DEVELOPMENT OF MODIFIED CYCLODEXTRINS FOR SELECTIVE ORGANIC SYNTHESIS

用于选择性有机合成的改性环糊精的开发

• 批准号: 04453085
• 负责人: KOMIYAMA Makoto
• 金额: $ 3.9万
• 依托单位: University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453085/
• 关键词: Cyclodextrin; Phenol; Formaldehyde; Modified cyclodextrin; Selective synthesis; 分子複合体; パラ選択性

Development of new method for the selective synthesis of valuable chemicals in industry is quite important from the viewpoints of ecology, resource, energy, and so on. Previously we reported that cyclodextrins, cyclic oligomers of glucose, are highly effective for the selective organic synthesis. Various fine chemicals were synthesized in almost 100 % selectivities and in high yields. However, the reactions catalyzed by cyclodextrins are rather limited, since the hydroxyl residues are only the catalytic ones available. Still better catalysts should be obtained if appropriate functional residues are introduced to cyclodextrins by chemical modification.Here we succeeded in the selective synthesis of 4-(hydroxymethyl)phenol from phenol and formaldehyde and of 4-(hydroxyethyl)phenol from phenol and acetaldehyde, by use of various modified cyclodextrins. The structures of the molecular complexes, formed in these reaction mixtures, are determined by NMR spectroscopy. The hydroxyl residue introduced by the chemical modification to the primary hydroxyl side of the cavity form hydrogen bond with the formaldehyde, resulting in the activation of the formaldehyde for the reaction. In addition, the formaldehyde is fixed in the vicinity of the papa-carbon of the phenol by the hydrogen bonding, and thus the electrophilic attack by the formaldehyde selectively proceeds at the para-carbon. Potentialities of the modified cyclodextrins as practical catalysts are strongly indicated.

从生态学、资源、能源等方面考虑，开发有价值的工业化学品的选择性合成新方法是十分重要的，我们以前报道过葡萄糖环状低聚物环糊精在选择性有机合成中具有很高的效率。合成了各种精细化学品，选择性接近100%，收率高.然而，由环糊精催化的反应是相当有限的，因为羟基残基仅是可用的催化残基。在此，我们成功地利用各种改性环糊精，由苯酚和甲醛选择性合成了4-羟甲基苯酚，由苯酚和乙醛选择性合成了4-羟乙基苯酚。在这些反应混合物中形成的分子复合物的结构通过NMR光谱测定。通过化学改性引入到空腔的伯羟基侧的羟基残基与甲醛形成氢键，导致甲醛活化反应。此外，甲醛通过氢键固定在苯酚的对位碳附近，因此甲醛的亲电攻击选择性地在对位碳处进行。的改性环糊精作为实用的催化剂的潜力强烈表明。

项目成果

M.Komiyama,S.Sawata,andY.Takeshige: "Cooperation of cyclodextrin and alkali-metal halide for regio-selective cleavage of ribonucloeside 2´,3´-cyclic phosphates" J.Am.Chem.Soc.114. 1070-1074 (1992)

M.Komiyama、S.Sawata 和 Y.Takeshige：“环糊精和碱金属卤化物的合作用于核糖核苷 2´,3´-环状磷酸酯的区域选择性裂解”J.Am.Chem.Soc.1070-1074。 (1992)

Makoto Komiyama: "Selective synthesis using cyclodextrin as catalyst 7.Preparation of 3-(hydroxymethyl)indole"" Supramolecular Chemistry. (発表予定).

Makoto Komiyama：“使用环糊精作为催化剂的选择性合成7.3-(羟甲基)吲哚的制备””超分子化学。（待提交）。

M.Komiyama, K.Higuchi, and H.Noguchi: "Selective synthesis using cyclodextrins as catalysts 7.Preparation of 3-(hydroxymethyl)indole from indole and formaldehyde" Supramolecular Chem.(to be submitted).

M.Komiyama，K.Higuchi，H.Noguchi：“使用环糊精作为催化剂的选择性合成7.从吲哚和甲醛制备3-（羟甲基）吲哚”超分子化学（待提交）。

Sinya Sawata: "Potassium fluoride for the promotion of β-cyclodextrin-induced regioselective P-0(3')cleavage" Journal of Physical Organic Chemistry. 5. 502-506 (1992)

Sinya Sawata：“氟化钾促进 β-环糊精诱导的区域选择性 P-0(3) 裂解”《物理有机化学杂志》，5. 502-506 (1992)。

諸角達也: "修飾シクロデキストリンを触媒とする4-(ヒドロキシメチル)フェノールの選択的合成"" 旭硝子財団研究報告. 61. 137-142 (1992)

Tatsuya Morozumi：“使用改性环糊精作为催化剂选择性合成 4-(羟甲基)苯酚”旭硝子基金会研究报告 61. 137-142 (1992)。