WO2006056608A2 - Carbonylation process and catalyst therefor - Google Patents
Carbonylation process and catalyst therefor Download PDFInfo
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- WO2006056608A2 WO2006056608A2 PCT/EP2005/056249 EP2005056249W WO2006056608A2 WO 2006056608 A2 WO2006056608 A2 WO 2006056608A2 EP 2005056249 W EP2005056249 W EP 2005056249W WO 2006056608 A2 WO2006056608 A2 WO 2006056608A2
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- substituted
- carbonylation
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- 0 CCCCc(cc1*2(C)ClC)cc(CCCC)c1OP2(*)*=C Chemical compound CCCCc(cc1*2(C)ClC)cc(CCCC)c1OP2(*)*=C 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Definitions
- the present invention relates to a carbonylation process and to a catalytic composition for use in such a process, in particular to catalytic compositions comprising complexes of palladium.
- Metal-containing catalytic compounds are known for use in connection with certain carbonylation reactions, for example in the production of certain carboxylic acids and carboxylic acid derivatives from an olefinic starting material, the carbonylation reaction taking place using carbon monoxide as the carbonylation reagent in the presence of a hydroxylic compound at elevated temperature and pressure. Examples of such prior art processes may be found in W. Reppe, Liebigs Ann. Chem., 583, 1 (1953). Group VIII metal catalysts are generally employed, such metals generally being capable of forming metal carbonyl compounds which appear to play an active role in some of these reactions.
- US Patent No. 3,437,676 discloses carbonylation catalysts based on palladium halide phosphine complexes, of which bis(triphenylphosphine) palladium dichloride is one prominent example.
- these catalysts seem to produce an unacceptably high proportion of branched chain products, and they also require the presence of strong acids such as hydrochloric acid to maintain high activity and selectivity.
- US Patent No. 3,437,676 discloses carbonylation catalysts based on palladium halide phosphine complexes, of which bis(triphenylphosphine) palladium dichloride is one prominent example.
- these catalysts seem to produce an unacceptably high proportion of branched chain products, and they also require the presence of strong acids such as hydrochloric acid to maintain high activity and selectivity.
- 3,887,595 Discloses a carbonylation process in which an olefinically unsaturated compound is contacted with carbon monoxide and a hydroxylic compound in the presence of a catalyst system consisting essentially of (a) zero-valent palladium or platinum complexed with a trisorganophosphine ligand and (b) excess ligand in an amount such that there are from about 10 to about 150 moles of said ligand per mote of said palladium or platinum complex,
- US Patent No. 3,509,209 discloses the hydroxycarbonylation of various olefins by carbon monoxide and water in the presence of hydrochloric or hydrobromic acid and a palladium-containing complex.
- FR-A-2529825 discloses a process for the preparation of ⁇ - or y- unsaturated acids by the carbonylation of a conjugated diene in the presence of water, a strong hydrohalic acid, a palladium-containing catalyst and a quaternary onium salt.
- EP-A-0648731 discloses a process for the hydroxycarbonylation of butadiene in the presence of palladium and crotyl chloride.
- US-A-20040068142 discloses a process for the manufacture of ⁇ - or ⁇ unsaturated carboxylic acids or of saturated carboxylic acids by reaction, with carbon, monoxide and water, of an unsaturated compound in the presence of a palladium catalyst,
- US-5780232 discloses a process for the manufacture of bromo-substituted tricyclic compounds; the first step in this sequence is reaction of substituted dibromo pyridine compounds with carbon monoxide and alcohols or amines in the presence of a palladium catalyst.
- the Pd catalyst loading is 10 mol%.
- US-5998820 discloses a process for the manufacture of tricyclic compounds, the first step in this sequence is reaction of substituted dibromo pyridine compounds with carbon monoxide and alcohols or amines in the presence of a palladium catalyst
- the Pd catalyst loadings are 3 or 10 mol%
- R, R 1 and R 2 are, independently, selected from hydrogen, hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy, alkenyl, substituted alkenyl, alkenoxy, substituted alkenoxy, aryl, substituted aryl, aryloxy, substituted aryloxy, alkaryl, substituted alkaryl, alkaryloxy, substituted alkaryloxy, alkenaryl, substituted alkenaryl, alkenaryloxy, substituted alkenaryloxy, aralkyl, substituted aralkyl, aralkoxy, substituted aralkoxy, aralkenyl, substituted aralkenyl, aralkenoxy, substituted araikenoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, heteroaryl, substituted heteroaryl, heteroalkyl, substituted heteroalkyl, substituted heteroalkyl, substituted
- n is from 0 to 4.
- Q is a halide or pseudohalide
- D is S, P, N or O
- X is oxygen, carbon, carbonyl, imine, benzylatnine, alkyl, substituted alkyl, alkenyl, substituted aikenyl, aryl, substituted aryi, alkaryl, substituted alkaryi, alkenaryl, substituted alkenaryl, aralkyi, substituted aralkyl, aralkenyi, substituted aralkenyl, cycloalkyi, substituted cycloalkyl, heteroaryl, substituted heteroaryl, heteroalkyl or substituted heteroalkyl; or
- the invention also provides the use of the catalytic complex having formula (I) as a catalyst in a carbonylation reaction. Also provided in accordance with the invention is a process for conducting a carbonylation reaction comprising providing a carbonylation substrate and contacting said substrate under carbonylation conditions with a carbonylation reagent in the presence of a catalytic complex of formula (I).
- Suitable carbonyiation substrates in accordance with the process of the invention include, by way of example, heteroaromatic bromides and chlorides such as 2-bromo pyridine, 2-chloropyr ⁇ dine, 2,5 dibromopicoline, 2-bromo quinoxaline, arylbromides such as bromoindoles, bromoanilines and bromoanisoles, aryltriflates such as 4-chlorophenyl triflate and benzyl halides or triflates such as benzyl bromide.
- R' is any suitable substituent group
- Z is any suitable leaving group
- Nu is any suitable nucleophite
- the Pd source/ligand comprises a catalytic complex in accordance with the invention, or a pre-catalytic complex and activating Iigand therefore.
- Suitable solvents include, by way of example, toluene, xylenes, 1 ,4 dioxane, acetonitrile and alcohols such as ethano! and butanol.
- Suitable nucleophiles include, by way of example, aliphatic amines and alcohols, aromatic amines and alcohols, allylic amines and alcohols, ammonia equivalents such as formamide or dimethyl formamide and carbon based nucleophiles such as boronic acids and esters.
- Suitable leaving groups include, by way of example, halides such as chlorides, bromides and iodides and phenol derivatives such as triflates.
- Prior art attempts to provide palladium catalysts for use in this scheme use a rather high proportion of palladium and associated Iigand complex. Typically 1-3 mol % Pd and 1-10 mol % Iigand are required.
- the inventors have found that the palladacycles identified under formula (I) when utilised as the Pd source in the reaction of scheme (I) typically allow much lower levels of palladium (typically ⁇ 1 mol %. preferably ⁇ 0.9 mol %, more preferably less than 0,75 mol % and most preferably less than 0.5 mol %) to be used.
- Palladium usage of from about 0.01 mol % to about 0.4 mol %, preferably from about 0.01 mol % to about 0.25 moi %, more preferably from 0.01 mol % to about 0.1 mol %, and most preferably from about 0.01 mol % to about 0.05 mol % are also contemplated within the scope of the invention.
- Q is Cl or a triflate.
- D is P.
- X is O.
- D and X together may form part of a further ring system on the palladacycle
- one, both or neither of D and X may be heteroatoms.
- D and X together may form part of an oxazoline ring system on the palladacycle.
- R is alkyl, preferably branched chain alkyl, preferably tertiary butyl.
- n is 2
- both R groups are situated in meta positions with respect to the palladium substituent
- R 1 and R 2 are both aryloxy substituents in one preferred catalytic complex according to the invention
- the catalytic complex according to the invention may be particularly useful in applications where conventional Pd catalyst composition is facile
- the catalytic complexes of the invention are found to be more stable than certain conventional catalysts
- the catalytic complex according to the invention may also be particularly useful in carbonylation processes which take place under reducing reaction conditions Under such conditions, many conventional Pd- containing carbonylation catalysts have a tendency to decompose to form inactive species in a short period of time, thus rendering the catalyst inactive
- inventive complexes may be used in carbonylation reactions at lower loading levels than many conventional Pd-containing catalysts in like-for-like conditions
- One particularly preferred catalytic complex in accordance with the invention has the general formula (Ii)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A catalytic complex Formula (I) for use in carbonylation reactions, wherein: R, R1 and R2 are independently selected from hydrogen, hydroxyl or from optionally substituted alkyl, alkoxy, alkenyl, alkenoxy, aryl, aryloxy, alkaryl, alkaryloxy, alkenaryl, alkenaryloxy, aralkyl, aralkoxy, aralkenyl, aralkenoxy, cycloalkyl, cycloalkyloxy, heteroaryl, heteroaryloxy, heteroalkyl or heteroalkyloxy; n is from 0 to 4; Q is a halide or pseudohalide; D is S, P, N or O; X is oxygen, carbon, carbonyl, imine, benzylamine, or optionally substituted alkyl, alkenyl, aryl, alkaryl, alkenaryl, aralkyl, aralkenyl, cycloalkyl, heteroaryl, or heteroalkyl; or D and X together form part of a further ring system on the palladacycle.
Description
DESCRIPTION Carbonylatlon Process and Catalytic Composition Therefor
The present invention relates to a carbonylation process and to a catalytic composition for use in such a process, in particular to catalytic compositions comprising complexes of palladium.
Metal-containing catalytic compounds are known for use in connection with certain carbonylation reactions, for example in the production of certain carboxylic acids and carboxylic acid derivatives from an olefinic starting material, the carbonylation reaction taking place using carbon monoxide as the carbonylation reagent in the presence of a hydroxylic compound at elevated temperature and pressure. Examples of such prior art processes may be found in W. Reppe, Liebigs Ann. Chem., 583, 1 (1953). Group VIII metal catalysts are generally employed, such metals generally being capable of forming metal carbonyl compounds which appear to play an active role in some of these reactions.
US Patent No. 3,437,676 discloses carbonylation catalysts based on palladium halide phosphine complexes, of which bis(triphenylphosphine) palladium dichloride is one prominent example. However, these catalysts seem to produce an unacceptably high proportion of branched chain products, and they also require the presence of strong acids such as hydrochloric acid to maintain high activity and selectivity.
US Patent No. 3,887,595 Discloses a carbonylation process in which an olefinically unsaturated compound is contacted with carbon monoxide and a hydroxylic compound in the presence of a catalyst system consisting essentially of (a) zero-valent palladium or platinum complexed with a trisorganophosphine ligand and (b) excess ligand in an amount such that there are from about 10 to about 150 moles of said ligand per mote of said palladium or platinum complex,
US Patent No. 3,509,209 discloses the hydroxycarbonylation of various olefins by carbon monoxide and water in the presence of hydrochloric or hydrobromic acid and a palladium-containing complex.
FR-A-2529825 discloses a process for the preparation of β- or y- unsaturated acids by the carbonylation of a conjugated diene in the presence of water, a strong hydrohalic acid, a palladium-containing catalyst and a quaternary onium salt.
EP-A-0648731 discloses a process for the hydroxycarbonylation of butadiene in the presence of palladium and crotyl chloride.
US-A-20040068142 discloses a process for the manufacture of β- or γ~ unsaturated carboxylic acids or of saturated carboxylic acids by reaction,
with carbon, monoxide and water, of an unsaturated compound in the presence of a palladium catalyst,
US-5780232 discloses a process for the manufacture of bromo-substituted tricyclic compounds; the first step in this sequence is reaction of substituted dibromo pyridine compounds with carbon monoxide and alcohols or amines in the presence of a palladium catalyst. In the example included here the Pd catalyst loading is 10 mol%.
US-5998820 discloses a process for the manufacture of tricyclic compounds, the first step in this sequence is reaction of substituted dibromo pyridine compounds with carbon monoxide and alcohols or amines in the presence of a palladium catalyst In the examples included here the Pd catalyst loadings are 3 or 10 mol%
Disclosed in Org. Lett 2004, 6, 2097 is the palladium catalysed carbonylation of heterocyclic chlorides and electron rich aryl bromides. For the effective carbonylation of the electron rich aryl bromides such as bromoanilines and bromoanisoles 3 mol% palladium was used.
Disclosed in Org. Lett. 2004, 6, 7 is the palladium catalysed carbonylation of bromoindoles For effective carbonylation 1 mol% palladium was used.
The above identified prior art processes all suffer from one or more of the following disadvantages: they use expensive catalytic reagents in unacceptably large quantities; they generate low yield, low selectivity, or both; they are unsuitable for commercial scale-up; the catalytic composition used are difficult to obtain, or to manufacture; activation of the carbonylation reaction by the catalyst is not sufficiently robust; or the catalyst has too short a lifetime.
According to the present invention there is provided a catalytic complex having the general formula (I):
wherein:
R, R1 and R2 are, independently, selected from hydrogen, hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy, alkenyl, substituted alkenyl, alkenoxy, substituted alkenoxy, aryl, substituted aryl, aryloxy, substituted aryloxy, alkaryl, substituted alkaryl, alkaryloxy, substituted alkaryloxy, alkenaryl, substituted alkenaryl, alkenaryloxy, substituted alkenaryloxy,
aralkyl, substituted aralkyl, aralkoxy, substituted aralkoxy, aralkenyl, substituted aralkenyl, aralkenoxy, substituted araikenoxy, cycloalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, heteroalkyl, substituted heteroalkyl, heteroalkyloxy and substituted heteroalkyloxy groups; and wherein each R may be the same or different;
n is from 0 to 4;
Q is a halide or pseudohalide;
D is S, P, N or O;
X is oxygen, carbon, carbonyl, imine, benzylatnine, alkyl, substituted alkyl, alkenyl, substituted aikenyl, aryl, substituted aryi, alkaryl, substituted alkaryi, alkenaryl, substituted alkenaryl, aralkyi, substituted aralkyl, aralkenyi, substituted aralkenyl, cycloalkyi, substituted cycloalkyl, heteroaryl, substituted heteroaryl, heteroalkyl or substituted heteroalkyl; or
D and X together form part of a further ring system on the palladacycle.
The invention also provides the use of the catalytic complex having formula (I) as a catalyst in a carbonylation reaction.
Also provided in accordance with the invention is a process for conducting a carbonylation reaction comprising providing a carbonylation substrate and contacting said substrate under carbonylation conditions with a carbonylation reagent in the presence of a catalytic complex of formula (I).
Suitable carbonyiation substrates in accordance with the process of the invention include, by way of example, heteroaromatic bromides and chlorides such as 2-bromo pyridine, 2-chloropyrϊdine, 2,5 dibromopicoline, 2-bromo quinoxaline, arylbromides such as bromoindoles, bromoanilines and bromoanisoles, aryltriflates such as 4-chlorophenyl triflate and benzyl halides or triflates such as benzyl bromide.
The palladium catalysed insertion of carbon monoxide into aryl or vinyl halides, pseudohalides or triflates, such catalytic insertion being conducted in the presence of a compound of formula (I) is in accordance with the invention. The invention is also concerned with the subsequent transformation the resulting intermediate Pd-acyl complex with a nucleophile, A generalised reaction scheme may be presented as follows:
Z is any suitable leaving group;
Nu is any suitable nucleophite; and
the Pd source/ligand comprises a catalytic complex in accordance with the invention, or a pre-catalytic complex and activating Iigand therefore.
Suitable solvents include, by way of example, toluene, xylenes, 1 ,4 dioxane, acetonitrile and alcohols such as ethano! and butanol.
Suitable nucleophiles include, by way of example, aliphatic amines and alcohols, aromatic amines and alcohols, allylic amines and alcohols, ammonia equivalents such as formamide or dimethyl formamide and carbon based nucleophiles such as boronic acids and esters.
Suitable leaving groups include, by way of example, halides such as chlorides, bromides and iodides and phenol derivatives such as triflates.
Prior art attempts to provide palladium catalysts for use in this scheme use a rather high proportion of palladium and associated Iigand complex. Typically 1-3 mol % Pd and 1-10 mol % Iigand are required.
The inventors have found that the palladacycles identified under formula (I) when utilised as the Pd source in the reaction of scheme (I) typically allow much lower levels of palladium (typically <1 mol %. preferably <0.9 mol %, more preferably less than 0,75 mol % and most preferably less than 0.5 mol %) to be used. Palladium usage of from about 0.01 mol % to about 0.4 mol %, preferably from about 0.01 mol % to about 0.25 moi %, more preferably from 0.01 mol % to about 0.1 mol %, and most preferably from about 0.01 mol % to about 0.05 mol % are also contemplated within the scope of the invention.
In one preferred catalytic complex according to the invention, Q is Cl or a triflate.
In another preferred catalytic complex according to the invention, D is P.
In another preferred catalytic complex according to the invention, X is O.
In the case where D and X together form part of a further ring system on the palladacycle, one, both or neither of D and X may be heteroatoms. For example, D and X together may form part of an oxazoline ring system on the palladacycle.
In still another preferred catalytic complex according to the invention, R is alkyl, preferably branched chain alkyl, preferably tertiary butyl.
in yet another preferred catalytic complex according to the invention, n is 2 Preferably both R groups are situated in meta positions with respect to the palladium substituent
R1 and R2 are both aryloxy substituents in one preferred catalytic complex according to the invention
The catalytic complex according to the invention may be particularly useful in applications where conventional Pd catalyst composition is facile The catalytic complexes of the invention are found to be more stable than certain conventional catalysts
The catalytic complex according to the invention may also be particularly useful in carbonylation processes which take place under reducing reaction conditions Under such conditions, many conventional Pd- containing carbonylation catalysts have a tendency to decompose to form inactive species in a short period of time, thus rendering the catalyst inactive
Because of the stability of the catalytic complexes of the invention particularly under reducing conditions the inventive complexes may be used in carbonylation reactions at lower loading levels than many conventional Pd-containing catalysts in like-for-like conditions
One particularly preferred catalytic complex in accordance with the invention has the general formula (Ii)
Example 1
The uptake of CO was monitored over time for the reaction of 4- bromoanisole with CO, and pipeπdine as the nucleophile The darker trace depicts the reaction with PdCI2(PhCN)2 as the Pd source, and the lighter trace depicts the same reaction with a catalytic complex of general formula (II) in accordance with the invention as the Pd source The results are depicted graphically below
] 'pipeline)
The results clearly show that at a Pd loading of 0.05 mo!% the catalytic complex in accordance with the invention allows substantially complete conversion to be attained in a useful time, whilst the equivalent reaction with PdGl2(PhCN)2 as the Pd source does not yield complete conversion.
Claims
1. A catalytic complex having the general formula (I
wherein:
R, R1 and R2 are, independently, selected from hydrogen, hydroxyl, alkyi, substituted alkyl, alkoxy, substituted alkoxy, alkenyl, substituted aikenyl, alkenoxy, substituted alkenoxy, aryl, substituted aryl, aryloxy, substituted aryloxy, alkaryl, substituted alkaryl, alkaryloxy, substituted alkaryloxy, alkenaryl, substituted alkenaryl, alkenaryloxy, substituted alkenaryloxy, aralkyl, substituted aralkyl, aralkoxy, substituted aralkoxy, aralkenyl, substituted aralkenyl, aralkenoxy, substituted aralkenoxy, cycioalkyl, substituted cycloalkyl, cycloalkyloxy, substituted cycloalkyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, heteroalkyl, substituted heteroalkyl, heteroalkySoxy and substituted heteroalkyloxy groups; and wherein each R may b,§ \h§ §ame or different;
n is from 0 to 4;
Q is a halide or pseudohalide;
D is S, P, N or O;
X is oxygen, carbon, carbonyl, imine, benzylamine, aikyl, substituted alky!, alkenyl, substituted alkenyl, aryl, substituted aryl, alkaryl, substituted alkaryl, alkenaryl, substituted alkenaryl, araikyl, substituted aralkyl, aralkenyl, substituted aralkenyl, cycloalkyl, substituted cycloalkyl, heteroaryi, substituted heteroaryl, heteroalkyl or substituted heteroalkyl; or
D and X together form part of a further ring system on the palladacycle.
2. A catalytic compϊex according to claim 1 wherein Q is Cl or a triflate.
3. A catalytic complex according to claim 1 or claim 2 wherein D is P,
4. A catalytic complex according to any one of claims 1 to 3 wherein X is O.
5. A catalytic complex according to any one of claims 1 to 4 wherein R is alky!.
6. A catalytic complex according to any one of claims 1 to 4 wherein
R is a branched chain alkyl.
7. A catalytic complex according to claim 6 wherein R is tertiary butyl,
8. A catalytic complex according any one of claims 1 to 7 wherein n is 2.
9. A catalytic complex according to claim 8 wherein both R groups are situated in meta positions with respect to the palladium substituent.
10, A catalytic complex according to any one of claims 1 to 9 wherein R1 and R2 are both aryloxy substituents,
11. A catalytic complex according to any one of claims 1 to 10 of formula (II): 
12. Use of the catalytic complex according to any one of claims 1 to 10 as a catalyst in a carbonylation reaction.
13. Use according to claim 11 wherein the carbonylation reaction is in accordance with the scheme:
wherein R' is any substituent group or groups;
Z is any leaving group;
Nu is any nucieophile; and The Pd source/Iigand comprises a catalytic complex in accordance with any one of claims 1 to 10
14 A process for conducting a carbonylation reaction comprising providing a carbonylation substrate and contacting said substrate under carbonylation conditions with a carbonylation reagent in the presence of a catalytic complex according to any one of claims 1 to
10
15 A process according to claim 13 wherein the catalyst loading with respect to the carbonylation substrate is <1mol %
16 A process according to claim 14 wherein the catalyst loading with respect to the carbonylation substrate is <0 5 mol %
17 A process according to claim 15 wherein the catalyst loading with respect to the carbonylation substrate is <0 25 mol %
18 A process according to claim 16 wherein the catalyst loading with respect to the carbonylation substrate is <0 1 mol %
19 A process according to any one of claims 12 to 17 conducted under reducing reaction conditions
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0426024A GB0426024D0 (en) | 2004-11-26 | 2004-11-26 | Carbonylation process and catalytic composition therefor |
| GB0426024.6 | 2004-11-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2006056608A2 true WO2006056608A2 (en) | 2006-06-01 |
| WO2006056608A3 WO2006056608A3 (en) | 2006-08-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2005/056249 WO2006056608A2 (en) | 2004-11-26 | 2005-11-25 | Carbonylation process and catalyst therefor |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB0426024D0 (en) |
| WO (1) | WO2006056608A2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002044188A1 (en) * | 2000-11-28 | 2002-06-06 | Johnson Matthey Public Limited Company | Palladacyclic compounds containing phosphorus donor ligands, the ligands and the use of the compounds in c-c coupling reactions |
| JP2004224883A (en) * | 2003-01-22 | 2004-08-12 | National Institute Of Advanced Industrial & Technology | Catalyst for producing polycarbonate and method for producing the polycarbonate |
-
2004
- 2004-11-26 GB GB0426024A patent/GB0426024D0/en not_active Ceased
-
2005
- 2005-11-25 WO PCT/EP2005/056249 patent/WO2006056608A2/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002044188A1 (en) * | 2000-11-28 | 2002-06-06 | Johnson Matthey Public Limited Company | Palladacyclic compounds containing phosphorus donor ligands, the ligands and the use of the compounds in c-c coupling reactions |
| JP2004224883A (en) * | 2003-01-22 | 2004-08-12 | National Institute Of Advanced Industrial & Technology | Catalyst for producing polycarbonate and method for producing the polycarbonate |
Non-Patent Citations (7)
| Title |
|---|
| ALBINATI, ALBERTO ET AL: "Synthesis and NMR spectroscopy of cyclopalladated tertiary phosphite complexes. X-ray crystal structure of Pd(.eta.5-C5H5)ÄP(OPh)2(OC6H4)Ü" ORGANOMETALLICS , 9(2), 379-87 CODEN: ORGND7; ISSN: 0276-7333, 1990, XP002382533 * |
| ALBISSON, DAVID A. ET AL: "Orthopalladated triarylphosphite complexes as highly efficient catalysts in the Heck reaction" TETRAHEDRON LETTERS , 39(52), 9793-9796 CODEN: TELEAY; ISSN: 0040-4039, 1998, XP004144320 * |
| BEDFORD, ROBIN B. ET AL: "Simple tricyclohexylphosphine-palladium complexes as efficient catalysts for the Stille coupling of deactivated aryl chlorides" CHEMICAL COMMUNICATIONS (CAMBRIDGE, UNITED KINGDOM) , (22), 2608-2609 CODEN: CHCOFS; ISSN: 1359-7345, 2002, XP002382532 * |
| BEDFORD, ROBIN B. ET AL: "The role of ligand transformations on the performance of phosphite- and phosphinite-based palladium catalysts in the Suzuki reaction" ORGANOMETALLICS , 22(7), 1364-1371 CODEN: ORGND7; ISSN: 0276-7333, 2003, XP001144917 * |
| BELLER ET AL: "Palladium-catalyzed carbonylation of holoindoles: No need for protecting groups" ORG. LETT., vol. 6, no. 1, 2004, pages 7-10, XP002382534 cited in the application * |
| BOHM, VOLKER P. W. ET AL: "Coordination chemistry and mechanisms of metal-catalyzed C-C coupling reactions; Part 12 nonaqueous ionic liquids: superior reaction media for the catalytic Heck-vinylation of chloroarenes" CHEMISTRY--A EUROPEAN JOURNAL , 6(6), 1017-1025 CODEN: CEUJED; ISSN: 0947-6539, 2000, XP002901206 * |
| PATENT ABSTRACTS OF JAPAN vol. 2003, no. 12, 5 December 2003 (2003-12-05) & JP 2004 224883 A (NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL & TECHNOLOGY; IDEMITSU PETRO), 12 August 2004 (2004-08-12) * |
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| Publication number | Publication date |
|---|---|
| GB0426024D0 (en) | 2004-12-29 |
| WO2006056608A3 (en) | 2006-08-03 |
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