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11. 发明授权

US4426537A Preparation of carboxylic acids by carbonylation of alcohols 失效
标题翻译：通过羰基化醇制备羧酸
公开(公告)号：US4426537A
公开(公告)日：1984-01-17
申请号：US260811
申请日：1981-05-05
申请人： Jean Gauthier-Lafaye , Robert Perron
发明人： Jean Gauthier-Lafaye , Robert Perron
IPC分类号： B01J23/00 , B01J27/00 , B01J27/20 , B01J31/00 , C07C51/00 , C07C51/12 , C07C53/00 , C07C53/08 , C07C67/00
CPC分类号： C07C51/12
摘要： Carboxylic acids having the structural formula R.sup.1 COOH, wherein R.sup.1 is a linear, branched or cyclic chain alkyl radical of from 1 to 6 carbon atoms or a phenyl-C.sub.n H.sub.2n -radical wherein 1.ltoreq.n.ltoreq.6, are prepared by carbonylating an alcohol having the formula R.sup.1 -OH with carbon monoxide in liquid phase, in the presence of a catalytically effective amount of nickel and an alkyl or acyl halide promoter therefor, at a temperature of at least about 120.degree. C. and under a total pressure of less than 200 bars, and said carbonylation being carried out in the presence of at least one lanthanide salt, and in an initial carboxylic acid reaction medium having the formula R.sup.2 -COOH, wherein R.sup.2 is defined as was R.sup.1 above, and further wherein R.sup.1 and R.sup.2 may be the same or different.
摘要翻译：具有结构式R 1 COOH的羧酸，其中R 1是具有1至6个碳原子的直链，支链或环状链烷基或苯基-C n H 2n - ，其中n 1 = n 6，是通过羰基化具有式R 1 -OH的醇与一氧化碳在液相中，在催化有效量的镍和其烷基或酰卤促进剂存在下，在至少约120℃的温度和总压力并且所述羰基化在至少一种镧系元素盐存在下进行，并且在具有式R 2 -COOH的初始羧酸反应介质中进行，其中R2定义为R 1，其中R 1和 R2可以相同或不同。

12. 发明授权

US06395927B1 Method for preparing acetic acid and/or methyl acetate by isomerization and carbonylation 失效
标题翻译：通过异构化和羰基化制备乙酸和/或乙酸甲酯的方法
公开(公告)号：US06395927B1
公开(公告)日：2002-05-28
申请号：US09142175
申请日：1998-09-23
申请人： Carl Patois , Robert Perron , Daniel Thiebaut
发明人： Carl Patois , Robert Perron , Daniel Thiebaut
IPC分类号： C07C5110
CPC分类号： C07C51/353 , C07C67/293 , C07C53/08 , C07C69/14
摘要： A method for preparing acetic acid and/or methyl acetate by simultaneous isomerization and carbonylation reactions. A reaction mixture is provided containing at least one reagent which provides formyl radicals and at least one further reagent which provides methyl radicals, together with water in an amount of at most 5% by weight, carbon monoxide at a partial pressure between 0.1·105 Pa and 25·105 Pa, a solvent and a catalytic system which contains at least one halogenated promoter and at least one iridium-based compound. In a typical reaction mixture, methyl formate is isomerized to form acetic acid according to the reaction: HCOOCH3CH3COOH while methanol undergoes carbonylation to form acetic acid according to the reaction: CH3OH+COCH3COOH The reagent which provides the formyl radicals is kept at or below 20% by weight of the reaction mixture, while the molar ratio of methyl radicals to formyl radicals in the mixture is greater than 1.
摘要翻译：通过同时异构化和羰基化反应制备乙酸和/或乙酸甲酯的方法。提供了含有至少一种提供甲酰基的试剂和至少一种其它试剂的反应混合物，所述试剂在0.1.105Pa的分压下，以至多5重量％的量与水一起提供一氧化碳和25.105Pa，溶剂和含有至少一种卤化助催化剂和至少一种铱基化合物的催化体系。在典型的反应混合物中，甲酸甲酯根据反应异构化形成乙酸，而甲醇根据反应进行羰基化形成乙酸：提供甲酰基的试剂保持在或低于20％（重量）反应混合物中甲基与甲酰基的摩尔比大于1。

13. 发明授权

US5625096A Hydroxycarbonylation of butadiene 失效
标题翻译：丁二烯的羟基羰基化
公开(公告)号：US5625096A
公开(公告)日：1997-04-29
申请号：US325077
申请日：1994-10-19
申请人： Phillipe Denis , Carl Patois , Robert Perron
发明人： Phillipe Denis , Carl Patois , Robert Perron
IPC分类号： B01J31/22 , C07B61/00 , C07C51/14 , C07C57/03
CPC分类号： C07C51/14
摘要： Butadiene or derivative thereof is selectively hydroxycarbonylated into at least one pentenoic acid (the pentenoic acids are themselves facilely converted, via hydroxycarbonylation, into adipic acid, a basic starting material for the production of nylon 66 polymers), by reacting same with carbon monoxide and water, at a pressure greater than atmospheric, in the presence of a catalytically effective amount of (1) a palladium catalyst which is soluble in the medium of reaction and (2) crotyl chloride, the amount of the crotyl chloride being at least two mol thereof per mole of palladium values and said palladium values/crotyl chloride at least in part comprising a palladium/crotyl pi-complex, and the amount of water present in the medium of reaction being no greater than about 20% by weight thereof.
摘要翻译：丁二烯或其衍生物选择性羟基羰基化成至少一种戊烯酸（戊烯酸本身通过羟基羰基化方便地转化成己二酸，用于生产尼龙66聚合物的基本原料），通过与一氧化碳和水反应在大于大气压的压力下，在催化有效量的（1）可溶于反应介质的钯催化剂和（2）巴洛西氯的存在下，巴淡罗丁氯的量为至少2摩尔至少部分包含钯/巴豆基pi复合物，并且反应介质中存在的水的量不大于其约20重量％。

14. 发明授权

US5081292A Preparation of .beta., .gamma.-unsaturated carboxylic acids 失效
标题翻译：（BETA），（氨基） - 脲基羧酸的制备
公开(公告)号：US5081292A
公开(公告)日：1992-01-14
申请号：US516737
申请日：1990-04-30
申请人： Philippe Denis , Jean Jenck , Robert Perron
发明人： Philippe Denis , Jean Jenck , Robert Perron
IPC分类号： B01J27/13 , B01J31/04 , B01J31/24 , C07B61/00 , C07C51/12 , C07C57/02 , C07C57/13 , C07C57/30 , C07C61/08
CPC分类号： C07C51/12
摘要： .beta., .gamma.-Unsaturated carboxylic acids, e.g., 3-hexene-1,6-dioic acid, are selectively prepared by carbonylating (with carbon monoxide) an allyl alcohol, e.g., a butenediol, at an elevated temperature and under superatmospheric pressure, in the presence of a catalytically effective amount of a palladium-based catalyst and at least one quaternary onium chloride of one of the Group VB elements nitrogen or phosphorus, such element being tetracoordinated via carbon atoms and with the proviso that such nitrogen atom may be coordinated to two pentavalent phosphorus atoms.
摘要翻译： β，γ-不饱和羧酸，例如3-己烯-1,6-二酸，通过在升高的温度和超大气压下羰基化（用一氧化碳）烯丙醇，例如丁烯二醇来选择性地制备，存在催化有效量的钯基催化剂和至少一种VB族元素氮或磷之一的季铵氯化物，该元素通过碳原子四配位，条件是这样的氮原子可以配位到两个五价磷原子。

15. 发明授权

US5026900A Process for the preparation of dialkyl malonates 失效
标题翻译：制备丙二酸二烷基酯的方法
公开(公告)号：US5026900A
公开(公告)日：1991-06-25
申请号：US353612
申请日：1989-05-18
申请人： Philippe Coste , Philippe Leconte , Robert Perron , Michel Baudoin
发明人： Philippe Coste , Philippe Leconte , Robert Perron , Michel Baudoin
IPC分类号： B01J31/20 , C07B61/00 , C07C67/36 , C07C69/38
CPC分类号： C07C69/38 , Y02P20/584
摘要： A process for the preparation of alkyl malonates by carbonylation of chloroacetate in the presence of a carbonyl source, a carbonylation catalyst, such as chromium carbonyl and an aliphatic alcohol, this reaction being carried out in a two-phase liquid medium.A process for recycling the catalyst also forms part of the invention.
摘要翻译：在羰基源，羰基化催化剂如羰基铬和脂肪醇的存在下羰基化氯乙酸酯制备烷基丙二酸酯的方法，该反应在两相液体介质中进行。用于再循环催化剂的方法也构成本发明的一部分。

16. 发明授权

US4618460A Process for the preparation of acetic anhydride 失效
标题翻译：制备乙酸酐的方法
公开(公告)号：US4618460A
公开(公告)日：1986-10-21
申请号：US585625
申请日：1984-03-07
申请人： Jean Gauthier-Lafaye , Robert Perron
发明人： Jean Gauthier-Lafaye , Robert Perron
IPC分类号： C07C53/12 , B01J31/00 , C07B61/00 , C07C51/00 , C07C51/56 , C07C67/00
CPC分类号： C07C51/56
摘要： The invention relates to a process for the preparation of acetic anhydride by carbonylation. In the process, carbon monoxide is reacted with methyl acetate in the liquid phase, in a carboxylic acid, in the presence of an effective amount of nickel, methyl iodide, an ionic iodide selected from the group consisting of quaternary ammonium iodides, quaternary phosphonium iodides, sodium iodide, potassium iodide and cesium iodide, and a co-catalyst selected from the group consisting of lithium salts and alkaline earth metal salts.
摘要翻译：本发明涉及通过羰基化制备乙酸酐的方法。在该过程中，一氧化碳与乙酸甲酯在液相中，在羧酸中，在有效量的镍，碘甲烷，碘化季铵，季碘化鏻，，碘化钠，碘化钾和碘化铯，以及选自锂盐和碱土金属盐的助催化剂。

17. 发明授权

US4609504A Process for the preparation of acetic anhydride 失效
标题翻译：制备乙酸酐的方法
公开(公告)号：US4609504A
公开(公告)日：1986-09-02
申请号：US331828
申请日：1981-12-17
申请人： Jean Gauthier-Lafaye , Robert Perron
发明人： Jean Gauthier-Lafaye , Robert Perron
IPC分类号： C07C53/12 , B01J31/00 , C07B61/00 , C07C51/00 , C07C51/56 , C07C67/00
CPC分类号： C07C51/56
摘要： The invention relates to a process for the preparation of acetic anhydride by carbonylation. In the process, carbon monoxide is reacted with methyl acetate in an anhydrous medium, in the liquid phase, in the presence of an effective amount of nickel, methyl iodide, a quaternary ammonium or quaternary phosphonium iodide and a lithium salt, the reaction medium initially containing acetic anhydride, if desired.
摘要翻译：本发明涉及通过羰基化制备乙酸酐的方法。在该过程中，一氧化碳与无水介质中的乙酸甲酯在液相中，在有效量的镍，甲基碘，季铵或季碘化鏻和锂盐的存在下反应，反应介质最初如果需要，含有乙酸酐。

18. 发明授权

US4500474A Carbonylation of methyl acetate 失效
标题翻译：乙酸甲酯的羰基化
公开(公告)号：US4500474A
公开(公告)日：1985-02-19
申请号：US387467
申请日：1982-06-11
申请人： Jean Gauthier-Lafaye , Robert Perron
发明人： Jean Gauthier-Lafaye , Robert Perron
IPC分类号： C07C53/12 , B01J31/00 , C07B61/00 , C07C51/00 , C07C51/54 , C07C51/56 , C07C67/00 , C07C51/12
CPC分类号： C07C51/56
摘要： Methyl acetate is carbonylated, advantageously to acetic anhydride, in a homogeneous liquid phase, in a virtually anhydrous reaction medium, in the presence of: (a) a cobalt source, (b) a ruthenium source, (c) an ionic iodide of the formula: A.sup.m+ I.sub.m.sup.- in which A.sup.m+ is a nitrogen group quaternary onium cation, an alkali metal or alkaline earth metal cation, or a lanthanide or actinide group metal cation, (c') if appropriate, a carboxylate of the formula: A'.sup.n+ (OCOR).sub.n.sup.-, in which n is 1 or 2 and A'.sup.n+ is defined as was A.sup.m+, with A'.sup.n+ and A.sup.m+ either being the same or different, and R is an alkyl, aralkyl or aryl radical having a maximum of 8 carbon atoms, and (d) hydrogen, the total amount of halogen compounds present in the carbonylation reaction medium (expressed in gram atoms of halogen and designated by X.sub.T) being such that the atomic ratio X.sub.T /(m.A.sup.m+ +n.A'.sup.n+) is less than or equal to 1.
摘要翻译：在（a）钴源，（b）钌源的存在下，在几乎无水的反应介质中，乙酸甲酯在均相液相中有利地羰基化，有利地为乙酸酐，（c）式：Am + Im-其中Am +是氮基季鎓阳离子，碱金属或碱土金属阳离子，或镧系元素或锕系金属阳离子，（c'）如果合适，下式的羧酸酯：A' n +（OCOR）n-，其中n为1或2，A'n +定义为Am +，其中A'n +和Am +相同或不同，R为具有最大值的烷基，芳烷基或芳基 8个碳原子和（d）氢，存在于羰基化反应介质中的卤素化合物的总量（用卤素的克原子表示，由XT表示）使原子比XT /（m.Am ++ n .A'n +）小于或等于1。

19. 发明授权

US5973197A Process for the preparation of carboxylic acids by carbonylation in the presence of rhodium 失效
标题翻译：在铑存在下通过羰基化制备羧酸的方法
公开(公告)号：US5973197A
公开(公告)日：1999-10-26
申请号：US836817
申请日：1997-04-21
申请人： Philippe Denis , Robert Perron , Joel Schwartz
发明人： Philippe Denis , Robert Perron , Joel Schwartz
IPC分类号： B01J23/46 , C07B41/08 , C07B61/00 , C07C51/12 , C07C51/44 , C07C53/00
CPC分类号： C07C51/12
摘要： A method for preparing carboxylic acids by carbonylating a reagent, particularly an alcohol, in the presence of a rhodium catalyst. According to the method, the liquid phase reaction is carried out in a first zone in the presence of a rhodium catalyst, and the resulting reaction mixture is partially vaporised in a second zone. The vaporised fraction containing the carboxylic acid is later purified and the unvaporised liquid fraction containing the catalyst is recirculated to the first zone. The method is charactracterised in that said unvaporised fraction is contacted with carbon monoxide in such a way that this compound is not returned to the second zone.
摘要翻译：一种在铑催化剂存在下羰基化试剂，特别是醇制备羧酸的方法。根据该方法，在铑催化剂存在下，在第一区域中进行液相反应，所得反应混合物在第二区域部分蒸发。随后纯化含有羧酸的蒸发级分，并将含有催化剂的未汽化的液体馏分再循环到第一区。该方法的特征在于，所述未蒸发的级分与一氧化碳接触，使得该化合物不会返回到第二区。

20. 发明授权

US5625094A Rhodium/iridium catalyzed synthesis of carboxylic acids or esters thereof 失效
标题翻译：铑/铱催化合成羧酸或其酯
公开(公告)号：US5625094A
公开(公告)日：1997-04-29
申请号：US450137
申请日：1995-05-26
申请人： Dominique Nobel , Robert Perron , Philippe Denis
发明人： Dominique Nobel , Robert Perron , Philippe Denis
IPC分类号： B01J23/46 , B01J27/13 , B01J31/22 , C07B61/00 , C07C51/10 , C07C51/12 , C07C53/08 , C07C53/122 , C07C53/124 , C07C53/126 , C07C67/36 , C07C67/37 , C07C69/14 , C07C69/24
CPC分类号： C07C51/12 , C07C67/36
摘要： Process for the preparation of a carboxylic acid or ester thereof. The process includes reacting at least one alcohol, alkyl or aryl halide, ether or ester, with carbon monoxide, in the presence of a catalytically effective amount of at least one rhodium compound or rhodium metal, at least one iridium compound or iridium metal, or at least one mixed rhodium/iridium compound, and at least one halogen-containing promoter therefor.
摘要翻译：制备羧酸或其酯的方法。该方法包括在催化有效量的至少一种铑化合物或铑金属，至少一种铱化合物或铱金属的存在下使至少一种醇，烷基或芳基卤化物，醚或酯与一氧化碳反应，或至少一种混合的铑/铱化合物和至少一种含卤素的促进剂。

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