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71. 发明授权

US06586599B1 Catalyzed coupling reactions of aryl halides with silanes 失效
标题翻译：芳基卤化物与硅烷的催化偶联反应
公开(公告)号：US06586599B1
公开(公告)日：2003-07-01
申请号：US09553542
申请日：2000-04-20
申请人： Steven P. Nolan , Hon Man Lee
发明人： Steven P. Nolan , Hon Man Lee
IPC分类号： C07D21322
CPC分类号： C07C67/343 , B01J31/1805 , B01J31/2273 , B01J31/2404 , B01J2231/42 , B01J2531/824 , B01J2531/828 , B01J2531/847 , C07B37/04 , C07B43/04 , C07B49/00 , C07C1/321 , C07C41/30 , C07C209/10 , C07C213/08 , C07D295/023 , C07D295/073 , C07D295/096 , C07C69/76 , C07C43/20
摘要： A process for conducting coupling reactions of aryl halides with unsaturated silanes is described. The processes use N-heterocyclic carbenes as ancillary ligands in these coupling reactions. A coupling of an aryl halide with an unsaturated silane can be carried out by mixing, in a liquid medium, at least one strong base; at least one aryl halide or aryl pseudohalide in which all substituents are other than silyl groups, wherein the aryl halide has, directly bonded to the aromatic ring(s), at least one chlorine atom, bromine atom, or iodine atom; at least one silane wherein the silicon atom is quaternary, wherein one group bound to the silicon atom is unsaturated at the alpha or beta position, and wherein each of the remaining groups bound to the silicon atom is a saturated hydrocarbyl or a saturated hydrocarbyloxy group; at least one nickel, palladium, or platinum compound, wherein the formal oxidation state of the metal is zero or two; and at least one N-heterocyclic carbene. One preferred type of N-heterocyclic carbene is an imidazoline-2-ylidene of the formula wherein R1 and R2 are each, independently, alkyl or aryl groups having at least 3 carbon atoms, R3 and R4 are each, independently, a hydrogen atom, a halogen atom, or a hydrocarbyl group.
摘要翻译：描述了芳基卤化物与不饱和硅烷进行偶联反应的方法。这些方法在这些偶联反应中使用N-杂环卡宾作为辅助配体。芳基卤化物与不饱和硅烷的偶联可以通过在液体介质中混合至少一个强碱来进行; 至少一种芳基卤或芳基卤化物，其中所有取代基都不是甲硅烷基，其中芳基卤已直接与芳环键合，至少一个氯原子，溴原子或碘原子; 至少一种硅烷，其中所述硅原子是季铵，其中与所述硅原子结合的基团在α或β位是不饱和的，并且其中与所述硅原子结合的剩余基团中的每一个为饱和烃基或饱和烃氧基; 至少一种镍，钯或铂化合物，其中金属的形式氧化态为零或二; 和至少一个N-杂环卡宾。 N-杂环卡宾的一种优选类型是式R 2的咪唑啉-2-亚基，R 2各自独立地为具有至少3个碳原子的烷基或芳基，R 3和R 4各自独立地为氢原子，卤素原子或烃基。

72. 发明授权

US06583307B2 Convenient and efficient Suzuki-Miyaura cross-coupling catalyzed by a palladium/diazabutadiene system 失效
标题翻译：方便高效的铃木 - 宫崎交叉耦合催化的钯/二氮杂双环系统
公开(公告)号：US06583307B2
公开(公告)日：2003-06-24
申请号：US10092753
申请日：2002-03-07
申请人： Steven P. Nolan , Gabriela Grasa
发明人： Steven P. Nolan , Gabriela Grasa
IPC分类号： C07C1514
CPC分类号： B01J31/1815 , B01J23/44 , B01J31/1805 , B01J31/183 , B01J31/2239 , B01J31/2291 , B01J2231/4211 , B01J2531/824 , C07B37/04 , C07C1/321 , C07C17/263 , C07C41/30 , C07C45/68 , C07C67/343 , C07C253/30 , C07C2531/02 , C07C2531/22 , C07D213/22 , C07D471/04 , C07C25/18 , C07C49/782 , C07C69/76 , C07C255/50 , C07C43/205
摘要： A Pd(OAc)2/diazabutadiene system has been developed for the catalytic cross-coupling of aryl halides with arylboronic acids. A combination of the diazabutadiene DAB-Cy (1, N,N′-Dicyclohexyl-1,4-dizabutadiene) and Pd(OAc)2 was found to form an excellent catalyst for the Suzuki-Miyaura cross-coupling of various aryl bromides and activated aryl chlorides with arylboronic acids.
摘要翻译：已经开发了Pd（OAc）2 /二氮杂双环系统用于芳基卤与芳基硼酸的催化交叉偶联。发现二氮杂双环十二烷二烯DAB-Cy（1，N，N'-二环己基-1,4-二氮杂二丁烯）和Pd（OAc）2的组合形成了用于各种芳基溴化物的Suzuki-Miyaura交叉偶联的优异催化剂，活性芳基氯与芳基硼酸。

73. 发明申请

US20030109713A1 Process for the catalytic synthesis of biaryls and polymers from aryl compounds 有权
标题翻译：从芳基化合物催化合成联芳基和聚合物的方法
公开(公告)号：US20030109713A1
公开(公告)日：2003-06-12
申请号：US10194859
申请日：2002-07-12
申请人： Board of Trustees operating Michigan State University
发明人： Milton R. Smith, III , Robert E. Maleczka
IPC分类号： C07C021/00 , C07D207/46 , C07D295/02
CPC分类号： C08G61/10 , B01J31/1805 , B01J31/22 , B01J31/2295 , B01J31/24 , B01J31/2404 , B01J31/2409 , B01J2231/4211 , B01J2531/822 , B01J2531/824 , B01J2531/827 , B01J2531/842 , C07C1/321 , C07C17/269 , C07C2531/22 , C07F5/025 , C07F15/0033 , C07F15/004 , C07F15/0073 , C07F15/008 , C07F17/02 , C08G2261/312 , C07C15/00 , C07C22/08 , C07C25/18
摘要： A process for producing organic substituted aromatic or heteroaromatic compounds including biaryl and biheteroaryl compounds in a two-step reaction. In the first step, the aromatic or heteroaromatic compound is borylated in a reaction comprising a borane or diborane reagent (any boron reagent where the boron reagent contains a BnullH, BnullB or BnullSi bond) and an iridium or rhodium catalytic complex. In the second step, a metal catalyst catalyzes the formation of the organic substituted aromatic or heteroaromatic compound from the borylated compound and an electrophile such as an aryl or organic halide, triflate (OSO2CF3), or nonaflate (OSO2C4F9). The steps in the process can be performed in a single reaction vessel or in separate reaction vessels. The present invention also provides a process for synthesis of complex polyphenylenes starting from halogenated aromatic compounds.
摘要翻译：一种在两步反应中制备包括联芳基和双杂芳基化合物的有机取代的芳族或杂芳族化合物的方法。在第一步中，在包含硼烷或乙硼烷试剂（硼试剂含有B-H，B-B或B-Si键的任何硼试剂）和铱或铑催化络合物的反应中，芳族或杂芳族化合物被硼酸化。在第二步中，金属催化剂催化从硼化化合物和亲电体如芳基或有机卤化物，三氟甲磺酸酯（OSO 2 CF 3）或非卤化物（OSO 2 C 4 F 9）形成有机取代的芳香族或杂芳族化合物。该方法中的步骤可以在单个反应容器中或在单独的反应容器中进行。本发明还提供从卤代芳族化合物开始合成络合聚苯的方法。

74. 发明授权

US06291722B1 Catalysis using phosphine oxide compounds 有权
标题翻译：使用氧化膦化合物进行催化
公开(公告)号：US06291722B1
公开(公告)日：2001-09-18
申请号：US09602714
申请日：2000-06-26
申请人： George Yanwu Li
发明人： George Yanwu Li
IPC分类号： C07C4100
CPC分类号： C07F9/5325 , B01J31/1875 , B01J2231/4211 , B01J2231/4233 , B01J2231/4283 , B01J2531/80 , B01J2531/824 , B01J2531/847 , C07B37/04 , C07C1/321 , C07C1/326 , C07C41/30 , C07C45/68 , C07C67/343 , C07C209/10 , C07C319/14 , C07C319/20 , C07C2531/22 , C07D211/12 , C07D295/023 , C07D295/073 , C07D295/096 , C07F9/46 , C07F9/5077 , C07C15/00 , C07C49/786 , C07C69/618 , C07C69/738 , C07C211/55 , C07C321/28 , C07C43/205 , C07C43/2055
摘要： Phosphine oxide compounds were used with transition metals, preferably palladium and nickel, to produce biaryls and arylamines via cross-coupling reactions with aryl halides and arylboronic acids, aryl Grignard reagents or amines.
摘要翻译：氧化膦化合物与过渡金属（优选钯和镍）一起使用，以通过与芳基卤化物和芳基硼酸，芳基格氏试剂或胺的交叉偶联反应制备联芳基和芳基胺。

75. 发明授权

US06288259B1 Alkene borates and a process for covalently coupling organic compounds 失效
标题翻译：烯烃硼酸盐和共价偶联有机化合物的方法
公开(公告)号：US06288259B1
公开(公告)日：2001-09-11
申请号：US09445457
申请日：2000-03-06
申请人： Sebastian Mario Marcuccio , Mary Rodopoulos , Helmut Weigold
发明人： Sebastian Mario Marcuccio , Mary Rodopoulos , Helmut Weigold
IPC分类号： C07F504
CPC分类号： C07C1/321 , C07B37/04 , C07C29/32 , C07C253/30 , C07D317/50 , C07F5/025 , C07C15/44 , C07C11/12 , C07C255/09 , C07C33/28 , C07C33/02
摘要： This invention describes a process for covalently coupling organic compounds which comprises reacting an olefinic compound having a halogen or halogen-like substituent at a coupling position with a diboron derivative in the presence of a Group VIII metal catalyst and a suitable base. The invention also describes a process for preparing alkene borate intermediates comprising reacting an olefinic compound having a halogen or halogen-like substituent with a diboron derivative in the presence of a Group VIII metal catalyst and a suitable base.
摘要翻译：本发明描述了共价偶联有机化合物的方法，其包括在VIII族金属催化剂和合适的碱的存在下，使偶联位置处的具有卤素或卤素取代基的烯属化合物与二硼衍生物反应。本发明还描述了一种制备硼酸中间体的方法，包括在VIII族金属催化剂和合适的碱的存在下使具有卤素或卤素取代基的烯属化合物与二硼衍生物反应。

76. 发明授权

US4814472A Diethynylated diphenyl hexafluoropropanes 失效
标题翻译：二乙氧基二苯基六氟丙烷
公开(公告)号：US4814472A
公开(公告)日：1989-03-21
申请号：US466271
申请日：1985-02-14
申请人： Kreisler S. Y. Lau
发明人： Kreisler S. Y. Lau
IPC分类号： C07C1/32 , C07C15/50 , C07C17/093 , C07F7/08
CPC分类号： C07F7/0809 , C07C1/321 , C07C15/50 , C07C17/093
摘要： There are disclosed diethynylated diphenyl hexafluoropropane compounds, which are suitable for forming copolymers and carbon-carbon composites. These compounds are prepared in high yields by first providing a dihalogenated diphenyl hexafluoropropane compound, coupling the dihalogenated compound with ethynyltrimethylsilane in the presence of an organometallic catalyst to form a silylated ethynyl terminated diphenyl substituted compound and subsequently desilylating the compound to form the desired diethynylated diphenyl hexafluoropropane compound.
摘要翻译：公开了二异戊基化二苯基六氟丙烷化合物，其适于形成共聚物和碳 - 碳复合材料。通过首先提供二卤代二苯基六氟丙烷化合物，在有机金属催化剂的存在下将二卤代化合物与乙炔基三甲基硅烷偶联以形成甲硅烷基化的乙炔基封端的二苯基取代的化合物，随后使该化合物脱甲硅烷化以形成所需的二异丙基二苯基六氟丙烷复合。

77. 发明授权

US3707489A Process of preparing ethylidene compounds 失效
标题翻译：制备乙二醇化合物的方法
公开(公告)号：US3707489A
公开(公告)日：1972-12-26
申请号：US3707489D
申请日：1971-01-19
申请人： JENAPHARM VEB
发明人： TEICHMULLER GERHARD , HARTMANN WERNER
IPC分类号： C07C1/32 , C07F7/18 , C07C167/20
CPC分类号： C07F7/1856 , C07C1/321 , C07C2601/14 , C07C11/113 , C07C13/19
摘要： PROCESS OF PREPARING ETHYLIDENE COMPOUNDS WITH DIFFERENT FUNDAMENTAL OR PARENT SUBSTANCES HAVING THE STRUCTURAL FORMULA:

CH3-CH=C(-CH3)2

WHEREIN R1 AND R2 EACH REPRESENT A SATURATED OR UNSATURATED ALIPHATIC GROUP WHICH CAN BE SUBSTITUTED BY FUNCTIONAL GROUPS AND WHEREIN R1 AND R2 TAKEN TOGETHER CAN FORM AN ALICYCLIC GROUP SUCH AS CYCLOPENTYL, CYCLOHEXYL AND THE LIKE, OR R1 AND R2 CAN BE JOINED TOGETHER TO FORM A CONDENSED HYROAROMATIC GROUP SUCH AS A PERHYDROINDANE, CYCLOPENTANO-PERHYDRONAPHTALINE OR CYCLOPENTANO-PERHYDROPHENANTHRENE GROUP, WHEREBY THE C-C BOUNDS OF THE PARENT SUBSTANCE ARE PREFERABLY UNSATURATED AND IN STEROID COMPOUNDS THE RING OF THE BASIC STRUCTURE CAN BE JOINED IN EITHER THE CIS- OR TRANSFORM WHICH COMPRISES REACTING AN EASILY HYDOLYZABLE DERIVATIVE OF VINYL AND ETHINYL CARBINOL, AS FOR INSTANCE AN ETHER, HAVING THE FORMULA:

R4-O-C(-R1)(-R2)-R3

WHEREIN R1 AND R2 ARE AS ABOVE DEFINED AND R3 IS VINYL OR ETHINYL AND R4 IS A TRIALKYLSILYL OR TETRAHYDROPYANYL GROUP WITH AN ALKALI METAL IN THE PRESENCE OF A PROTON DONOR AND LIQUID AMMONIA. THESE COMPOUNDS ARE PARTICULARLY ADAPTED FOR USE AS INTERMEDIATES FOR USE IN PREPARING HIGHLY ACTIVE STEROID COMPOUNDS, AS FOR EXAMPLE, 19-NOR PREGNANE DERIVATIVES.

78. 发明授权

US3265689A Process for the production of substituted azulenes 失效
公开(公告)号：US3265689A
公开(公告)日：1966-08-09
申请号：US48515965
申请日：1965-09-07
申请人： STUDIENGESELLSCHAFT KOHLE G M
发明人： KLAUS HAFNER , HEINRICH PELSTER
IPC分类号： C07C1/00 , C07C1/32 , C07C2/86 , C07C13/52
CPC分类号： C07C13/52 , C07C1/00 , C07C1/321 , C07C1/325 , C07C2/867 , C07C2602/30 , Y10S585/931 , Y10S585/935

79. 发明授权

US3134823A Process involving the reaction of group i-b metal compounds with an organoboron compound in the presence of a strong base 失效
标题翻译：涉及i-b族金属化合物与有机硼化合物在强碱存在下反应的方法
公开(公告)号：US3134823A
公开(公告)日：1964-05-26
申请号：US7511060
申请日：1960-12-12
申请人： BROWN HERBERT C
发明人： BROWN HERBERT C
IPC分类号： C07C1/32 , C07F5/02
CPC分类号： C07F5/027 , C07C1/321 , Y10S585/931 , Y10S585/942 , C07C9/10

80. 发明授权

US3065281A Isomerization of non-terminal olefins 失效
标题翻译：非末端烯烃的异构化
公开(公告)号：US3065281A
公开(公告)日：1962-11-20
申请号：US85224359
申请日：1959-11-12
申请人： SUN OIL CO
发明人： HALL JR LEWIS W , THOMAS CHARLES L
IPC分类号： C07C1/32
CPC分类号： C07C1/321

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