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    Phosphite-promoted ruthenium-cobalt catalysts for the dealkoxyhydroxymethylation of acetals to form glycol ethers
    71.
    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

    申请人： D. Michael Duggan ,  James E. Lyons ,  Harry K. Myers, Jr.

    发明人： D. Michael Duggan ,  James E. Lyons ,  Harry K. Myers, Jr.

    IPC分类号： B01J31/20 ,  C07C41/01 ,  C07C41/30 ,  C07C43/13

    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。

    Ruthenium-cobalt carbonyl catalysts for the dealkoxyhydroxymethylation of acetals to form glycol ethers
    72.
    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

    申请人： D. Michael Duggan ,  Harry K. Myers, Jr. ,  James E. Lyons

    发明人： D. Michael Duggan ,  Harry K. Myers, Jr. ,  James E. Lyons

    IPC分类号： B01J31/20 ,  C07C41/01 ,  C07C41/30 ,  C07C43/13 ,  B01J31/12

    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。

    Catalytic oxidation of propylene to allyl acetate
    73.
    发明授权
    Catalytic oxidation of propylene to allyl acetate 失效
    丙烯催化氧化成乙酸烯丙酯

    公开(公告)号：US4602104A

    公开(公告)日：1986-07-22

    申请号：US722094

    申请日：1985-04-10

    申请人： James E. Lyons ,  George Suld

    发明人： James E. Lyons ,  George Suld

    IPC分类号： C07C67/055 ,  C07C67/05

    CPC分类号： C07C67/055

    摘要： Propylene is oxidized directly to allyl acetate in the presence of acetic acid with air or oxygen in the liquid phase under moderate reaction conditions employing a palladium-on-carbon catalyst which has been pre-treated by activating it with propylene at temperatures of greater than about 50.degree. C., preferably from 60.degree. to 150.degree. C., for a period of time sufficient to form a small but perceptible quantity of said activated catalyst, preferably for at least 10 minutes in the substantial absence of oxygen.

    摘要翻译： 在中等反应条件下，乙酸与乙酸在空气或氧气的存在下，丙烯直接氧化为乙酸烯丙酯，使用钯 - 碳催化剂，该催化剂已经通过丙烯在大于约 50℃，优选60℃至150℃，时间足以形成小但可察觉量的所述活化催化剂，优选在基本上不存在氧气的情况下至少10分钟。

    Process for the oxidation of butenes to linear acetates
    74.
    发明授权
    Process for the oxidation of butenes to linear acetates 失效
    将丁烯氧化成线性乙酸酯的方法

    公开(公告)号：US4602103A

    公开(公告)日：1986-07-22

    申请号：US721627

    申请日：1985-04-10

    申请人： James E. Lyons

    发明人： James E. Lyons

    IPC分类号： C07C67/055 ,  C07C69/16 ,  C07C67/05

    CPC分类号： C07C67/055

    摘要： C.sub.4 olefins comprising cis- and trans-butane-2 and butene-1 may be oxidized to their corresponding mono- and diacetates in the presence of acetic acid and an olefin-activated palladium catalyst under mild conditions. With this catalyst, and depending in part upon the solvent employed, as well as other operating conditions, the formation of linear allylic 1-acetates over the corresponding branched compounds can be favored in order to increase the yield of the corresponding linear 1,4-diacetates. The latter, in turn, may then be converted, for example, to butanediol by known hydrogenation methods.In a similar manner, isobutylene may be converted to a dialcohol.

    摘要翻译： 在温和条件下，在乙酸和烯烃活化的钯催化剂存在下，包含顺式和反式丁烷-2和丁烯-1的C 4烯烃可以被氧化成它们相应的单和二乙酸酯。 使用该催化剂，并且部分取决于所用的溶剂以及其它操作条件，可以有利于在相应的支化化合物上形成线性烯丙基1-乙酸酯，以便提高相应的线性1,4- 二乙酸酯 然后，后者又可以通过已知的氢化方法转化为例如丁二醇。 以类似的方式，异丁烯可以转化为二醇。

    Palladium catalyzed oxy-acetylation of phenyl acetate to meta-acetoxyacetophenone
    75.
    发明授权
    Palladium catalyzed oxy-acetylation of phenyl acetate to meta-acetoxyacetophenone 失效
    钯催化氧乙酰化乙酸苯酯至间 - 乙酰氧基苯乙酮

    公开(公告)号：US4469883A

    公开(公告)日：1984-09-04

    申请号：US262158

    申请日：1981-05-11

    申请人： Chao-Yang Hsu ,  James E. Lyons

    发明人： Chao-Yang Hsu ,  James E. Lyons

    IPC分类号： B01J20060101 ,  C07C20060101 ,  C07C49/825 ,  C07C67/00 ,  C07C67/29 ,  C07C69/14 ,  C07C69/157

    CPC分类号： C07C67/293

    摘要： Acetoxyacetophenone is the predominant product when phenyl acetate, acetic acid and acetic anhydride are reacted in the presence of palladium and a gas mixture containing an inert gas and more than 13 vol. % oxygen. Secondary products are hydroxyacetophenone and phenylene diacetates. The meta isomers predominate when a metal acetate is present in the reaction mixture. Mineral acids cause shift to ortho isomers.

    摘要翻译： 当乙酸，乙酸和乙酸酐在钯和含有惰性气体的气体混合物和大于13体积％的气体混合物存在下反应时，乙酰氧基苯乙酮是主要产物。 ％氧气。 次要产物是羟基苯乙酮和亚苯基二乙酸酯。 当反应混合物中存在金属乙酸盐时，间位异构体占主导地位。 矿物酸会转移到邻位异构体。

    Novel homogeneous transition-metal catalyzed geometric isomerization of cyclic epoxy alcohols
    79.
    发明授权
    Novel homogeneous transition-metal catalyzed geometric isomerization of cyclic epoxy alcohols 失效
    环状环氧醇的新型均相过渡金属催化几何异构化

    公开(公告)号：US4123445A

    公开(公告)日：1978-10-31

    申请号：US523310

    申请日：1974-11-13

    申请人： James E. Lyons

    发明人： James E. Lyons

    IPC分类号： C07D303/14 ,  C07D301/00

    CPC分类号： C07D303/14

    摘要： Geometrical isomerization of cyclic epoxy alcohols such as cis- or trans-1,2-epoxy-3-hydroxycyclohexane may be equlibrated by the use of soluble transition metal complexes having the formulaLxM.sup.n Xywherein L is a neutral ligand such as a phosphine, arsine, stibine, amine, olefin, diene, CO or the like, x is an integer of from 0-6 but when x is 2 or more L may be the same or different; M is a Group VIII metal; n is an integer of from 0-3 and denotes the valence state of the metal; X is an anionic ligand such as hydrogen, chloride, bromide, iodide, lower alkyl, trichlorostanato, cyano or the like; y is an integer of from 0-3 which is equal to n but when y is 2 or 3, X may be the same or different. When n is 0, then x equals at least 1, but when either x or y is 0, then the other integer must be at least 1.

    摘要翻译： 环状环氧醇如顺式或反式-1,2-环氧-3-羟基环己烷的几何异构化可以通过使用具有下式的可溶性过渡金属络合物进行偶联：其中L是中性配体，例如膦，胂， 锑，胺，烯烃，二烯，CO等，x为0-6的整数，但当x为2以上时，L可以相同或不同; M是VIII族金属; n为0-3的整数，表示金属的价态; X是阴离子配体，例如氢，氯，溴，碘，低级烷基，三氯苯磺酰基，氰基等; y是0-3的整数，其等于n，但当y为2或3时，X可以相同或不同。 当n为0时，x等于至少1，但是当x或y为0时，另一个整数必须至少为1。