公开(公告)号：US4376864A

公开(公告)日：1983-03-15

申请号：US320131

申请日：1981-11-10

Applicant: Karlheinz Drauz ,  Axel Kleemann ,  Marc Samson

Inventor： Karlheinz Drauz ,  Axel Kleemann ,  Marc Samson

IPC: C07D207/16 ,  C07D317/30 ,  C07D319/06 ,  C07D405/06

CPC classification number: C07D207/16 ,  C07D317/30 ,  C07D319/06

Abstract: The invention is directed to cyclic acetals of glutamic acid-.gamma.-semialdehyde of the formula ##STR1## in which A is an unsubstituted alkylene group having 2 to 3 carbon atoms or such an alkylene group substituted by 1 to 2 methyl groups and to a method of producing a compound of formula (I) by reaction of a compound of the general formula ##STR2## in which A is as defined above with hydrogen cyanide or a cyanide ion supplying compound, ammonia or an ammonium ion supplying compound and carbon dioxide or a carbonate ion supplying compound and basic hydrolysis of the reaction mixture obtained and to using the compound of formula (I) to produce D,L-proline.

Abstract translation: 本发明涉及式（I）的谷氨酸-γ-甲醛的环状缩醛，其中A为未取代的具有2至3个碳原子的亚烷基或亚烷基被1至2个甲基取代， 涉及制备式（I）化合物的方法，其中通式为其中A定义如上所定义的化合物与氰化氢或氰化物离子供应化合物反应，提供氨或铵离子 化合物和二氧化碳或碳酸根离子供应化合物和所得反应混合物的碱性水解和使用式（I）化合物产生D，L-脯氨酸。

公开(公告)号：US4590305A

公开(公告)日：1986-05-20

申请号：US587651

申请日：1984-03-08

Applicant: Karlheinz Drauz ,  Axel Kleemann

Inventor： Karlheinz Drauz ,  Axel Kleemann

IPC: B01J27/00 ,  C07B61/00 ,  C07C27/00 ,  C07C37/60 ,  C07C39/08 ,  C07C67/00 ,  C07C37/00

CPC classification number: C07C37/60 ,  Y02P20/582

Abstract: The known nuclear hydroxylation of phenol or substituted phenols or phenol ethers with organic solutions of hydrogen peroxide in the presence of a catalyst is carried out in improved manner by employing both (1) a special, practically water free solution of hydrogen peroxide in an organic solvent which forms an azeotrope with water, which azeotrope boils below the boiling point of hydrogen peroxide, and (2) selenium dioxide as a catalyst. Through this, the nuclear hydroxylation is substantially simpler than previously. Besides, for the first time, it is possible to control the ortho to para ratio or the two ortho ratios to each other.

Abstract translation: 在催化剂存在下，已知的酚或取代酚或苯酚醚与过氧化氢有机溶液的核羟基化作用是通过使用（1）特殊的实际上无水的过氧化氢在有机溶剂中的溶液来进行的 其与水形成共沸物，其共沸物沸点低于过氧化氢的沸点，和（2）二氧化硒作为催化剂。 由此，核羟基化比以前更简单。 此外，第一次可以将邻位对比或两个邻位比彼此控制。

公开(公告)号：US4482760A

公开(公告)日：1984-11-13

申请号：US552106

申请日：1983-11-16

Applicant: Axel Kleemann ,  Klaus Deller ,  Karlheinz Drauz ,  Bernd Lehmann

Inventor： Axel Kleemann ,  Klaus Deller ,  Karlheinz Drauz ,  Bernd Lehmann

IPC: C07C43/13 ,  B01J23/00 ,  B01J31/00 ,  C07B61/00 ,  C07C27/00 ,  C07C29/00 ,  C07C31/20 ,  C07C33/26 ,  C07C41/00 ,  C07C67/00 ,  C07D307/42 ,  C07C7/00

CPC classification number: C07C29/00

Abstract: 1,2-Diols of the formula: ##STR1## where R.sub.1 and R.sub.2 are hydrogen, alkyl of 1 to 10 carbon atoms or such as alkyl substituted by a halogen, a hydroxy group, a phenyl group, a methoxy group, or an ethoxy group, a phenyl group or a furyl group or R.sub.1 and R.sub.2 together form an alkylene group of 2 to 7 carbon atoms are formed by hydrogenating a correspondingly substituted cyanohydrin in an aqueous medium first in the presence of a hydrogenation catalyst and an acid at a temperature between -20.degree. and +25.degree. C. and a hydrogen pressure of less than 10 bar until per mole of cyanohydrin employed there is taken up one mole of hydrogen and then the hydrogenation continued to the end of the absorption of hydrogen in the presence of metallic nickel at a temperature between 30.degree. and 100.degree. C. and a hydrogen pressure between 10 and 150 bar.

Abstract translation: 具有下式的1,2-二醇：其中R 1和R 2是氢，1至10个碳原子的烷基或被卤素，羟基，苯基，甲氧基， 或乙氧基，苯基或呋喃基或R 1和R 2一起形成2至7个碳原子的亚烷基通过在氢化催化剂和酸存在下首先在水性介质中氢化相应地取代的羟腈而形成 在-20℃至+25℃的温度和小于10巴的氢气压力下，直到每摩尔使用的氰醇为止，吸收1摩尔氢气，然后氢化继续到氢气吸收的最后 金属镍的存在温度在30℃至100℃之间，氢气压力在10至150巴之间。

公开(公告)号：US4628126A

公开(公告)日：1986-12-09

申请号：US588847

申请日：1984-03-12

Applicant: Karlheinz Drauz ,  Axel Kleemann

Inventor： Karlheinz Drauz ,  Axel Kleemann

IPC: B01J27/00 ,  B01J27/02 ,  C07B61/00 ,  C07C27/00 ,  C07C37/60 ,  C07C39/08 ,  C07C67/00 ,  C07C37/00

CPC classification number: C07C37/60 ,  Y02P20/582

Abstract: The nuclear hydroxylation of phenol with organic solutions of hydrogen peroxide in the presence of a catalyst is carried out in improved manner by employing both (1) a special, practically water free solution of hydrogen peroxide in an organic solvent which does not form an azeotrope with water or whose highest azeotrope with water, boil near or above the boiling point of hydrogen peroxide, and (2) employing as a catalyst XO.sub.2 where X is sulfur, selenium, or tellurium. Besides increasing the yield and the ability to carry out the reaction in a simpler manner when selenium dioxide is employed as a catalyst, there can also be controlled the ortho-para ratio, respectively, the ortho-ortho ratio of the product.

Abstract translation: 在催化剂存在下，用过氧化氢的有机溶液对苯酚进行核羟基化处理是通过使用（1）特殊的实际上无水的过氧化氢在不与共沸物形成共沸物的有机溶剂中， 水或其与水的共沸物最高，沸点接近或高于过氧化氢的沸点，和（2）使用X为硫，硒或碲的催化剂XO2。 当使用二氧化硒作为催化剂时，除了增加产率和以更简单的方式进行反应的能力之外，还可以分别控制产物的邻位比。

公开(公告)号：US4551562A

公开(公告)日：1985-11-05

申请号：US588999

申请日：1984-03-13

Applicant: Karlheinz Drauz ,  Axel Kleemann

Inventor： Karlheinz Drauz ,  Axel Kleemann

IPC: B01J27/00 ,  B01J27/02 ,  C07B61/00 ,  C07C27/00 ,  C07C37/60 ,  C07C39/08 ,  C07C67/00 ,  C07C41/26

CPC classification number: C07C37/60 ,  Y02P20/582

Abstract: The nuclear hydroxylation of phenol with organic solutions of hydrogen peroxide in the presence of a catalyst is carried out in improved manner by employing both (1) a special, practically water free solution of hydrogen peroxide in an organic solvent which does not form an azeotrope with water or whose highest azeotrope with water, boil near or above the boiling point of hydrogen peroxide, and (2) employing as a catalyst XO.sub.2 where X is sulfur, selenium, or tellurium. Besides increasing the yield and the ability to carry out the reaction in a simpler manner when selenium dioxide is employed as a catalyst, there can also be controlled the ortho-para ratio, respectively, the ortho-ortho ratio of the product.

公开(公告)号：US4430509A

公开(公告)日：1984-02-07

申请号：US460858

申请日：1983-01-25

Applicant: Horst Bethge ,  Karlheinz Drauz ,  Axel Kleemann ,  Jurgen Martens ,  Horst Weigel

Inventor： Horst Bethge ,  Karlheinz Drauz ,  Axel Kleemann ,  Jurgen Martens ,  Horst Weigel

IPC: C07B57/00 ,  C07B31/00 ,  C07C67/00 ,  C07C313/00 ,  C07C319/28 ,  C07C323/58 ,  C07H9/06 ,  C07H15/14 ,  C07B19/00

CPC classification number: C07H15/14

Abstract: To separate the racemate (R,S)-cysteine, the racemate is condensed in an inert solvent with an enantiomerically enantiomeric monosaccharide of the group of aldoses having 4 to 7 carbon atoms to form the corresponding 2-substituted thiazolidin-4-carboxylic acid and the mixture of diastereomers obtained separated from each other. Subsequently, the isolated unitary diastereomers are reacted in an inert solvent with a carbonyl reagent to split the ring and the enantiomerically pure cysteine in each case is isolated as such or as the corresponding cystine.

Abstract translation: 为了分离外消旋体（R，S） - 半胱氨酸，外消旋体在惰性溶剂中与具有4至7个碳原子的醛糖组的对映异构体对映异构体单糖缩合形成相应的2-取代的噻唑烷-4-羧酸， 获得的非对映异构体的混合物彼此分离。 随后，将分离的单一非对映异构体在惰性溶剂中与羰基试剂反应以分裂环，并且每种情况下的对映体纯的半胱氨酸本身或相应的胱氨酸分离。

公开(公告)号：US4760199A

公开(公告)日：1988-07-26

申请号：US81366

申请日：1987-08-04

Applicant: Karlheinz Drauz ,  Axel Kleemann

Inventor： Karlheinz Drauz ,  Axel Kleemann

IPC: C07C37/58 ,  B01J27/00 ,  C01B15/017 ,  C07C27/00 ,  C07C67/00 ,  C07C37/60

CPC classification number: C01B15/017

Abstract: The production of solutions of hydrogen peroxide in phenol or its derivatives, e.g. hydrocarbyl substituted phenols, halo substituted phenols or phenol ethers, is carried out in a single step. Practically no loss of hydrogen peroxide occurs since a total distillation of hydrogen peroxide together with phenol or phenol derivative is avoided. Simultaneously the solutions obtained are practically free from water. The mixture of phenol or phenol derivative and aqueous hydrogen peroxide is treated with a material that boils below the boiling point of hydrogen peroxide, phenol or phenol derivative or forms an azeotrope with water that boils below the boiling point of hydrogen peroxide, phenol or phenol derivative and the water removed as an azeotrope. The solution of hydrogen peroxide in phenol or phenol derivative which remains behind is suitable for carrying out oxidation reactions and above all, also for hydroxylation reactions. The latter as especially advantageously carried out in the presence of sulfur-, selenium-, or tellurium oxide.

Abstract translation: 生产苯酚或其衍生物中过氧化氢的溶液，例如。 烃基取代的酚，卤代酚或苯酚醚在一个步骤中进行。 实际上不会发生过氧化氢的损失，因为避免了与苯酚或苯酚衍生物一起完全蒸馏过氧化氢。 同时获得的溶液实际上不含水。 苯酚或苯酚衍生物与过氧化氢水溶液的混合物用沸点低于过氧化氢，苯酚或苯酚衍生物的沸点的物质处理，或与沸点低于过氧化氢，苯酚或苯酚衍生物沸点的水形成共沸物 并将水作为共沸物除去。 过氧化氢在苯酚或苯酚衍生物中残留的溶液适用于进行氧化反应，尤其是羟基化反应。 后者特别有利地在硫，硒或氧化碲的存在下进行。

公开(公告)号：US4728743A

公开(公告)日：1988-03-01

申请号：US72707

申请日：1987-07-13

Applicant: Karlheinz Drauz ,  Axel Kleemann ,  Elizabeth Wolf-Heuss

Inventor： Karlheinz Drauz ,  Axel Kleemann ,  Elizabeth Wolf-Heuss

IPC: A01N43/08 ,  C07C67/00 ,  C07C253/00 ,  C07C255/17 ,  C07C255/31 ,  C07C255/32 ,  C07C255/40 ,  C07C255/45 ,  C07C255/56 ,  C07D307/54 ,  C07D307/68 ,  C07D333/24 ,  C07D333/38 ,  C07D333/22 ,  A01N43/02 ,  C07C121/50

CPC classification number: C07C255/00 ,  C07C253/30 ,  C07D307/54 ,  C07D333/24

Abstract: 3-oxonitriles are produced by reaction of carboxylic acid esters with carboxylic acid nitriles in the presence of 70 to 80% suspension of sodium hydride in white oil. The oxonitrile are intermediate products for the production of 3-oxocarboxylic acid amides or esters and pesticides.

Abstract translation: 在70至80％的氢化钠在白油中的悬浮液存在下，通过羧酸酯与羧酸腈的反应制备3-氧杂腈。 氧腈是用于生产3-氧代羧酸酰胺或酯和农药的中间产物。

公开(公告)号：US4716237A

公开(公告)日：1987-12-29

申请号：US475395

申请日：1983-03-15

Applicant: Karlheinz Drauz ,  Axel Kleemann ,  Elisabeth Wolf-Heuss

Inventor： Karlheinz Drauz ,  Axel Kleemann ,  Elisabeth Wolf-Heuss

IPC: A01N43/08 ,  C07C67/00 ,  C07C253/00 ,  C07C255/17 ,  C07C255/31 ,  C07C255/32 ,  C07C255/40 ,  C07C255/45 ,  C07C255/56 ,  C07D307/54 ,  C07D307/68 ,  C07D333/24 ,  C07D333/38 ,  C07C121/34 ,  C07C121/76

CPC classification number: C07C255/00 ,  C07C253/30 ,  C07D307/54 ,  C07D333/24

Abstract: 3-oxonitriles are produced by reaction of carboxylic acid esters with carboxylic acid nitriles in the presence of 70 to 80% suspension of sodium hydride in white oil. The oxonitrile are intermediate products for the production of 3-oxocarboxylic acid amides or esters and pesticides.

公开(公告)号：US4618730A

公开(公告)日：1986-10-21

申请号：US587652

申请日：1984-03-08

Applicant: Karlheinz Drauz ,  Axel Kleemann

Inventor： Karlheinz Drauz ,  Axel Kleemann

IPC: C07C27/00 ,  C07C37/60 ,  C07C39/08 ,  C07C67/00 ,  C07C39/10

CPC classification number: C07C37/60 ,  Y02P20/582

Abstract: The known nuclear hydroxylation of phenol with organic solutions of hydrogen peroxide in the presence of a catalyst is carried out in improved manner by employing both (1) a special, practically water free solution of hydrogen peroxide in an organic solvent which forms an azeotrope with water, which azeotrope boils below the boiling point of hydrogen peroxide, and (2) sulfur dioxide as a catalyst. Through this, the nuclear hydroxylation is substantially simpler than previously; difficult separations, e.g., from water-phenol, or the separation and recovery of the catalyst are eliminated. Besides, the yields are increased.

Abstract translation: 在催化剂存在下，酚与有机过氧化物的已知核羟基化反应是通过使用（1）在与水形成共沸物的有机溶剂中的特殊的实际上无水的过氧化氢溶液来进行的 ，其共沸物沸点低于过氧化氢的沸点，和（2）二氧化硫作为催化剂。 通过这一点，核羟基化比以前简单得多; 难以分离，例如来自水 - 苯酚，或者分离和回收催化剂。 此外，收益率上升。