二乙胺盐酸盐,然后分别与2-甲基苯胺、4-叔丁基苯胺、4-甲基苯胺在130℃反应50 h,得2-甲基苯基哌嗪盐酸盐、4-叔丁基苯基哌嗪盐酸盐、4-甲基苯基哌嗪盐酸盐3个目标化合物,收率分别为78%、61%、67%。其结构经1HNMR、13CNMR、MS证实与目标化合物的结构一致。     

1-(2,3-二氯苯基)哌嗪盐酸盐的合成新方法

1-(2,3-二氯苯基)哌嗪盐酸盐是重要的医药中间体。以二乙醇胺为起始原料,经氯代反应制得β,β'-二氯代二乙基胺盐酸盐,然后在水溶液中不使用催化剂条件下与2,3-二氯苯胺经环合反应合成目标化合物1-(2,3-二氯苯基)哌嗪盐酸盐。产物结构经红外光谱、核磁共振氢谱分析验证与目标化合物的结构一致。该方法经济环保,简单易操作。     

卤素取代苯基哌嗪盐酸盐合成工艺研究

卤素取代苯基哌嗪盐酸盐是治疗过敏、抗抑郁及抗高血压等药物的重要中间体,以二乙醇胺为起始原料,经氯代反应、与卤素取代苯胺的亲核取代反应得到了7个卤代苯基哌嗪盐酸盐,其结构经红外光谱、质谱、核磁共振氢谱确认。通过对投料比和反应时间的研究,确定了一条较优的合成路线,该路线中原料易得,反应容易控制,收率较高,为工业化生产奠定了技术基础。     

1-（3-氯-2-甲基苯基）哌嗪盐酸盐的合成研究

目的：研究1-（3-氯-2-甲基苯基）哌嗪盐酸盐的最佳合成工艺。方法：以二乙醇胺为起始原料，经SOCL2氯代合成β，β’一二氯代二乙基胺盐酸盐，然后在碳酸钠的作用下与3-氯-2-甲基苯胺经环合反应合成目标化合物．并通过正交实验筛选最佳工艺条件。结果：通过正交实验筛选得到1-（3-氯-2-甲基苯基）哌嗪盐酸盐的最佳合成工艺条件，其结构经^1HNMR及IR表征，产率为63．2％。结论：该目标化合物的合成路线简单易操作，且得到较高的产率适合工业生产。     

联苯取代哌嗪丙醇类α1受体阻滞剂的合成

芳基哌嗪类化合物是一类具有α1受体亚型选择性的α1受体阻滞剂。文章采用苯酚与3-氯-1,2-环氧丙烷反应得到苯氧基取代环氧丙烷,再用联苯取代哌嗪对环氧开环,合成了联苯取代哌嗪-2-丙醇类衍生物,总收率达64%以上。合成的目标化合物均经MS和1H-NMR谱进行了结构确认。     

新型喹唑啉类α1受体阻滞剂的合成研究

以二乙醇胺为起始原料,经卤代反应制得双（2-卤乙基）胺氢卤酸盐,通过与取代苯胺进行环合反应而制得取代苯基哌嗪,再与2-氯-4-氨基-6,7-二甲氧基喹唑啉反应生成目标化合物。     

5-乙酰胺甲基-3-[3-氟-4-（1-哌嗪基苯基）]异噁唑啉的合成

以3,4-二氟苯甲醛、盐酸羟胺为原料,经缩合反应、氯代反应制得3,4-二氟苯肟氯代物（3）;以烯丙基胺为原料经乙酰化反应制得乙酰烯丙基胺（4）;化合物3与化合物4经环合反应、哌嗪取代反应合成终产物5-乙酰胺甲基-3-[3-氟-4-（1-哌嗪基苯基）]异噁唑啉（呈）。总收率为30．2％,纯度为99．1％（HPLC）。     

N-苯基哌嗪的合成

N-苯基哌嗪是合成低毒中枢性非成瘾性镇咳药—1苯基4-（2,3—二羟基丙基）哌嗪,和高效低毒、口服有效的广谱抗体表及体内真菌药物——1—乙酰基-4-（4-羟基苯基）哌嗪的重要中间体,近年来对哌嗪类化合物构效关系的研究,表明该类化合物具有不同程度5-羟基色胺受体阻断活性,并且将该部分与其它部分载体相结合可使化合物具有中枢或外周降压活性,哌嗪类化合物的合成与研究日益受到人们的重视,但国内对苯基哌嗪化合物的合成报道很少。目前是利用取代苯胺和双—（2-卤代乙基）胺进行环化反应的方法合成N-芳基哌嗪。但是,由于双—（2-卤代乙基）胺的毒性和取代芳基胺的低有效性的影响使得这种合成方法的发展受到相当大的限制,特别是多芳基胺。其他的合成方法主要有：（1）在固体A1203的作用下苯胺与双（2-卤代乙基）胺进行环化合成;（2）胺基锂与烷氧基本衍生物的亲核反应;（3）用氟芳烃—三羰基铬络合物发生亲电芳香取代反应。     

阿魏酰哌嗪盐酸盐的合成

目的：合成阿魏酰哌嗪盐酸盐。方法：以阿魏酸为起始原料,对羟基进行乙酰化保护,得到乙酰阿魏酸,经酰氯化后与哌嗪反应得到单取代哌嗪衍生物,除去乙酰基得到目标物。结果与结论：合成得到了阿魏酰哌嗪,目标化合物通过IR,1HNMR和MS等确证,产率为56．9％。     

烷氧基卤代吡啶及其二苯基膦衍生物的合成研究

设计合成了新型手性催化剂的中间体。以氯代吡啶为原料,经烷氧基取代,选择性单溴代,合成了系列烷氧基溴代吡啶,最后利用锂化反应的区域选择性,制备了二苯基膦烷氧基溴代吡啶;并对反应选择性进行了重点讨论。     

Ionic polymers with tunable liquid‐crystalline properties

Side‐chain polyesters were synthesized from N‐octyl‐, N‐dodecyl‐ or N‐hexadecyl‐diethanolamine and succinic acid anhydride. These polyesters were then transformed into polyester hydrochlorides by protonation of the amino groups using different amounts of HCl (20–100 mol%). Above 60 mol% the reaction is not quantitative and a degree of protonation of up to 88% is obtained. The structures of the synthesized polyesters and their hydrochlorides were determined by ¹H nuclear magnetic resonance spectroscopy. The thermal properties of the synthesized polyesters and their hydrochlorides were also studied using differential scanning calorimetry in relation to the side‐chain length and the degree of polyester protonation. The polyester with octyl side chains and its hydrochlorides were amorphous liquids at room temperature, while the polyester and polyester hydrochlorides with hexadecyl side chains formed a smectic crystalline phase, S_mB, or its tilted analogues. The polyester with a dodecyl side chain was also an amorphous liquid at room temperature, while its hydrochlorides with various degrees of protonation were smectic liquid crystals, as determined by X‐ray diffraction. By simply varying the degree of protonation the liquid crystal isotropization temperature was increased from 32 °C to 82 °C. Copyright © 2011 Society of Chemical Industry     

Side-chain polyesters and polyester hydrochlorides based on terephthalic acid

Side-chain polyesters and polyester hydrochlorides were synthesized from α-(bis(2-hydroxyethyl)amino)-ω-(4′-methoxy biphenyl-4-oxy) alkanes with different spacer lengths (Cn-diol, n=6, 8, 10) and terephthaloyl chloride. Since N-substituted diethanolamine acts as a stronger acid acceptor than triethylamine or pyridine, polyester hydrochlorides are formed during polyesterification instead of polyesters. Polyesters can be prepared from a chloroform solution of polyester hydrochlorides by extraction of HCl. During the polyesterification, linear polymers as well as cyclic oligomers are formed. All polymers were analyzed by ¹H NMR, size exclusion chromatography (SEC), differential scanning calorimetry (DSC), X-ray spectroscopy (XND) and polarizing optical microscopy (POM). Polyesters and polyester hydrochlorides differ greatly in solubility and thermal properties. Although no liquid crystalline phase transitions were detected for either kind of polymer, an ordered structure was observed in XRD experiments for both polymers and was ascribed to a crystal smectic E phase.     

Separation and Determination of Some Amines by Ion-Exchange Chromatography

Abstract

Papers impregnated with stannic molybdate have been used to chromatograph various amine hydrochlorides in varying concentrations of aqueous sodium nitrate and hydrochloric acid solutions. Various important separations are listed. The theoretical behavior of the movement of amine hydrochlorides on these papers is discussed with the help of plots of pH vs R_M .     

Dithio and thiono. Esters. 61. Synthesis of α-Amino Dithioesters and Endothiodipeptides

The α-amino ester hydrochlorides ( 1 ) are converted into N-protected α-amino amides ( 3 ), α-amino thioamides ( 4 ) and α-amino dithiomethylesters ( 5 ). Condensation of 5 with the alkali salts of α-amino acids gives rise to the endothiodipeptide alkali salts ( 7 ).     

铜和硫酸铜选择性催化合成单取代苯基哌嗪的新方法

报道了无溶剂条件下用铜和硫酸铜作催化剂由溴苯与哌嗪选择性合成单取代苯基哌嗪的新方法，并初步研究了溶剂、反应时间、反应温度对反应产率的影响。     

4-取代氨基喹唑啉的简便合成

以2-氨基苯甲腈为原料,DMF为反应试剂和溶剂,在苯磺酰氯的存在下高产率地合成了中间体亚胺啶的盐酸盐,该盐酸盐用NaOH溶液处理以后得到固态中间体亚胺啶,此中间体不须纯化,直接在乙酸中与乙醇胺或苯胺反应较高产率合成了6种标题化合物,并用IR、1HNMR和MS进行了表征。     

Modification of montmorillonite by cationic polyesters

Novel types of polyester hydrochlorides and polyesters were synthesized from N-octyl- or N-methyldiethanolamine and organic acid chlorides with varying chain length. Their structure, molar masses and glass transition temperatures were determined. Montmorillonite (MMT) was modified by cation exchange with the polyester hydrochlorides. The basal spacing was not significantly influenced by the length of organic acid chain but increased with the length of the alkyl group attached to nitrogen atom. Cation ratio of MMT and hydrochloride must have been at least 1:3 for quantitative cation exchange, indicating that only a part of polycation chain adheres to MMT surface. Hydrophobicity and organic content increased with increased exchange ratio, reaching approximately constant levels at ratios above 1:3.     

A simple method for the preparation of stable chitooligomers

The chitosan was degraded by the cheap, efficient, and commercially available enzymes in hydrochloric acid solution. The effect of molar ratio of added HCl to ? NH₂ of chitosan on the degradation was investigated, and the favorable ratio was between 0.50 and 0.95. The chitooligomer hydrochlorides were directly prepared by this simple method. The chitooligomer hydrochlorides were characterized by thermogravimetric analysis, differential thermal analysis, and Fourier transform infrared. These results show that the obtained chitooligomer hydrochlorides were much more stable than the chitooligomer acetates. This preparation procedure of chitooligomer hydrochlorides was simple and cheap, and helpful for the preservation of chitooligomers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009