公开(公告)号：US6002037A

公开(公告)日：1999-12-14

申请号：US949831

申请日：1997-10-14

Applicant: Ei-ichi Negishi ,  Denis Y. Kondakov

Inventor： Ei-ichi Negishi ,  Denis Y. Kondakov

IPC: C07B53/00 ,  C07C29/44 ,  C07F5/06 ,  C07C27/00

CPC classification number: C07B53/00 ,  C07C29/44 ,  C07F5/062 ,  C07F5/063 ,  C07B2200/07 ,  C07C2101/14

Abstract: The present invention describes the Zr-catalyzed asymmetric carboalumination of alkenes to produce chiral alkylalanes that can be converted to various chiral organic compounds, such as isoalkyl alcohols, in highly enantiomeric excess. More particularly, the asymmetric addition of alkylaluminums to terminal alkenes under the influence of a catalyst such as a chiral zirconocene derivative produces chiral alkylaluminums that can be oxidized to 2-alkyl-substituted products (particularly alcohols) in greater than 60% enantiomeric excess. The ee figures can often exceed 95%. The organoalanes produces by the inventive process can be converted to a wide variety of other organic compounds of interest in the production of vitamins, pharmaceuticals and other medicinally and biologically important compounds, including vitamins and antibiotics.

Abstract translation: 本发明描述了烯烃的Zr催化的不对称碳铝化以产生手性烷基烷烃，其可以以高度对映体过量转化为各种手性有机化合物，例如异烷基醇。 更具体地说，在催化剂如手性二茂锆衍生物的影响下，将烷基铝不对称加成到末端烯烃产生手性烷基铝，其可被以大于60％的对映体过量氧化成2-烷基取代的产物（特别是醇）。 ee数字通常可以超过95％。 通过本发明方法产生的有机亚烷烃可以转化为生产维生素，药物和其它医学和生物学上重要的化合物（包括维生素和抗生素）的各种其它有用的有机化合物。

公开(公告)号：US5597937A

公开(公告)日：1997-01-28

申请号：US438686

申请日：1995-05-11

Applicant: Edward G. Samsel

Inventor： Edward G. Samsel

IPC: C07C1/32 ,  C07F5/06

CPC classification number: C07F5/063 ,  C07C1/327 ,  C07C2531/14 ,  C07C2531/22

Abstract: A deep olefin internal olefin is reacted with a C.sub.3-4 primary alkyl aluminum chloride in the liquid phase in the presence of a catalyst system formed from (i) a dicyclopentadienyl dihalide or halohydride of zirconium or hafnium and (ii) a hydridic co-catalyst component. Unlike prior art procedures, negligible quantities of by-product paraffins are formed in the process.

Abstract translation: 在由（i）二环戊二烯基二卤化物或锆或铪的卤化氢形成的催化剂体系的存在下，液相中的深烯烃内烯烃与C3-4伯烷基氯化铝反应，和（ii）氢化助催化剂 零件。 与现有技术的方法不同，在该过程中形成了可忽略量的副产物链烷烃。

公开(公告)号：US4364872A

公开(公告)日：1982-12-21

申请号：US282493

申请日：1981-07-13

Applicant: Steven P. Diefenbach

Inventor： Steven P. Diefenbach

IPC: B01J27/00 ,  B01J31/00 ,  C07F5/06

CPC classification number: C07F5/063

Abstract: A method of making trimethylaluminum wherein an aluminum trialkyl having at least two carbon atoms in the alkyl group is reacted with a methyl halide in the presence of a bismuth catalyst to form trimethylaluminum and an alkyl halide. A hydrocarbon solvent provides increased reaction rates.

Abstract translation: 制备三甲基铝的方法，其中烷基中具有至少两个碳原子的三烷基铝在铋催化剂的存在下与甲基卤化物反应形成三甲基铝和烷基卤化物。 烃溶剂提供增加的反应速率。

公开(公告)号：US4251453A

公开(公告)日：1981-02-17

申请号：US68779

申请日：1979-08-22

Applicant: Harry D. Garrison

Inventor： Harry D. Garrison

IPC: C07F5/06

CPC classification number: C07F5/063

Abstract: An improved method is disclosed for continuously purifying crude aluminum alkyls containing solid contaminants such as aluminum particles comprising passing crude aluminum alkyls into a first holding vessel, the contents of said vessel being continuously passed under pressure through a tubular filter having an upstream inner surface and a downstream outer surface, solids-containing aluminum alkyls passing through said tubular filter returning to the holding vessel, and purified aluminum alkyls passing through the filter wall exiting through the downstream outer surface, and recovered; monitoring the solids content of the holding vessel and ceasing crude aluminum alkyl flow into said holding vessel when solid contents reach undesirably high levels, thereafter passing said crude aluminum alkyls into an alternate holding vessel and filter, then further passing the contents of said first holding vessel through said tubular filter until substantially all remaining aluminum alkyls have passed through the filter to recovery, and purging the contents of said first holding vessel before filtration is resumed.

Abstract translation: 公开了一种改进的方法，用于连续纯化含有固体污染物的粗铝烷基化物，所述固体污染物包括将粗烷基铝转化为第一保持容器，所述容器的内容物在压力下连续通过具有上游内表面和 下游外表面，通过所述管状过滤器返回到保持容器的含固体的烷基铝，以及通过从下游外表面离开的过滤壁的纯化的烷基铝，并回收; 监测固定容器的固体含量，并且当固体含量达到不合需要的高水平时停止粗铝烷基流入所述保持容器，之后将所述粗制烷基铝烷基转化成替代的保持容器和过滤器，然后进一步使所述第一保持容器 通过所述管式过滤器直到基本上剩余的所有的烷基铝都已经通过过滤器以回收，并且在过滤之前清除所述第一保持容器的内容物。

公开(公告)号：US3960912A

公开(公告)日：1976-06-01

申请号：US531738

申请日：1974-12-11

Applicant: Karl Heinz Mueller ,  Hans-Juergen Hubert

Inventor： Karl Heinz Mueller ,  Hans-Juergen Hubert

IPC: C07F5/06 ,  C08F4/42

CPC classification number: C07F5/063

Abstract: A process for the preparation of a trialkyl aluminum compound of the formula (RCH.sub.2 CH.sub.2).sub.3 Al, wherein R is hydrogen or alkyl having 1 to 18 carbon atoms, which process comprises (A) reacting aluminum, hydrogen, and a mixture of said trialkyl aluminum compound and the corresponding dialkyl aluminum hydride in a first stage to form a first product which is said dialkyl aluminum hydride alone or in admixture with unreacted trialkyl aluminum compound; (B) reacting said first product with an olefin of the formula RCH=CH.sub.2, where R has its earlier meaning, in a second stage to form a second product which is a mixture of said trialkyl aluminum compound and the corresponding dialkyl aluminum hydride; and (C) recycling a portion of this second product from said second stage to said first stage and reacting the remainder of said second product with further olefin of the formula RCH=CH.sub.2 in a third stage to form said trialkyl aluminum compound.

Abstract translation: 一种制备式（RCH 2 CH 2）3 Al的三烷基铝化合物的方法，其中R是氢或具有1至18个碳原子的烷基，该方法包括（A）使铝，氢和所述三烷基铝化合物的混合物 和相应的二烷基氢化铝在第一阶段中以形成第一产物，其是单独的所述二烷基氢化铝或与未反应的三烷基铝化合物的混合物; （B）在第二阶段使所述第一产物与式RCH = CH 2的烯烃反应，其中R具有其早期含义，以形成第二产物，其是所述三烷基铝化合物和相应的二烷基氢化铝的混合物; 和（C）将所述第二产物的一部分从所述第二阶段再循环到所述第一阶段，并将所述第二产物的剩余部分与另外的式RCH = CH 2的烯烃在第三阶段中反应以形成所述三烷基铝化合物。

公开(公告)号：US3712923A

公开(公告)日：1973-01-23

申请号：US3712923D

申请日：1971-01-18

Applicant: CONTINENTAL OIL CO

Inventor： MOTZ K ,  FRIEND J

IPC: C07F5/06

CPC classification number: C07F5/063

Abstract: THE PRESENT INVENTION RELATES TO AN IMPROVED PROCESS FOR THE PRODUCTION OF TRIALKYL ALUMINUM COMPOUNDS USING ALUMINUM, HYDROGEN AND OLEFINIC MATERIALS AS THE REACTANTS. BY THE PRESENT INVENTION, A PROCESS IS PROVIDE WHICH MINIMIZES THE LOSS OF ALUMINUM DUE TO THE DECOMPOSITION OF THE INTERMEDIATE FORMED IN THE PRODUCES, DIALKYL ALUMIUCT, TRIALKYL ALUMINUM. A TRIALKYL ALUMINUM COMPOUND UCT, TRIALKYL ALUMINUM. A TRIALKYL ALUMINUM COMPOUND IS REACTED WITH ALUMINUM META AND HYDROGEN AT AN ELEVATED PRESSURE TO FORM AN INTERMEDIATE DIALKYL ALUMINUM HYDRIDE REACTION PRODUCT. THE INTERMEDIATE REACTION PRODUCT IS REACTED WITH AN OLEFINIC MATERIAL AT THE ELEVATED PRESSURE SO THAT A QUANTITY OF TRIALKYL ALUMINUM IS FORMED SUFFICIENT TO REDUCE THE CONCENTRATION OF THE DIALKYL ALUMINUM HYDRIDE INTERMEDIATE TO A LEVEL EQUAL TO OR SLIGHTLY BELOW THE EQUILIBRIUM CONCENTRATION THEREOF THAT WOULD EXITS AT A REDUCED PRESSURE. THE PRESSURE ON THE INTERMEDIATE REACTION PRODUCT IS THEN LOWERED TO SAID REDUCED PRESSURE AND THE INTERMEDIATE REACTION PRODUCT IS REACTED WITH ADDITIONAL OLEFINIC MATERIAL TO COMPLETE THE FORMATION OF THE TRIALKYL ALUMINUM PRODUCT.

公开(公告)号：US3651114A

公开(公告)日：1972-03-21

申请号：US3651114D

申请日：1969-11-28

Applicant: ETHYL CORP

Inventor： CRAGG HOYT J ,  LINDSAY KENNETH L

IPC: C07C29/54 ,  C07F5/06

CPC classification number: C07C29/54 ,  C07F5/063 ,  C07C31/04 ,  C07C31/125 ,  C07C31/12 ,  C07C31/08 ,  C07C31/10

Abstract: IMPROVEMENTS IN REACTIONS FOR PRODUCING ORGANO ALUMINUM COMPOUNDS ARE DESCRIBED. THE IMPROVEMENTS INVOLVE CONTROL OF THE PROPORTIONS OF REACTANTS FED FOR REACTIONS INVOLVING ALUMINUM, OLEFIN AND HYDROGEN IN THE PRESENCE OF AN ORGANO ALUMINUM COMPOUND. IT IS DISCLOSED THAT SIGNIFICANTLY INCREASED REACTION RATES ARE OBTAINED WHEN OLEFIN AND HYDROGEN ARE FED AT A RATIO SUBSTANTIALLY HIGHER THAN THE 2:1 MOLAR RATIO TAUGHT AS SUITABLE OR EVEN UNIMPORTANT BY MUCH OF THE PRIOR ART.

公开(公告)号：US3627808A

公开(公告)日：1971-12-14

申请号：US3627808D

申请日：1968-12-02

Applicant: HUELS CHEMISCHE WERKE AG

Inventor： STRECK ROLAND

IPC: C06B43/00 ,  C07F5/06

CPC classification number: C06B43/00 ,  C07F5/063

Abstract: For the production of triphenylaluminum in high yields, (C6H5)n AlCl3 n is reacted with AlR3 wherein n is a member above O and less than 3 and R represents lower alkyl.

公开(公告)号：US3505375A

公开(公告)日：1970-04-07

申请号：US3505375D

申请日：1966-11-01

Applicant: ETHYL CORP

Inventor： GAUTREAUX MARCELIAN F ,  WIKMAN ANDREW O

IPC: C07F5/06

CPC classification number: C07F5/063

Abstract: 1,172,745. Aluminium trialkyls. ETHYL CORP. 1 Nov., 1967 [1 Nov., 1966], No. 49604/67. Heading C2J. Aluminium trialkyls are produced by reacting aluminium, hydrogen and an olefin in the presence of at least one organo compound of a metal of Groups III B , IV B and V B (Deming) as catalyst. Specified metals are Ti, Nb, Zr. The catalyst may be an alkoxide, e.g. a C 2 - C 20 , preferably C 2 -C 6 tetralkoxide: the use of Ti(Oi-Pr) 4 to prepare AlEt 3 or Al(i-Bu) 3 and of Ti(OEt) 4 or TiEt(OEt) 3 to prepare AlEt 3 are mentioned. 0À01-5%, preferably 0À04- 2%, by weight (based an weight of aluminium) of a lower alkoxide of Ti, Nb or Zr may be used. Catalysts may be added directly or may be generated in situ, and may be used in conjunction with known aluminium activation techniques.

公开(公告)号：US3445494A

公开(公告)日：1969-05-20

申请号：US3445494D

申请日：1968-06-26

Applicant: CONTINENTAL OIL CO

Inventor： ACCIARRI JERRY A

IPC: C07F5/06

CPC classification number: C07F5/063 ,  C07F5/065