4-氯丁醛的合成工艺及工艺中的三废回收处理

以4-氯丁醇为原料,氯铬酸吡啶盐为氧化剂,氧化剂制备完毕不结晶、分离直接带水后,滴加4-氯丁醇进行氧化反应,反应液经过硅胶柱分离,再蒸馏得4-氯丁醛,工艺稳定,含量达96%以上,收率达60%,可工业化生产;同时进行了氧化剂的处理回收利用研究。国内资料没有介绍氯铬酸吡啶盐的处理方法,通过实验找到了三废处理的方法。     

3-溴代丁醛缩乙二醇的合成改进

巴豆醛先与溴化氢加成，再与乙二醇缩醛化得到3-溴代丁醛缩乙二醇，收率80．8％。     

4-氯-2-羟基苯乙酮的合成

以3-氨基苯酚为原料,经酰化、甲基化反应和Fries重排反应制得N-(4-乙酰基-3-羟基苯基)乙酰胺,再经去乙酰化、重氮化和Sandmeyer反应得到4-氯-2-羟基苯乙酮,总收率约44%.     

4-氯丁醛缩二甲醇的制备

4-氯丁醛缩二甲醇(1)是合成色胺类药物,如佐米格(zomitriptan)、舒马曲坦(sumatriptan)和褪黑激素(melatonin)等的中间体[1,2].文献[3]用对甲苯磺酰氯保护1,4-丁二醇的单羟基后,进行选择性氧化得醛,再经缩醛化、氯化制得1,总收率低于20%.     

2-正丁基-4-氯-5-甲酰基咪唑的合成新路线

目的：合成抗高血压药氯沙坦的关键中间体2-正丁基-4-氯-5-甲酰基咪唑。方法：戊腈与甲醇在甲醇钠的作用下加成得到1-甲氧基-1-亚胺戊烷（2）,经取代、环合得到目标化合物2-正丁基-4-氯-5-甲酰基咪唑（1）。结论：本工艺具有试剂易得,反应条件温和,收率高（59.02%）的特点,适合工业化生产。     

4-氨基-2-氯吡啶的合成

4-氨基-2-氯吡啶(1)是医药及农药中间体[1～3],主要有以下3条合成路线:(1)2-氯-4-乙酰基吡啶与盐酸羟胺反应生成相应的肟,经Beckmann重排得到的2-氯-4-乙酰胺基吡啶再经水解制得,总收率77.8%[4,5].(2)2-氯-4-氨甲酰基吡啶在PhI(OAc)2作用下进行Hofmann重排制得,总收率85.4%[6].     

2-氯-4-氨基-6,7-二甲氧基喹唑啉的合成

目的合成2-氯-4-氨基-6,7-二甲氧基喹唑啉。方法以香草醛为原料,经甲基化、硝化、氧化、还原、环合、氯化、胺化等反应制得目标化合物。结果及结论该实验方法总收率26%,反应条件温和,操作简便,适合工业化生产。     

4-氨基-5-氯-2-乙氧基苯甲酸的合成

目的合成4-氨基-5-氯-2-乙氧基苯甲酸。方法以对氨基水杨酸钠为原料,经酸化、甲酯化、乙酰化、乙基化、氯代、水解等六步反应得到枸橼酸莫沙必利的主要中间体4-氨基-5-氯-2-乙基苯甲酸。结果与结论本合成工艺提高了收率,降低了成本,更适合工业化生产,本工艺总收率为62.4%。     

3-氯-4-(3-氟苄氧基)苯胺的合成

目的开发一条适合产业化的3-氯-4-（3-氟苄氧基）苯胺的合成工艺路线。方法以间氟氯苄和2-氯-4-硝基苯酚为原料,依次经碳酸钾存在下的缩合反应、铁粉／氯化铵还原得到3-氯-4-（3-氟苄氧基）苯胺。结果总收率为82％。所得产物经TLC、熔点和核磁共振氢谱表征,具有高纯度。结论本方法原料价廉易得,操作简便,环境污染更小,预期适合工业化生产。     

盐酸氯普鲁卡因的合成

目的合成盐酸氯普鲁卡因并改进工艺。方法以2-氯-4-硝基苯甲酸为起始物料,经过还原、酯化、成盐3步反应制得盐酸氯普鲁卡因。结果目标物经IR、1H-NMR、13C-NMR和MS确证结构,反应总收率达到73.9%,纯度为99.76%。结论该合成路线操作简便、反应条件温和,适于工业化生产。     

Synthesis and characterization of cyclic acetal based degradable hydrogels.

While many synthetic, hydrolytically degradable hydrogels have been developed for biomedical applications, there are only a few examples whose polymer backbone does not form acidic products upon degradation. In order to address this concern, we proposed to develop a hydrogel based on a cyclic acetal unit that produces diols and propanals upon hydrolytic degradation. In particular, we proposed the fabrication of hydrogels formed by the free radical polymerization of two diacrylate monomers, 5-ethyl-5-(hydroxymethyl)-beta,beta-dimethyl-1,3-dioxane-2-ethanol diacrylate (EHD), a cyclic acetal having two acryl groups, and poly(ethylene glycol)diacrylate (PEGDA). However, the hydrophobicity of the EHD monomer inhibits hydrogel fabrication. Therefore this work develops a strategy to form hydrogels with a co-monomer system, one of which is hydrophobic, and subsequently describes the properties of the resulting hydrogel. Using benzoyl peroxide as an initiator and N,N-dimethyl-p-toluidine as an accelerator, the EHD and PEGDA monomers were reacted in an acetone/water co-solvent system. The chemical structure of the resulting EH-PEG [5-ethyl-5-(hydroxymethyl)-beta,beta-dimethyl-1,3-dioxane-2-ethanol-co-PEG] hydrogel was then characterized by FT-IR. Physicochemical properties of the EH-PEG hydrogel, including swelling degree, sol fraction, and contact angle, were determined so as to characterize the properties of these materials and ultimately investigate their use in drug delivery and tissue engineering applications. Results showed that EH-PEG hydrogel may be formed using the co-solvent system. Further results indicated that swelling degree is dependent upon initiator concentration, monomer concentration, and molar ratios of monomers, while sol fraction significantly depended on initiator concentration and monomer concentration, only. These results demonstrate the ability to fabricate hydrogels using EHD and PEGDA system as well as to control the properties of the resulting hydrophilic networks.     

Erythromycin A 11,12-methylene acetal

Erythromycin A 11,12-methylene acetal (5) and the corresponding 9-methoxime, 9-dihydro, and 8-hydroxy derivatives have been prepared and their antibacterial activities compared with those of erythromycin A and its 11,12-cyclic carbonate. The simple methylene acetal 5 showed excellent activity against Gram-positive organisms in vitro.     

邻醌鬼臼脂素的合成及其体外抗肿瘤细胞活性

鬼臼脂素类衍生物体内作用模式之一是经氧化生成醌式中间体而进一步发挥作用,本文作者设计合成了４－去氧－４β－酰胺基－３′,4′－邻醌式鬼臼脂素,泱节其体外抑制ＫＢ细胞和Ｌ１２１０白血病细胞活性,并对结果进行了探讨。     

Synthesis of diacetoxy acetal derivatives of santonin and their enhancing effects on HL-60 leukemia cell differentiation

Several diacetoxy acetal analogues have been synthesized from santonin and assessed for their ability of inducing or enhancing the differentiation of human HL-60 leukemia cells. The compounds themselves had little effect on HL-60 cell differentiation. However, three analogues, 2a, 3a, and 5b, synergistically enhanced 1,25-dihydroxyvitamin D3 [1,25-(OH)2D3]-induced HL-60 cell differentiation when combined with 5 nM of dihydroxyvitamin D3 [1,25-(OH)2D3], a well-known differentiation inducer. Especially, the compound 5b profoundly enhanced the 1,25-(OH)2D3]-induced HL-60 cell differentiation.     

4′—甲基—N—叔丁基—1′，2—联苯磺酰胺的合成

4′-甲基 - N-叔丁基 - 1′,2 -联苯磺酰胺 ( 1 )是合成血管紧张素 受体拮抗剂如 MK- 996的关键中间体 [1] ,可以对溴甲苯 ( 2 )为原料 ,按图 1所示方法合成。　　文献[2 ] 用中间体 3和 Sn( CH3 ) 3 Cl合成 4-三甲基锡甲苯以制备 1 ,本文改用价格、毒性均较低的Sn( n- Bu) 3 Cl,二者反应收率相当 ;文献 [3 ]由 5合成6,收率为 35 % ,以 6合成 7时 ,收率为 84% [2 ] ,分步操作反应总收率为 2 9% ,本文无需分离中间体 6,直接将反应混和物投入氯仿中 ,并与叔丁胺反应制得7,产率提高为 60 %。实验部分4-三正丁基锡甲苯 ( 4 )Mg( 0 .4g,1 6…     

4-吡啶丁醇的合成

目的:合成4-吡啶丁醇。方法:以4-溴吡啶盐酸盐为原料,经缩合、成盐、催化氢化再游离共4步反应得到目标产物。结果与结论:目标产物的化学结构经1HNMR确证,反应条件温和,操作简单,适宜工业化生产,总收率65.1%。