Synthesis of Novel, Highly Reactive Sulfur-containing Species by Taking Advantage of Steric Protection

利用空间保护合成新型高活性含硫物质

• 批准号: 16550045
• 负责人: OKAZAKI Renji
• 金额: $ 2.3万
• 依托单位: Japan Women's University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550045/
• 关键词: steric protection; thioaldehyde; thioacyl halide; thiophilic reaction; carbon monosulfide; carbanion; carbene; チオカルボニル化合物; 二硫化炭素; 有機リチウム試剤; チオアシリムイオン; チオフリック反応; X線結晶解析

We have synthesized two types of highly reactive organosulfur species by taking advantage of steric protection due to bulky substituents such as 2,4,6-tri-t-butylphenyl (Mes^*) and 4-t-butyl-2,6-bis[(2,2",6,6"-tetrametyl-m-terphenyl-2'-yl)methyl]phenyl(Bmt). Reaction of stable thioaldehyde Mes^*CHS, synthesized by us as the first stable thioaldehyde, with N-bromo- or N-chlorosuccinimide gave the corresponding thioacyl halides Mes^*C(=S)X(X=Br,Cl), which reacted with alcohols, thiols or amines to afford thioesters, dithioesters or thioamides. BmtLi attacked on the sulfur of CS_2 (thiophilic reaction) to produce highly reactive anionic species having carbene character, (BmtS)(LiS)C : (1),which was in equiliprium with dimeric species, (BmtS)(LiS)C=C(SLi)(SBmt) (2).Anionic species 1 and 2 were also formed when HC(=S)(SBmt) was deprotonated with lithium tetramethylpiperidide and quenched with a variety of alkyl halides. Anion 1 was stabe at -78℃ but decomposed into C=S and BmtSLi at -30℃. This represents a novel method for the generation of C=S.

我们利用2，4，6-三叔丁基苯基(MES^*)和4-t-butyl-2，6-bis[(2，2“，6，6”-tetrametyl-m-terphenyl-2‘-yl)methyl]phenyl(Bmt).等大分子取代基的空间保护作用，合成了两种高活性有机硫化合物由我们合成的第一个稳定的硫代醛Mes^*CHS与N-溴或N-氯代丁二酰亚胺反应，得到相应的硫代酰基卤化物Mes^*C(=S)X(X=Br，Cl)，再与醇、硫醇或胺反应得到硫代酯、二硫代酯或硫代酰胺。BmtLi作用于CS2的硫(亲硫基反应)生成具有卡宾性质的高活性阴离子物种(BmtS)(Lis)C：(1)与二聚体物种(BmtS)(Lis)C=C(SLi)(Sbmt)(2)。HC(=S)(Sbmt)(Sbmt)经四甲基吡啶锂去质子化和各种卤代烷基化合物猝灭后，也形成阴离子物种1和2。阴离子1在-78℃时稳定，在-30℃时分解为C=S和BmtSLi。这代表了一种产生C=S的新方法。

项目成果

理科年表(主な有機化学反応)

科学年表（主要有机化学反应）

• 发表时间: 2005
• 作者: K.Mogi;K.Takenaka;R.Okazaki;M.Saito;M.Saito;R.Okazaki;岡崎 廉治
• 通讯作者: 岡崎 廉治

Tin-Chalcogen Double-Bond Compound, Stannanethione and Stannaneselone : Synthesis, Structure, and Reactivities

锡硫双键化合物、锡硫酮和锡烷酮：合成、结构和反应性

• 发表时间: 2004
• 期刊: J. Am. Chem. Soc. 126
• 作者: K.Mogi;K.Takenaka;R.Okazaki;M.Saito
• 通讯作者: M.Saito

Deprotonation of Aryl Methanedithioate by Lithium Amides : Formation of Lithium Arylthio(thioxo) methanide Having Unique Reactivity

氨基锂对芳基甲烷二硫代酯的去质子化：形成具有独特反应性的芳基硫代（硫代）甲烷化锂

• 发表时间: 2005
• 期刊: Chem. Lett. 34
• 作者: W.Nakanishi;S.Hayashi;T.Nakai;W.Nakanishi;K.Mogi
• 通讯作者: K.Mogi

Deprotonation of Aryl Methanedithioate by Lithium Amide : Formation of Lithium Arylthio(thioxo)methanide Having Unique Reactivity

氨基锂对芳基甲烷二硫代酯的去质子化：形成具有独特反应性的芳硫基（硫代）甲烷化锂

• 发表时间: 2005
• 期刊: Chem.Lett. 34
• 作者: W.Nakanishi;S.Hayashi;T.Nakai;W.Nakanishi;K.Mogi;K.Mogi
• 通讯作者: K.Mogi

Deprotonation of Aryl Methanedithioate by Lithium Amides : Formation of Lithium Arylthio (thioxo) methanide Having Unique Reactivity

氨基锂对芳基甲烷二硫代酯的去质子化：形成具有独特反应性的芳基硫代（硫代）甲烷化锂

• 发表时间: 2005
• 期刊: Chem.Lett. 34
• 作者: K.Mogi;K.Takenaka;R.Okazaki
• 通讯作者: R.Okazaki