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81. 发明公开

EP1379485A4 SELECTIVE RING-OPENING CROSS-METATHESIS OF CYCLOOLEFINS 审中-公开
标题翻译：环烯烃开环选择性交叉复分解
公开(公告)号：EP1379485A4
公开(公告)日：2005-08-31
申请号：EP02728658
申请日：2002-04-01
申请人： CALIFORNIA INST OF TECHN
发明人： MORGAN JOHN P , MORRILL CHRISTIE , GRUBBS ROBERT H , CHOI TAE-LIM
IPC分类号： C07D233/02 , B01J31/22 , B01J31/24 , C07B61/00 , C07C6/06 , C07C45/69 , C07C47/21 , C07C49/203 , C07C51/353 , C07C57/13 , C07C67/347 , C07C69/587 , C07C69/602 , C07C69/74 , C07F15/00 , C07F19/00 , C07C6/02 , C07C6/04
CPC分类号： C07C67/343 , B01J31/18 , B01J31/2226 , B01J31/2273 , B01J31/24 , B01J31/2404 , B01J2231/543 , B01J2531/80 , B01J2531/821 , B01J2540/32 , C07C6/06 , C07C45/68 , C07C51/353 , C07C67/475 , C07C2531/22 , C07C47/21 , C07C49/203 , C07C57/13 , C07C69/587 , C07C69/757 , C07C69/74 , C07C69/602
摘要： A catalytic method is provided for a ring-opening cross-metathesis reaction between a cycloolefinic substrate and a second olefinic reactant, wherein the catalyst used is a transition metal alkylidene complex substituted with an N-heterocyclic carbene ligand. The substrates are selected so that the rate of the cross-metathesis reaction of the second olefinic reactant, kCM, is greater than or equal to the rate of the ring-opening metathesis reaction, kRo. In this way, the predominant ROCM product is a monomer, dimer, and/or oligomer, but not a polymer. The invention additionally provides for selective production of an end-differentiated olefinic product, using trisubstituted cycloolefins as substrates and/or a subsequent cross-metathesis reaction following an initial ROCM step. The cycloolefinic substrates include low-strain olefins such as cyclohexene as well as higher strain olefins such as cyclooctene.

82. 发明公开

EP0837885A4 PEROXIDE CROSSLINKING OF ROMP POLYMERS 失效
标题翻译： PEROXIDVERNETZUNG VON ROMP POLYMEREN
公开(公告)号：EP0837885A4
公开(公告)日：2003-05-21
申请号：EP96924356
申请日：1996-07-03
申请人： CALIFORNIA INST OF TECHN
发明人： GRUBBS ROBERT H , WOODSON CHARLES S JR
IPC分类号： C08F4/80 , C08F2/00 , C08F32/00 , C08G61/08 , C08F8/00
CPC分类号： C08G61/08
摘要： Methods of forming polycycloolefins having high crosslink density are disclosed. Olefins are polymerized via a metathesis mechanism in the presence of a crosslinking agent and a catalyst. The crosslinking agent generally comprises a peroxide that decomposes into reactive species forming crosslinks during post-cure. The catalyst is a ruthenium or osmium carbene complex of general formula (I), wherein M is Os or Ru; R and R are independently selected from hydrogen or a hydrocarbon selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C2-C20 alkoxycarbonyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy and aryloxy; X and X are independently selected from any anionic ligand; and L and L are independently selected from any neutral electron donor. Preferably, L and L are trialkylphosphine ligands and at least one of the alkyl groups on the phosphine ligand may be a secondary alkyl or cycloalkyl group, especially P(isopropyl)3, P(cyclopentyl)3 and P(cyclohexyl)3. Preferred crosslinking agents are peroxides, such as t-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexyne-3, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexane or mixtures thereof. Olefins may be cyclic (e.g., monocyclic, bicyclic or tricyclic) or acyclic. Norbornene or norbornene derivatives are especially preferred.
摘要翻译：公开了形成交联密度高的聚环烯烃的方法。在交联剂和催化剂存在下，烯烃通过复分解机理聚合。交联剂通常包含在后固化期间分解成反应性物质形成交联的过氧化物。催化剂是下式的钌或锇卡宾络合物：其中M是Os或Ru; R和R 1独立地选自氢或选自C 1 -C 20烷基，C 2 -C 20烯基，C 2 -C 20炔基，C 2 -C 20烷氧基羰基，芳基，C 1 -C 20羧酸酯，C 1 -C 20烷氧基，C 2 -C 20烯氧基，C 2 -C 20炔氧基和芳氧基; X和X 1独立地选自任何阴离子配体; L和L 1独立地选自任何中性电子给体。优选地，L和L1是三烷基膦配体，并且膦配体上的至少一个烷基可以是仲烷基或环烷基，特别是P（异丙基）3，P（环戊基）3和P（环己基）3。优选的交联剂是过氧化物，例如叔丁基过氧化物，2,5-二甲基-2,5-二 - （叔丁基过氧）己炔-3，二叔丁基过氧化物和2,5-二甲基-2，（叔丁基过氧）己烷或其混合物。烯烃可以是环状的（例如单环，双环或三环）或无环的。降冰片烯或降冰片烯衍生物是特别优选的。

83. 发明公开

EP0970069A4 TEMPLATE-DIRECTED RING-CLOSING METATHESIS AND RING-OPENING METATHESIS POLYMERIZATION OF FUNCTIONALIZED DIENES 失效
标题翻译： MATRIZENGESTEURERTE RINGSCHLUSSMETHATHESE UND RINGEFEFNUNGSMETHATHESE-POLYMERISATION VON FUNKTIONALISIERTEN DIENEN
公开(公告)号：EP0970069A4
公开(公告)日：2002-05-02
申请号：EP97952650
申请日：1997-12-19
申请人： CALIFORNIA INST OF TECHN
发明人： GRUBBS ROBERT H , MARSELLA MICHAEL J , MAYNARD HEATHER D
IPC分类号： C07D323/00 , C08F2/00 , C08G65/329 , C08F34/02
CPC分类号： C07D323/00 , C08G65/329
摘要： Functionalized cyclic olefins and methods for making the same are disclosed. Methods include template-directed ring-closing metathesis ('RCM') of functionalized acyclic dienes and template-directed depolymerization of functionalized polymers possessing regularly spaced sties of unsaturation. Although the template species may be any anion, cation, or dipolar compound, cationic species, especially alkali metals, are preferred. Functionalized polymers with regularly spaced sites of unsaturation and methods for making the same are also disclosed. One method for synthesizing these polymers is by ring-opening metathesis polymerization ('ROMP') of functionalized cyclic olefins. The metathesis catalysts for both RCM and ROMP reaction are ruthenium or osmium carbene complex catalysts of formula (I) where M is Os or Ru; R and R1 each may be hydrogen, C¿2?-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl or C1-C20 alkylsulfinyl; X and X?1¿ may be any anionic ligand; and L and L1 may be any neutral electron donor.
摘要翻译：公开了官能化的环状烯烃及其制备方法。方法包括功能化无环二烯的模板定向闭环复分解（'RCM'）和具有规则间隔不饱和度的官能化聚合物的模板定向解聚。尽管模板物质可以是任何阴离子，阳离子或偶极化合物，但阳离子物质，特别是碱金属是优选的。还公开了具有规则间隔的不饱和位点的官能化聚合物及其制备方法。合成这些聚合物的一种方法是通过官能化环烯烃的开环易位聚合（'ROMP'）。用于RCM和ROMP反应的复分解催化剂是式（I）的钌或锇卡宾络合物催化剂，其中M是Os或Ru; R和R1各自可以是氢，C 2 -C 20烯基，C 2 -C 20炔基，C 1 -C 20烷基，芳基，C 1 -C 20羧酸酯，C 1 -C 20烷氧基，C 2 -C 20烯氧基，C 2 -C 20炔氧基， C 2 -C 20烷氧基羰基，C 1 -C 20烷硫基，C 1 -C 20烷基磺酰基或C 1 -C 20烷基亚磺酰基; X和X→1可以是任何阴离子配体; L和L1可以是任何中性电子供体。

84. 发明专利

CA3010522A1 NEW STABLE SILYLATING REAGENTS 未知
公开(公告)号：CA3010522A1
公开(公告)日：2017-08-31
申请号：CA3010522
申请日：2017-02-22
申请人： CALIFORNIA INST OF TECHN
发明人： TOUTOV ANTON , LIU WENBO , SCHUMAN DAVID P , STOLTZ BRIAN M , GRUBBS ROBERT H
IPC分类号： C07F7/08
摘要： The present invention is directed to compositions for silylating organic substrates containing C-H or O-H bonds, especially heteroaromatic substrates. The compositions are derived from the preconditioning of mixtures of hydrosilanes or organodisilanes with bases, including metal hydroxide and metal alkoxide bases. In some embodiments, the preconditioning results in the formation of reactive silicon hydride species.

85. 发明专利

CA3006976A1 OLEFIN METATHESIS CATALYSTS 未知
公开(公告)号：CA3006976A1
公开(公告)日：2017-06-15
申请号：CA3006976
申请日：2016-12-09
申请人： CALIFORNIA INST OF TECHN , UMICORE AG & CO KG
发明人： JOHNS ADAM M , MONTGOMERY T PATRIC , AHMED TONIA S , GRUBBS ROBERT H , PEDERSON RICHARD L
IPC分类号： C07C6/06 , B01J31/22
摘要： This invention relates generally to metathesis catalysts and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in Z and E selective olefin metathesis reactions. The invention has utility in the fields of organometallics and organic synthesis.

86. 发明专利

CA2985368A1 LIGHT ADJUSTABLE INTRAOCULAR LENSES USING UPCONVERTING NANOPARTICLES AND NEAR INFRARED (NIR) LIGHT 未知
公开(公告)号：CA2985368A1
公开(公告)日：2016-11-17
申请号：CA2985368
申请日：2016-05-13
申请人： CALIFORNIA INST OF TECHN
发明人： GRUBBS ROBERT H , MANGOLD SHANE L
IPC分类号： C08L101/12 , A61F2/16 , A61K9/00 , C08J3/28 , C09K11/61 , C09K11/78 , C09K11/85
摘要： This disclosure relates compositions comprising upconverting nanocrystals and photoactive compositions and methods using these compositions to modify treat myopia and other ocular conditions. In some cases, the methods use near infrared irradiation to adjust the refractive power of light adjustable ocular lenses. Other methods improve the mechanical strength of the sclera directly.

87. 发明专利

CA2579664C SYNTHESIS OF RUTHENIUM OR OSMIUM METATHESIS CATALYSTS 未知
公开(公告)号：CA2579664C
公开(公告)日：2011-06-28
申请号：CA2579664
申请日：1997-11-10
申请人： CALIFORNIA INST OF TECHN
发明人： GRUBBS ROBERT H , BELDERRAIN THOMAS T , BROWN SETH N , WILHELM THOMAS E
IPC分类号： C07F15/00 , A61F2/06 , B01J31/00 , B01J31/22 , B01J31/24 , C07F9/02 , C07F9/50
摘要： The present invention relates to the synthesis of highly active ruthenium and osmium carbene metathesis catalyst in good yield from readily available starting materials. The catalysts that may be synthesized are of general formula (I) wherein: M is ruthenium or osmium; X and X1 are independently any anionic ligand; L and L1 are any neutral electron donor ligand; and, R and R1 are each hydrogen or one of the following substituent groups: C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, aryl, C1--C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2- C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsufinyl. Optionally, the substituent group may be substituted with one or more groups selected from C1-C5 alkyl, halogen, C1-C5 alkoxy, and aryl. When the substitute aryl group is phenyl, it may be further substituted with one or more groups selected from a halogen, a C1-C5 alkyl, or a C1-C5 alkoxy. Specific synthetic protocols for vinyl alkylidene catalysts wherein R is hydrogen and R1 is -CHCR12R13 and nonvinyl alkyldiene catalysts are also disclosed. In addition to the ease of synthesis (typically a one-step synthesis), the reactions generally may be run at or above room temperature and the resulting products usually may be used without extensive post synthesis purification.

88. 发明专利

DE60042645D1 未知
公开(公告)号：DE60042645D1
公开(公告)日：2009-09-10
申请号：DE60042645
申请日：2000-03-17
申请人： CALIFORNIA INST OF TECHN
发明人： GRUBBS ROBERT H , BIELAWSKI CHRISTOPHER
IPC分类号： C08F32/00 , C08F4/40 , C08F4/44 , C08F293/00 , C08F295/00 , C08F297/00 , C08G61/08 , C08L53/00 , C08L53/02
摘要： The invention discloses a method for preparing a triblock copolymer of the formula:comprising:(a) contacting a cycloalkene with a chain transfer agent of the formula:in the presence of a metal carbene metathesis catalyst to form a telechelic polymer; and(d) contacting the telechelic polymer with an alkene of the formulain the presence of an ATRP organometallic catalystwherein n and m are integers; Z is an ATRP initiator and -Y=Y- is an alkenyl group; and, R' is selected from the group consisting of aryl, nitrile and C1-C20 carboxylate, wherein R' is substituted or unsubstituted. The invention also discloses a method for preparing a diblock copolymer. In addition, the invention encompasses a triblock copolymer having no 1,2-PBD structure in the PBD portion of the copolymer.

89. 发明专利

DE69733830D1 未知
公开(公告)号：DE69733830D1
公开(公告)日：2005-09-01
申请号：DE69733830
申请日：1997-11-10
申请人： CALIFORNIA INST OF TECHN
发明人： GRUBBS ROBERT H , BELDERRAIN TOMAS R , BROWN SETH N , WILHELM THOMAS E
IPC分类号： A61F2/06 , B01J31/00 , B01J31/22 , B01J31/24 , C07F9/02 , C07F9/50 , C07F15/00 , B32B3/24
摘要： The present invention relates to the synthesis of ruthenium and osmium carbene metathesis catalysts of the formula or of the formula by reacting unsaturated alkene or alkyne compounds with hydrogen containing ruthenium or osmium complexes as and to the synthesis of certain of the hydrogen containing ruthenium or osmium complexes used in the synthetic methods mentioned above.

90. 发明专利

AT288079T 未知
公开(公告)号：AT288079T
公开(公告)日：2005-02-15
申请号：AT98939894
申请日：1998-08-07
申请人： CALIFORNIA INST OF TECHN , CYRANO SCIENCES INC
发明人： GOODMAN RODNEY M , LEWIS NATHAN S , GRUBBS ROBERT H , DIXSON JEFFREY
IPC分类号： G01N27/12 , G01N27/22 , G01N33/00

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