公开(公告)号：US08283276B2

公开(公告)日：2012-10-09

申请号：US12744293

申请日：2008-11-19

Applicant: Joost Nikolaas Hendrik Reek ,  Frederic William Patureau ,  Mark Kuil ,  Albertus Jacobus Sandee ,  Jurjen Meeuwissen

Inventor： Joost Nikolaas Hendrik Reek ,  Frederic William Patureau ,  Mark Kuil ,  Albertus Jacobus Sandee ,  Jurjen Meeuwissen

IPC: B01J31/00 ,  C07F15/00 ,  C07C231/12 ,  C07C67/303 ,  C07C45/69 ,  C07C5/10 ,  C07D209/08 ,  C08G69/08

CPC classification number: 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

Abstract: 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.

Abstract translation: 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。

公开(公告)号：USRE37106E1

公开(公告)日：2001-03-20

申请号：US08394538

申请日：1995-02-22

Applicant: Karl-Heinz Aleksander Ostoja Starzewski

Inventor： Karl-Heinz Aleksander Ostoja Starzewski

IPC: C10L116

CPC classification number: C07C49/813 ,  B01J31/1875 ,  B01J31/2247 ,  B01J31/2291 ,  B01J31/2295 ,  B01J31/24 ,  B01J31/2404 ,  B01J2531/847 ,  C07B37/02 ,  C07C2/04 ,  C07C15/44 ,  C07C17/275 ,  C07C25/24 ,  C07C45/69 ,  C07C49/784 ,  C07C49/796 ,  C07C2531/22

Abstract: 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° to 160° C. and an ethylene pressure of 1 to 200 bar. Styrene derivatives extended with ethylene, of the formula in which R19 denotes hydrogen, C1-C4-alkyl, vinyl or chlorine and R38 denotes C1-C4-alkyl, C2-C4-alkenyl, C2-C7-acyl, flourine, chlorine or bromine and m assumes values of 4-104, with the exception of compounds wherein R19 denotes hydrogen and R38 denotes i-butyl or benzoyl, and m assumes the value 4, are new.

Abstract translation: 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 。 乙烯延伸的苯乙烯衍生物，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 - 烯基，C 2 -C 7 - 酰基，芴，氯或溴，并表示值 的4-104，除了其中R 19表示氢并且R 38表示异丁基或苯甲酰基，m表示数值4的化合物，是新的。

公开(公告)号：US4310716A

公开(公告)日：1982-01-12

申请号：US179005

申请日：1980-08-18

Applicant: David L. Beach ,  James J. Harrison

Inventor： David L. Beach ,  James J. Harrison

IPC: 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 classification number: B01J31/2247 ,  B01J31/2404 ,  C07C2/36 ,  C07F15/04 ,  C08F110/02 ,  B01J2231/20 ,  B01J2531/847 ,  B01J2540/32 ,  B01J31/1895 ,  C07C2531/24 ,  Y02P30/42

Abstract: Ethylene is oligomerized by reacting ethylene in methanol under oligomerization conditions in contact 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 carbon atoms, preferably from about two to about 20 carbon atoms; cycloalkyl radicals having from about three to about 40 carbon atoms, preferably 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. There is thus obtained a reaction product containing (A) a methanol phase having dissolved therein the nickel ylide catalyst and (B) an alpha olefin phase. These two phases are then separated from each other to recover the alpha olefin phase. The use of methanol as the solvent medium causes the reaction product to resolve itself into two phases, an upper phase containing most of the oligomer product and a lower methanol phase carrying the catalyst dissolved therein. This permits easy separation of the product from the reaction mixture and also permits effective recycle of methanol with dissolved catalyst. The product obtained contains normal alpha olefins having from about four to about 100 carbon atoms, generally from about four to about 50 carbon atoms.

公开(公告)号：US11833495B2

公开(公告)日：2023-12-05

申请号：US18124708

申请日：2023-03-22

Applicant: University of Houston System

Inventor： Loi Hung Do ,  Zhongzheng Cai ,  Thi Tran ,  Dawei Xiao

IPC: C08F10/02 ,  B01J31/22 ,  C08F4/70

CPC classification number: B01J31/2243 ,  B01J31/2247 ,  C08F4/7014 ,  C08F10/02 ,  B01J2531/0205 ,  B01J2531/0297 ,  B01J2531/824 ,  B01J2531/847 ,  C08F2410/03

Abstract: 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.

公开(公告)号：US20150307537A1

公开(公告)日：2015-10-29

申请号：US14698500

申请日：2015-04-28

Applicant: IFP Energies nouvelles ,  Universiteit Van Amsterdam

Inventor： Pierre BOULENS ,  Pierre-Alain BREUIL ,  Joost REEK ,  Helene OLIVIER-BOURBIGOU

IPC: C07F15/04 ,  C07C211/65 ,  C07F9/28 ,  C07C2/32 ,  B01J31/18

CPC classification number: 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

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US20110003959A1

公开(公告)日：2011-01-06

申请号：US12744293

申请日：2008-11-19

Applicant: Joost Nikolaas Hendrik Reek ,  Frederic William Patureau ,  Mark Kuil ,  Albertus Jacobus Sandee ,  Jurjen Meeuwissen

Inventor： Joost Nikolaas Hendrik Reek ,  Frederic William Patureau ,  Mark Kuil ,  Albertus Jacobus Sandee ,  Jurjen Meeuwissen

IPC: C07F15/00 ,  C07C231/12 ,  C07C67/303 ,  C07D209/08 ,  C07C45/69 ,  C08G69/08 ,  C07C5/10

CPC classification number: 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

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US20100292449A1

公开(公告)日：2010-11-18

申请号：US12665387

申请日：2008-06-16

Applicant: Arran Alexander Dickon Tulloch ,  Alan Cooper ,  Robert Hume Duncan

Inventor： Arran Alexander Dickon Tulloch ,  Alan Cooper ,  Robert Hume Duncan

IPC: C07C291/08 ,  B01J31/12 ,  C07C69/80

CPC classification number: B01J31/2243 ,  B01J31/2247 ,  B01J2231/342 ,  B01J2231/42 ,  B01J2231/70 ,  B01J2531/31 ,  B01J2531/46 ,  B01J2531/48 ,  B01J2531/842 ,  B01J2531/96

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US06939982B2

公开(公告)日：2005-09-06

申请号：US10435777

申请日：2003-05-12

Applicant: Amir H. Hoveyda ,  Joshua Van Veldhuizen ,  Steven B. Garber ,  Jason S. Kingsbury

Inventor： Amir H. Hoveyda ,  Joshua Van Veldhuizen ,  Steven B. Garber ,  Jason S. Kingsbury

IPC: C07F11/00 ,  C07F15/00 ,  C07C255/00

CPC classification number: 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

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US20040019212A1

公开(公告)日：2004-01-29

申请号：US10435777

申请日：2003-05-12

Applicant: Trustees of Boston College

Inventor： Amir H. Hoveyda ,  Joshua Van Veldhuizen ,  Steven B. Garber ,  Jason S. Kingsbury

IPC: C07F011/00

CPC classification number: 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

Abstract: 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.

Abstract translation: 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。

公开(公告)号：USRE34706E

公开(公告)日：1994-08-23

申请号：US84379

申请日：1993-06-29

Applicant: Karl-Heinz A. O. Starzewski

Inventor： Karl-Heinz A. O. Starzewski

IPC: 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 ,  C07C2/02 ,  C07C2/46 ,  C07C2/64 ,  C07C2/66

CPC classification number: 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

Abstract: 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 -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.