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    • 21. 发明授权
    • Preparation of riboflavin
    • 核黄素的制备
    • US4567261A
    • 1986-01-28
    • US570457
    • 1984-01-13
    • Hansgeorg ErnstWolfram SchmidtJoachim Paust
    • Hansgeorg ErnstWolfram SchmidtJoachim Paust
    • C07D475/14C07D475/02
    • C07D475/02
    • Riboflavin of the formula I ##STR1## is prepared by condensing a 4,5-dimethyl-N-(D)-ribityl-2-phenylazoaniline of the formula II ##STR2## where R is H or --Cl, --NO.sub.2 or --CH.sub.3 in the o- or p-position, with barbituric acid of the formula III ##STR3## in the presence of an acid as the condensing agent, by an improved process in which the acidic condensing agent used is an aliphatic or cycloaliphatic/aliphatic tertiary carboxylic acid of the general formula IV ##STR4## where R.sup.1, R.sup.2 and R.sup.3 are each a lower alkyl group, R.sup.1, R.sup.2 and R.sup.3 together containing 3 to 20, preferably 3 to 10, carbon atoms, or R.sup.1 is a lower alkyl group, in particular methyl, and R.sup.2 and R.sup.3 together form a tetramethylene or pentamethylene group.The process can be particularly advantageously carried out using trimethylacetic acid or a commercial mixture of saturated tertiary carboxylic acids, e.g. Versatic .sup.R 10-acid.
    • 式I(I)的核黄素通过将式II的4,5-二甲基-N-(D) - 二乙基苯基偶氮苯胺(II)缩合制备,其中R是H或-Cl ,在邻位或对位的-NO 2或-CH 3与通式III的巴比妥酸(III)在作为缩合剂的酸存在下,通过改进的方法,其中使用酸性缩合剂 是通式IV(IV)的脂族或脂环族/脂肪族三羧酸,其中R 1,R 2和R 3各自为低级烷基,R 1,R 2和R 3一起含有3至20,优选3至10, 碳原子,或R 1是低级烷基,特别是甲基,R 2和R 3一起形成四亚甲基或五亚甲基。 该方法可以特别有利地使用三甲基乙酸或饱和叔羧酸的商业混合物,例如, 通用R10酸。
    • 29. 发明授权
    • Preparation of alkyl O,O-dialkyl-.gamma.-phosphonotiglates
    • 烷基O,O-二烷基-γ-膦酸吡啶的制备
    • US4937308A
    • 1990-06-26
    • US205283
    • 1988-06-10
    • Guenter H. KnausHansgeorg ErnstMarco ThyesJoachim Paust
    • Guenter H. KnausHansgeorg ErnstMarco ThyesJoachim Paust
    • C07F9/40
    • C07F9/4015
    • Alkyl .gamma.-halotiglates of the general formula I ##STR1## where X is Cl or Br and R.sup.2 is alkyl of 1 to 3 carbon atoms, having a high E isomer content, are prepared by a process in which(a) the corresponding 2-methyl-but-3-enoate of the general formula II ##STR2## is reacted with chlorine or bromine in the absence of a solvent and (b) the resulting 2-methyl-3,4-dihalobutyrate of the general formula III ##STR3## is dehydrohalogenated by reaction with a solution of an alkali metal hydroxide in an alcohol R.sup.2 OH, where R.sup.2 has the stated meaning, or in a mixture of water and an alcohol R.sup.2 OH, and the products are further processed to give O,O-dialkyl-.gamma.-phosphonotiglates of the general formula IV ##STR4## where R.sup.1 is alkyl of 1 to 4 carbon atoms and R.sup.2 is alkyl of 1 to 3 carbon atoms, preferably ethyl, by reaction with a trialkyl phosphite and thermal isomerization. The process gives C.sub.5 building blocks which are extremely interesting for polyene chemistry, the said building blocks being obtained in good yields and essentially in the form of the required E isomers.
    • 通过以下方法制备通式I的烷基γ-卤代吡咯烷酮,其中X是Cl或Br,R2是具有高E异构体含量的1至3个碳原子的烷基,其中(a) 在不存在溶剂的情况下,使通式II(II)的相应的2-甲基 - 丁-3-烯酸酯与氯或溴反应,和(b)所得的2-甲基-3,4-二卤代丁酸酯 通过与碱金属氢氧化物在醇R2OH中的溶液(其中R2具有所述含义)或在水和醇R2OH的混合物中进行反应脱卤化氢,并将产物进一步加工 得到通式IV(IV)的O,O-二烷基-γ-膦腈吡咯烷酮,其中R 1为1至4个碳原子的烷基,R 2为1至3个碳原子的烷基,优选为乙基,通过与 亚磷酸三烷基酯和热异构化。 该方法提供了对多烯化学非常有趣的C5构建块,所述构建块以良好的产率获得并且基本上以所需的E异构体的形式获得。