脂肪仲胺合成及应用

本文介绍了脂肪仲胺的反应原理、生产工艺及其应用。     

脂肪仲胺工艺研究

本文叙述了脂肪仲胺的生产方法及反应机理,研究了最佳反应条件。     

高级脂肪胺合成新工艺的研究

通过对油脂一步法制备脂肪腈继而加氢合成脂肪工艺的探讨,研究了催化剂、反应温度、反应时间及氨气流量对反应产率的影响,确定了合理脂肪胺合成工艺流程及最佳工艺条件,所得脂肪腈的产率达９４％,与传统脂肪胺合成工艺相比,具有流程短,产率高,无腐蚀性等优点。     

高级脂肪胺合成新工艺的研究

通过对油脂一步法制备脂肪脂继而加氢合成脂肪胺工艺的探讨，研究了催化剂、反应温度、反应时间及氨气流量对反应产率的影响，确定了合理脂肪胶合成丁艺流程及最佳工艺条件，所得脂肪股的产率达94％，与传统脂肪胺合成工艺相比，具有流程短，产率高，无腐蚀性等优点。     

红外光谱法定量分析高级脂肪腈

IR中,脂肪腈～三氯甲烷溶液在2250cm~-1波数处显示特征的吸收。应用基线法测定其吸光度,可快速、简便地定量分析高级脂肪腈。     

脂肪胺生产技术及市场展望

叙述了脂肪伯胺、脂肪仲胺、脂肪叔胺的生产方法。介绍了脂肪胺的用途及市场展望。     

引进脂肪胺生产装置工艺特点

介绍引进意大利ＧＩＡＮＡＺＺＡ公司的脂肪胺生产装置工艺过程,采用间歇式液要法制取脂肪腈,批料操作时间１０ｈ,最终脂肪腈的酸值在０．５以下,伯胺反应温度１３０℃￣１４０℃,反应压力１．２ＭＰａ￣１．６ＭＰａ,仲胺反应温度２００℃￣２２０℃,反应器中２ｈ￣４ｈ即可反应完成。提出了脂肪腈装置存在的问题及相应的解决方案。     

Selective Hydrogenation of Fatty Nitriles to Primary Fatty Amines: Catalyst Evaluation and Optimization Starting from Octanenitrile

In this contribution, an evaluation of the potential of various homogeneous and heterogeneous catalysts for a selective hydrogenation of fatty nitriles toward primary amines is reported exemplified for the conversion of octanenitrile into octane‐1‐amine as a model reaction. When using heterogeneous catalysts such as the ruthenium catalyst Ru/C, the palladium catalyst Pd/C, and the platinum catalyst Pt/Al₂O₃, low selectivities in the hydrogenation are observed, thus leading to a large portion of secondary and tertiary amine side‐products. For example, when using Ru/C as a heterogeneous catalyst, high conversions of up to 99% are obtained but the selectivity remains low with a percentage of the primary amine being at 60% at the highest. The study further reveals a high potential of homogeneous ruthenium and manganese catalysts. When also taking into account economical considerations with respect to the metal price, in particular, manganese catalysts turn out to be attractive for the desired transformation and their application in the model reaction leads to the desired primary amine product with excellent conversion, selectivity, and high yield. Practical Applications: This work describes an optimized hydrogenation process for transforming fatty nitriles to their corresponding primary amines. In general, fatty amines belong to the most applied fatty acid‐derived compounds in the chemical industry with an annual product volume exceeding 800 000 tons per year in 2011 and are widely required in the chemical industry since such compounds are either directly used in home products such as fabric softeners, dishwashing liquids, car wash detergents, or carpet cleaners or in a broad range of industrial products, for example, lubricating additives, flotation agents, dispersants, emulsifiers, corrosion inhibitors, fungicides, and bactericides, showing additional major applications, e.g., in the detergents industry. Among them primary amines play an important industrial role. However, a major concern of current processes is the lack of selectivity and the formation of secondary and tertiary amines as side‐products. By modifying a recently developed catalytic system based on manganese as economically attractive and environmentally benign metal component an efficient and selective access to fatty amines when starting from the corresponding nitriles is achieved. For example, hydrogenation of octanenitrile leads to a synthesis of octane‐1‐amine with >99% conversion and excellent selectivity with formation of secondary and tertiary amine side‐products being suppressed to an amount of <1%.     

Rational Biocatalyst Design for a Cyanide-Free Synthesis of Long-Chain Fatty Nitriles from Their Aldoximes

Recently, the capability of the aldoxime dehydratase from Bacillus sp. (OxdB) for the transformation of fatty aldoximes into fatty nitriles with impressive substrate loadings is reported. However, the substrate scope of this biocatalyst turned out to be limited in terms of the chain length with decanal oxime being the substrate with the longest well tolerated n-alkyl chain. Besides the increased bulkiness of the long-chain aldoximes, their strongly decreased water solubility represents a further hurdle for an efficient biotransformation. Addressing this challenge of an expanded substrate spectrum comprising long-chain fatty aldoximes, this work investigates the substrate solubility and enzyme kinetics in combination with molecular modeling in order to find an enzyme mutant being suitable for C12- to C16-aldoximes. Both, fatty aldoxime solubility in water and the active site of the wild-type enzyme OxdB are identified as critical issues for an efficient biotransformation of these substrates. The activity issue is addressed by a rational design of a mutant using a homology modeling as well as a molecular modeling software suitable for enzymes. With the resulting double mutant OxdB-F289A/L293A, this report can achieve successful biotransformations with the C12- to C16-aldoximes at substrate concentrations of 250 × 10⁻³ to 1000 × 10⁻³ m . For example, an excellent conversion of >99% is obtained with tetradecanal oxime. Practical applications: Fatty nitriles with a prolonged chain length of C12 or more are of high interest in industry due to their use for the production of fatty amines on large technical scale. As an alternative route, fatty nitriles can be generated from their aldoximes by means of an aldoxime dehydratase (Oxd) as biocatalyst. The conversion of long-chain fatty aldoximes, however, remained a challenge up to now. This work describes the optimization of the aldoxime dehydratase OxdB from Bacillus sp. for the dehydration of nonsoluble bulky fatty aldoximes. The created variant can convert long chain fatty aldoximes toward the corresponding nitrile as demonstrated for C12- to C16-nitriles. In addition, high conversion (of up to >99%) is achieved when operating at high substrate concentrations of up to 1000 × 10⁻³ m , thus making this approach interesting for industrial applications.     

硫酸氢钠催化醛与羟胺反应“一锅煮”法合成腈类化合物

研究了一系列取代苯甲醛、杂环醛和脂肪醛与盐酸羟胺在酸催化剂存在条件下合成相应腈的新方法,考察了原料配比、催化剂种类、反应时间、溶剂用量及温度等因素对反应的影响。结果表明,合成目标物的优化工艺条件为:n(醛)∶n(盐酸羟胺)=1.0∶1.4,催化剂为硫酸氢钠,相转移催化剂为四丁基溴化铵,135℃反应4⁷ h,收率达68.6%7 h,收率达68.6%⁹7.9%。具有生产成本低、反应条件温和、易于工业化生产的优点。     

氯乙酸高碳脂肪醇酯的合成

以氯化钙为催化剂，苯为带水剂，分别以辛醇、十二醇、十四醇、十六醇、十八醇和氯乙酸在回流温度下反应5h，合成了相应的氯乙酸高碳脂肪醇酯，分别记为化合物1－5。较佳工艺条件为：n（氯乙酸）：n（脂肪醇）＝1.2：1，反应温度为130℃，W（催化剂）5％。通过减压蒸馏提纯了氯乙酸辛酯和氯乙酸十二酯，其余三种产物用无水乙醇重结晶。用IR表征了产物的结构。     

油酸酰胺的常压合成

对常压下以油酸和氨气为原料催化合成油酸酰胺的方法进行了研究，选出了合适的催化剂和较好的工艺条件。     

Enantioselective Biotransformations of Nitriles in Organic Synthesis

Recent advances in enantioselective biotransformations of nitriles utilizing nitrile-hydrolyzing microorganisms and enzymes are summarized in this article. Various examples of biocatalytic synthesis of highly enantiopure carboxylic acids including amino acids, hydroxyl acids, cyclopropanecarboxylic acids and amide derivatives and oxiranecarboxamides are presented. The enantioselectivity of the nitrile hydratases, nitrilases and amideses is discussed.     

麦芽糖醇脂肪酸酯的制备研究

以麦芽糖醇和脂肪酰氯为主要原料合成麦芽糖醇脂肪酸酯。通过对影响反应的催化剂用量、溶剂的用量、反应温度、反应时间、原料配比等主要因素的考察,发现在以麦芽糖醇糖/脂肪酰氯为1∶1.25,催化剂(碳酸钾)用量为麦芽糖醇用量的15%~20%,溶剂(冰醋酸)/麦芽糖醇的用量比为6~7mL/1g,反应温度110℃的条件下,反应10h,麦芽糖醇脂肪酸酯的收率可达93%~95%。     

Nickel-Catalyzed Reductive Coupling of Vinyl Triflates and 1,4-Dicyanobenzene to Access Alkenyl Nitriles

We report a vinyl cyanation reaction of vinyl triflates and readily available 1,4-dicyanobenzene through a nickel-catalyzed reductive coupling process. The reaction is operated under mild conditions with remarkable functional-group compatibility. Cyclic vinyl triflates with various ring sizes and substituents at different positions all reacted smoothly. The synthetic utility is demonstrated by the derivatization of pharmaceutical and natural compounds, a scale-up synthesis, and various functional group transformations. Preliminary mechanistic studies demonstrate that vinyl triflates are more reactive than 1,4-dicyanobenzene towards the oxidative addition to nickel catalyst.     

脂肪腈催化氢化制伯胺工艺中常用抑制剂氨,氨水,碱水的作用性能的研究

本文叙述了脂肪腈催化氢化反应机理及常用抑制剂的作用机理,并用试验的方法对氨,氨水及碱水的作用性能进行了比较。