A new route to lactam precursors from cycloalkanes: direct production of nitrosocycloalkanes or cycloalkanone oximes by using tert-butyl nitrite and N-hydroxyphthalimide.-猫眼课题宝

DOI：

10.1002/anie.200352741

发表时间：

2004-02

期刊：

Angewandte Chemie

影响因子：

通讯作者：

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文献类型：

作者：

Tomotaka Hirabayashi;S. Sakaguchi;Y. Ishii

为大宗和商品化学品的生产开发一种创新方法，特别是考虑到对环境的影响的方法，在全世界的工业化学中变得越来越重要。[1，2] ε-己内酰胺是生产尼龙6最广泛使用的单体之一; 1998年世界ε-己内酰胺的生产能力约为420万吨。[3]目前，ε-己内酰胺通过以下方法生产（方案1）：1）衍生自环己酮和羟胺的环己酮肟的贝克曼重排（路线A）或通过环己烷的光亚硝化（PNC）方法衍生自环己烷和NOCl的环己酮肟的贝克曼重排（路线B），或2）环己烷羧酸与NOHSO 4的亚硝化（路线C）。在这些方法中，路线A是最常用的，占全球ε-己内酰胺总产量的约70%。然而，这种方法有几个缺点。环己酮通过环己烷的有氧氧化提供，这导致环己酮和环己醇的混合物（K/A油），但环己烷的转化率必须保持在仅3-6%以避免形成进一步的氧化产物如己二酸和戊二酸。[4]该方法的另一个严重缺点是在羟胺生产和贝克曼重排工艺中同时产生大量的硫酸铵废物。[3]近年来，ε-己内酰胺及其前体的合成方法有了新的发展。EniChem Co.的研究人员通过在硅酸钛-1（TS-1）催化下用过氧化氢和氨对环己酮进行氨肟化，然后在住友化学公司开发的高含量硅酸盐催化剂存在下进行贝克曼重排来合成肟。[3，5]托马斯及其同事报道称，双官能过渡金属离子取代的磷酸铝分子筛促进环己酮与氨和过氧化氢或分子氧的反应，沿着少量的ε-己内酰胺得到环己酮肟。[6]然而，这些方法需要环己酮作为起始材料。如果能够实现环己烷直接转化为ε-己内酰胺前体，则该反应将代表一种创新方法。虽然PNC工艺适合这一目的，但非常腐蚀性的NOCl必须与HCl一起用作关键化合物。[1]此外，环己酮肟以其盐酸盐的形式获得，并且NOCl的形成非常麻烦。因此，需要开发一种新的环己烷亚硝化或肟化体系来克服这些缺点。（皮诺;通过N-羟基邻苯二甲酰亚胺（NHPI）与分子氧在存在或不存在过渡金属盐或二氧化氮的情况下反应原位产生）用作碳自由基产生催化剂（CRPC），并在相对温和的条件下从烃中的C2 H4键中夺取氢原子。[7]例如，在分子氧下，在催化量的NHPI与[Mn（acac）2]（acac=乙酰丙酮化物）结合的存在下，将环己烷氧化，得到环己基自由基，其最终以高产率转化为己二酸。[8]环己烷也有效地硝化处理二氧化氮和NHPI形成硝基环己烷。[9]在我们对NHPI催化的环己烷官能化的研究过程中，我们发现环己烷的亚硝化

The development of an innovative methodology for the production of bulk and commodity chemicals, in particular one that takes account of effects on the environment, becomes more and more important in industrial chemistry worldwide.[1, 2] ε-Caprolactam is one of the monomers most widely used for the production of nylon6; the world production capacity of ε-caprolactam in 1998 was about 4.2 million tons.[3] Currently, ε-caprolactam is produced by the following methods (Scheme 1): 1) Beckmann rearrangement of cyclohexanone oxime derived from cyclohexanone and hydroxylamine (Route A) or from cyclohexane and NOCl by the photonitrosation of cyclohexane (PNC) process (Route B), or 2) nitrosation of cyclohexane carboxylic acid with NOHSO4 (Route C). Of these approaches, Route A is most often employed and accounts for about 70% of the total production of ε-caprolactam worldwide. However, this method has several drawbacks. Cyclohexanone is supplied by the aerobic oxidation of cyclohexane, which leads to a mixture of cyclohexanone and cyclohexanol (K/A oil), but the conversion of cyclohexane must be kept at only 3–6% to avoid the formation of further oxidation products such as adipic acid and glutaric acid.[4] Another serious drawback of this method is the coproduction of a large amount of ammonium sulfate waste in both the hydroxylamine production and the Beckmann rearrangement processes.[3] Several new approaches to the synthesis of ε-caprolactam and its precursors have recently been developed. Researchers at EniChem Co. have synthesized the oxime by ammoximation of cyclohexanone with hydrogen peroxide and ammonia catalyzed by titanium silicate-1 (TS-1), followed by Beckmann rearrangement in the presence of a high-content silicate catalyst developed by Sumitomo Chemical Co.[3, 5] Thomas and co-workers have reported that a bifunctional transitionmetal-ion-substituted aluminophosphate molecular sieve promotes the reaction of cyclohexanone with ammonia and hydrogen peroxide or molecular oxygen to give cyclohexanone oxime along with a small amount of ε-caprolactam.[6] These methods, however, require cyclohexanone as the starting material. If direct conversion of cyclohexane into εcaprolactam precursor could be achieved, the reaction would represent an innovative method. Although the PNC process fits this purpose, very corrosive NOCl must be used as a key compound together with HCl.[1] In addition, cyclohexanone oxime is obtained as its hydrochloric acid salt and the formation of NOCl is very troublesome. Therefore, the development of a new system for the nitrosation or oximation of cyclohexane that overcomes these disadvantages is desirable.We have shown previously that the phthalimide N-oxyl radical (PINO; generated in situ by reaction of N-hydroxyphthalimide (NHPI) with dioxygen in the presence or absence of a transition-metal salt or nitrogen dioxide) serves as a carbon-radical-producing catalyst (CRPC) and abstracts hydrogen atoms from CÀH bonds in hydrocarbons under relatively mild conditions.[7] For example, cyclohexane was oxidized in the presence of a catalytic amount of NHPI combined with [Mn (acac) 2](acac= acetylacetonate) under dioxygen to give a cyclohexyl radical, which was eventually converted into adipic acid in high yield.[8] Cyclohexane was also efficiently nitrated by treatment with nitrogen dioxide and NHPI to form nitrocyclohexane.[9] In the course of our studies on the NHPI-catalyzed functionalization of cyclohexane, we have now found that the nitrosation of cyclohexane

A new route to lactam precursors from cycloalkanes: direct production of nitrosocycloalkanes or cycloalkanone oximes by using tert-butyl nitrite and N-hydroxyphthalimide.

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