公开(公告)号：US4158095A

公开(公告)日：1979-06-12

申请号：US872951

申请日：1978-01-26

申请人： Franciscus H. A. M. J. Vandenbooren ,  Egidius J. M. Verheijen

发明人： Franciscus H. A. M. J. Vandenbooren ,  Egidius J. M. Verheijen

IPC分类号： C07C273/18 ,  C07C275/16 ,  C07D233/76 ,  C07C127/15

CPC分类号： C07C273/1854 ,  C07D233/76

摘要： An improved process for the preparation of 5-(4-aminobutyl)-hydantoin and/or 2-ureido-6-amino-hexanoic acid amide by the liquid phase hydrogenation of 5-(3-cyanopropyl)-hydantoin and/or 2-ureido-5-cyano-pentanoic acid amide in the presence of ammonia, hydrogen and a hydrogenation catalyst. Catalyst dissolution into the reaction medium is reduced by utilizing a hydrogenation catalyst in a solid bed form and causing the compounds to be hydrogenated to pass through such solid bed catalyst.

摘要翻译： 通过5-（3-氰基丙基） - 乙内酰脲和/或2-氨基己酸酰胺的液相氢化制备5-（4-氨基丁基） - 乙内酰脲和/或2-脲基-6-氨基 - 己酸酰胺的改进方法， 脲基-5-氰基 - 戊酸酰胺在氨，氢气和氢化催化剂存在下反应。 通过使用固体床形式的氢化催化剂并使化合物被氢化以通过这种固体床催化剂来减少催化剂溶解到反应介质中的溶解。

公开(公告)号：US4146695A

公开(公告)日：1979-03-27

申请号：US799655

申请日：1977-05-23

申请人： Lambertus J. M. A. VAN DE Leemput

发明人： Lambertus J. M. A. VAN DE Leemput

IPC分类号： C07D319/02 ,  C08F4/00 ,  C08F4/24 ,  C08F4/42 ,  C08F4/60 ,  C08F4/78 ,  C08F10/00 ,  C08F110/02 ,  C08F4/62

CPC分类号： C08F10/00

摘要： The invention is directed to new catalysts consisting of a chromium compound and an organometal compound of an element of Group II or III of the periodic system on a carrier, the process for preparing the catalyst and its use in polymerizing 1-alkenes containing 2 to 8 carbon atoms, optionally admixed with at most 10 mole% of at least one other 1-alkene of 2 to 8 carbon atoms.

公开(公告)号：US4131634A

公开(公告)日：1978-12-26

申请号：US678877

申请日：1976-04-21

申请人： Hendrikus J. G. Paulen

发明人： Hendrikus J. G. Paulen

IPC分类号： C08L7/00 ,  C08L9/00 ,  C08L21/00 ,  C08L23/00 ,  C08L23/16 ,  C08L101/00 ,  C08L9/06 ,  C08L19/00

CPC分类号： C08L9/00 ,  C08L23/16 ,  C08L9/06

摘要： Rubber mixtures consisting of (1) 20 - 75 parts of a copolymer containing 60 - 80% by weight of ethylene, 20 - 40% by weight of an .alpha.-alkene, and 0 - 20% by weight of one or more polyenes and having, in the unvulcanized state, an elongation at rupture of over 800% and a tensile strength of between 10 and 100 kg/cm.sup.2 ; (2) 80 - 25 parts of at least one polymeric material which is a styrene-butadiene copolymer; polybutadiene or polyisoprene; and (3) a tackifier resin and optionally conventional fillers and additives, wherein the mixture of (1), (2) and (3) has an elongation at rupture of at least 800% and a tensile strength of between 1.3 and 50 kg/cm.sup.2.

摘要翻译： 橡胶混合物由（1）20-75份含60-80％（重量）乙烯，20-40％（重量）α-烯烃和0-20％（重量）一种或多种多烯的共聚物组成，并且具有 在未硫化状态下，断裂伸长率超过800％，拉伸强度在10-100kg / cm2之间; （2）80-25份作为苯乙烯 - 丁二烯共聚物的至少一种聚合物材料; 聚丁二烯或聚异戊二烯; （3）增粘树脂和任选的常规填料和添加剂，其中（1），（2）和（3）的混合物的断裂伸长率至少为800％，拉伸强度在1.3至50kg / cm2。

公开(公告)号：US4117000A

公开(公告)日：1978-09-26

申请号：US827334

申请日：1977-08-24

申请人： Theodorus Balg ,  Constant M. A. Cramers ,  Hendrikus J. G. Maessen

发明人： Theodorus Balg ,  Constant M. A. Cramers ,  Hendrikus J. G. Maessen

IPC分类号： C07B61/00 ,  B01J31/00 ,  B01J31/02 ,  C07C20060101 ,  C07C67/00 ,  C07C253/00 ,  C07C255/17 ,  C07C121/34 ,  C07C120/00

CPC分类号： C07C255/00 ,  Y02P20/582

摘要： A process is described for improving the synthesis of 4-oxocapronitrile by adding an inert solvent to the atmospheric pressure distillation of the reaction mixture so that the temperature of said distillation is maintained below about 195.degree. C.

公开(公告)号：US4113440A

公开(公告)日：1978-09-12

申请号：US709080

申请日：1976-07-27

申请人： Dirk Klaasen

发明人： Dirk Klaasen

IPC分类号： B01J10/00 ,  C08F10/00 ,  B01J8/08

CPC分类号： B01J10/00 ,  C08F10/00 ,  Y10T137/0329 ,  Y10T137/8593 ,  Y10T137/86187

摘要： A recycle system for polymerization of monomers to produce polymers of wide-molecular weight distribution comprising two reactors and two conduit lines disposed between said two reactors for forming a cyclic path, and means disposed in said lines for conveying the contents of one of said reactors to the other without affecting the polymerization conditions in each of said reactors which conditions may be different.

公开(公告)号：US4109090A

公开(公告)日：1978-08-22

申请号：US778743

申请日：1977-03-17

申请人： Rudolf van Hardeveld ,  Petrus F.A.M. Hendriks

发明人： Rudolf van Hardeveld ,  Petrus F.A.M. Hendriks

IPC分类号： C07D251/60 ,  B05B7/00 ,  B05B7/04 ,  B05B7/06 ,  B05B7/08

CPC分类号： B05B7/0458

摘要： A two phase sprayer and process are disclosed in which the sprayer has a liquid supply tube surrounded by a coaxial gas or gas mixture supply tube which extends beyond the length of the liquid supply tube where the gas flow surrounds and atomizes the expelled liquid. The sprayer has a unique structure in part characterized by a narrowed taper gas supply tube which converges towards the outlet at an angle of 70.degree.-90.degree. with respect to the sprayer axis. The internally-positioned, coaxial liquid supply tube is chamfered also at a similar 70.degree.-90.degree. angle, the gas and liquid tubes at their outlet being essentially parallel.The joint of the narrowing part of the gas tube and the outflow channel is rounded.These sprayers efficiently spray relatively large amounts of liquid at low gas velocities and are particularly adapted for spraying a mixture of urea and ammonia into a bed of reactive, fluidized particles to form melamine without destroying desirable features of the fluidized bed into which the urea/ammonia mixture is sprayed.

公开(公告)号：US4094904A

公开(公告)日：1978-06-13

申请号：US748398

申请日：1976-12-08

申请人： Wilhelmus H. J. Boesten

发明人： Wilhelmus H. J. Boesten

IPC分类号： C07C231/00 ,  C07B55/00 ,  C07C67/00 ,  C07C231/12 ,  C07C231/16 ,  C07C237/20 ,  C07C103/28

CPC分类号： C07B55/00

摘要： The invention is directed to a process for the racemization of optically active phenyl glycine amide with or without a substituted phenyl group by heating the opticaly active phenyl glycine amide in a solvent in the presence of a ketone and of an acid having a dissociation constant below 1.8 .times. 10.sup.-4.BACKGROUND OF THE INVENTIONThe resolution of a mixture of D- and L-phenyl glycine amide by means of an optically active acid is described in my co-pending U.S. patent applications Ser. No. 623,928, filed Oct. 20, 1975, and now U.S. Pat. No. 4,036,852 and Ser. No. 733,851, filed Oct. 19, 1976. An improved process for the resolution of a mixture of D- and L-phenyl glycine amide by means of an optically active acid is described in my co-pending U.S. patent application Ser. No. 748,399 filed concurrently herewith. The entire specification and claims of each of these three patent applications is incorporated by reference in the present specification.The invention relates to a process of racemizing an optically active phenyl glycine amide with or without a substituted phenyl group. The phenyl group may be substituted by a substituent such as a hydroxy, halogen, nitro, or amino group. These substituted optically active phenyl glycine amides can be prepared from the corresponding amino acid by esterification followed by aminolysis of the ester with ammonia as described in the Journal of the American Chemical Soc. vol. 71 (1949) page 78, 79.If desired, the racemized amide can be hydrolyzed to yield the corresponding amino acid again. Phenyl glycine amide can be hydrolyzed in a simple manner to form phenyl glycine, for example, by treatment with sulfuric acid, as described in the Journal of the Chemical Society, pages 393-397 (1966).In the preparation of an optically active phenyl glycine amide from a mixture of D- and L-phenyl glycine amide, both antipodes of the racemate are produced. If unequal amounts of the antipodes are desired, the undesired antipode can be racemized and the resulting racemate subjected to further resolution. As used in the present specification, "a mixture of L- and D-phenyl glycine amide" means either a racemate of phenyl glycine amide, or mixtures of the racemate with either L-phenyl glycine amide or D-phenyl glycine amide.The optically active phenyl glycines which can be easily obtained from the resolved optically active phenyl glycine amides are valuable compounds. For example, D-phenyl glycine is employed as a starting material for the preparation of .alpha.-amino benzyl penicillin. L-phenyl glycine provides a starting material for the sweetening agent L-asparagin-L-phenyl glycine alkyl ester.SUMMARY OF THE INVENTIONAccording to the invention, a process has been discovered comprising racemizing an optically active phenyl glycine amide, the phenyl group of which may be substituted, in an accelerated manner. It has been found that the racemization of a optically active phenyl glycine amide can be desirably conducted by heating the optically active phenyl glycine amide to be racemized in a solvent in the presence of a ketone and of an acid having a dissociation constant below 1.8 .times. 10.sup.-4. As used in the present application, it is to be understood that "an optically active phenyl glycine amide" includes both unsubstituted optically active phenyl glycine amide and optically active phenyl glycine amide in which the phenyl group is substituted with, for example, a hydroxy, halogen, nitro or amino group.It is therefore an object of the present invention to racemize an optically active phenyl glycine amide in an accelerated manner.Surprising, it has been found that the object of the present invention can be realized by racemizing an optically active phenyl glycine amide in the presence of a ketone and of an acid having a dissociation constant below 1.8 .times. 10.sup.-4.DETAILED DESCRIPTION OF THE INVENTIONThe invention is directed to a process of racemizing an optically active phenyl glycine amide, the phenyl group of which may be substituted, in a solvent in the presence of a ketone and of an acid having a dissociation constant below 1.8 .times. 10.sup.-4.Suitable acids are, for example, formic acid and acetic acid. In addition, use may be made of optically active acids e.g. optically active pyrrolidone-5-carboxylic acid and optically active N-acetyl phenyl glycine. These optically active acids are also suitable for the optical resolution of mixtures of D- and L-phenyl glycine amide, as described in my co-pending applications incorporated herein by reference.In the process of the present invention, preferably a quantity of acid is used which is equivalent to the quantity of phenyl glycine amide. An amount less than an equivalent amount, e.g. half the equivalent amount, of acid can also be used, but in that case undesirable side reactions may occur. A quantity of acid which is in excess of the equivalent of the phenyl glycine amide present may also be used, although there is no particular advantage in using excess acid.The racemizing process of the present invention is preferably effected at a temperature between about 35.degree. and about 150.degree. C. It is preferred to effect the racemizing process of the present invention at a temperature between about 50.degree. and about 100.degree. C.The ketone used in the racemizing process of the present invention may be selected from the group consisting of acetone, methyl ethyl ketone, pentanone, cyclohexanone, and mixtures thereof. It is believed that other ketones will also be operative in the process of the present invention.The amount of ketone used in the process of the present invention may be varied within wide limits. It has been found that a small quantity of ketone, for example 0.1 mole of ketone per mole of phenyl glycine amide is effective in the process of the present invention. Of course, larger amounts of ketone may also be used. If the amount of ketone used is sufficiently large, the ketone can also serve as a solvent for the racemizing mixture. However, it is also contemplated in the process of the present invention that other solvents may be used. For example, water, an alcohol, benzene, toluene, chloroform, and ethyl acetate may also be used as solvents.The process of the present invention will be further illustrated by the following examples, which are intended to be illustrative only and are meant to include all techniques equivalent thereto.EXAMPLESEXAMPLE IIn a flask equipped with a stirrer and a reflux cooler a solution of 1.5 g (0.01 gmole) L-phenyl glycine amide and 0.6 ml (0.01 gmole) acetic acid in 20 ml water and 80 ml acetone is boiled for 24 hours (58.degree. C), with stirring and reflux.After cooling to 20.degree. C, the rotation of this solution is determined. It is[.alpha.].sub.D.sup. 20 = 0.3.degree.The rotation of the original solution is:[.alpha.].sub.D.sup. 20 = 5.1.degree..Comparison of these rotation values shows (50 - 50 .times. 0,3/5,1) .times. 2 = 94% of the L-phenyl glycine amide to have been racemized.EXAMPLE IIIn a flask equipped with a stirrer and a reflux cooler a solution of 1.5 g (0.01 gmole) L-phenyl glycine amide, 0.4 ml (0.011 gmole) formic acid in 50 ml methyl ethyl ketone and 10 ml water is boiled with reflux for 20 hours (80.degree. C).After cooling to 20.degree. C, the rotation of this solution is[.alpha.].sub.D.sup. 20 = +0.9.degree..the rotation of the original solution is[.alpha.].sub.D.sup. 20 = +7.7.degree..comparison of the rotation values shows 88% of the L-phenyl glycine amide to have been racemized.EXAMPLE IIIIn a flask equipped with a stirrer and a reflux cooler 1.5 g (0.01 gmole) L-phenyl glycine amide and 0.6 ml (0.01 gmole) acetic acid in a mixture of 50 ml methanol and 0.45 ml (0.005 gmole) methyl ethyl ketone is boiled with reflux for 6 hours at 60.degree. C.After cooling to 20.degree. C the rotation of the resulting solution is measured. It is[.alpha.].sub.D.sup. 20 = 5.05.degree.the rotation of the original solution is[.alpha.].sub.D.sup. 20 = 8.90.degree.comparison of the rotation values shows 44% of the L-phenyl glycine amide to have been racemized.EXAMPLE FOR COMPARISONExample III is repeated, this time without addition of methyl ethyl ketone.After 6 hours' boiling, the rotation of the solution is[.alpha.].sub.D.sup. 20 = 8.40.degree..comparison of the rotation values shows only 6% of the L-phenyl glycine amide to have been racemized.EXAMPLE IVIn a flask equipped with a stirrer and a reflux cooler 4.5 g L-phenyl glycine amide and 3.9 g D-2-pyrrolidone-5-carboxylic acid in 200 ml methanol and 10 ml acetone is heated at boiling temperature for 25 hours whilst being stirred.After cooling to 20.degree. C, 3 ml concentrated hydrochloric acid (35%-wt.) is added. Next, the reaction mixture is concentrated in vacuo (12 mm Hg) at 30.degree. C to a volume of 40 ml. The DL-phenyl glycine amide.HCl formed in this way is recovered on a filter and washed on this filter with 5 ml[.alpha.].sub.D.sup. 20 = +0.4.degree. (c = 0.8; water)In Beilstein 14, III, p. 1189. the specific rotation of L-phenyl glycine amide. HC1 is given as[.alpha.].sub.D.sup. 20 = +100.8.degree. (c = 0.8; water).Comparison of the rotation values shows 99,5% of the L-phenylglycine amide to have been racemized.Thus it is apparent that there has been provided in accordance with the invention, a process for the racemization of optically active phenyl glycine amide that fully satisfies the objects, aims, and advantages set forth above. While the invention has been described in conjunction with specific embodiments thereof, it is apparent that many alternatives, modifications, and variations will be evident to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the following claims. methanol. After drying, the resulting salt weighs 4.4 g. The specific rotation of this salt is

摘要翻译： 本发明涉及一种通过在酮和一种解离常数低于1.8的酸的存在下在溶剂中加热光学活性苯基甘氨酸酰胺来使具有或不具有取代的苯基的光学活性苯基甘氨酸酰胺外消旋化的方法 x 10-4。

公开(公告)号：US4036830A

公开(公告)日：1977-07-19

申请号：US681745

申请日：1976-04-29

申请人： Abraham H. de Rooij ,  Reijer Goettsch

发明人： Abraham H. de Rooij ,  Reijer Goettsch

IPC分类号： C01C1/24 ,  C07D201/16

CPC分类号： C07D201/16

摘要： A process for recovering substantially pure .epsilon.-caprolactam from a contaminated solution thereof is disclosed by concentrating, if needed, the caprolactam content of the solution to about 60-75 weight percent then extracting the concentrated solution with an organic solvent such as benzene or the like, then recovering the resulting caprolactam-laden organic solution.

摘要翻译： 通过将需要的己内酰胺含量浓缩至约60-75％（重量），然后用有机溶剂如苯等萃取浓缩溶液来公开从其污染溶液中回收基本上纯的ε-己内酰胺的方法 ，然后回收所得的己内酰胺负载有机溶液。

公开(公告)号：US4014952A

公开(公告)日：1977-03-29

申请号：US596096

申请日：1975-07-15

申请人： Eduard H. Adema ,  Albert A. Van Geenen ,  Marinus J. A. M. Den Otter

发明人： Eduard H. Adema ,  Albert A. Van Geenen ,  Marinus J. A. M. Den Otter

IPC分类号： B01J23/72 ,  B01J27/00 ,  B01J27/18 ,  B01J37/28 ,  C07B61/00 ,  C07C1/00 ,  C07C2/86 ,  C07C11/18 ,  C07C67/00 ,  C07C1/20

CPC分类号： B01J37/28 ,  B01J23/72 ,  B01J27/18 ,  C07C2/867 ,  C07C2521/08 ,  C07C2527/167

摘要： Preparation of isoprene by conversion of isobutylene or an isobutylene-containing composition with formaldehyde in the gas phase, according to a one-step method, at temperatures of 150.degree. - 400.degree. C, and in the presence of a catalyst.

摘要翻译： 通过在气相中，按照一步法，在150-400℃的温度和催化剂的存在下，通过异丁烯或含异丁烯的组合物与甲醛的转化来制备异戊二烯。

公开(公告)号：US4014818A

公开(公告)日：1977-03-29

申请号：US527285

申请日：1974-11-26

申请人： Johannes H. Tebben ,  Cornelis A. M. Weterings

发明人： Johannes H. Tebben ,  Cornelis A. M. Weterings

IPC分类号： B01J21/08 ,  B01J23/755 ,  C11C3/12 ,  B01J29/10

CPC分类号： B01J23/755 ,  C11C3/123

摘要： For high-surface area hydrogenation nickel catalyst compositions, a silica carrier obtained by subjecting an alkali water glass to neutralization with sulfuric acid and spray-drying to form the silica carrier which has substantially no tendency to coalesce when used in processes requiring precipitation of an insoluble nickel compound onto the carrier.

摘要翻译： 对于高表面积氢化镍催化剂组合物，通过使碱水玻璃用硫酸中和并喷雾干燥形成二氧化硅载体而获得的二氧化硅载体，当在需要沉淀不溶性的方法中使用时，基本上不会凝聚的倾向 镍化合物到载体上。