公开(公告)号：EP0902786A1

公开(公告)日：1999-03-24

申请号：EP97923475.0

申请日：1997-04-28

申请人： ALBEMARLE CORPORATION

发明人： SENARATNE, K., Pushpananda, A.

IPC分类号： C07F9

CPC分类号： C07F9/5077 ,  C07F9/5018

摘要： Phosphines having two aryl groups and one alkyl-substituted cycloalkyl group bonded to a phosphorus atom are formed by reacting an alkali metal diarylphosphide with a monoalkyl- or polyalkyl-substituted cycloalkyl mesylate or tosylate in which an alkyl group is in the 2-position, in a liquid reaction medium in which these reactants are soluble. This process avoids complications associated with prior known process technology for producing such phosphines. The phosphines are useful as ligands for making noble metal catalysts.

摘要翻译： 具有与磷原子键合的两个芳基和一个烷基取代的环烷基的膦是通过使碱金属二芳基膦与其中烷基位于2-位的单烷基或多烷基取代的甲磺酸环烷基酯或甲苯磺酸酯在 这些反应物可溶于其中的液体反应介质。 该过程避免了用于生产这种膦的现有已知工艺技术的并发症。 膦可用作制备贵金属催化剂的配体。

公开(公告)号：EP0902786B1

公开(公告)日：2005-06-22

申请号：EP97923475.4

申请日：1997-04-28

申请人： ALBEMARLE CORPORATION

发明人： SENARATNE, K., Pushpananda, A.

IPC分类号： C07F9/50

CPC分类号： C07F9/5077 ,  C07F9/5018

公开(公告)号：EP0970094B1

公开(公告)日：2003-01-15

申请号：EP98908508.9

申请日：1998-02-09

申请人： ALBEMARLE CORPORATION

发明人： WU, Tse-Chong ,  SENARATNE, K., Pushpananda, A.

IPC分类号： C07F9/50

CPC分类号： C07F9/5095

摘要： A process for the purification of trihydrocarbylphosphine having at least one aryl group and at least one alkyl or cycloalkyl group in the molecule, from a reaction mass comprising the trihydrocarbylphosphine, the process comprising crystallizing the reaction mass using a solvent consisting essentially of methanol. The process provides for the unexpectedly efficient production of trihydrocarbylphosphine compounds having purities of at least 97 mol%, and more preferably at least about 99 mol%. Another embodiment of the invention is neomenthyldiphenylphosphine having a purity of at least 97 mol% produced by crystallizing neomenthyldiphenylphosphine having a purity of less than 97 mol% using a solvent consisting essentially of methanol.

摘要翻译： 从包含三烃基膦的反应物质中纯化在分子中具有至少一个芳基和至少一个烷基或环烷基的三烃基膦的方法，该方法包括使用基本上由甲醇组成的溶剂使反应物质结晶。 该方法提供了具有至少97摩尔％，更优选至少约99摩尔％纯度的三烃基膦化合物的出乎意料的有效生产。 本发明的另一个实施方案是新羟基二苯基膦，其纯度至少为97摩尔％，其通过使用基本上由甲醇组成的溶剂结晶具有小于97摩尔％纯度的新薄荷基二苯基膦产生。

公开(公告)号：EP0979210A1

公开(公告)日：2000-02-16

申请号：EP98919922.9

申请日：1998-04-23

申请人： ALBEMARLE CORPORATION

发明人： SENARATNE, K., Pushpananda, A. ,  ORIHUELA, Felix, M. ,  MALCOLM, Arcelio, J.

IPC分类号： C01G9/04 ,  C07C17/16

CPC分类号： C07C17/16 ,  C01G9/04 ,  Y02P20/582

摘要： Gaseous anhydrous hydrogen chloride is introduced into an aqueous solution of zinc chloride under conditions effective to produce a more efficient Lucas reagent than a Lucas reagent made by mixing solid, anhydrous zinc chloride with 38 % hydrochloric acid. For example, the reaction rate of such Lucas reagent with levo-menthol is much faster and requires a much shorter reaction period than Lucas reagent formed in the conventional manner from anhydrous, solid zinc chloride and concentrated (38 %) hydrochloric acid. Also, the conversion to levo-menthyl chloride was higher when using Lucas reagent formed using gaseous anhydrous hydrogen chloride and aqueous zinc chloride solution. Also, Lucas reagent made in this manner is highly amenable to recycling, and requires only addition thereto of hydrogen chloride to replenish the catalyst for an ensuing run.

公开(公告)号：EP0889896A1

公开(公告)日：1999-01-13

申请号：EP97916918.0

申请日：1997-03-24

申请人： ALBEMARLE CORPORATION

发明人： SENARATNE, K., Pushpananda, A. ,  MALCOLM, Arcelio, J. ,  ORIHUELA, Felix, M. ,  ELNAGAR, Hassan, Y.

IPC分类号： C07F9

CPC分类号： C07F9/5077

摘要： Partially sterically-hindered cycloalkyl chlorides are reacted with lithium diarylphosphides in inert liquid hydrocarbon reaction media to form cycloalkyldiarylphosphines. Aryl lithium is coproduced. The process makes it possible to avoid, or at least substantially eliminate, the interaction with or cleavage of cyclic ether reaction media such as tetrahydrofuran, previously the solvent of choice for conducting this type of reaction. Also during the conduct of the present process the chloro-substituted cycloalkane does not undergo any appreciable reaction with the coproduced aryl lithium as it is formed. Thus improvements both in yield and quality of the cycloalkyldiarylphosphine product are made possible. A comprehensive three-step process for converting triarylphosphine to cycloalkyldiarylphosphine is also described.

摘要翻译： 部分空间位阻的环烷基氯化物与锂二芳基磷化物在惰性液体烃反应介质中反应形成环烷基二芳基膦。 芳基锂是联产的。 该方法可以避免或者至少基本上消除环醚反应介质如四氢呋喃与预先用于进行这类反应的溶剂的相互作用或裂解。 在进行本发明方法的过程中，氯取代的环烷烃在形成时与联产生的芳基锂不发生明显的反应。 因此，环烷基二芳基膦产物的收率和质量的改善成为可能。 还描述了将三芳基膦转化为环烷基二芳基膦的综合三步法。

公开(公告)号：EP0889895B1

公开(公告)日：2001-11-14

申请号：EP97916917.4

申请日：1997-03-24

申请人： ALBEMARLE CORPORATION

发明人： SENARATNE, K., Pushpananda, A. ,  MALCOLM, Arcelio, J. ,  ORIHUELA, Felix, M. ,  ELNAGAR, Hassan, Y.

IPC分类号： C07F9/50

CPC分类号： C07F9/5077

公开(公告)号：EP0889896B1

公开(公告)日：2001-10-24

申请号：EP97916918.2

申请日：1997-03-24

申请人： ALBEMARLE CORPORATION

发明人： SENARATNE, K., Pushpananda, A. ,  MALCOLM, Arcelio, J. ,  ORIHUELA, Felix, M. ,  ELNAGAR, Hassan, Y.

IPC分类号： C07F9/50

CPC分类号： C07F9/5077

公开(公告)号：EP0970094A1

公开(公告)日：2000-01-12

申请号：EP98908508.9

申请日：1998-02-09

申请人： ALBEMARLE CORPORATION

发明人： WU, Tse-Chong ,  SENARATNE, K., Pushpananda, A.

IPC分类号： C07F9/50

CPC分类号： C07F9/5095

摘要： A process for the purification of trihydrocarbylphosphine having at least one aryl group and at least one alkyl or cycloalkyl group in the molecule, from a reaction mass comprising the trihydrocarbylphosphine, the process comprising crystallizing the reaction mass using a solvent consisting essentially of methanol. The process provides for the unexpectedly efficient production of trihydrocarbylphosphine compounds having purities of at least 97 mol%, and more preferably at least about 99 mol%. Another embodiment of the invention is neomenthyldiphenylphosphine having a purity of at least 97 mol% produced by crystallizing neomenthyldiphenylphosphine having a purity of less than 97 mol% using a solvent consisting essentially of methanol.

摘要翻译： 从包含三烃基膦的反应物质中纯化在分子中具有至少一个芳基和至少一个烷基或环烷基的三烃基膦的方法，该方法包括使用基本上由甲醇组成的溶剂使反应物质结晶。 该方法提供了具有至少97摩尔％，更优选至少约99摩尔％纯度的三烃基膦化合物的出乎意料的有效生产。 本发明的另一个实施方案是新羟基二苯基膦，其纯度至少为97摩尔％，其通过使用基本上由甲醇组成的溶剂结晶具有小于97摩尔％纯度的新薄荷基二苯基膦产生。

公开(公告)号：EP0889895A1

公开(公告)日：1999-01-13

申请号：EP97916917.0

申请日：1997-03-24

申请人： ALBEMARLE CORPORATION

发明人： SENARATNE, K., Pushpananda, A. ,  MALCOLM, Arcelio, J. ,  ORIHUELA, Felix, M. ,  ELNAGAR, Hassan, Y.

IPC分类号： C07F9

CPC分类号： C07F9/5077

摘要： By reacting certain partially sterically-hindered chloro-substituted cycloalkanes with sodium and/or potassium diarylphosphides in an ether reaction medium, not only are useful cycloalkyldiarylphosphines produced, but in addition the chloro-substituted cycloalkane does not undergo any appreciable reaction with the coproduced aryl sodium and/or aryl potassium as it is formed. Moreover, the process makes it possible to avoid or at least to greatly reduce interaction with or cleavage of cyclic ether reaction media such as tetrahydrofuran. Thus the process makes possible improvements both in yield and quality of the cycloalkyldiarylphosphite product. A two-stage process conducted in an ether reaction medium is also described. In the first stage the sodium and/or potassium diarylphosphine reactant is produced by reaction between sodium and/or potassium and triarylphosphine.

摘要翻译： 通过在醚反应介质中使某些部分空间位阻的氯取代的环烷烃与二芳基磷酸钠和/或钾反应，不仅可以制备有用的环烷基二芳基膦，而且氯取代的环烷烃不会与共产生的芳基钠发生任何显着的反应 和/或芳基钾，因为它形成。 此外，该方法可避免或至少大大减少环醚反应介质如四氢呋喃的相互作用或裂解。 因此该方法可以在环烷基二芳基亚磷酸酯产物的产率和质量方面进行改进。 还描述了在醚反应介质中进行的两阶段过程。 在第一阶段中，钠和/或钾二芳基膦反应物通过钠和/或钾与三芳基膦之间的反应产生。