公开(公告)号：US4109090A

公开(公告)日：1978-08-22

申请号：US778743

申请日：1977-03-17

Applicant: Rudolf van Hardeveld ,  Petrus F.A.M. Hendriks

Inventor： Rudolf van Hardeveld ,  Petrus F.A.M. Hendriks

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

CPC classification number: B05B7/0458

Abstract: 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

Applicant: Wilhelmus H. J. Boesten

Inventor： Wilhelmus H. J. Boesten

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

CPC classification number: C07B55/00

Abstract: 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

Abstract translation: 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

Applicant: Abraham H. de Rooij ,  Reijer Goettsch

Inventor： Abraham H. de Rooij ,  Reijer Goettsch

IPC: C01C1/24 ,  C07D201/16

CPC classification number: C07D201/16

Abstract: 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.

Abstract translation: 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

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

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

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

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

Abstract: 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.

Abstract translation: 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

Applicant: Johannes H. Tebben ,  Cornelis A. M. Weterings

Inventor： Johannes H. Tebben ,  Cornelis A. M. Weterings

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

CPC classification number: B01J23/755 ,  C11C3/123

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US3995001A

公开(公告)日：1976-11-30

申请号：US434992

申请日：1974-01-21

Applicant: Hubertus J. Vroomans ,  Cornelis E.P.V. Van Den Berg

Inventor： Hubertus J. Vroomans ,  Cornelis E.P.V. Van Den Berg

IPC: D01D5/40 ,  D01D5/11 ,  D21H13/10 ,  B22D23/08

CPC classification number: D01D5/11

Abstract: Polymer fibers are made from a solution of polymer in solvent by subjecting the solution to shear forces in a confining space by introducing a gas stream into the space in a manner to create a rotary gas flow therein and to cool the solution to a temperature at which polymer precipitates from the solution in the form of fibers.

Abstract translation: 聚合物纤维由聚合物在溶剂中的溶液制成，通过在限制空间内通过将气流引入空间中以在其中产生旋转气流的方式将溶液转化为剪切力，并将溶液冷却至 聚合物以纤维的形式从溶液中沉淀出来。

公开(公告)号：US3988132A

公开(公告)日：1976-10-26

申请号：US551293

申请日：1975-02-20

Applicant: Leendert Oranje

Inventor： Leendert Oranje

IPC: B04C5/00 ,  B01D45/16 ,  B04C5/02 ,  B04C5/103 ,  B01D45/12

CPC classification number: B04C5/103 ,  B01D45/16 ,  B04C5/02

Abstract: This invention relates to a device for separating particles from a gas stream which consists essentially of a cylindrical vessel having a feed pipe connected thereto and intersecting the axis of said vessel; an axial discharge pipe connected to and protruding into said vessel, a sleeve located with some clearance around said discharge pipe and having fixed thereto a plurality of helicoidal first impeller blades so as to cause the gas feed to rotate; means located within said vessel and below said blades to discharge said particles; said device being further characterized by a plurality of spiral second impeller blades extending perpendicularly below and above, and being fixed to, said helicoidal first impeller blades, such that one vertical edge of each of said spiral blades touches said sleeve along, essentially, a straight vertical line, that the other, essentially straight, vertical edge of each spiral blade is located at a distance from the surface of said sleeve which is between 0.33 and 0.90 of the distance between said sleeve and the inner wall of said vessel and that said spiral blades extend to beyond the lower edges of said helicoidal blades.

Abstract translation: 本发明涉及一种用于从气流中分离颗粒的装置，其基本上由圆柱形容器组成，该圆柱形容器具有连接到其上并与所述容器的轴线相交的进料管; 连接并突出到所述容器中的轴向排放管，围绕所述排放管具有一定间隙的套筒，并且固定有多个螺旋形第一叶轮叶片，以使气体进给旋转; 装置位于所述容器内并位于所述叶片下方以排出所述颗粒; 所述装置的特征还在于，多个螺旋形第二叶轮叶片垂直于所述螺旋形第一叶轮叶片垂直地延伸并固定，使得每个所述螺旋叶片的一个垂直边缘沿着基本上直线 垂直线，每个螺旋叶片的另一个基本上直的垂直边缘位于距所述套筒的表面一定距离处，所述套筒与所述容器的内壁之间的距离在0.33和0.90之间，并且所述螺旋 叶片延伸到所述螺旋叶片的下边缘之外。

公开(公告)号：US3975335A

公开(公告)日：1976-08-17

申请号：US168417

申请日：1971-08-02

Applicant: Meindert Tiessens ,  Henricus J. M. Van Gorcom

Inventor： Meindert Tiessens ,  Henricus J. M. Van Gorcom

IPC: C08F10/00 ,  C08F210/00 ,  C08D3/04 ,  C08D1/14 ,  C08D9/00

CPC classification number: C08F210/00 ,  C08F10/00

Abstract: The present disclosure relates to the preparation of curable polymers of ethylene with at least one .alpha.-alkene and a 5-alkylidene norbornene-2 showing a reduced cold-flow obtained by the incorporation of dicyclopentadiene in amounts of at least 0.2 % and preferably between 0.4 and 2.2 % by weight with respect to the amount of polymer and in a molar ratio of less than 1 : 5 to the norbornene derivative.

Abstract translation: 本公开内容涉及乙烯与至少一种α-烯烃和5-亚烷基降冰片烯-2的可固化聚合物的制备，其显示了通过将二环戊二烯的并入量降低至少0.2％，优选在0.4之间的冷流 相对于聚合物的量为2.2重量％，并且与降冰片烯衍生物的摩尔比小于1:5。

公开(公告)号：US3975274A

公开(公告)日：1976-08-17

申请号：US541691

申请日：1975-01-16

Applicant: Johan P. Nommensen

Inventor： Johan P. Nommensen

IPC: B01D29/46 ,  B01D20060101 ,  B01D25/34 ,  B01D29/44 ,  B01D29/48 ,  B01D35/20 ,  B01D37/00 ,  B01D25/20

CPC classification number: B01D29/48

Abstract: The invention relates to filter candles of the type in which the fluid medium flows through a circumferential wall into the interior of the filter and the particles are collected at the outside. The circumferential wall is formed of sectional members defining narrow slots between them. At intervals the stream of fluid is interrupted and a reverse fluid pressure pulse is effected in the fluid inside the filter of sufficient magnitude to enlarge the slots to create a back flow of fluid through the enlarged slots to remove thereby the accumulated particles from the slots.

Abstract translation: 本发明涉及这种类型的过滤蜡烛，其中流体介质通过周向壁流入过滤器的内部，并且颗粒在外部被收集。 圆周壁由在它们之间限定狭缝的截面构件形成。 每隔一段时间，流体流被中断，并且在过滤器内的流体中产生足够大的反向流体压力脉冲，以扩大槽，以产生通过扩大的槽的流体的逆流，从而从槽中移除累积的颗粒。

公开(公告)号：US3970742A

公开(公告)日：1976-07-20

申请号：US535838

申请日：1974-12-23

Applicant: Johannes D. M. Verstegen

Inventor： Johannes D. M. Verstegen

IPC: C01C3/00 ,  C01C3/14

CPC classification number: C01C3/001

Abstract: The invention is directed to a process for preparing cyanic acid from urea, comprising atomizing urea in a tubular reactor in the presence of a stream of a carrier gas to obviate the formation and deposition of by-products on the inner walls of the tubular reactor, thereby increasing the efficiency and production yields of the process.

Abstract translation: 本发明涉及一种从尿素制备氰酸的方法，包括在载体气流存在下在管式反应器中雾化尿素以避免副产物在管状反应器的内壁上的形成和沉积， 从而提高该方法的效率和产量。