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1.发明授权Phosphite-promoted ruthenium-cobalt catalysts for the dealkoxyhydroxymethylation of acetals to form glycol ethers 失效亚磷酸酯促进的钌 - 钴催化剂用于缩醛的脱烷基羟甲基化以形成二醇醚
公开(公告)号：US4692426A
公开(公告)日：1987-09-08
申请号：US901861
申请日：1986-08-29
CPC分类号： B01J31/0259 , B01J31/1608 , B01J31/185 , B01J31/20 , B01J31/2265 , C07C41/01 , C07C41/30 , C07C43/13 , B01J2231/34 , B01J2231/641 , B01J2531/0211 , B01J2531/821 , B01J2531/845
摘要： Ruthenium-cobalt carbonyl catalysts which have been promoted with an organophosphite effectively catalyze the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas, i.e., CO and H.sub.2, in the presence of this phosphite-promoted ruthenium carbonyl cobalt catalyst to form the monomethyl ether of ethylene glycol. In a like manner acetaldehyde may be converted to the corresponding propylene glycol monoether. The process may advantageously be carried out with high yields and selectivities in the presence of a polar or non-polar organic solvent in combination with the catalyst system of this invention.The invention is also directed to certain of the organophosphite-promoted cobalt and ruthenium-cobalt carbonyl catalyst systems per se.
摘要翻译： 已经用有机亚磷酸酯促进的钌 - 钴羰基催化剂有效地催化醛缩醛的脱烷基羟甲基化以形成二醇单醚。 在该亚磷酸盐促进的羰基钴钌催化剂的存在下，例如甲醛可以与合成气即CO和H 2反应，形成乙二醇的单甲基醚。 以类似方式，乙醛可以转化成相应的丙二醇单醚。 在极性或非极性有机溶剂与本发明的催化剂体系的组合下，该方法可以有利地以高产率和选择性进行。 本发明还涉及某些有机亚磷酸酯促进的钴和钌 - 钴羰基催化剂体系本身。
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2.发明授权Ruthenium-cobalt carbonyl catalysts for the dealkoxyhydroxymethylation of acetals to form glycol ethers 失效用于乙缩醛脱甲基羟甲基化形成二醇醚的钌 - 钴羰基催化剂
公开(公告)号：US4652542A
公开(公告)日：1987-03-24
申请号：US782805
申请日：1985-10-02
CPC分类号： B01J31/1608 , B01J31/20 , B01J31/2265 , C07C41/01 , C07C41/30 , C07C43/13 , B01J2231/34 , B01J2231/641 , B01J2531/0211 , B01J2531/821 , B01J2531/845
摘要： The cobalt carbonyl catalyst R.sup.5 CCo.sub.3 (CO).sub.9, desirably with Ru.sub.3 (CO).sub.12, wherein R.sup.5 is hydrogen; alkyl, preferably C.sub.1-5 lower alkyl; cycloalkyl or substituted cycloalkyl; cycloalkenyl, such as cyclohexenyl or cyclooctenyl; C.sub.1-12 alkoxy, such as methoxy or propoxy; aryl or alkyl-, cycloalkyl-, alkoxy-, halo-, or cyano-substituted aryl; cyano; or a silyl carbyne moiety of the formula R.sub.3.sup.6 Si, wherein R.sup.6 is alkyl or aryl, effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas; i.e., CO and H.sub.2, in the presence of this catalyst system to form the corresponding ethylene glycol monomethyl ether.
摘要翻译： 钴羰基催化剂R5CCo3（CO）9，理想地含有Ru 3（CO）12，其中R 5是氢; 烷基，优选C 1-5低级烷基; 环烷基或取代的环烷基; 环烯基，例如环己烯基或环辛烯基; C 1-12烷氧基，如甲氧基或丙氧基; 芳基或烷基 - ，环烷基 - ，烷氧基 - ，卤代或氰基取代的芳基; 氰基; 或式R36Si的甲硅烷基卡宾部分，其中R6是烷基或芳基，有效地催化醛缩醛的脱烷基羟甲基化以形成二醇单醚。 甲缩醛例如可以与合成气反应; 即CO和H 2，在该催化剂体系的存在下形成相应的乙二醇单甲醚。
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3.发明授权Ruthenium-cobalt carbonyl catalysts for the dealkoxyhydroxymethylation of acetals to form glycol ethers 失效用于乙缩醛脱甲基羟甲基化形成二醇醚的钌 - 钴羰基催化剂
公开(公告)号：US4663489A
公开(公告)日：1987-05-05
申请号：US859514
申请日：1986-05-05
CPC分类号： B01J31/1608 , B01J31/20 , B01J31/2265 , C07C41/01 , C07C41/30 , C07C43/13 , B01J2231/34 , B01J2231/641 , B01J2531/0211 , B01J2531/821 , B01J2531/845
摘要： The cobalt carbonyl catalyst R.sup.5 CCo.sub.3 (CO).sub.9, desirably with Ru.sub.3 (CO).sub.12, wherein R.sup.5 is hydrogen; alkyl, preferably C.sub.1-5 lower alkyl; cycloalkyl or substituted cycloalkyl; cycloalkenyl, such as cyclohexenyl or cyclooctenyl; C.sub.1-12 alkoxy, such as methoxy or propoxy; aryl or alkyl-, cycloalkyl-, alkoxy-, halo-, or cyano-substituted aryl; cyano; or a silyl carbyne moiety of the formula R.sub.3.sup.6 Si, wherein R.sup.6 is alkyl or aryl, effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas; i.e., CO and H.sub.2, in the presence of this catalyst system to form the corresponding ethylene glycol monomethyl ether.The novel catalyst combination of R.sup.5 CCo.sub.3 (CO).sub.9 and Ru.sub.3 (CO).sub.12 is likewise claimed herein.
摘要翻译： 钴羰基催化剂R5CCo3（CO）9，理想地含有Ru 3（CO）12，其中R 5是氢; 烷基，优选C 1-5低级烷基; 环烷基或取代的环烷基; 环烯基，例如环己烯基或环辛烯基; C 1-12烷氧基，如甲氧基或丙氧基; 芳基或烷基 - ，环烷基 - ，烷氧基 - ，卤代或氰基取代的芳基; 氰基; 或式R36Si的甲硅烷基卡宾部分，其中R6是烷基或芳基，有效地催化醛缩醛的脱烷基羟甲基化以形成二醇单醚。 甲缩醛例如可以与合成气反应; 即CO和H 2，在该催化剂体系的存在下形成相应的乙二醇单甲醚。 本文还要求R5CCo3（CO）9和Ru3（CO）12）的新型催化剂组合。
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4.发明授权Ruthenium-cobalt carbonyl metal cluster catalysts for the dealkoxyhydroxymethylation of acetals to form glycol ethers 失效钌钴羰基金属簇催化剂，用于乙缩醛脱甲基羟甲基化形成二醇醚
公开(公告)号：US4618729A
公开(公告)日：1986-10-21
申请号：US782807
申请日：1985-10-02
CPC分类号： B01J31/20 , C07C41/01 , C07C41/30 , B01J2231/34 , B01J2231/641 , B01J2531/0211 , B01J2531/821 , B01J2531/845
摘要： The ruthenium-cobalt carbonyl metal cluster catalyst Co.sub.2 Ru(CO).sub.11 effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas, i.e., CO and H.sub.2, in the presence of this ruthenium-cobalt cluster catalyst to form the monomethyl ether of ethylene glycol.
摘要翻译： 钌钴羰基金属簇催化剂Co2Ru（CO）11有效地催化醛缩醛的脱烷基羟甲基化形成二醇单醚。 在这种钌 - 钴簇催化剂的存在下，例如甲缩醛可与合成气（即CO和H 2）反应，形成乙二醇的单甲基醚。
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公开(公告)号：US5817881A
公开(公告)日：1998-10-06
申请号：US902931
申请日：1997-07-30
IPC分类号： B01J23/881 , B01J27/188 , C07C29/50 , C07C45/33
CPC分类号： C07C29/50 , B01J23/881 , B01J27/188 , C07C45/33
摘要： Alkanes are catalytically oxidized in air or oxygen using iron-substituted polyoxoanions (POAs) of the formula: H.sub.e-z �(n-C.sub.4 H.sub.9).sub.4 N!.sub.z (XM.sub.11 M'O.sub.39).sup.-eThe M' (e.g., iron(III)/iron(II)) reduction potential of the POAs is affected by selection of the central atom X and the framework metal M, and by the number of tetrabutyl-ammonium groups. Decreased Fe(III)/Fe(II) reduction potential has been found to correlate to increased oxidation activity.
摘要翻译： 烷烃在空气或氧气中使用下式的铁取代的聚氧阴离子（POA）催化氧化：He-z [（n-C4H9）4N] z（XM11M'O39）-e M'（例如铁（III）/ 铁（II））还原电位受中心原子X和骨架金属M的选择以及四丁基铵基团的数量的影响。 已经发现Fe（III）/ Fe（II）还原电位的降低与增加的氧化活性相关。
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6.发明授权Process for making codimers of norbornadiene and phenylacetylenes using a cobalt catalyst 失效使用钴催化剂制备降冰片二烯和苯乙炔的共聚物的方法
公开(公告)号：US4132742A
公开(公告)日：1979-01-02
申请号：US842813
申请日：1977-10-17
CPC分类号： C07C2/42 , C07C2103/86 , C07C2531/14 , C07C2531/22 , C07C2531/24
摘要： Novel codimers (I) of norbornadiene and phenylacetylenes and their hydrogenated derivatives (II), having the following structures ##STR1## wherein R is a hydrogen, a phenyl, or a phenyl having alkyl substituents and R.sub.1 is a phenyl or a phenyl having alkyl substituents and processes for preparing both are disclosed. Codimer (II) can be used as a high energy fuel or a diluent for such a fuel. Process for making codimer (I) involves reacting norbornadiene and phenylacetylene or diphenylacetylene with a catalyst system of cobaltic or cobaltous acetylacetonate, 1,2-bisdiphenylphosphino ethane and an alkyl aluminum chloride.
摘要翻译： 降冰片二烯和苯乙炔及其氢化衍生物（II）的新型共聚物（I）及其氢化衍生物（II），其具有以下结构：其中R是氢，苯基或具有烷基取代基的苯基，R 1是具有烷基取代基的苯基或苯基 并公开了制备两者的方法。 Codimer（II）可用作这种燃料的高能燃料或稀释剂。 制备编码（I）的方法包括使降冰片二烯和苯基乙炔或二苯基乙炔与钴或钴乙酰丙酮化合物的催化剂体系，1,2-双二苯基膦基乙烷和烷基氯化铝反应。
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公开(公告)号：US4100216A
公开(公告)日：1978-07-11
申请号：US819445
申请日：1977-07-27
CPC分类号： C07C2/42
摘要： Norbornadiene and isoprene are catalytically codimerized to an olefinic codimer. Used is a three-component homogeneous catalytic system consisting of cobaltic or cobaltous acetylacetonate, 1,2-bisdiphenylphosphino ethane and an alkyl aluminum chloride. The codimer upon hydrogenation forms .beta.-methyltetramethylene nortricyclane having utility as a diluent for a high energy hydrocarbon missile fuel.
摘要翻译： 降冰片二烯和异戊二烯被催化同分异构化成烯属共聚体。 使用由钴或钴乙酰丙酮化合物，1,2-双二苯基膦基乙烷和烷基氯化铝组成的三组分均相催化体系。 加氢时的同分子化形式可用作高能烃类导弹燃料的稀释剂的β-甲基四亚甲基核桃素。
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公开(公告)号：US4859798A
公开(公告)日：1989-08-22
申请号：US211008
申请日：1988-06-24
IPC分类号： B01J27/188 , B01J27/199 , C07C29/50 , C07C45/33
CPC分类号： B01J23/002 , B01J27/188 , B01J27/199 , C07C29/50 , C07C45/33 , B01J2523/00
摘要： Alkanes are oxidized in the liquid phase at relatively low temperatures using heteropolyacids or polyoxoanions promoted with azide or certain metals. Such azide catalysts are also part of the invention.
摘要翻译： 在相对低的温度下，使用杂多酸或用叠氮化物或某些金属促进的聚氧阴离子，在液相中使烷烃氧化。 这种叠氮化物催化剂也是本发明的一部分。
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公开(公告)号：US4201731A
公开(公告)日：1980-05-06
申请号：US933229
申请日：1978-08-14
CPC分类号： C10L1/04 , B01J31/0267 , B01J31/143 , B01J31/2234 , B01J31/2404 , C07C13/68 , C07C2/42 , B01J2531/845 , C07C2103/86 , C07C2531/14 , C07C2531/22 , C07C2531/24 , Y10S149/12
摘要： Norbornadiene and 1,3-pentadiene are catalytically codimerized to an olefinic codimer using a three-component homogeneous catalytic system of cobaltic or cobaltous acetylacetonate, triphenylphosphine and an alkyl aluminum chloride. The codimer, after hydrogenation, has utility as a high energy missile fuel or a diluent for a higher viscous missile fuel.
摘要翻译： 降冰片二烯和1,3-戊二烯使用钴或钴乙酰丙酮化合物的三组分均相催化体系，三苯基膦和烷基氯化铝催化同分异构化成烯属共聚体。 氢化后的同系物可用作高能导弹燃料或用于较高粘度的导弹燃料的稀释剂。
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公开(公告)号：US4916101A
公开(公告)日：1990-04-10
申请号：US279903
申请日：1988-12-05
IPC分类号： B01J23/85 , B01J27/186 , B01J27/188 , B01J27/199 , B01J37/08 , C01B25/16 , C01B25/24 , C01B25/45 , C01B33/00 , C01B33/20 , C01B39/10 , C01G41/00 , C07C211/63
CPC分类号： B01J27/188 , B01J23/85 , B01J37/086 , C01B25/16 , C01B33/00 , C01G41/006 , C01P2006/60
摘要： Polyoxoanions are converted to the corresponding heteropolyacids by conversion to their tetrabutylammonium salt followed by pyrolysis.
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