Abstract:
A process for the preparation of an carboxylic anhydride by reaction of an ethylenically unsaturated compound with carbon monoxide and an carboxylic acid in the presence of a catalyst involving: a) a source of a group VIII metal; b) a bidentate diphosphine of formula I, wherein R1 represents a bivalent radical that together with the phosphorus atom to which it is attached is an optionally substituted 2-phospha-tricyclo[3.3.1.1 {3,7}]-decyl group or a derivative thereof in which one or more of the carbon atoms are replaced by heteroatoms (“2-PA” group); wherein R2 and R3 independently represent univalent radicals of up to 20 atoms or jointly form a bivalent radical of up to 20 atoms; and wherein R represents a bivalent organic bridging group; and, c) a complexing anion; wherein the complexing anion is the anion of the carboxylic acid. A process wherein the carboxylic acid is prepared in-situ and use of the carboxylic anhydride as an acylation agent.
Abstract:
A process for the carbonylation of an ethylenically unsaturated compound with carbon monoxide and a co-reactant. The carbonylation reaction is carried out in the presence of a novel catalyst involving: a) a source of a group VIII metal; b)a bidentate diphosphine of formula I, wherein R1 represents a bivalent radical that together with the phosphorus atom to which it is attached is an optionally substituted 2-phospha-tricyclo[3.3.1.1{3,7}]- decyl group or a derivative thereof in which one or more of the carbon atoms are replaced by heteroatoms (“2-PA” group); wherein R2 and R3 independently represent univalent radicals of up to 20 atoms or jointly form a bivalent radical of up to 20 atoms; and wherein A1 and A2 independently represent optionally substituted alkylene groups and R represents an optionally substituted aromatic group; and, c) a source of anions.
Abstract:
Process for the telomerization of a conjugated diene,wherein the conjugated diene is reacted with a compound containing an active hydrogen atom and having a formula R′—H in the presence of a telomerization catalyst based on: (a) a source of group VIII metal, (b) a bidentate ligand wherein the bidentate ligand has the general formula I R1R2M1—R—M2R3R4 (I) wherein M1 and M2 are independently P, As or Sb; R1, R2, R3 and R4 independently represent a monovalent aliphatic group; or R1, R2 and M1 together and/or R3, R4 and M2 together independently represent an optionally substituted aliphatic cyclic group with at least 5 ring atoms, of which one is the M1 or M2 atom, respectively; R represents a bivalent organic bridging group; and novel bidentate diphosphines which can be used in this process.
Abstract:
Process for the telomerization of a conjugated diene, wherein the conjugated diene is reacted with a compound containing an active hydrogen atom and having a formula R′—H in the presence of a telomerization catalyst based on: (a) a source of group VIII metal, (b) a bidentate ligand wherein the bidentate ligand has the general formula I R1R2M1—R—M2R3R4 (I) wherein M1 and M2 are independently P, As or Sb; R1, R2, R3 and R4 independently represent a monovalent aliphatic group; or R1, R2 and M1 together and/or R3, R4 and M2 together independently represent an optionally substituted aliphatic cyclic group with at least 5 ring atoms, of which one is the M1 or M2 atom, respectively; R represents a bivalent organic bridging group; and novel bidentate diphosphines which can be used in this process.
Abstract:
Bidentate ligand of formula (I), R1R2M1-R-M2R3R4 wherein M1 and M2 each indenpendently represent P, As or Sb; R1, R2, R3 and R4 each independently represent the same or a different optionally substituted organic group and at least one of R1, R2, R3 and R4 contains a tertiary carbon atom through which the group is linked to M1 or M2; and R represents a bridging group based on a trimethylene group connecting M1 and M2 of which the middle carbon atom is double bonded to a non-metal element chosen from group 14, 15 or 16 of the periodic table of elements. Catalyst comprising this bidentate ligand and carbonylation process n which this catalyst is used.
Abstract:
Process for the telomerization of a conjugated diene,wherein the conjugated diene is reacted with a compound containing an active hydrogen atom and having a formula R′—H in the presence of a telomerization catalyst based on:(a) a source of group VIII metal,(b) a bidentate ligandwherein the bidentate ligand has the general formula I R1R2M1-R-M2R3R4 (I) wherein M1 and M2 are independently P, As or Sb; R1, R2, R3 and R4 independently represent a monovalent aliphatic group; or R1, R2 and M1 together and/or R3, R4 and M2 together independently represent an optionally substituted aliphatic cyclic group with at least 5 ring atoms, of which one is the M1 or M2 atom, respectively; R represents a bivalent organic bridging group; and novel bidentate diphosphines which can be used in this process.
Abstract:
A process for producing primary alcohols from secondary alcohols and/or tertiary alcohols and/or ketones, wherein the process comprises reacting a compound selected from a secondary alcohol, a tertiary alcohol, a ketone, or mixtures thereof, with carbon monoxide and hydrogen in the presence of a catalyst based on: (i) a source of Group VIII metal, (ii) a bidentate ligand having the general formula (I): R1R2M1-R-M2R3R4 (I) wherein M1 and M2 are independently P, As or Sb; R1 and R2 together represent a bivalent substituted or unsubstituted cyclic aliphatic group whereby the two free valencies are linked to M1; R3 and R4 independently represent a substituted or unsubstituted hydrocarbyl group, or together represent a bivalent or non-substituted cyclic group whereby the two free valencies are linked to M2; and R represents a bivalent aliphatic bridging group; and (iii) an acid having a pKa of 3 or less which is in excess over the Group VIII metal.
Abstract translation:由仲醇和/或叔醇和/或酮生产伯醇的方法,其中该方法包括使选自仲醇,叔醇,酮或其混合物的化合物与一氧化碳和氢气在 基于以下的催化剂的存在:(i)第VIII族金属源,(ii)具有通式(I)的二齿配体:<?在线公式描述=“在线式”末端=“铅 “”> R“1”2“2”“”“”“”“”“”“”“”“”“”“”“”“”“”“”“”“”“”“”“”“”“ (I)<?in-line-formula description =“In-line Formulas”end =“tail”?>其中M 1和M 2 < / SUP>独立为P,As或Sb; R 1和R 2一起代表二价取代或未取代的环状脂族基,其中两个自由价与M 1连接; R 3和R 4独立地表示取代或未取代的烃基,或一起表示二价或未取代的环状基团,由此两个自由价与M 2 ; R表示二价脂肪族桥基; 和(iii)具有超过第Ⅷ族金属的pK a <3的3或更小的酸。
Abstract:
A process for converting an olefin having x carbon atoms into an olefin having x+1 carbon atoms wherein the process comprises the steps of: (i) reacting an olefin having x carbon atoms with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to produce an alcohol having x+1 carbon atoms, and (ii) dehydrating the alcohol produced in step (i) in the presence of a dehydration catalyst to produce an olefin having x+1 carbon atoms characterized in that the hydroformylation catalyst used in step (i) is based on: (a) a source of cobalt, and (b) a ligand which contains phosphorus and nitrogen.
Abstract:
A process for the carbonylation of a conjugated diene to a dicarboxylic acid, comprising the steps of (a) contacting a conjugated diene with carbon monoxide and water in the presence of a catalyst system including a source of palladium, a source of an anion and a bidentate phosphine ligand, to obtain a mixture comprising an ethylenically unsaturated acid and reversible diene adducts; (b) separating the obtained reaction mixture into a gaseous stream comprising unreacted conjugated diene and carbon monoxide, a first normally liquid stream comprising at least part of the ethylenically unsaturated acid and the reversible diene adducts, and a second normally liquid stream comprising the catalyst system in admixture with the ethylenically unsaturated acid; (c) recycling the second liquid stream obtained in step (b) to step (a); (d) separating the first liquid product stream obtained in step (b) into a stream comprising the ethylenically unsaturated acid and a stream comprising the reversible diene adducts; and (e) contacting the stream comprising the ethylenically unsaturated acid obtained in step (d) with carbon monoxide and water in the presence of a second catalyst system including a source of palladium, a source of an anion and a bidentate phosphine ligand.
Abstract:
A process for the preparation of a dicarboxylic acid, comprising the steps of (a) contacting a conjugated diene with carbon monoxide and water in the presence of a catalyst system including a source of palladium, a source of an anion and a bidentate phosphine ligand, to obtain a mixture comprising an ethylenically unsaturated acid product; (b) reacting the mixture obtained in step (a) further with carbon monoxide and water to obtain the dicarboxylic acid in admixture with the ethylenically unsaturated acid; (c) separating the dicarboxylic acid from a liquid filtrate comprising the catalyst system; and (d) recycling at least part of the obtained liquid filtrate to step (a).