活性N-甲基氨基甲酸酯的简易合成法

近年来,三氯甲基氯代甲酸酯(1)或双-(三氯甲基)碳酸酯(2)经常作为光气资源用于有机合成中。较之高毒的光气,这些液态或结晶状的光气同效体则具有更易贮存的优点。通常,化合物(1)和(2)用于羟基或氨基的氯甲基化或羧化反应、羧酸的氯化反应,以及由醛制取α-氯代氯甲酸酯。以此类反应为基础,可以合成许多重要的中间体,其中一些化合物在肽类化合物的合成等得到了广泛的应用。在药物的研究中,作者合成了烷基亚硝基脲。其利用相应的氨烷基氨基酸与活化的N-甲基-N-亚硝基琥珀酰基氨基甲酸酯的耦合反应,用于嵌入到DNA甲基铃结构。而此亚硝     

三光气法合成N-硝基-N-(2,4,6-三氯苯基)氨基甲酰氯

用三光气法合成了N 硝基 N (2,4,6 三氯苯基)氨基甲酰氯,并进行了结构表征。结果表明,用三氯甲基碳酸酯代替光气合成该化合物反应安全,条件温和,选择性好,收率高,消除了光气的危险性。     

绿色化工产品固体光气的合成及应用

固体光气是近年来迅速发展的绿色化工产品,主要通过碳酸二甲酯的光催化氯化反应合成,有四氯化碳溶剂法和碳酸二甲酯本体法工艺。它是工业广泛使用的剧毒羰基化试剂光气的理想代替品,可以与醇、胺、羧酸、醛和酰胺等化合物反应,替代光气制备多种重要有机化合物,在有机合成、医药、农药、染料、高分子材料等领域具有广泛的应用前景。     

三光气—光气的替代品

光气（COCl2）广泛地用于有机合成中，例如，在形成氯甲酸酯、异氰酸酯、酰氯、聚碳酸酯、杂环和其它有关化合物。光气是很毒的气体，因此需要小心地处理。只需少量光气的实验室，光气仍是不实用的气体。三光气（二（三氯甲基）碳酸酯）是晶体，能在通常的安全措施下，可称取小量的本品，有助于在小规模下反应。三光气由二甲基碳酸酯完全光氯化制取。在纯的状态，到100℃仍是稳定的，能在室温下长时间贮存而没有分解。在有活性炭或亲核试剂（胺或酰胺）存在下会形成光气，甚至在室温下。在Lewis酸（氯化铝）存在下，三光气分解形成四氯化…     

氯代酯中游离氯杂质对合成EHP的影响

一、前言氯甲酸异辛酯同其它氯代酯一样,都是由相应的醇与光气反应制得,反应式如下:式中 R为2—乙基己基氯代酯中所残留的游离氯就是残余反应物光气和副产物氯化氢。在氯代酯与Na_2O_2水溶液反应合成过氧化二碳酸二异辛酯(简称EHP)时,氯化氢和光气也同时很快地与该碱性溶液(Na_2O_2可视为强碱弱酸盐)发生化学作用,使反应温度不好控制,降低了加料速度,并消耗NaOH和H_2O_2。反应式如下: 二、不同游离氯含量的氯代酯对合成EHP的影响及有关副反应消耗的考察在合成EHP时,副反应耗Na_2O_2不仅与氯代酯中残留的游离氯有关,还与其它反应条件有关(其它副反应也可消耗Na_2O_2)。但试验证实,尽管合成条件有所变动,副反     

湍球塔破坏光气的测试小结

光气是化学工业中一种重要的酰基化剂,由光气出发可产生一系列甲酸酯类化合物,特别是氨基甲酸酯类农药和巨碳酸酯工业,用途十分广泛。在“速灭威”生产过程中,它是制备其重要中间体氯甲酸间甲苯酯的主要原料之一。光气又是剧毒气体,按国家规定车间空气中最高允许浓度为0.5毫克/立方米,因此在光气生产和使用过程中为了不使逸出的光气污染环境、毒害人体健康等,需要对其进行处理,然后再经烟囱排空。     

光气化产品的开发和应用

概述光气，学名，碳酸氯。分子式：COC12。光气是一种剧毒气体，但在化学工业中不仅是重要的酸化剂，而且是用途广泛的有机化工原料。目前已开发的光气化产品可分为四类：卧氯类（R－COCI）、氯甲酸酯类仅一OCOCI）、染料中间体和异氰酸酯类（RN＝C＝O）。卧氯类有：芳香环酚氯（如苯甲酸氯、脂肪酸氯（C；，H3氯甲酸酯类包括芳香环酯异氰酸酯类主要是芳香环异氰酸酯，如甲苯二异氰酸酯等，以及茶环异氰酸酯D和脂肪异氰酸酯［OCN（CH。）。NCO］。用光气可以直接生产染料和染料中间体，如直接耐晒桃红BK、直接耐晒红F3B等。中…     

氯甲酸乙硫醇酯的合成

由光气与乙硫醇合成氯甲酸乙硫醇酯。     

光气生产技术及光气化产品开发进展

综述了光气生产工艺技术、安全措施及主要光气下游产品种类。介绍了国内外光气生产及应用现状，涉及一氧化碳制备、氯气干燥、光气合成、废气处理和安全生产等技术。简述了光气化产品开发研究方向，提出重点开发IPDI(异佛尔酮二异氰酸酯)、NDI(1，5-萘二异氰酸酯)、氯磺酰异氰酸酯和较大分子量的氯代甲酸酯等光气化产品。     

软聚氯乙烯塑料的气味分析研究

采用气相色谱-质谱法(GC-MS)对3种软聚氯乙(烯S-PVC)试样的挥发性有机物进行了测试,分析了产生气味的物质。结果表明:试样产生的挥发性有机物为烃类化合物、醇和醛、酯等羰基化合物,产生气味的化合物主要是羰基化合物;添加抗氧剂可阻止增塑剂和其他烃类的氧化,减少S-PVC塑料气味的产生。     

美洛西林钠的合成

美洛西林钠是一种新型半合成青霉素。在以往的文献中其合成过程中都要使用剧毒品光气作为反应物。今以2-咪唑烷酮为起始原料，经甲磺酰化、酰化等四步反应，合成了酰脲类青霉素美洛西林钠。在合成过程中用氯甲酸三氯甲酯替代光气对其重要中间体l-氯甲酰基-3-甲磺酰基-2-咪唑烷酮的合成工艺进行了改进，不仅避免了使用光气，而且收率也从文献值70％提高到75％。     

Preparation of Isocyanates from Linseed,Safflower and Tall Oil Fatty Acids: I

Fatty acids from linseed, safflower and tall oils were converted to the corresponding isocyanates by two methods. In the first method linseed and safflower fatty acids were converted to the acid chloride either with thionyl chloride or oxalyl chloride and the acid chlorides were converted to the azide which was finally decomposed into the isocyanate. Yields of isocyanates were related to the method used to prepare the parent acid chlorides, the oxalyl chloride procedure giving higher yields of isocyanates. Loss in unsaturation from acids to isocyanates was slight. The tall oil isocyanates were prepared in hig yields via the phosgene method, thus, fatty acids to nitriles to amines, to the amine hydrochloride which were then reacted with phosgene. The isocyanates prepared by this procedure contained one more CH₂ group than those prepared via the first mentioned method. The infrared spectra of all isocyanates were essentially identical.     

Iron oxide catalyzed reduction of acid chlorides to aldehydes with hydrosilanes

Iron-catalyzed reduction of acid chlorides to the corresponding aldehydes with a hydrosilane as a reducing agent has been developed. A simple mixture of a commercially available iron oxide (FeO) and tris(2,4,6-trimethoxyphenyl)phosphine (TMPP) as a catalyst realized the reduction of acid chlorides to the corresponding aldehydes under mild reaction conditions.     

酰氯的合成方法及其应用新进展

以羧酸和酰化试剂为原料进行反应,是现今合成酰氯的主要方法。根据酰化试剂的不同,系统地介绍了三氯化磷法、五氯化磷法、氯化亚砜法、光气法、固体光气法和四氯化碳法。同时对酰氯作为中间体在医药、农药、资源环境等方面的研究和应用进行了相应的介绍和展望。     

The preparation of fatty acid chlorides

Summary Fatty acid chlorides of lauric, myristic, palmitic, stearic, oleic, elaidic, and linoleic acids were prepared using phosphorus tri- and pentachlorides, oxalyl chloride, and thionyl chloride as chlorinating agents. On the basis of yields, ease of handling, and cost of reagent, phosphorus tri- and pentachlorides are superior to other chlorinating agents for the preparation of the higher fatty acid chlorides for use as intermediates in the preparation of pure saturated fatty acid glycerides of known structure. The unsaturated fatty acid chlorides are, however, best prepared from oxalyl chloride. The use of phosgene, which has been patented for the preparation of acid chlorides, failed to effect efficient conversion of the higher fatty acids to the corresponding chlorides. The analysis of the fatty acid chlorides by conversion to anilides provides a simple and easy means for ascertaining the extent of conversion of fatty acids to chlorides. By means of this method it is possible to follow readily the course of the reaction in order to determine when complete conversion of fatty acid to fatty acid chloride has been effected. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Imidazolidinderivate aus Oxalamidinen

Derivatives of Imidazolidines from Oxalic Amidines Tetraarylsubstituted oxalic amidines 1 react with acyl chlorides, phosgene, thiophosgene, chlorocarbonylsulfenylchloride, isocyaniddichlorides, and N-aroyl-1-chlorothio-formimidoylchlorides 7 to give the corresponding 5-membered heterocycles 3, 4, 5 and 8 . Isocyanates 9 and isothiocyanates 10 react with oxalic amidines to yield imidazolidines 11, 12 and ureas 13, 14 . Hydrolysis of 3–5, 8, 11, 12 leads to the corresponding oxo compounds 15, 16 .     

Recyclable polystyrene-based polymeric reagent for the reduction of acid chlorides

Summary A polymeric reagent, polystyryldiphenyl-phosphine tetrahydroborate copper, has been prepared by chemical modification of cross linked polystyrene using a fourstep reaction sequence involving a ligand exchange reaction for the binding of cuprous chloride to the phosphine resin. The reagent is very effective in the reduction of acid chlorides to aldehydes and can be regenerated easily without loss of activity.     

Nickel‐Catalyzed Synthesis of Phosphonium Salts from Aryl Halides and Triphenylphosphine

An efficient method to synthesize functionalized tetraarylphosphonium salts is described. The nickel‐catalyzed coupling reaction between aryl iodides, bromides, chlorides, or triflates and triphenylphosphine generates tetraarylphosphonium salts in high yields. The coupling is wide in scope and tolerates a variety of functional groups such as alcohols, amides, ketones, aldehydes, phenols, phosphines and amines.     

光气反应器的发展及优化

针对光气反应器的发展完善进行了比较分析 ,并结合国内一些光气反应器换代生产经验 ,着重推介了适合我国中、小型光气生产装置的列管式双管板光气反应器