本文關(guān)鍵詞： 醇氧化 選擇性氧化 銅催化 氧化腈化 氨基酸 氨水　出處：《浙江工業(yè)大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

【摘要】：醇選擇性氧化制備腈和醛是有機合成中一類非常重要的反應(yīng)。本論文針對當(dāng)前醇選擇性氧化反應(yīng)中存在的問題,發(fā)展了兩類配體輔助調(diào)控銅催化醇選擇性氧化制備腈和醛的新方法。設(shè)計了分別采用N-苯基甘氨酸和氨水作為有效配體,以氧氣(或空氣)為氧化劑,在油相(或水相)中高效、高選擇性氧化芳香伯醇、烯丙基醇、雜環(huán)芳香醇為相應(yīng)腈和醛的新體系。首先,氨基酸被選作一種N,O-二齒配體代替?zhèn)鹘y(tǒng)N,N-二齒配體,探究其在銅催化醇選擇性氧化腈化反應(yīng)中的作用。在以氨水(4.0 equiv.)為氮源的條件下,通過對各種天然氨基酸、功能化氨基酸、銅催化劑、溶劑、反應(yīng)溫度等影響因素的系統(tǒng)優(yōu)化,得到最佳反應(yīng)條件:底物醇(1.0 mmol)、CuI(5 mol%)、TEMPO(2,2,6,6-四甲基哌啶氧)(5 mol%)、N-苯基甘氨酸(5 mol%)、NaOH(10 mol%)、NH3(aq.25-28%w/w,300μL,4.0 mmol)、CH3OH(2.0 mL)。在最優(yōu)條件下,一系列底物可以高選擇性的氧化成目標(biāo)產(chǎn)物,并顯示出很好的官能團(tuán)容忍性。此外,當(dāng)反應(yīng)規(guī)模放大后,底物轉(zhuǎn)化率以及產(chǎn)物選擇性并沒有明顯降低。結(jié)合研究結(jié)果以及相關(guān)報道,對可能的反應(yīng)機理進(jìn)行了探討。其次,在水相中以氨水充當(dāng)一種最簡單的含氮配體,研究了銅催化一級醇選擇性氧化的反應(yīng)。通過對實驗條件系統(tǒng)篩選,發(fā)現(xiàn)水相中一級醇選擇性氧化制備腈或醛的過程可以通過控制氨水的用量實現(xiàn)。在最優(yōu)條件下,當(dāng)氨水的用量為8當(dāng)量時,底物選擇性轉(zhuǎn)化為腈;當(dāng)氨水的用量為7.9 mol%時,則選擇性氧化為醛。另外,過量氨水的再利用實驗結(jié)果表明,當(dāng)氨水的用量從8當(dāng)量降為3當(dāng)量,經(jīng)過5次循環(huán)再利用之后,反應(yīng)的轉(zhuǎn)化率和選擇性沒有明顯的變化。
[Abstract]:Selective oxidation of alcohols to nitrile and aldehydes is a very important reaction in organic synthesis. Two kinds of ligands were developed to control the selective oxidation of copper catalyzed alcohols to produce nitrile and aldehydes. N- phenylglycine and ammonia were used as effective ligands respectively. Oxygen (or air) was used as oxidant. Highly selective oxidation of aromatic primary alcohols, allyl alcohols and heterocyclic aromatic aromatic alcohols in oil (or aqueous) phase is a new system of nitrile and aldehydes. N-didentate ligands were used to study the role of N-didentate ligands in the selective oxidation of nitrile alcohols catalyzed by copper. In the presence of ammonia water as nitrogen source, various natural amino acids were studied. The optimum reaction conditions of functional amino acid, copper catalyst, solvent, reaction temperature and so on were optimized. The optimum reaction conditions were obtained as follows: substrate 1. 0 mmol / L CuI + 5 mol / L). TEMPO2, 2, 2, 6, 6-tetramethylpiperidinoxomethoxy, 5 mols, 5 mols of N- phenylglycine and 10 mol of NaOHU). NH _ 3a _ Q _ (25-28) and w / w _ (300 渭 L) (4.0 mmol / L) Ch _ 3OH ~ (2 +) / L ~ (2. 0), under the optimum conditions. A series of substrates can be oxidized to target products with high selectivity and show good functional tolerance. In addition, when the scale of the reaction is enlarged. The substrate conversion and product selectivity were not significantly decreased. Combined with the results of the study and related reports, the possible reaction mechanism was discussed. Secondly, ammonia was used as the simplest nitrogen-containing ligand in aqueous phase. The selective oxidation of primary alcohols catalyzed by copper was studied. It is found that the process of selective oxidation of first-order alcohols to nitrile or aldehydes in aqueous phase can be achieved by controlling the amount of ammonia water. Under the optimal conditions, when the amount of ammonia water is 8 equivalent, the substrate can be selectively converted to nitrile. When the amount of ammonia water was 7.9 mol%, it was selectively oxidized to aldehydes. In addition, the reutilization experiment of excessive ammonia water showed that the amount of ammonia water decreased from 8 to 3 equivalent. After five reuses, the conversion and selectivity of the reaction did not change significantly.
【學(xué)位授予單位】：浙江工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O621.251

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