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    • 1. 发明授权
    • Preparation of 4-halobenzyl alcohols
    • 制备4-卤代苄醇
    • US5254752A
    • 1993-10-19
    • US960774
    • 1992-10-14
    • Franz MergerMartin BrudermuellerMartin Schmidt-Radde
    • Franz MergerMartin BrudermuellerMartin Schmidt-Radde
    • C07C29/141C07C29/145C07C33/46C07C41/18C07C43/174C07C27/04
    • C07C29/141C07C29/145C07C33/46
    • The invention provides a process for the preparation of a 4-halobenzyl alcohol of the formula ##STR1## where R.sup.1 is hydrogen, C.sub.1 - to C.sub.20 -alkyl, C.sub.2 - to C.sub.20 -alkoxyalkyl, C.sub.3 - to C.sub.20 -cycloalkyl, or C.sub.4 - to C.sub.30 -cycloalkylalkyl,R.sup.2 is C.sub.1 - to C.sub.20 -alkyl, C.sub.2 - to C.sub.20 -alkoxyalkyl, C.sub.3 - to C.sub.20 -cycloalkyl or C.sub.4 - to C.sub.30 -cycloalkylalkyl,X is halogen andm is 0 to 2,by reacting a haloaromatic carbonyl compound of the formula ##STR2## where R.sup.1, R.sup.2, X and m are as defined above, with hydrogen on a hydrogenation catalyst consisting essentially of copper oxide (I), copper oxide (II) and mixtures thereof in the presence of at least one primary, secondary or tertiary amine selected from the group consisting of acyclic, cyclic and heterocyclic aliphatic amines, in the presence or absence of an inert solvent, at from 50.degree. to 130.degree. C. and at from 10 to 200 bar.
    • 本发明提供制备式(I)的4-卤代苄醇的方法,其中R 1是氢,C 1 -C 20烷基,C 2 -C 20烷氧基烷基,C 3 -C 20环烷基或 C 4 -C 30 - 环烷基烷基,R 2是C 1〜C 20 - 烷基,C 2〜C 20 - 烷氧基烷基,C 3〜C 20 - 环烷基或C 4〜C 30 - 环烷基烷基,X是卤素,m是0〜2, 其中R1,R2,X和m如上所定义的式(II)的卤代芳基羰基化合物与氢在基本上由氧化铜(I),氧化铜(II)和它们的混合物组成的氢化催化剂上 在惰性溶剂存在或不存在下,在50-130℃和10-200℃下存在至少一种选自无环,环状和杂环脂族胺的伯,仲或叔胺 酒吧。
    • 3. 发明授权
    • Preparation of 3-(hydroxyphenyl)propionaldehydes and their hydrogenation
to 3-(hydroxyphenyl)propanols
    • 3-(羟基苯基)丙醛的制备及其氢化为3-(羟基苯基)丙醇
    • US5304685A
    • 1994-04-19
    • US037881
    • 1993-03-26
    • Franz MergerMartin Schmidt-Radde
    • Franz MergerMartin Schmidt-Radde
    • C07B61/00C07C37/00C07C39/11C07C45/68C07C45/71C07C47/27C07C45/00C07C29/14
    • C07C39/11C07C45/71C07C47/27
    • A process for preparing 3-(hydroxyphenyl)propionaldehydes of the formula I ##STR1## and, where appropriate, for preparing 3-(hydroxyphenyl)propanols of the formula II ##STR2## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each hydrogen, C.sub.1 -C.sub.20 -alkyl, C.sub.3 -C.sub.20 -cycloalkyl, C.sub.4 -C.sub.20 -alkylcycloalkyl, C.sub.4 -C.sub.20 -cycloalkylalkyl or C.sub.5 -C.sub.20 -alkylcycloalkylalkyl,R.sup.3 and R.sup.4 are each aryl, C.sub.7 -C.sub.20 -aralkyl, heterocycloalkyl or C.sub.3 -C.sub.20 -heterocycloalkylalkyl, entailsa) reacting phenols of the formula III ##STR3## where R.sup.1 and R.sup.2 have the abovementioned meanings, with 3-hydroxypropionaldehydes of the formula IV ##STR4## where R.sup.3 and R.sup.4 have the abovementioned meanings, in the presence of a basic catalyst at from 90.degree. to 230.degree. C. and under from 0.01 to 50 bar and, where appropriate,b) treating the resulting 3-(hydroxyphenyl)propionaldehydes of the formula I ##STR5## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the abovementioned meanings, with hydrogen in the presence of a hydrogenation catalyst at from 0.degree. to 250.degree. C. and under from 0.1 to 300 bar.
    • 制备式I(I)的3-(羟基苯基)丙醛的方法,以及适当时制备式II的3-(羟基苯基)丙醇的方法,其中R 1,R 2,R 3和 R 4各自为氢,C 1 -C 20 - 烷基,C 3 -C 20 - 环烷基,C 4 -C 20 - 烷基环烷基,C 4 -C 20 - 环烷基烷基或C 5 -C 20 - 烷基环烷基烷基,R 3和R 4各自为芳基,C 7 -C 20 - 芳烷基,杂环烷基或 C 3 -C 20杂环烷基烷基需要a)使具有上述含义的式III化合物III(III)的酚与式IV的3-羟基丙醛反应,其中R 3和R 4具有 在碱性催化剂存在下,在90〜230℃,0.01〜50巴下,适当时,b)处理得到的式(I)的3-(羟基苯基)丙醛 I)其中R 1,R 2,R 3和R 4具有上述含义,在氢化催化剂存在下,在0〜250℃下, 0.1至300巴。
    • 9. 发明授权
    • 3-substituted 2-hydroxy-3-formylpropionic esters, the preparation
thereof and the use thereof for preparing 3-substituted 3-formylacrylic
esters
    • 3-取代的2-羟基-3-甲酰基丙酸酯,其制备及其用于制备3-取代的3-甲酰基丙烯酸酯的用途
    • US5256813A
    • 1993-10-26
    • US883342
    • 1992-05-15
    • Franz MergerJuergen Frank
    • Franz MergerJuergen Frank
    • C07C69/675C07C69/732
    • C07C69/675
    • A 3-substituted 2-hydroxy-3-formylpropionic ester of the formula I ##STR1## where R.sup.1 is lower alkyl, and R.sup.2 is straight-chain or branched alkyl of 1 to 10 carbon atoms, is obtained by adding an alkanal of the fomrula II ##STR2## and an alkyl glyoxylate of the formula III ##STR3## simultaneously to a catalyst system composed of a salt or a mixture of a secondary amine and a carboxylic acid in such a way that the temperature does not exceed 90.degree. C., preferably 80.degree. C., or else adding one of the reactants of the formula II or III to a mixture of the catalyst system described above and the other reactant in such a way that the temperature does not exceed 90.degree. C. The 2-hydroxy-3-formylpropionic eater of the formula I can be converted by treatment with dehydrating agents, especially acetic anhydride, into good yields of the corresponding 3-substituted 3-formylacrylic ester.
    • 其中R1是低级烷基,R2是具有1-10个碳原子的直链或支链烷基的式Ⅰ的3-取代的2-羟基-3-甲酰基丙酸酯是通过将烷基 的II型和式III(III)的烷基乙醛酸盐同时与由仲胺和羧酸的盐或混合物组成的催化剂体系,使得 温度不超过90℃,优选80℃,或者将一种式II或III的反应物加入到上述催化剂体系和另一种反应物的混合物中,使得温度不 超过90℃。式I的2-羟基-3-甲酰基丙酸酯可以通过用脱水剂,特别是乙酸酐处理转化成相应3-取代的3-甲酰基丙烯酸酯的良好产率。