公开(公告)号：US08703994B2

公开(公告)日：2014-04-22

申请号：US13559011

申请日：2012-07-26

申请人： Thomas Schaub ,  Rocco Paciello ,  Marek Pazicky ,  Giuseppe Fachinetti ,  Debora Preti

发明人： Thomas Schaub ,  Rocco Paciello ,  Marek Pazicky ,  Giuseppe Fachinetti ,  Debora Preti

IPC分类号： C07C69/02 ,  C07C67/00 ,  C07C233/00

CPC分类号： C07C231/10 ,  C07C67/36 ,  C07C233/03 ,  C07C69/06

摘要： A process for preparing carboxylic acid derivatives of the formula H—(C═O)—R, R is OR1 or NR2R3, R1 is optionally substituted C1-C15-alkyl, C5-C10-cycloalkyl, C5-C10-heterocyclyl, C5-C10-aryl or C5-C10-heteroaryl, substituents are C1-C15-alkyl, C1-C6-alkoxy, C5-C10-cycloalkyl or C5-C10-aryl; R2 and R3 are independently hydrogen or optionally substituted C1-C15-alkyl, C5-C10 cycloalkyl, C5-C10-heterocyclyl, C5-C10-aryl or C5-C10-heteroaryl, substituents are selected from the group consisting of C1-C15-alkyl, C5-C10-cycloalkyl and C5-C10-aryl or R2 and R3 together with the nitrogen atom form a five- or six-membered ring which optionally comprises one or more heteroatoms selected from O, S and N and bearing the substituent R4, R4 is hydrogen or C1-C6-alkyl; by reacting a reaction mixture comprising carbon dioxide, hydrogen and an alcohol of the formula R1—OH or an amine of the formula NHR2R3 in the presence of a catalyst comprising gold at a pressure from 0.2 to 30 MPa and a temperature from 20 to 200° C. in a hydrogenation reactor.

摘要翻译： 制备式H-（C = O）-R的羧酸衍生物的方法，R是OR 1或NR 2 R 3，R 1是任选取代的C 1 -C 15 - 烷基，C 5 -C 10 - 环烷基，C 5 -C 10 - 杂环基， C 10 - 芳基或C 5 -C 10 - 杂芳基，取代基是C 1 -C 15 - 烷基，C 1 -C 6 - 烷氧基，C 5 -C 10 - 环烷基或C 5 -C 10 - 芳基; R 2和R 3独立地为氢或任选取代的C 1 -C 15 - 烷基，C 5 -C 10环烷基，C 5 -C 10 - 杂环基，C 5 -C 10 - 芳基或C 5 -C 10 - 杂芳基，取代基选自C 1 -C 15 - 烷基，C 5 -C 10 - 环烷基和C 5 -C 10 - 芳基或R 2和R 3与氮原子一起形成五元或六元环，其任选地包含一个或多个选自O，S和N的杂原子并带有取代基R4 R4是氢或C1-C6-烷基; 在包含金的催化剂的存在下，在0.2〜30MPa的压力和20〜200℃的温度下，使包含二氧化碳，氢气和式R 1 -OH的醇或式NHR 2 R 3的胺的反应混合物反应， C.在氢化反应器中。

公开(公告)号：US20120232309A1

公开(公告)日：2012-09-13

申请号：US13415174

申请日：2012-03-08

申请人： Thomas SCHAUB ,  Boris Buschhaus ,  Marion Kristina Brinks ,  Mathias Schelwies ,  Rocco Paciello ,  Johann-Peter Melder ,  Martin Merger

发明人： Thomas SCHAUB ,  Boris Buschhaus ,  Marion Kristina Brinks ,  Mathias Schelwies ,  Rocco Paciello ,  Johann-Peter Melder ,  Martin Merger

IPC分类号： C07C209/16 ,  C07C211/02

CPC分类号： C07C213/02 ,  C07C215/08 ,  C07C217/08

摘要： Preparing a primary amine by alcohol amination of alcohol with ammonia and elimination of water includes reacting, in a homogeneously catalyzed reaction, a mixture of alcohol, ammonia, nonpolar solvent, and catalyst, in a liquid phase, to obtain a product mixture. The process then includes phase separating the product mixture into a polar product phase and a nonpolar product phase, and separating off the nonpolar product phase. At least some of the nonpolar phase returns to the homogenously catalyzed reaction. The process further includes separating off amination product from the polar product phase. At least some of the catalyst is in the nonpolar phase, and the catalyst accumulates in the nonpolar phase.

摘要翻译： 通过醇与醇的氨基化反应制备伯胺并除去水包括在均相催化的反应中，将醇，氨，非极性溶剂和催化剂的混合物在液相中反应，得到产物混合物。 然后，该方法包括将产物混合物相分离成极性产物相和非极性产物相，并将非极性产物相分离。 至少一些非极性相返回均匀催化反应。 该方法还包括从极性产物相分离胺化产物。 至少一些催化剂处于非极性相，并且催化剂积聚在非极性相中。

公开(公告)号：US20120022290A1

公开(公告)日：2012-01-26

申请号：US13171928

申请日：2011-06-29

申请人： Thomas Schaub ,  Donata Maria Fries ,  Rocco Paciello ,  Klaus-Dieter Mohl ,  Martin Schäfer ,  Stefan Rittinger ,  Daniel Schneider

发明人： Thomas Schaub ,  Donata Maria Fries ,  Rocco Paciello ,  Klaus-Dieter Mohl ,  Martin Schäfer ,  Stefan Rittinger ,  Daniel Schneider

IPC分类号： C07C51/15

CPC分类号： C07C51/44 ,  C07C51/15 ,  C07C51/48 ,  C07C53/02

摘要： A process for preparing formic acid by reaction of carbon dioxide (1) with hydrogen (2) in a hydrogenation reactor (I) in the presence of a catalyst comprising an element of group 8, 9 or 10 of the Periodic Table, a tertiary amine comprising at least 12 carbon atoms per molecule and a polar solvent comprising one or more monoalcohols selected from among methanol, ethanol, propanols and butanols, to form formic acid/amine adducts as intermediates which are subsequently thermally dissociated, where the work-up of the output (3) from the hydrogenation reactor (I) is carried out by addition of water so as to increase the distribution coefficient of the catalyst between the upper phase (4) and the lower phase.

摘要翻译： 在含有元素周期表第8,9,10族元素的催化剂存在下，在氢化反应器（I）中，通过二氧化碳（1）与氢气（2）的反应制备甲酸的方法， 每分子含有至少12个碳原子的极性溶剂和包含一种或多种选自甲醇，乙醇，丙醇和丁醇的一元醇的极性溶剂，以形成甲酸/胺加合物作为随后热解离的中间体，其中后处理 通过加入水进行加氢反应器（I）的输出（3），以增加催化剂在上相（4）和下相之间的分配系数。

公开(公告)号：US20110028746A1

公开(公告)日：2011-02-03

申请号：US12934743

申请日：2009-03-25

申请人： Jens Rudolph ,  Joachim Schmidt-Leithoff ,  Rocco Paciello ,  Bernhard Breit ,  Thomas Smejkal

发明人： Jens Rudolph ,  Joachim Schmidt-Leithoff ,  Rocco Paciello ,  Bernhard Breit ,  Thomas Smejkal

IPC分类号： C07C45/49 ,  C07C319/12 ,  C07F7/08 ,  C07C51/14 ,  C07C269/06 ,  C07C67/36

CPC分类号： C07C45/50 ,  B01J31/2404 ,  B01J2231/321 ,  B01J2531/004 ,  C07C67/29 ,  C07C2601/14 ,  C07F7/1892 ,  C07C47/228 ,  C07C47/11 ,  C07C49/185 ,  C07C47/277 ,  C07C47/21 ,  C07C47/198 ,  C07C47/02 ,  C07C69/78

摘要： The present invention relates to a process for preparing aldehydes by reacting an α,β-unsaturated carboxylic acid or a salt thereof with carbon monoxide and hydrogen in the presence of a catalyst comprising at least one complex of a metal of transition group VIII of the Periodic Table of the Elements with at least one compound of the formula (I), where Pn is pnicogen; W is a divalent bridging group having from 1 to 8 bridge atoms between the flanking bonds; R1 is a functional group capable of forming at least one intermolecular, noncovalent bond with the —X(═O)OH group of the compound of the formula (I); R2, R3 are each in each case optionally substituted alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or together with the pnicogen atom and together with the groups Y2 and Y3 if present form an optionally fused and optionally substituted 5- to 8-membered heterocycle; a, b and c are each 0 or 1; and Y1,2,3 are each, independently of one another, O, S, NRa or SiRbRc, where Ra,b,c are each H or in each case optionally substituted alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; and the use of the above-described catalyst for the decarboxylative hydroformylation of α,β-unsaturated carboxylic acids.

摘要翻译： 本发明涉及一种通过使α-，β-不饱和羧酸或其盐与一氧化碳和氢气在催化剂存在下反应来制备醛的方法，所述催化剂包含至少一种式 具有式（I）的至少一种化合物的元素周期表，其中Pn是pnicogen; W是在侧翼键之间具有1至8个桥原子的二价桥连基团; R1是能够与式（I）化合物的-X（= O）OH基团形成至少一个分子间，非共价键的官能团; R2，R3各自为任选取代的烷基，环烷基，杂环烷基，芳基或杂芳基，或与pnicogen原子一起并与Y2和Y3基团一起形成任选稠合的和任选取代的5-至8-元杂环; a，b和c各自为0或1; 其中R a，b，c各自为H，或者在每种情况下均为任选取代的烷基，环烷基，杂环烷基，芳基或杂芳基;其中R 1和R 2各自独立地为O，S，NR a或SiR b R c。 以及使用上述催化剂进行α，β-不饱和羧酸的脱羧加氢甲酰化反应。

公开(公告)号：US20100331573A1

公开(公告)日：2010-12-30

申请号：US12823338

申请日：2010-06-25

申请人： Thomas Schaub ,  Rocco Paciello ,  Klaus-Dieter Mohl ,  Daniel Schneider ,  Martin Schäfer ,  Stefan Rittinger

发明人： Thomas Schaub ,  Rocco Paciello ,  Klaus-Dieter Mohl ,  Daniel Schneider ,  Martin Schäfer ,  Stefan Rittinger

IPC分类号： C07C51/44

CPC分类号： C07C51/02 ,  C07C51/41 ,  C07C51/44 ,  C07C53/02 ,  C07C53/06

摘要： Process for preparing formic acid by hydrogenation of carbon dioxide in the presence of a catalyst comprising an element of group 8, 9 or 10 of the Periodic Table, a tertiary amine and a polar solvent at a pressure of from 0.2 to 30 MPa abs and a temperature of from 20 to 200° C. to form two liquid phases, separation of the two liquid phases, wherein the liquid phase (B) enriched with the tertiary amine is recirculated to the hydrogenation reactor and the formic acid/amine adduct from the liquid phase (A) enriched with the formic acid/amine adduct and the polar solvent is thermally dissociated into free formic acid and free tertiary amine in a distillation unit and the tertiary amine liberated in the dissociation and the polar solvent are recirculated to the hydrogenation reactor.

摘要翻译： 在包含元素周期表第8,9或10族元素的催化剂，叔胺和极性溶剂的存在下，通过二氧化碳的氢化制备甲酸的方法，压力为0.2-30MPa abs，和 温度为20至200℃以形成两个液相，分离两个液相，其中富含叔胺的液相（B）再循环到氢化反应器中，并将来自液体的甲酸/胺加合物 富含甲酸/胺加合物和极性溶剂的相（A）在蒸馏单元中热解离成游离甲酸和游离叔胺，并且在解离中释放的叔胺和极性溶剂再循环到氢化反应器中。

公开(公告)号：US20100240896A1

公开(公告)日：2010-09-23

申请号：US12741296

申请日：2008-11-04

申请人： Jens Rudolph ,  Joachim Schmidt-Leithoff ,  Rocco Paciello ,  Bernhard Breit ,  Tomas Smejkal

发明人： Jens Rudolph ,  Joachim Schmidt-Leithoff ,  Rocco Paciello ,  Bernhard Breit ,  Tomas Smejkal

IPC分类号： C07C51/373 ,  C07F9/28 ,  C07D213/04 ,  C07F15/00 ,  C07F15/06

CPC分类号： C07F15/008 ,  C07F9/5022 ,  C07F9/58

摘要： The present invention relates to a process for the hydroformylation of compounds of the formula (I), where X is C, P(Rx), P(O—Rx) S or S(═O), where Rx is H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; A is a divalent bridging group having from 1 to 4 bridging atoms; and R1 is H, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; or salts thereof; in which the compound of the formula (I) is reacted with carbon monoxide and hydrogen in the presence of a catalyst comprising a complex of a metal of transition group VIII with a compound of the formula (II), where Pn is a pnicogen atom; W is a divalent bridging group having from 1 to 8 bridging atoms; R2 is a functional group capable of forming an intermolecular, noncovalent bond with the group —X(═O)OH; R3, R4 are each alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl; a, b, c are each 0 or 1; and Y1, Y2 and Y3 are each O, S, NRa or SiRbRc; and also compounds of the formula (II.a), where W′ is a divalent bridging group having from 1 to 5 bridging atoms between the flanking bonds, Z is O, S, S(═O), S(═O)2, N(RIX) or C(RIX)(RX); and RI to RX are each, independently of one another, H, halogen, nitro, cyano, amino, alkyl, etc.; or two radicals RI, RII, RIV, RVI, RVIII and RIX together represent the second part of a double bond.

摘要翻译： 本发明涉及式（I）化合物加氢甲酰化的方法，其中X为C，P（Rx），P（O-Rx）S或S（= O）），其中Rx为H，烷基， 环烷基，杂环烷基，芳基或杂芳基; A是具有1至4个桥连原子的二价桥连基团; R 1为H，烷基，烯基，炔基，环烷基，杂环烷基，芳基或杂芳基; 或其盐; 其中式（I）的化合物与一氧化碳和氢气在包含过渡族VIII的金属与式（II）的化合物的络合物的存在下反应，其中Pn是酚醛原子; W是具有1至8个桥连原子的二价桥连基团; R2是能够与基团-X（= O）OH形成分子间，非共价键的官能团; R 3，R 4各自为烷基，环烷基，杂环烷基，芳基或杂芳基; a，b，c各自为0或1; Y1，Y2和Y3分别为O，S，NRa或SiRbRc; 以及式（II.a）化合物，其中W'是在侧翼键之间具有1至5个桥连原子的二价桥连基团，Z是O，S，S（= O），S（= O）2 ，N（RIX）或C（RIX）（RX）; R 1和R 2各自独立地为H，卤素，硝基，氰基，氨基，烷基等; 或两个基团RI，RII，RIV，RVI，RVIII和RIX一起表示双键的第二部分。

公开(公告)号：US07557240B2

公开(公告)日：2009-07-07

申请号：US11571725

申请日：2005-07-06

申请人： Frank Hettche ,  Christoph Jäkel ,  Marko Friedrich ,  Rocco Paciello

发明人： Frank Hettche ,  Christoph Jäkel ,  Marko Friedrich ,  Rocco Paciello

IPC分类号： C07C69/34

CPC分类号： C07C67/303 ,  C07B2200/07 ,  C07C69/34

摘要： The invention relates to a process for preparing optically active alkylsuccinic acid monoalkyl esters of the formula (I) where D and E are independently of one another H, C1-C10 alkyl, R is C1-C10 alkyl, aryl or alkylaryl.

摘要翻译： 本发明涉及一种制备式（I）的光学活性烷基琥珀酸单烷基酯的方法，其中D和E彼此独立地为H，C1-C10烷基，R为C1-C10烷基，芳基或烷基芳基。

公开(公告)号：US20070100168A1

公开(公告)日：2007-05-03

申请号：US10581802

申请日：2004-12-14

申请人： Rainer Papp ,  Rocco Paciello ,  Christoph Benisch

发明人： Rainer Papp ,  Rocco Paciello ,  Christoph Benisch

IPC分类号： C07C45/49

CPC分类号： C07C209/26 ,  C07C29/141 ,  C07C47/347 ,  C07C2603/68 ,  C07C211/19 ,  C07C31/278

摘要： Process for preparing tricyclodecanedialdehyde by hydroformylation of dicyclopentadiene by means of a CO/H2 mixture at elevated temperature and under superatmospheric pressure in the presence of a rhodium catalyst which has not been modified by means of a ligand and is homogeneously dissolved in the hydroformylation medium, wherein the hydroformylation is carried out at a pressure of from 200 to 350 bar in at least two reaction zones, with a reaction temperature of from 80 to 120° C. being set in a first reaction zone and a reaction temperature of from 120 to 150° C. being set in a reaction zone following this reaction zone, with the proviso that the reaction temperature in the subsequent reaction zone is at least 5° C. higher than in the preceding reaction zone.

摘要翻译： 在高温和超大气压下，在没有通过配体修饰的铑催化剂存在下，通过二环戊二烯加氢甲酰化二环戊二烯制备三环癸二醛的方法， 均匀地溶解在加氢甲酰基化介质中，其中加氢甲酰化在至少两个反应区中在200-350巴的压力下进行，反应温度为80-120℃设定在第一反应区和 在该反应区之后的反应区中设置120至150℃的反应温度，条件是后续反应区中的反应温度比前述反应区高至少5℃。

公开(公告)号：US06573414B2

公开(公告)日：2003-06-03

申请号：US10181461

申请日：2002-07-18

申请人： Michael Richard McAtee ,  Rocco Paciello ,  Michael-Dieter Ulbrich

发明人： Michael Richard McAtee ,  Rocco Paciello ,  Michael-Dieter Ulbrich

IPC分类号： C07C2720

CPC分类号： C01B3/382 ,  C01B3/36 ,  C01B3/48 ,  C01B2203/0233 ,  C01B2203/0238 ,  C01B2203/0261 ,  C01B2203/0283 ,  C01B2203/04 ,  C01B2203/0415 ,  C01B2203/0425 ,  C01B2203/0475 ,  C01B2203/049 ,  C01B2203/06 ,  C01B2203/065 ,  C01B2203/0877 ,  C01B2203/0883 ,  C01B2203/1011 ,  C01B2203/1041 ,  C01B2203/1047 ,  C01B2203/1052 ,  C01B2203/1241 ,  C01B2203/1258 ,  C01B2203/142 ,  C07C29/141 ,  C07C45/50 ,  C07C47/02 ,  C07C31/125

摘要： A process for preparing C9-alcohols comprises a) providing a C4-hydrocarbon stream comprising butene and butane; b) subjecting the C4-hydrocarbon stream to oligomerization over an olefin oligomerization catalyst and fractionating the resulting reaction mixture to give an octene-containing stream and a butene-depleted C4-hydrocarbon stream; c) subjecting the butene-depleted C4-hydrocarbon stream to steam reforming or partial oxidation to give carbon monoxide and hydrogen; d) hydroformylating the octene-containing stream by means of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to form C9-aldehydes, where the carbon monoxide used and/or the hydrogen used originate at least in part from step c); and e) catalytically hydrogenating the C9-aldehydes by means of hydrogen. In a variant of the process, part of the butenes present in the C4-hydrocarbon stream are hydroformylated to form C5-aldehydes, these are subjected to an aldol condensation and the product of the aldol condensation is hydrogenated to form C10-alcohols. The process allows the C4-hydrocarbon stream used to be substantially utilized as material.

摘要翻译： 制备C9-醇的方法包括a）提供包含丁烯和丁烷的C 4烃流; b）使C 4烃流体在烯烃低聚催化剂上进行低聚反应，并分馏得到的反应混合物，得到含辛烯的料流和失碳的C 4烃料流; c）使经过丁烯的C4-烃流进行蒸汽重整或部分氧化以产生一氧化碳和氢; d）通过一氧化碳和氢气在加氢甲酰化催化剂存在下加氢甲酰化含辛烯的物流以形成C9-醛，其中使用的一氧化碳和/或所用氢气至少部分地源于步骤c）。 和e）通过氢催化氢化C 9 - 醛。 在该方法的变体中，存在于C 4烃流中的部分丁烯被加氢甲酰化以形成C5-醛，它们经历醛醇缩合，醛醇缩合的产物被氢化形成C10-醇。 该方法允许用作基本使用的C4-烃流。

公开(公告)号：US6121481A

公开(公告)日：2000-09-19

申请号：US230837

申请日：1999-02-01

申请人： Rolf Fischer ,  Rocco Paciello ,  Michael Roper ,  Werner Schnurr

发明人： Rolf Fischer ,  Rocco Paciello ,  Michael Roper ,  Werner Schnurr

IPC分类号： B01J23/44 ,  B01J23/46 ,  B01J23/75 ,  C07B61/00 ,  C07C209/48 ,  C07C209/60 ,  C07C211/12 ,  C07C253/30 ,  C07C255/24 ,  C07C253/00

CPC分类号： C07C253/30 ,  C07C209/60

摘要： The invention concerns a process for the preparation of 6-aminocapronitrile or 6-aminocapronitrile-hexamethylene diamine mixtures by: a) reacting 5-formylvaleronitrile with ammonia and hydrogen in the presence of hydrogenation catalysts selected from the group consisting of metals or metal compounds rhenium, copper and elements of group VIII of the periodic table of elements, a hydrogenation discharge product being obtained; and b) extracting from the hydrogenation discharge product 6-aminocapronitrile and optionally hexamethylene diamine, provided that the hydrogenation catalyst does not contain copper, nickel or copper and nickel as it's only components.

摘要翻译： PCT No.PCT / EP97 / 03987第 371日期1999年2月1日 102（e）1999年2月1日PCT 1997年7月23日PCT公布。 公开号WO98 / 05631 日期1998年2月12日本发明涉及通过以下方法制备6-氨基己腈或6-氨基己腈 - 六亚甲基二胺混合物的方法：a）在选自金属的氢化催化剂存在下，使5-甲酰基戊腈与氨和氢反应 或金属化合物铼，铜和元素周期表第Ⅷ族元素，得到氢化放电产物; 和b）从氢化放电产物6-氨基己腈和任选的六亚甲基二胺中提取，条件是氢化催化剂不含铜，镍或铜和镍，因为它是唯一的组分。