脂肪伯胺的合成及工业化研究进展

有机胺在化工、医药、生命科学等领域有着广泛的应用,可作为染料、日用品原料以及抗生素、生物碱、临床医学药物等。在众多胺类化合物中,伯胺是最基础的结构单元,其应用在胺类化合物中也最为广泛。随着经济社会的快速发展与人们生活质量的提高,伯胺,尤其是脂肪伯胺的市场需求量与日俱增,脂肪伯胺的合成及工业化制备已成为一个重要领域。经过了数十年的发展,脂肪伯胺的生产技术已经取得了巨大的成果,但仍然存在一些问题,例如苛刻的反应条件、催化剂性能不足、污染严重、工艺复杂等。本文以脂肪伯胺的工业生产以及热点制备方法为研究对象,针对工业上制备脂肪伯胺的工艺进行了汇总归纳(包括卤代烃胺化法、醇还原胺化法,腈加氢还原法、烯烃直接胺化法、羧酸胺化法等),并举例说明各制备方法在工业生产中的实际应用,分析比较各工艺方案的优劣,并对当前的研究热点——通过羰基还原胺化制备脂肪伯胺的方法进行了研究进展的阐述,指出该制备方法在未来工业应用的潜力与挑战。     

高级脂肪胺的合成

考察了从植物油脂生产高级脂肪胺的方法。以自制催化剂,在高压釜中分别研究了氢分压、氨分压、温度、水分、抑制剂、催化剂含量等对转化率、收率的影响。     

环十二烷基胺的合成研究

环十二烷基胺（Ⅰ）可以由硝基环十二烷的还原［１,２］、或环十二碳烯在硫酸存在下与氢氰酸加成［３,４］或环十二酮（Ⅱ）的还原胺化法来制备。其中后者是为最简洁、合理的方法。前人曾报道Ⅱ与氨反应,催化氢化还原的方法获得较高收率的Ⅰ［５］：Ｏ（Ⅱ）＋ＮＨ３Ｈ...     

胺烷基二茂铁环钯化物的合成与表征

通过胺烷基二茂铁衍生物Ｎａ２ＰｄＣｌ４的反应合成了环钯化物和钯配合物，并总结了产物的ＩＲ及＾１ＨＮＭＲ谱的特征和规律。     

醇类脱氢胺化合成有机胺

介绍了醇类脱氢胺化,该法具有原料易得,成本低,无污染等优点。     

聚异丁烯胺汽油清净剂的合成过程研究

研究了用溴化加成法合成新一代的汽油清净剂聚丁烯胺(PIBA)。将高活性聚异丁烯与HBr气体在过氧化物存在下进行自由基反马氏加成反应生成溴化聚异丁烯,然后再与氨进行亲核取代反应生成聚异丁烯胺。实验研究了溶剂,反应时间,反应温度以及引发剂的加入量对反应过程的影响,基本确定了最佳反应条件。     

高级脂肪胺的合成

考察了从植物油脂生产高级脂肪胺的方法。以自制催化剂,在高压釜中分别研究了氢分压、氨分压、温度、水分、抑制剂、催化剂含量等对转化率、收率的影响。     

十二烷基胺的制备

以十二酸、氨气、氢气为原料,在氨解催化剂,加氢催化剂的作用下,反应合成了十二烷基胺。介绍了制备的试验方法及过程,同时讨论了反应温度,氨气分压,催化剂等对十二胺质量的影响,得到了制备反应的最佳条件。     

脂肪伯胺的生产

介绍脂肪伯胺的生产方法、产品规格、质量控制。讨论反应温度、反应压力、催化剂的浓度、氨循环速率、冷凝温度对脂肪腈的反应速率、得率、能量消耗的影响。     

醇类脱氢胺化合成有机胺

介绍了醇类脱氢胺化。该法具有原料易得、成本低、无污染等优点。     

合成脂肪醇催化胺化制叔胺的反应研究

在Cu-Ni催化剂作用下利用C12-13合成醇(OXO醇)进行催化胺化反应,并与月桂醇的胺化反应进行比较,结果表明：月桂醇胺化反应3h,醇的转化率达99．9％,单烷基叔胺选择性为95．6％,OXO醇的转化率为91．3％,选择性为96．6％。胺化产物的色质分析结果表明：剩余脂肪醇全部为2-位支链的脂肪醇。OXO醇转化率不高的主要因素是所含2-位支链阻碍了脂肪醇在催化剂表面的吸附。OXO合成脂肪醇催化胺化制叔胺的主要问题是醇的转化率相对较低。     

正丁醇的催化胺化反应的研究

本文在氢气及加氢催化剂的存在下,以氨水为胺化剂,对正丁醇催化胺化制备正丁胺的反应进行了研究,探讨了氨醇比,氨水浓度、温度、时间、氢压以及催化剂用量对反应的影响,在本文提出的条件下,正丁醇单程转化率达４７．５％,正丁胺单程产率为４６．２％,反应选择性为９７．３％。     

三丙酮胺精制方法研究

论述了三丙酮胺纯度对加氢和还原胺化反应的影响。使用纯度较高的三丙酮胺有利于加氢和还原胺化反应的进行及产品的分离。确定了以丙酮为溶剂的重结晶方法提纯三丙酮胺,可使三丙酮胺质量分数达到９８．６％。结晶母液可以不经分离,而直接用于合成三丙酮胺     

手性拆分剂2-苯基-1-对-甲苯基乙胺的合成研究

研究了拆分剂2-苯基-1-对-甲苯基乙胺的合成路线,先通过傅克酰基化反应,温度控制在10℃左右,反应时间为5~6 h,合成2-苯基-1-对-甲苯基乙酮;然后通过胺化反应,温度控制在80~85℃,反应时间10 h,得到2-苯基-1-对-甲苯基乙酮肟;最后通过高压釜催化剂进行加氢,压力控制在2 MPa,温度控制在60℃,反应约4 h,生成2-苯基-1-对-甲苯基乙胺。     

Cobalt‐Catalyzed Direct Amination of Arenes with Alkylamines via Bidentate‐Chelation Assistance

Cobalt‐catalyzed C−H amination of arenes with alkylamines by the assistance of 8‐aminoquinoline as auxiliary through sp² C−H bond functionalization has been achieved. Attractive features of this protocol include the low loading of the cobalt catalyst and the readily available reagents.

     

苯丙酮酸胺化加氢制备DL-苯丙氨酸

报导了由苯丙酮酸通过胺化及加氢合成ＤＬ－苯丙氨酸的研究工作,主要对胺化加氢的反应条件如温度、压力、氨水用量等工艺条件进行了详细研究。结果表明,由苯丙酮酸合成ＤＬ－苯丙氨酸的收率可达到９５％左右,是一条具有良好工业化前景的路线。     

Flexibility analysis for continuous ibuprofen manufacturing processes

Continuous ibuprofen (a widespread used analgesic drug) manufacturing is full of superiorities and is a fertile field both in industry and academia since it can not only effectively treat rheumatic and other chronic and painful diseases, but also shows great potential in dental diseases. As one of central elements of operability analysis, flexibility analysis is in charge of the quantitative assessment of the capability to guarantee the feasible operation in face of variations on uncertain parameters. In this paper, we focus on the flexibility index calculation for the continuous ibuprofen manufacturing process. We update existing state-of-the-art formulations, which traditionally lead to the max-max-max optimization problem, to approach the calculation of the flexibility index with a favorable manner. Advantages regarding the size of the mathematical model and the computational CPU time of the modified method are examined by four cases. In addition to identifying the flexibility index without any consideration of control variables, we also investigate the effects of different combinations of control variables on the flexibility property to reveal the benefits from taking recourse actions into account. Results from systematic investigations are expected to provide a solid basis for the further control system design and optimal operation of continuous ibuprofen manufacturing.     

Petri-net based scheduling strategy for semiconductor manufacturing processes

Semiconductor manufacturing is a highly automated and capital-intensive industrial process. The operating cost of a wafer processing plant is in general closely related to the design and management of its process flows. Traditionally, the task of production scheduling is performed manually on the basis of past experiences. There are thus real incentives to develop a systematic approach to construct a mathematical programming model in order to reduce the chance of human errors and to ensure operational efficiency in implementing the resulting schedules. To this end, the Petri nets are adopted in this work to accurately model the semiconductor manufacturing activities. The token movements in a Petri net are represented with the well-established scheduling model for batch chemical processes, and the optimal schedule of the given semiconductor process can then be determined accordingly. The feasibility and effectiveness of this scheduling strategy is demonstrated in the present paper with three examples, i.e., the final test process, the re-entrant flow process, and the photolithography-etching process.     

General Construction of Amine via Reduction of N=X (X = C,O, H) Bonds Mediated by Supported Nickel Boride Nanoclusters

Amines play an important role in synthesizing drugs, pesticides, dyes, etc. Herein, we report on an efficient catalyst for the general construction of amine mediated by nickel boride nanoclusters supported by a TS-1 molecular sieve. Efficient production of amines was achieved via catalytic hydrogenation of N=X (X = C, O, H) bonds. In addition, the catalyst maintains excellent performance upon recycling. Compared with the previous reports, the high activity, simple preparation and reusability of the Ni-B catalyst in this work make it promising for industrial application in the production of amines.