Synthesis, Structure, and Reactivity of Aromatic compounds and Alkenes Carrying Two Bulky substituents on Adjacent Positions

相邻位置带有两个大取代基的芳香族化合物和烯烃的合成、结构和反应性

• 批准号: 02640383
• 负责人: NAKAYAMA Juzo
• 金额: $ 1.28万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640383/
• 关键词: tert-butyl; 1-adamantyl; X-ray analysis; dynamic NMR; thiophenes; thiophene 1, 1-dioxides; overcrowded molecules; pyridazine; Oージーtーブチルベンゼン; Oージー1ーアダマンチルベンゼン; 1ー(1ーアダマンチル)ー2ーtーブチルベンゼン; 単結晶X線構造解析; 立体障害; チオフェン1,1ージオキシド; 酸化; 3,4ージー1ーアダマンチルチオフェ

In 1985 we developed a new thiophene synthesis which involves intramolecular reductive coupling of readily obtainable diketo sulfides. 'ne new method is very versatile and allows the preparation of a wide variety of thiophenes including 3, 4-di-t-buty-and3, 4-di-l-adamantylthiophenes(land2). By using 1 and 2 as the starting materials, a series of aromatic compounds and alkenes carrying two t-butyl and I-adamantyl groups on adjacent positions were satisfactorily synthesized and their properties were studied as summarized below.1)New compounds, 3, 4-di-t-butylfuran, selenophene, and pyrrole were synthesized starring from I and their properites were studied by using NMR and MMP2 calculations.2)A sterically hindered cycloalkene carrying two t-butyls in cis orientation, 2, 3-di-t-butylbicyclo[2.2.2]octene, was synthesized by Diels-Alder reaction of 3, 4-di-t-butyltliiophene 1, 1-dioxide ; which is readily obtainable from 1, and its structure and chemical reactivities were studied in detail.3)Dismethyl 4, 5-di-t-butyl-3, 6-dimethylphthalate, dimethyl 4, 5-di-l-adamantyl-3, 6-dimethylphathalate, dimethyl 4-adamantyl-3-t-butyl-3, 6-dimethylphathale were synthesized and their structures were investigated by X-ray single crystal structure analyses and dynamic ^1H and ^<13>C NMR.4)A new pyridazine synthesis which utilizes the Dieals-Alder reaction of thiopliene I, I-dioxides with N-phenyltriazoline-3, 5-dione was developed.5)Oxidation of thiophetie 1, I -dioxides carrying bulky substituents on 3- and 4-positions was found to give the corresponding epoxides as the initial products which undergo a new rearrangement leading to the corresponding thietes 1, 1 -dioxides.

1985年，我们开发了一种新的噻吩合成，其中涉及可容易获得的二甲硫化物的分子内还原性偶联。 'NE新方法非常通用，并允许制备各种硫烯，包括3个，4-Di-T-Buty-and3，4-Di-L-l-Adamantylthythythiophenes（Land2）。 By using 1 and 2 as the starting materials, a series of aromatic compounds and alkenes carrying two t-butyl and I-adamantyl groups on adjacent positions were satisfactorily synthesized and their properties were studied as summarized below.1)New compounds, 3, 4-di-t-butylfuran, selenophene, and pyrrole were synthesized starring from I and their properites were studied by using NMR 2）在CIS取向中携带两个T丁基的空间阻碍的环烷基，2，3-Di-t-T-叔丁基微粒细菌[2.2.2] octene通过3，4-Di-T-T-T-T-T-叔丁基二酚1，1-二氧化物的3，4-Di-T-T-T-T-T-叔丁基二磷的反应合成。详细研究了它的结构和化学反应能力。3）甲基4、5-DI-T-d-叔丁基-3、6-二甲基乙酸酯，二甲基4、5-DI-DI-l-亚甲基-3、6-二甲基苯甲酸盐，6-二甲基苯甲酸酯，二甲基4-甲基4-亚辅基-3-T-T-T-二氨基 - 3--3-二氨基硫酸盐及6-二氨基硫酸盐，是二氨基硫酸盐，是6-二硫代的结构，是合成的，是二氨基甲烷 X-ray single crystal structure analyses and dynamic ^1H and ^<13>C NMR.4)A new pyridazine synthesis which utilizes the Dieals-Alder reaction of thiopliene I, I-dioxides with N-phenyltriazoline-3, 5-dione was developed.5)Oxidation of thiophetie 1, I -dioxides carrying bulky substituents on 3- and发现4位将相应的环氧化物作为初始产物，该产品经历了新的重排，导致相应的Thietes 1，1-二氧化物。

项目成果

J.Nakayama,R.Hasemi,N.Nakamura,and F.Iwasaki: "Synthesis,Properties,and Structures of a Series of Aromatic Compounds Carrying Two Highly Bulky Substituents on Adjacent Positions"

J.Nakayama、R.Hasemi、N.Nakamura 和 F.Iwasaki：“一系列在相邻位置上带有两个大体积取代基的芳香族化合物的合成、性质和结构”

Juzo Nakayama and Atsushi Hirashima: "Synthesis and Properties of Sterically Hindered Cycloalkenes Carrying Two tertーButyls in Cis Orientation.2,3ーDiーtertーbutylーbicycl[2.2.2]octー2ーene Derivatives" The Journal of the American Chemical Society. 112. 7648-76

Juzo Nakayama 和 Atsushi Hirashima：“顺式方向带有两个叔丁基的空间位阻环烯的合成和性质。2,3-二叔丁基-双环[2.2.2]辛-2-烯衍生物”美国化学会。112。7648-76

Juzo Nakayama: " "Synthesis and Properties of Sterically Hindered Cycloalkenes Carrying Two tert-Butyls in Cis Orientation. 2, 3-Di-tert-butylbicyclo [2.2.2. ] oct-2-ene Derivatives"" Journal of the American Chemical Society. 112. 7648-7653 (1990)

Juzo Nakayama：“带有两个顺式叔丁基的空间位阻环烯的合成和性质。

J.Nakayama and Y.Kamiyama: "Oxidation of Thiophene 1,1ーDioxides.Formation of the Epoxides and Their Rearrangement to the Corresponding Thietes"

J.Nakayama 和 Y.Kamiyama：“噻吩 1,1-二氧化物的氧化。环氧化物的形成及其重排为相应的噻吩”

Juzo Nakayama and Ryuji Hasemi: "First Synthesis of Aromatic Compounds Carrying Two 1ーAdamantyls on on Adjacent Positions: 3,4ーDiー1ーadamantylthiophene,oーDiー1ーadamanーtylbenzene,and 4,5ーDiー1ーadamantylpyridazine" The Journal of the American Chemical Society.

Juzo Nakayama 和 Ryuji Hasemi：“首次合成在相邻位置上带有两个 1-金刚烷基的芳香族化合物：3,4-Di-1-金刚烷基噻吩、o-Di-1-金刚烷基苯和 4,5-Di-1 -金刚烷基哒嗪”美国化学会杂志。