本文選題：仿生催化 + 鐵催化　； 參考：《浙江工業(yè)大學(xué)》2016年碩士論文

【摘要】：醇類化合物選擇性氧化制備相應(yīng)的醛或酮是有機(jī)化學(xué)及化工中非常重要的一類反應(yīng)。本論文采用天然氨基酸作為高效的N,O-二齒配體,采用氧氣作為最終的綠色氧化劑,模擬含鐵酶催化氧化過程,發(fā)展了一類仿生鐵催化醇選擇性氧化制備醛或酮的新方法。該方法具有廣泛的底物適用性以及良好的官能團(tuán)兼容性,一級(jí)芐醇、二級(jí)芐醇、含雜原子的芳香醇、烯丙基醇等都可以被高效的轉(zhuǎn)化為相應(yīng)的醛或酮。首先,以甲硫氨酸,異亮氨酸,組氨酸,甘氨酸,丙氨酸,纈氨酸,苯丙氨酸,半胱氨酸為起始原料制備了多種N-Ac、N-Cbz、N-Fmoc、N-Boc以及N-芳基等官能化的天然氨基酸配體,并且通過~1HNMR,~(13)CNMR等檢測手段對(duì)所制備的配體進(jìn)行了結(jié)構(gòu)確認(rèn)。然后,采用這些官能化氨基酸作為配體(包括天然氨基酸和非天然氨基酸)、以對(duì)甲基苯甲醇為模型底物,系統(tǒng)考察了鐵鹽、溶劑、添加劑等影響因素對(duì)醇氧化反應(yīng)收率和選擇性的影響,從而,獲得最佳反應(yīng)條件:1 mmol芳香一級(jí)醇,5 mol%FeCl_3為催化劑,10 mol%L-纈氨酸為配體,10 mol%TEMPO(2,2,6,6-四甲基哌啶-氮-氧化物)為輔助催化劑,氧氣作為最終氧化劑。在含有700 mg 4?分子篩的甲苯中回流條件下,該催化體系可以高效、高選擇性的將一級(jí)芐醇、烯丙基醇以及雜芳醇等氧化成為相應(yīng)的醛,原料轉(zhuǎn)化率大部分99%,反應(yīng)選擇性99%。在芳香伯醇氧化條件的基礎(chǔ)上,通過對(duì)鐵鹽、氨基酸、TEMPO、添加劑和反應(yīng)時(shí)間等因素對(duì)二級(jí)醇氧化條件的系統(tǒng)的考察,從而得到了二級(jí)芐醇最優(yōu)氧化條件:1 mmol二級(jí)芐醇,10 mol%FeCl3為催化劑,10 mol%L-纈氨酸為配體,10 mol%TEMPO作為輔助催化劑,氧氣作為最終氧化劑。在含有700 mg 4?分子篩的甲苯中回流條件下,該催化體系可以高效、高選擇性的將二級(jí)芐醇、烯丙基醇以及雜芳醇等氧化成為相應(yīng)的酮,原料轉(zhuǎn)化率高達(dá)99%,反應(yīng)選擇性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%.
【學(xué)位授予單位】：浙江工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O621.251

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