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1. 发明授权

US11712686B2 Heterobimetallic catalysts and site-differentiated ligands for preparation thereof 有权
公开(公告)号：US11712686B2
公开(公告)日：2023-08-01
申请号：US17681073
申请日：2022-02-25
申请人： University of Houston System
发明人： Loi Hung Do , Zhongzheng Cai , Thi Tran , Dawei Xiao
IPC分类号： B01J31/22 , C08F4/70 , C08F10/02
CPC分类号： B01J31/2243 , B01J31/2247 , C08F4/7014 , C08F10/02 , B01J2531/0205 , B01J2531/0297 , B01J2531/824 , B01J2531/847 , C08F2410/03
摘要： Phosphine phosphonate and phenoxyphosphine ligands bearing polyethylene glycol (PEG) chains are used as described herein to produce heterobimetallic catalysts. The ligands can be metallated selectively with palladium or nickel and secondary metal ions to provide well-defined heterobimetallic compounds. These heterobimetallic complexes exhibit accelerated reaction rates and greater thermal stability in olefin polymerization compared to other catalysts.

2. 发明申请

US20180318819A1 NICKEL-BASED CATALYTIC COMPOSITION IN THE PRESENCE OF A SPECIFIC ACTIVATOR AND USE THEREOF IN A OLEFIN OLIGOMERSATION METHOD 审中-公开
公开(公告)号：US20180318819A1
公开(公告)日：2018-11-08
申请号：US15772374
申请日：2016-10-20
申请人： IFP Energies nouvelles
发明人： Pierre-Alain BREUIL , Emmanuel PELLIER
IPC分类号： B01J31/40 , C07C2/32
CPC分类号： B01J31/403 , B01J31/0227 , B01J31/0231 , B01J31/0237 , B01J31/0255 , B01J31/0264 , B01J31/0271 , B01J31/143 , B01J31/186 , B01J31/2247 , B01J31/24 , B01J31/2404 , B01J2231/20 , B01J2531/847 , B01J2540/10 , B01J2540/20 , B01J2540/325 , C07C2/32 , C07C11/08 , C07C11/107 , C07C2531/025 , C07C2531/14 , C07C2531/24 , C08F110/02
摘要： The invention describes a novel nickel-based composition. The invention also concerns the use of said composition as a catalytic composition in an olefin oligomerization process.

3. 发明授权

US5180872A Process for the preparation of styrene derivatives extended at the double bond by ethylene and having a double bond remaining in the extension chain formed and new styrene derivatives extended with ethylene 失效
标题翻译：制备苯乙烯衍生物的方法在乙烯双酚键上延伸，并且在延伸链形成的双键和新的苯乙烯衍生物中扩展乙烯
公开(公告)号：US5180872A
公开(公告)日：1993-01-19
申请号：US704751
申请日：1991-05-23
申请人： Karl-Heinz A. O. Starzewski
发明人： Karl-Heinz A. O. Starzewski
IPC分类号： B01J31/22 , B01J31/18 , B01J31/24 , C07B37/02 , C07B61/00 , C07C2/04 , C07C15/44 , C07C17/26 , C07C17/275 , C07C25/24 , C07C45/69 , C07C49/784 , C07C49/796 , C07C49/813 , C08F4/26 , C08F12/00 , C08F12/08
CPC分类号： C07C49/813 , B01J31/1875 , B01J31/2247 , B01J31/2295 , B01J31/24 , B01J31/2404 , C07B37/02 , C07C15/44 , C07C17/275 , C07C2/04 , C07C25/24 , C07C45/69 , C07C49/784 , C07C49/796 , B01J2531/847 , B01J31/2291 , C07C2531/22
摘要： The title compounds can be prepared by reaction of a styrene derivative with ethylene in the presence of a nickel catalyst which carries a phosphorus-oxygen chelate ligand, at a temperature of 20.degree.to 160.degree. C. and an ethylene pressure of 1 to 200 bar. Styrene derivatives extended with ethylene, of the formula ##STR1## in which R.sup.19 denotes hydrogen, C.sub.1 -C.sub.4 -alkyl, vinyl or chlorine and R.sup.38 denotes C.sub.1 -C.sub.4 -alkyl, C.sub.2 -C.sub.4 -alkenyl, C.sub.2 -C.sub.7 -acyl, flourine, chlorine or bromine andm assumes values of 4-104,with the exception of compounds wherein R.sup.19 denotes hydrogen and R.sup.38 denotes i-butyl or benzoyl, and m assumes the value 4, are new.
摘要翻译：标题化合物可以通过苯乙烯衍生物与乙烯在携带磷 - 氧螯合配体的镍催化剂存在下，在20至160℃的温度和1至200巴的乙烯压力下反应来制备。苯乙烯衍生物用乙烯延伸，其结构式为：其中R 19表示氢，C 1 -C 4烷基，乙烯基或氯，R 38表示C 1 -C 4烷基，C 2 -C 4链烯基，C 2 -C 7酰基，氯或溴，m为4-104的值，除了其中R 19表示氢，R 38表示异丁基或苯甲酰基，m为4的化合物是新的。

4. 发明授权

US4293727A Process for the oligomerization of ethylene 失效
标题翻译：乙烯低聚方法
公开(公告)号：US4293727A
公开(公告)日：1981-10-06
申请号：US179076
申请日：1980-08-18
申请人： David L. Beach , James J. Harrison
发明人： David L. Beach , James J. Harrison
IPC分类号： C07C2/32 , B01J31/00 , B01J31/18 , B01J31/22 , B01J31/24 , C07B61/00 , C07C1/00 , C07C2/36 , C07C11/02 , C07C67/00 , C07F15/04 , C08F110/02 , C07C2/02
CPC分类号： B01J31/2404 , B01J31/1895 , B01J31/2247 , C07C2/36 , C07F15/04 , C08F110/02 , B01J2231/20 , B01J2531/847 , B01J2540/32 , C07C2531/24
摘要： Ethylene is oligomerized by contacting ethylene under oligomerization conditions with a nickel ylide defined by the following Formula I: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are either alike or different members selected from the group consisting of hydrogen, alkyl radicals having from about one to about 24 carbon atoms, preferably from about one to about 10 carbon atoms; aryl radicals having from about six to about 20 carbon atoms, preferably from about six to about 10 carbon atoms; alkenyl radicals having from about two to about 30 carbons atoms, preferably from about two to about 20 carbon atoms; cycloalkyl radicals having from about three to about 40 carbon atoms, preferably from about three to about 30 carbon atoms; aralkyl and alkaryl radicals having from about six to about 40 carbon atoms, preferably from about six to about 30 carbon atoms; a halogen radical selected from the group consisting of fluorine, chlorine, bromine and iodine, preferably chlorine; a hydroxyl group; an alkoxy or aryloxy group; and a hydrocarbyl group, such as defined above, carrying halogen, hydroxyl or alkoxy or aryloxy; provided that at least one, preferably from about one to about four, of each of R.sub.1 to R.sub.8 is a sulfonato group (--SO.sub.3.sup.-) or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl group carrying a sulfonato group; M is sulfur or oxygen, preferably oxygen; E is phosphorus, arsenic, antimony or nitrogen, preferably phosphorus; and F is phosphorus, arsenic or antimony, preferably phosphorus. This process is characterized by a relatively high reaction rate at low temperatures and pressures and results in the production of relatively high proportions of desirable trimer, tetramer, pentamer, and higher olefinic products.
摘要翻译：乙烯通过在低聚条件下与乙烯接触，通过下列通式I所定义的镍叶立德使其低聚：其中R1，R2，R3，R4，R5，R6，R7和R8是相同或不同的成员，的氢，具有约1至约24个碳原子，优选约1至约10个碳原子的烷基; 具有约6至约20个碳原子，优选约6至约10个碳原子的芳基; 具有约2至约30个碳原子，优选约2至约20个碳原子的烯基; 具有约3至约40个碳原子，优选约3至约30个碳原子的环烷基; 具有约6至约40个碳原子，优选约6至约30个碳原子的芳烷基和烷芳基; 选自氟，氯，溴和碘的卤素，优选氯; 羟基; 烷氧基或芳氧基; 和如上所定义的含有卤素，羟基或烷氧基或芳氧基的烃基; 条件是R 1至R 8中的至少一个，优选约1至约4个为磺酸基（-SO 3 - ）或带有磺酸基的烷基，芳基，烯基，环烷基，芳烷基或烷芳基; M是硫或氧，优选氧; E是磷，砷，锑或氮，优选磷; F是磷，砷或锑，优选磷。该方法的特征在于在低温和低压下的相对较高的反应速率，并导致产生相对较高比例的所需三聚体，四聚体，五聚物和更高级烯烃产物。

5. 发明授权

US3686351A Alpha-olefin production 失效
标题翻译： ALPHA-OLEFIN生产
公开(公告)号：US3686351A
公开(公告)日：1972-08-22
申请号：US3686351D
申请日：1971-07-16
申请人： SHELL OIL CO
发明人： MASON RONALD F
IPC分类号： B01J31/26 , C07C2/36 , C07C3/10
CPC分类号： B01J31/146 , B01J31/2221 , B01J31/2247 , B01J31/28 , B01J31/30 , B01J2231/20 , B01J2531/847 , C07C2/36 , C07C2527/128 , C07C2531/14 , C07C2531/24
摘要： Ethylene is oligomerized to linear, alpha-olefins by reacting ethylene in liquid phase solution in the presence of a catalyst composition produced by contacting in the presence of ethylene (1) a simple divalent nickel salt (2) a boron hydride reducing agent (3) a phosphinooacetic acid or alkali metal salt thereof.
摘要翻译：在乙烯存在下（1）单价二价镍盐（2）硼氢化物还原剂（3）的存在下，使乙烯在液相溶液中反应生成的催化剂组合物，使乙烯低聚成线性α-烯烃，膦酰乙酸或其碱金属盐。

6. 发明授权

US11833495B2 Heterobimetallic catalysts and site-differentiated ligands for preparation thereof 有权
公开(公告)号：US11833495B2
公开(公告)日：2023-12-05
申请号：US18124708
申请日：2023-03-22
申请人： University of Houston System
发明人： Loi Hung Do , Zhongzheng Cai , Thi Tran , Dawei Xiao
IPC分类号： C08F10/02 , B01J31/22 , C08F4/70
CPC分类号： B01J31/2243 , B01J31/2247 , C08F4/7014 , C08F10/02 , B01J2531/0205 , B01J2531/0297 , B01J2531/824 , B01J2531/847 , C08F2410/03
摘要： Phosphine phosphonate and phenoxyphosphine ligands bearing polyethylene glycol (PEG) chains are used as described herein to produce heterobimetallic catalysts. The ligands can be metallated selectively with palladium or nickel and secondary metal ions to provide well-defined heterobimetallic compounds. These heterobimetallic complexes exhibit accelerated reaction rates and greater thermal stability in olefin polymerization compared to other catalysts.

7. 发明申请

US20150307537A1 NOVEL CYCLIC NICKEL-BASED COMPLEXES AND THEIR USE IN A PROCESS FOR THE TRANSFORMATION OF OLEFINS 有权
标题翻译：新型循环镍基复合物及其在烯烃转化过程中的应用
公开(公告)号：US20150307537A1
公开(公告)日：2015-10-29
申请号：US14698500
申请日：2015-04-28
申请人： IFP Energies nouvelles , Universiteit Van Amsterdam
发明人： Pierre BOULENS , Pierre-Alain BREUIL , Joost REEK , Helene OLIVIER-BOURBIGOU
IPC分类号： C07F15/04 , C07C211/65 , C07F9/28 , C07C2/32 , B01J31/18
CPC分类号： C07F15/045 , B01J31/1845 , B01J31/188 , B01J31/2247 , B01J31/2256 , B01J31/24 , B01J2231/20 , B01J2531/0213 , B01J2531/847 , C07C2/32 , C07C211/65 , C07C2531/22 , C07F9/28
摘要： The invention describes a novel type of nickel-based complex and its preparation method. The invention also concerns the use of said complex in a process for the transformation of olefins.
摘要翻译：本发明描述了一种新型的镍基络合物及其制备方法。本发明还涉及所述络合物在烯烃转化方法中的用途。

8. 发明申请

US20110003959A1 COORDINATION COMPLEX SYSTEM COMPRISING TAUTOMERIC LIGANDS 有权
标题翻译：协调复杂系统，包含TAUTOMERIC LIGANDS
公开(公告)号：US20110003959A1
公开(公告)日：2011-01-06
申请号：US12744293
申请日：2008-11-19
申请人： Joost Nikolaas Hendrik Reek , Frederic William Patureau , Mark Kuil , Albertus Jacobus Sandee , Jurjen Meeuwissen
发明人： Joost Nikolaas Hendrik Reek , Frederic William Patureau , Mark Kuil , Albertus Jacobus Sandee , Jurjen Meeuwissen
IPC分类号： C07F15/00 , C07C231/12 , C07C67/303 , C07D209/08 , C07C45/69 , C08G69/08 , C07C5/10
CPC分类号： C07F15/008 , B01J31/2247 , B01J2231/321 , B01J2231/643 , B01J2231/645 , B01J2531/822 , B01J2531/827 , B01J2531/828 , C07B2200/11 , C07C45/50 , C07C45/505 , C07C45/55 , C07C67/303 , C07C231/12 , C07C69/34 , C07C47/228 , C07C47/02 , C07C233/47 , C07C233/05
摘要： The invention relates to a coordination complex system comprising a ligand having the formula: R1—SO2—NH—P (XR2)2 (1a); or R1—SO2—N═PH (XR2)2 (1b); or R1—SO(OH)═N—P(XR2)2 (1c); wherein X is independently O, S, NH, or a bond; R1 and R2 are independently selected from hydrogen and substituted or unsubstituted alkyl or aryl; wherein at least one equivalent of the ligand is complexed to an equivalent of a metal selected from a transition metal and lanthanide. The invention also relates to the use of said coordination complexes as catalysts in the hydroformylation, hydrogenation, transfer hydrogenation, hydrocyanation, polymerization, isomerization, carbonylation, cross-coupling, metathesis, CH activation, allylic substitution, aldol condensation, or Michael addition.
摘要翻译：本发明涉及包含具有下式的配体的配位络合物体系：R1-SO2-NH-P（XR2）2（1a）; 或R1-SO2-N = PH（XR2）2（1b）; 或R1-SO（OH）= N-P（XR2）2（1c）; 其中X独立地为O，S，NH或键; R 1和R 2独立地选自氢和取代或未取代的烷基或芳基; 其中至少一当量的配体与选自过渡金属和镧系元素的金属的当量络合。本发明还涉及所述配位络合物在加氢甲酰化，氢化，转移氢化，氢氰化，聚合，异构化，羰基化，交叉偶联，复分解，CH活化，烯丙基取代，醛醇缩合或迈克尔加成中的用途。

9. 发明申请

US20100292449A1 WATER-STABLE COMPOUNDS, CATALYSTS AND CATALYSED REACTIONS 审中-公开
标题翻译：水稳定化合物，催化剂和催化反应
公开(公告)号：US20100292449A1
公开(公告)日：2010-11-18
申请号：US12665387
申请日：2008-06-16
申请人： Arran Alexander Dickon Tulloch , Alan Cooper , Robert Hume Duncan
发明人： Arran Alexander Dickon Tulloch , Alan Cooper , Robert Hume Duncan
IPC分类号： C07C291/08 , B01J31/12 , C07C69/80
CPC分类号： B01J31/2243 , B01J31/2247 , B01J2231/342 , B01J2231/42 , B01J2231/70 , B01J2531/31 , B01J2531/46 , B01J2531/48 , B01J2531/842 , B01J2531/96
摘要： The invention provides a method of carrying out a Lewis-acid catalysed organic reaction in the presence of a Lewis acid catalyst comprising a metal-organic compound having the following formula: M(HO(CR1R2)z)a(O(CR1R2)z)bY—(CR3R4)χ-Y((CR1R2)zO)c((CR1R2)zOH)d.nR5OH (Formula I) in which: M is a metal atom, preferably titanium, zirconium, hafnium or iron (III) Y is selected from P and N, but Ss very preferably N; each R1, R2, R3 and R4 is independently selected from H, alkyl, aryl, substituted alkyl or substituted aryl, R5 is hydrogen, an alkyl group, a hydroxy-functionalised alkyl group, a polyoxyalkylmoiety, R6O or R7COO where R6 and R7 may each represent H, alkyl, aryl or alkyl-aryl; d and a are each O or 1, b and c are each 1 or 2, b+c=the valency of M, a+b+c+d=4, each z is independently 1, 2, 3 or 4; x represents the least number of C atoms between the Y atoms and is 2 or 3 and n is a number in the range from 0 to 4. The metal-organic compound forms a stable hydrate in water which retains Lewis-acid catalytic properties.
摘要翻译：本发明提供一种在路易斯酸催化剂存在下进行路易斯酸催化的有机反应的方法，该路易斯酸催化剂包含具有下式的金属有机化合物：M（HO（CR 1 R 2）z）a（O（CR 1 R 2）z） bY-（CR3R4）χ-Y（（CR1R2）zO）c（（CR1R2）zOH）d.nR5OH（式I）其中：M是金属原子，优选钛，锆，铪或铁（III）Y是选自P和N，但S优选为N; 每个R 1，R 2，R 3和R 4独立地选自H，烷基，芳基，取代的烷基或取代的芳基，R 5是氢，烷基，羟基官能化的烷基，聚氧烷基摩尔，R6O或R7COO，其中R6和R7可以各自表示H，烷基，芳基或烷基 - 芳基; d和a各自为O或1，b和c各自为1或2，b + c = M的化合价，a + b + c + d = 4，每个z独立地为1,2,3或4; x表示Y原子之间的C原子数最少，为2或3，n为0至4的数。该金属有机化合物在水中形成稳定的水合物，保留路易斯酸催化性能。

10. 发明授权

US06939982B2 Recyclable chiral metathesis catalysts 失效
标题翻译：可回收手性复分解催化剂
公开(公告)号：US06939982B2
公开(公告)日：2005-09-06
申请号：US10435777
申请日：2003-05-12
申请人： Amir H. Hoveyda , Joshua Van Veldhuizen , Steven B. Garber , Jason S. Kingsbury
发明人： Amir H. Hoveyda , Joshua Van Veldhuizen , Steven B. Garber , Jason S. Kingsbury
IPC分类号： C07F11/00 , C07F15/00 , C07C255/00
CPC分类号： C07F15/0046 , B01J31/2208 , B01J31/2226 , B01J31/2247 , B01J31/226 , B01J31/2273 , B01J31/2278 , B01J2231/543 , B01J2531/0266 , B01J2531/64 , B01J2531/66 , B01J2531/821 , B01J2531/822 , C07F11/005 , C07F15/002 , C07F15/0073
摘要： The present invention relates to chiral metal catalysts for stereoselective olefin metathesis reactions, which are recyclable and reusable in such metathesis reactions. The chiral metal-based metathesis catalysts of the invention comprise multidentate optically active or racemic chiral ligands that enable their use in asymmetric synthetic processes, such as for example, in ring-opening and ring-closing metathesis reactions (ROM and RCM, respectively) of alkenes. The catalysts of the invention are organometallic complexes of multivalent metals comprising one or more chiral bidentate ligands that exhibit superior reactivity and stereoselectivity properties. The present invention also provides methods of making such catalysts and methods for utilizing them in catalyzing stereoselective olefin metathesis reactions to provide asymmetric products in relatively high enantiomeric or stereoisomeric excess.
摘要翻译：本发明涉及用于立体选择性烯烃复分解反应的手性金属催化剂，其在这种复分解反应中是可回收利用和可重复使用的。本发明的手性基于金属的复分解催化剂包括多齿光学活性或外消旋手性配体，使其能够用于不对称合成过程，例如开环和闭环复分解反应（分别为ROM和RCM）烯烃本发明的催化剂是包含一种或多种手性二齿配位体的多价金属的有机金属络合物，其表现出优异的反应性和立体选择性。本发明还提供了制备这种催化剂的方法和用于催化立体选择性烯烃复分解反应以提供具有相对高的对映异构体或立体异构体过量的不对称产物的方法。

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