氨基酸促进的铁催化醇的有氧氧化反应研究

发布时间：2018-06-07 13:56

本文选题：仿生催化 + 铁催化　；参考：《浙江工业大学》2016年硕士论文

【摘要】：醇类化合物选择性氧化制备相应的醛或酮是有机化学及化工中非常重要的一类反应。本论文采用天然氨基酸作为高效的N,O-二齿配体,采用氧气作为最终的绿色氧化剂,模拟含铁酶催化氧化过程,发展了一类仿生铁催化醇选择性氧化制备醛或酮的新方法。该方法具有广泛的底物适用性以及良好的官能团兼容性,一级苄醇、二级苄醇、含杂原子的芳香醇、烯丙基醇等都可以被高效的转化为相应的醛或酮。首先,以甲硫氨酸,异亮氨酸,组氨酸,甘氨酸,丙氨酸,缬氨酸,苯丙氨酸,半胱氨酸为起始原料制备了多种N-Ac、N-Cbz、N-Fmoc、N-Boc以及N-芳基等官能化的天然氨基酸配体,并且通过~1HNMR,~(13)CNMR等检测手段对所制备的配体进行了结构确认。然后,采用这些官能化氨基酸作为配体(包括天然氨基酸和非天然氨基酸)、以对甲基苯甲醇为模型底物,系统考察了铁盐、溶剂、添加剂等影响因素对醇氧化反应收率和选择性的影响,从而,获得最佳反应条件:1 mmol芳香一级醇,5 mol%FeCl_3为催化剂,10 mol%L-缬氨酸为配体,10 mol%TEMPO(2,2,6,6-四甲基哌啶-氮-氧化物)为辅助催化剂,氧气作为最终氧化剂。在含有700 mg 4?分子筛的甲苯中回流条件下,该催化体系可以高效、高选择性的将一级苄醇、烯丙基醇以及杂芳醇等氧化成为相应的醛,原料转化率大部分99%,反应选择性99%。在芳香伯醇氧化条件的基础上,通过对铁盐、氨基酸、TEMPO、添加剂和反应时间等因素对二级醇氧化条件的系统的考察,从而得到了二级苄醇最优氧化条件:1 mmol二级苄醇,10 mol%FeCl3为催化剂,10 mol%L-缬氨酸为配体,10 mol%TEMPO作为辅助催化剂,氧气作为最终氧化剂。在含有700 mg 4?分子筛的甲苯中回流条件下,该催化体系可以高效、高选择性的将二级苄醇、烯丙基醇以及杂芳醇等氧化成为相应的酮,原料转化率高达99%,反应选择性99%。
[Abstract]:The selective oxidation of alcohols for the preparation of aldehydes or ketones is a very important reaction in organic chemistry and chemical industry. In this paper, natural amino acids are used as an efficient N, O- two tooth ligand, and oxygen is used as the final green oxidant to simulate the catalytic oxidation of ferric enzyme, and a class of ferric catalyzed alcohol selective oxidation is developed. A new method for preparing aldehydes or ketones. This method has extensive substrate applicability and good functional group compatibility. First class benzyl alcohol, two class benzyl alcohol, aromatic alcohols containing hetero atoms, allyl alcohol, etc. can be efficiently converted to corresponding aldehydes or ketones. First, methionine, isoalinic acid, histidine, alanine, valine, valine, phenylpropyl ammonia, and alanine, glycine, glycine, glycine, alanine, alanine, alanine, Acid and cysteine are used as starting materials to prepare a variety of natural amino acid ligands, such as N-Ac, N-Cbz, N-Fmoc, N-Boc and N- aryl, and confirm the structure of the ligands by ~1HNMR, ~ (13) CNMR, and then use these functionalized aminoacids as ligands (both natural and non natural amino acids). The effect of iron salt, solvent, additive and other factors on the yield and selectivity of alcohol oxidation reaction was systematically investigated with methyl benzyl alcohol as the model substrate. The optimum reaction conditions were obtained: 1 mmol aromatic first alcohols, 5 mol%FeCl_3 as catalysts, 10 mol%L- valine as ligands and 10 mol%TEMPO (2,2,6,6- four methylpiperidine nitrogen oxide). Auxiliary catalyst, oxygen is the final oxidant. Under the reflux condition containing 700 mg 4? Molecular sieve in toluene, the catalytic system can be highly efficient and highly selective to oxidize the first benzyl alcohol, allyl alcohol and hetero aromatic alcohol to corresponding aldehydes. The conversion rate of raw materials is 99%, and the reaction selective 99%. is based on the oxidation conditions of aromatic alcohols. The optimal oxidation conditions of two grade benzyl alcohols were obtained by the system of iron salt, amino acid, TEMPO, additive and reaction time. The optimal oxidation conditions of two grade benzyl alcohol were obtained: 1 mmol two benzyl alcohol, 10 mol%FeCl3 as catalyst, 10 mol%L- valine as ligand, 10 mol% TEMPO as auxiliary catalyst and oxygen as the final oxidant. It contained 7. Under the reflux condition of toluene in 00 mg 4? Molecular sieve, the catalytic system can be highly efficient and highly selective to oxidize two grade benzyl alcohol, allyl alcohol and hetero aromatic alcohol to corresponding ketones. The conversion rate of raw materials is up to 99%, and the reaction selectivity is 99%.
【学位授予单位】：浙江工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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