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    • 25. 发明申请
    • Method for Producing Substituted Diamantanes
    • 生成取代的金刚烷的方法
    • US20100036153A1
    • 2010-02-11
    • US12086058
    • 2006-12-04
    • Peter R. SchreinerAndrey A. Fokin
    • Peter R. SchreinerAndrey A. Fokin
    • C07C35/44C07C239/08C07C233/08C07C61/125C07C69/753
    • C07C203/08C07C29/12C07C51/353C07C67/11C07C2603/90C07C35/44C07C61/135C07C69/013C07C69/14
    • The invention at hand provides at least dinitroxylated diamantanes. In addition, it provides methods for producing substituted diamantanes with high yields and selectivity.According to the invention, dinitroxylated diamantanes are suitable for being reacted with nucleophiles to form the corresponding disubstituted diamantanes. Surprisingly, it was discovered that at least dinitroxylated or hydroxylated diamantanes are rearranged in the presence of a strong acid, creating at least 4,9-nitroxylated or hydroxylated diamantanes. On the basis of this, 4,9-substituted diamantanes are able to be produced in a targeted manner by reaction with further nucleophiles.Thus, the invention at hand provides the following methods according to the present invention for producing at least disubstituted diamantanes: a) at least dinitroxylation, followed by the substitution of all nitroxy groups by a nucleophile or b) at least dinitroxylation, subsequent rearrangement in the presence of a strong acid, after realised rearrangement all nitroxy groups are replaced by a nucleophile or c) at least dinitroxylation, subsequent reaction with water (as nucleophile), rearrangement of the at least dihydroxylated compound in the presence of a strong acid, after realised rearrangement all hydroxy groups are replaced by another nucleophile.
    • 本发明至少提供二硝基甲酰化的二金刚烷。 此外,它提供了以高产率和选择性生产取代的二金刚烷的方法。 根据本发明,二硝基氧化的二金刚烷适于与亲核试剂反应以形成相应的二取代的二金刚烷。 令人惊奇的是,发现在强酸存在下重新排列了二硝基氧化或羟基化的二金刚烷,产生了至少4,9-氨基氧化或羟基化的金刚烷。 基于此,4,9-取代的二金刚烷可以通过与另外的亲核试剂反应而以目标方式制备。 因此,本发明提供了根据本发明的用于生产至少二取代的二金刚烷的以下方法:a)至少二硝基甲酰化,然后用亲核试剂取代所有硝基,或b)至少二硝基甲酰化,随后在 强酸的存在,在实现重排之后,所有的硝基都被亲核试剂取代,或c)至少二硝基甲酰化,随后与水(作为亲核试剂)反应,在强酸存在下重排至少二羟基化的化合物, 重排所有羟基被另一个亲核试剂取代。
    • 30. 发明授权
    • Method for preparing ester condensate
    • 制备酯缩合物的方法
    • US07301045B2
    • 2007-11-27
    • US10399233
    • 2001-08-23
    • Kazuaki IshiharaHisashi Yamamoto
    • Kazuaki IshiharaHisashi Yamamoto
    • C07C69/74C07C69/76C07C321/00
    • B01J31/0212B01J27/135B01J31/2208B01J2231/40B01J2531/40C07C67/08C07C327/22C07D309/30C08G63/81C08G63/85C07C69/007C07C69/013C07C69/017C07C69/003C07C69/612C07C69/618C07C69/75C07C69/24C07C69/734C07C69/78
    • The present invention provides a method for preparing ester or thioester that can conduct catalytic esterification reaction with an equimolar amount of carboxylic acid and alcohol, or catalytic thioesterification reaction with carboxylic acid and an equimolar amount or small amount of thiol, and can be expected as an industrial method that needs an enormous amount of synthesis in the light of green chemistry. By using hafnium chloride (IV), especially tetravalent hafnium compounds represented by hafnium chloride (IV)·(THF)2 or hafnium (IV)t-butoxide as a (poly) condensation catalyst, direct condensation reaction is conducted from carboxylic acid and an equimolar amount of alcohol or a little smaller amount of thiol, in the nonpolar solvent such as toluene and the like, in a deoxidization atmosphere and under heating reflux, and the reaction synthesizes ester monomer or thioester monomer, polyester or polythioester. When heating reflux is conducted by using a nonpolar solvent, it is preferable to remove azeotropic water from the reaction system.
    • 本发明提供了一种制备可与等摩尔量的羧酸和醇进行催化酯化反应或与羧酸和等摩尔量或少量硫醇进行催化酯基酯化反应的酯或硫酯的方法,并且可以作为 在绿色化学方面需要大量合成的工业方法。 通过使用氯化铪(IV),特别是作为(多)缩合催化剂的氯化铪(IV)(THF)2 H 2或叔(叔丁醇)铪代表的四价铪化合物,直接缩合反应 在脱氧气氛和加热回流下,在非极性溶剂如甲苯等中,从羧酸和等摩尔量的醇或少量的硫醇进行反应,合成酯单体或硫酯单体,聚酯 或聚硫酯。 当使用非极性溶剂进行加热回流时,优选从反应体系中除去共沸水。