公开(公告)号：US4088676A

公开(公告)日：1978-05-09

申请号：US678825

申请日：1976-04-28

申请人： Willi Hofen ,  Gunter Prescher ,  Gerd Siekmann ,  Gunter Wolf

发明人： Willi Hofen ,  Gunter Prescher ,  Gerd Siekmann ,  Gunter Wolf

IPC分类号： B01D3/00 ,  C07C67/00 ,  C07C407/00 ,  C07C409/24 ,  C07C409/26 ,  C07C179/10

CPC分类号： C07C409/24 ,  C07C407/00 ,  C07C407/003 ,  Y10S203/06

摘要： A process for the continuous preparation of organic solutions of percarboxylic acids by reaction of an aqueous solution of hydrogen peroxide with the corresponding carboxylic acid in the presence of an acid, water-soluble catalyst which boils above 160.degree. C., extraction of the percarboxylic acid from the resulting reaction mixture using an organic solvent which is immiscible with water, reconcentration of the raffinate, which essentially contains hydrogen peroxide and the acid catalyst, by distilling off water in a distillation column and recycle of the raffinate, concentrated in this way, into the reaction with the carboxylic acid. The raffinate is divided into two partial streams in a ratio of 1 to 25:1. The raffinate is fed to a distillation column which is operated under reduced pressure and which has at least two take-off weirs as tray inserts, the first take-off weir being at least two theoretical plates above the sump phase, the second take-off weir being arranged at least two theoretical plates above the first take-off weir and the section of column between the second take-off weir and the top of the column having at least two theoretical plates. The larger partial stream of the raffinate is passed into the column below the first take-off weir and the smaller partial stream is passed into the column below the second take-off weir. Water is removed at the top of the distillation column. A first side stream, which essentially contains the hydrogen peroxide from the small partial stream of the raffinate from the extraction, is withdrawn from the second take-off weir and is a 2 to 40% strength by weight aqueous solution of hydrogen peroxide, which is optionally fed, together with the larger partial stream of the raffinate from the extraction, into the column below the first take-off weir. A second side stream is withdrawn from the first take-off weir and is an aqueous solution of the acid catalyst which optionally can be further worked up and re-used. The re-concentrated aqueous solution of hydrogen peroxide and acid catalyst, withdrawn as a sump product from the distillation, is recycled into the reaction with carboxylic acid. A third side stream can be taken from a third take-off weir which is arranged not more than 2 theoretical plates below the first take-off weir.The following applications are related to the process hereof for production of propylene oxide as being directed to aspects of the process, some of which are disclosed herein.______________________________________ German Serial U.S. Atty's Docket U.S. Serial No. No. No. ______________________________________ P 25 19 288.5 Bayer 2883 678,819 P 25 19 300.4 Bayer 2884 678,820 P 25 19 299.8 Bayer 2885 678,821 P 25 19 298.7-42 Bayer 2886 678,822 P 25 19 297.6 Bayer 2887 678,823 P 25 19 295.4 Bayer 2888 678,824 P 25 19 292.1-42 Bayer 2890 678,826 P 25 19 291.0-42 Bayer 2891 678,827 P 25 19 289.6 Bayer 2892 678,828 P 25 19 297.4 Bayer 2893 678,829 ______________________________________ All of the German applications were filed Apr. 30, 1975. Those applications are incorporated herein by reference.

公开(公告)号：US4988829A

公开(公告)日：1991-01-29

申请号：US373770

申请日：1989-06-30

申请人： Paul Fiedler ,  Martin Littmann ,  Manfred Lenthe ,  Achim Noak ,  Gerd Siekmann

发明人： Paul Fiedler ,  Martin Littmann ,  Manfred Lenthe ,  Achim Noak ,  Gerd Siekmann

IPC分类号： C07D303/08

CPC分类号： C07D303/08

摘要： A process for making the known fungicide intermediate 2-(4-chlorophenyl ethyl)-2-tert.-butyloxirane of the formula ##STR1## comprising (a) mixing a solution of trimethylsulphonium bromide of the formula(CH.sub.3).sub.3 S.sup..sym. Br.sup..crclbar. (II) in a methanol/toluene mixture with preheated toluene and simultaneously distilling off a methanol/toluene mixture at a temperature between 65.degree. and 110.degree. C. until a suspension having a solids content between 10 and 70% by weight is formed, and(b) reacting the suspension of trimethylsulphonium bromide in toluene thus obtained with 1-(4-chlorophenyl)-4,4-dimethylpentan-3-one of the formula ##STR2## in the presence of solid potassium hydroxide, diethylene glycol and water at a temperature between 20.degree. and 120.degree. C., the amounts of the reaction components being such that per mole of 1-(4-chlorophenyl)-4,4-dimethylpentan-3-one of the formula (III) there are presentbetween 1 and 2 moles of trimethylsulphonium bromide of the formula (II),between 2 and 3 moles of solid potassium hydroxide and alsobetween 0.1 and 10% by weight of diethylene glycol and between 0.5 and 12% by weight of water, relative to 1-(4-chlorophenyl)-4,4-dimethylpentan-3-one of the formula (III).

摘要翻译： 制备已知的杀真菌剂中间体式（I）的2-（4-氯苯基乙基）-2-叔丁基环氧乙烷的方法包括（a）将式（CH3）3S的三甲基锍溴化物 +）Br（ - ）（II）的甲醇/甲苯混合物中，同时在65-110℃的温度下蒸馏除去甲醇/甲苯混合物，直到固体含量为10至70％ ，并且（b）使由此获得的甲苯中的三甲基锍溴化物的悬浮液与式（III）的1-（4-氯苯基）-4,4-二甲基戊-3-酮在存在 固体氢氧化钾，二甘醇和水，温度在20℃至120℃之间，反应组分的量使得每摩尔1-（4-氯苯基）-4,4-二甲基戊-3-酮为 式（III）中存在1至2摩尔式（II）的三甲基锍溴化物，2至3小时 固体氢氧化钾和0.1至10重量％的二甘醇和0.5至12重量％的水相对于式（I）的1-（4-氯苯基）-4,4-二甲基戊-3-酮， （三）。

公开(公告)号：US4089892A

公开(公告)日：1978-05-16

申请号：US678829

申请日：1976-04-28

申请人： Willi Hofen ,  Gerd Schreyer ,  Rolf Wirthwein ,  Helmut Waldmann ,  Gerd Siekmann

发明人： Willi Hofen ,  Gerd Schreyer ,  Rolf Wirthwein ,  Helmut Waldmann ,  Gerd Siekmann

IPC分类号： C07C67/00 ,  C07C407/00 ,  C07C409/24 ,  C07C179/10 ,  B01D3/00

CPC分类号： C07C407/00 ,  C07C407/003

摘要： Process for continuous production of substantially anhydrous solutions of percarboxylic acid in solvent. Aqueous hydrogen peroxide is first reacted with the corresponding carboxylic acid in the presence of acid catalyst to form percarboxylic acid and water (1). The percarboxylic acid is extracted with solvent (5), to provide a solvent phase containing the percarboxylic acid (11) and an aqueous raffinate (7). The solvent phase is subjected to distillation (12) to provide the anhydrous solution (13). In this distillation (12) the hydrogen peroxide remaining in the solvent phase produced in the extraction (5), is distilled off together with water and some solvent, and the hydrogen peroxide is recovered as an aqueous phase and recycled (14). The aqueous raffinate, which contains hydrogen peroxide, is distilled to remove water (8) and the resulting concentrate is recycled (2) for use in the reaction (1).

摘要翻译： 连续生产基本上无水的过羧酸溶剂在溶剂中的方法。 首先在酸催化剂存在下，将过氧化氢水溶液与相应的羧酸反应生成过羧酸和水（1）。 用溶剂（5）萃取过羧酸，提供含有过羧酸（11）和含水萃余液（7）的溶剂相。 对溶剂相进行蒸馏（12）以提供无水溶液（13）。 在该蒸馏（12）中，在萃取（5）中产生的溶剂相中剩余的过氧化氢与水和一些溶剂一起蒸馏出去，并将过氧化氢作为水相回收并回收（14）。 含有过氧化氢的含水萃余液被蒸馏以除去水（8），并将所得浓缩物再循环（2）用于反应（1）。

公开(公告)号：US4344897A

公开(公告)日：1982-08-17

申请号：US102817

申请日：1979-12-13

申请人： Ralf Goedecke ,  Willi Hofen ,  Hermann Seifert ,  Gerd Siekmann

发明人： Ralf Goedecke ,  Willi Hofen ,  Hermann Seifert ,  Gerd Siekmann

IPC分类号： C07C67/00 ,  C07C407/00 ,  C07C409/24 ,  C07C409/26 ,  C07C179/00 ,  B01D3/36

CPC分类号： C07C407/003 ,  C07C407/00

摘要： In a process for the continuous preparation of pure organic solutions of percarboxylic acids having 2 to 5 carbon atoms, by(a) contacting aqueous hydrogen peroxide with a carboxylic acid containing 2 to 5 carbon atoms in the presence of an acid catalyst at a feed molar ratio of H.sub.2 O.sub.2 to carboxylic acid of 0.5:1 to 30:1,(b) isolating an extract essentially containing the percarboxylic acid and possibly the corresponding carboxylic acid not converted in stage (a), by extracting the reaction mixture obtained according to stage (a) with an organic solvent,(c) treating the extract with water or an aqueous solution in an extraction unit provided with one to ten theoretical separation stages and(d) dehydrating the solution of the percarboxylic acid and organic solvent obtained according to (c), by azeotropic distillation,the improvement wherein the organic phase of the top product of the azeotropic distillation, obtained during the dehydration according to (d), is entirely or partially recycled to stage (c) and/or entirely or partially recycled to stage (b).

摘要翻译： 在连续制备具有2至5个碳原子的过羧酸的纯有机溶液的方法中，通过（a）在酸催化剂存在下，在进料摩尔浓度下使过氧化氢水与含2-5个碳原子的羧酸接触 H 2 O 2与羧酸的比例为0.5:1至30:1，（b）通过提取根据阶段（a）获得的反应混合物，分离基本上含有过羧酸的萃取物和可能的（a）阶段未转化的相应羧酸， （c）用有机溶剂处理提取物，（c）在提供有1到10个理论分离阶段的提取单元中用水或水溶液处理提取物，和（d）使根据（c）获得的过羧酸和有机溶剂的溶液脱水 ），通过共沸蒸馏，其中根据（d）在脱水期间获得的共沸蒸馏的顶部产物的有机相完全或部分地回收 循环到阶段（c）和/或完全或部分地循环到阶段（b）。

公开(公告)号：US4313879A

公开(公告)日：1982-02-02

申请号：US179622

申请日：1980-08-20

申请人： Herbert Klenk ,  Rolf Wirthwein ,  Gerd Siekmann ,  Wulf Schwerdtel

发明人： Herbert Klenk ,  Rolf Wirthwein ,  Gerd Siekmann ,  Wulf Schwerdtel

IPC分类号： C07D313/04 ,  C07D315/00

CPC分类号： C07D315/00

摘要： The invention relates to a process for the production of .epsilon.-caprolactone having a purity of 99.9% and increased color and storage stability which comprises feeding .epsilon.-caprolactone, which has been made by reacting cyclohexanone with a solution of a percarboxylic acid, into a first distillation unit, operating at 0.1 to 500 mbars and drawing off as the top product a mixture consisting of .epsilon.-caprolactone and lower-boiling impurities, feeding the bottom product of said first distillation unit into a second distillation unit, operating at 0.1 to 500 mbars and then drawing off the pure .epsilon.-caprolactone as the top product. The .epsilon.-caprolactone is useful as an intermediate for the production of known useful compounds such as polyesterols which are subsequently converted to polyurethanes.

摘要翻译： 本发明涉及一种生产纯度为99.9％，颜色和储存稳定性提高的ε-己内酯的方法，包括将环己酮与过羧酸反应制得的ε-己内酯进料到第一 蒸馏单元，操作为0.1至500mbar，并作为顶部产物抽出由ε-己内酯和低沸点杂质组成的混合物，将所述第一蒸馏单元的底部产物进料到第二蒸馏单元中，操作为0.1至500mbar 然后取出纯ε-己内酯作为顶级产品。 ε-己内酯可用作生产已知有用化合物如聚酯的中间体，随后将其转化为聚氨酯。