GB2216036A - Process and catalyst for the carbo-amination or carbo-amidation of olefins - Google Patents
Process and catalyst for the carbo-amination or carbo-amidation of olefins Download PDFInfo
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- GB2216036A GB2216036A GB8807806A GB8807806A GB2216036A GB 2216036 A GB2216036 A GB 2216036A GB 8807806 A GB8807806 A GB 8807806A GB 8807806 A GB8807806 A GB 8807806A GB 2216036 A GB2216036 A GB 2216036A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- 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
-
- 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
-
- 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
- B01J2531/821—Ruthenium
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for the carbo-amination or carbo-amidation of olefins comprises contacting an olefinically unsaturated compound with a compound having structure H-NR1R2 and with CO in the presence of a catalyst system prepared by combining: (a) a ruthenium compound, and (b) a compound having an anion of an acid with a pKa value <3,5. The ruthenium compound may be the tris acetylacetonate and compound (b) may be orthophosphoric acid, a dibasic metal salt thereof, p-toluene sulphonic acid or hexafluorophosphoric acid.
Description
PROCESS FOR THE CARBO-AMINATION OR
CARBO-AMIDATION OF OLEFINS
The invention relates to a process for the carbo-amination or carbo-amidation of olefins. The also relates to a novel composition suitable for use in such a process.
U.S. Patent Specification 4,313,893 discloses a process for the production of esters, acetals, ethers, amides and mixtures thereof, wherein the branched ester or amide product predominates, comprising contacting an olefinically unsaturated compound in the liquid phase at a temperature in the range of about 50 to about 150 C and a pressure in the range of about 7 to about 172 bar with carbon monoxide and a compound containing a replaceable hydrogen atom in the presence of a catalyst comprising at least one of cobalt carbonyl and ruthenium carbonyl and a promotor ligand. The compound containing a replaceable hydrogen atom is defined as an alcohol, a secondary amine or molecular hydrogen, whereas the olefinically unsaturated compound allegedly should have at least one nitrile moiety.However, all the examples relate to the conversion of an alcohol (mostly methanol) as the replaceable hydrogen-containing compound with carbon monoxide and acrylonitrile, propylene or allyl alcohol as olefinically unsaturated compound in the presence of a cobalt catalyst system. So, contrary to the broad range of products claimed in said US patent specification, only the production of ester compounds is substantiated in the examples.
It has now surprisingly been found that mono-, di- or triacyl amines (primary, secondary or tertiary amides) are formed at a high selectivity at relatively low temperature and low pressure by contacting an olefinically unsaturated compound with carbon monoxide in the presence of ammonia, an amine compound or an amide compound, and in the presence of a ruthenium catalyst system, thereby yielding predominantly the linear amide product in case of the conversion of an
-olefinically unsaturated compound having more than 2 carbon atoms.
Therefore, the invention provides a process for the carbo-amination or carbo-amidation of olefins, which process comprises contacting an olefinically unsaturated compound in the liquid phase with carbon monoxide or a carbon monoxide-containing fluid and a compound having the structure H-NR1R2 wherein R1 and R2 are each independently selected from hydrogen, a hydrocarbon group or a group 3 in which independently may be hydrogen or 3 -C(O)-R , in which R independently may be hydrogen or a
1 and 2 hydrocarbon group, or R1 and R2, together with the nitrogen atom to which they are attached, form a heterocyclic group, the hydrocarbon moieties R1, R2 and/or R3 optionally containing as further reactive groups one or more primary or secondary amino and/or aminocarbonyl groups, in the presence of a catalyst system obtainable by combining: component (a) : - a ruthenium compound, and component (b): - a compound having an anion of an acid with
a 15 pKa value < 3,5 (measured at 25 C in
aqueous solution).
It has been found that the present catalyst system is very stable and, therefore, can be used for a very long
can be used for a very long time. Further the catalyst system promotes the production of the linear product, i.e. in case an -olefinically unsaturated compound is converted, the carbo-amination or carbo-amidation takes place at the terminal carbon atom, whereas the above mentioned U.S. patent predominantly yields the branched (ester) products.
Component (a) of the catalyst system of the present invention is a ruthenium compound. This ruthenium compound may contain, for example, a cationic ruthenium complex with an oxidation state of 1 or 3, whereas also zero-valency ruthenium compounds such as dodecacarbonyl triruthenium can be used. Suitable ruthenium compounds are for example ruthenium oxides and other ruthenium salts, such as halides etc. Very good results have been obtained by ruthenium tris acetylacetonate.
Component (b) of the present catalyst system is a compound having an anion of an acid with a pKa value < 3,5 (measured at 25 OC in aqueous solution). The acids may be selected from a wide range of organic and inorganic acids, such as for example hydrohalogenic acids, carboxylic acids, substituted carboxylic acids such as haloacetic acids, orthophosporic acid, pyrophosphoric acid, phosphonic acids, sulphonic acids etc. Suitable acids preferably have a pKa value < 2,5. Preferably component (b) comprises a compound selected from phosphoric acid or a metal salt thereof, in particular a dibasic metal salt, more preferably an alkali metal salt and most preferably the sodium salt, p-toluene sulphonic acid or hexafluoro phosphoric acid.
The way of preparing the catalyst system is not critical. The catalyst system may be prepared in situ in the reaction mixture by adding components (a) and (b) separately. Components (a) and (b) may also be mixed first and then added to the reactor before, simultaneously with or after one or more of the reactants. Mixing of the components (a) and (b) may take place as such or in a suitable vehicle.
Components (a) and (b) may even be united in one compound, for instance the ruthenium salt of the anion of acid compound (b).
Component (b) preferably is present in a quantity in the range of from 0,1 to 100 equivalents, more preferably from 1 to 20 equivalents per gram-atom of ruthenium.
The olefinically unsaturated compound may be an unsubstituted or substituted branched or straight alkene or cycloalkene, preferably having from 2 to 30 and in particular from 2 to 20 carbon atoms. The olefinically unsaturated compound may contain more than one double bond, preferably from 1 to 3 double bonds. When substituted, the olefinically unsaturated compound preferably contains reaction-inert substituent groups such as, for example one or more halogen atoms or cyano, ester, ether, aryl groups etc. It will be appreciated, that when the olefinically unsaturated compound is substituted by groups which are not inert under the reaction conditions, competitive side-reactions may occur resulting in a lower yield of the desired acyl amine compound. Nevertheless, if such competitive reactions are desired, the olefinically unsaturated compound may contain other reactive substituents.In the process of the present invention the preferred olefinically unsaturated compound is an alkene having from 2 to 10 carbon atoms. Suitable compounds having the structure HNR1R2 are those containing at least one hydrogen atom attached to the nitrogen atom of an ammonia, amine or amide compound. Therefore as well ammonia, primary and secondary amines and primary and secondary amides (in which latter case R1 and/or R2 is -C(o)-R3) may be used. The substituents of these amine and amide compounds (R1, R2 and
R3) are not critical, provided that R3 is not an acyl group.
1 2 3
Thus, the substituents R , R2 and R3 may be the same or different and represent a hydrogen atom or a hydrocarbon group, the hydrocarbon group preferably having from 1 to 20 carbon atoms. The hydrocarbon group may optionally be substituted by further primary or secondary amino and/or amino carbonyl groups thus forming a di- or polyamine, dior polyamide or amino substituted amide etc. In case R1 and/or R2 are different from hydrogen and from an acyl group, a mono- or disubstituted primary amide (monoacyl amine) compound results. On the other hand, if R1 and/or R2 represent an acyl group (-C (0) -R3) then the resulting product is a di- or triacyl amine.The substitutents R1, R2 3 and R3 preferably do not contain further reactive substituents (apart from amino or amino carbonyl groups) in order to prevent the occurence of competitive side-reactions. However, as explained in connection with the olefinically unsaturated compound above, if desired, such further reactive substituents may be present. As indicated hereinbefore, the groups R and R , together with the nitrogen atom to which they are attached, may also form a heterocyclic system, which may be aromatic. This heterocyclic system may also be substituted by further reactive amino and/or amino carbonyl groups.In the process according to the invention preferably a compound having the structure H-NR1R2 is used, wherein R1, R2 and R3 each are independently selected from hydrogen, an alkyl or cycloalkyl group having from 1 to 20 carbon atoms, or an aromatic group. More preferably R1, R2 and R3 each are independently selected from hydrogen, an alkyl group having from 1 to 4 carbon atoms or a phenyl group. Suitable compounds are, for example, ammonia, diethyl amine, monopropyl amine, propionamide and aniline.
The molar ratio between the compound having structure
H-NR1R2 and the olefinically unsaturated compound is not critical and may vary within wide ranges, with a molar ratio varying between from 10:1 to 1:10 being preferred.
The third reactant in the present process is carbon monoxide or a carbon monoxide containing fluid. Therefore mixtures of carbon monoxide and an inert gas such as carbon dioxide, helium, argon, nitrogen etc. may also be used.
The molar ratio of the carbon monoxide to the olefinically unsaturated compound can vary within a wide range, with a ratio of 1:10 to 10:1 being preferred.
It will be appreciated, that the quantity of catalyst system used in the present process is not critical, ääbut preferably from 10 7 to 10'1 moles of the catalyst system are used per mole of olefinically unsaturated compound.
The carbo-amination or carbo-amidation of the olefinically unsaturated compound is carried out in the liquid phase. Therefore, in case the olefinically unsaturated compound and/or the compound having structure
H-NR1R2 is a liquid or the primary reaction product obtained is liquid, the reaction may be carried out without an additional liquid solvent. However, a reaction-inert liquid solvent may be used advantageously. Especially in the case that gaseous starting materials are used and/or gaseous reaction products are formed, such a liquid solvent preferably is used. In a preferred embodiment of the process of the present invention an aprotic solvent is used. This aprotic solvent may be selected from a wide range of solvents, and suitable aprotic solvents are for example ethers, polyethers, sulphones and N-disubstituted amides, such as for example dialkyl formamides.Particularly suitable are the group of polyethers such as for instance the dimethyl ether of diethylene glycol (diglyme) or of tetraethylene glycol (tetraglyme). Other solvents that may be used are for instance dimethyl sulphoxide, di-isopropyl sulphone, tetrahydrothiophene l,l-dioxide (also referred to as sulfolane), acetone, chloroform, methyl isobutyl ketone or di-isopropyl ether.
The process according to the present invention may be carried out at a temperature and pressure which are not critical and may vary within wide ranges. The process is preferably carried out at a temperature in the range of from 50 to 250 OC and at pressure in the range of from 5 tot 200 bar. Suitable reaction conditions were found to be a temperature in the range of from 100 to 200 C and a pressure in the range of from 10 to 80 bar.
The process according to the invention may be carried out bachwise, continuously or semi-continuously. The reaction mixtures obtained may be subjected to suitable catalyst and product separating or recovery processes comprising one or more steps, such as precipitation, solvent extraction, distillation, fractionation or adsorption. The catalyst system as well as unconverted starting compounds or solvent, if present, may be partially or totally recycled to the reaction zone.
According to another aspect the invention relates to a composition suitable for use in the carbo-amination or carbo-amidation of an olefinically unsaturated compound obtainable by combining the following components: component (a) - a ruthenium compound, and component (b) - a compound having an anion of an acid with a
pKa value < 3,5 (measured at 25 OC in
aqueous solution).
Preferably component (a) comprises ruthenium tris acetylacetonate. Component (b) of the present catalytic composition advantageously comprises a compound selected from orthophosphoric acid or a dibasic metal salt thereof, p-toluene sulphonic acid or hexafluoro phosphoric acid.
Under the dibasic metal salts of orthophosphoric acid, the dibasic alkali metal salts and especially the sodium salts are preferred. Component (b) preferably is present in a quantity in the range of from 0,1 to 100 equivalents, more preferably from 1 to 20 equivalents, per gram-atom of ruthenium. Optionally, components (a) and (b) are mixed with an aprotic solvent.
The present invention will further be illustrated by reference to the following examples and comparative example.
The experiments were all carried out in a 300 ml magnetically stirred Hastelloy C autoclave ("Hastelloy" is a trademark). The reaction mixtures obtained were analysed by means of standard gas-liquid chromatography techniques.
The term "selectivity" towards a certain amide compound, as used in the examples, expressed in molar percents, is defined as 100 x a:b, in which "a" is the amount of the H-NR1R2 starting compound that has been converted into that certain amide and "b" is the total amount of said starting compound that has been converted.
Further, the term "linearity" as used in the examples and expressed as a percentage, relates to the quantity of linear amide product formed in case of converting an -olefinically unsaturated compound, i.e. the percentage of amide product in which the carbo-amination or carbo-amidation has taken place at the terminal carbon atom.
The conversion rate of the compound having the structure H-NR1R2 is expressed in gram-mol per gram-atom Ru per hour.
Example 1
50 ml of diglyme (dimethylether of diethylene glycol), 20 ml of diethyl amine, 0,2 mmols of ruthenium tris acetylacetonate and 2 mmols of orthophosphoric acid were placed in the autoclave. Next, the autoclave was flushed with carbon monoxide to remove air and then sealed, charged with carbon monoxide until a partial pressure of 20 bar was obtained. Finally, ethylene was charged until a partial pressure thereof of 20 bar was obtained. Then the reactor was heated to 175 OC and the reaction was allowed to proceed for 5 hours. The autoclave was then cooled down to ambient temperature, depressurized and opened for product analysis.
The diethyl amine conversion rate was measured to be 50. The selectivity for the product N,N-diethyl propionamide was 96%. The major by-product was found to be N,N-diethyl formamide.
Example 2
The procedure outlined in example 1 was followed, except that 2 mmols of sodium hydroxide were added, thus forming together with the 2- mmols of orthophosphoric acid in situ the dibasic sodium salt of orthophosphoric acid. The diethyl amine conversion rate was found to be 65 whereas the selectivity for the product N,N-diethyl propionamide was 96%. The major by-product was N,N-diethyl formamide.
Example 3
The procedure outlined in example 1 was followed, except that the starting compound diethyl amine was replaced by 20 ml of monopropyl amine. The conversion rate of monopropyl amine was found to be 90. The selectivity for the product N-propyl propionamide was 87%. The major by-product was N-propyl formamide.
Example 4
The same procedure as outlined in example 3 was followed, except that instead of ethylene with a partial pressure of 20 bar now 20 ml of -octene were used. It was found, that the monopropyl amine conversion rate amounted to 190. The selectivity towards the amide product formed was found to be 34%. The linearity of the above-mentioned amide product was 90%, i.e. 90% of the amide product produced was
N-propyl nonanamide. The major by-product was N-propyl formamide.
Example 5
The same reactants were used as in example 4 according to the procedure described in said example, only the 2 mmols of orthophosphoric acid were replaced 2 mmols of p-toluene sulphonic acid. The monopropyl amine conversion rate was found to be very high, namely 250. The selectivity for the amide product was 41%, whereas the linearity of this product was 87%, the major product thus being N-propyl nonanamide.
The major by-product was found to be N-propyl formamide.
Example 6
The same procedure was used as decribed in example 4, except that instead of 2 mmols of orthophosphoric acid now 2 mmols of hexafluoro phosphoric acid were used. The N-propyl amine conversion rate was measured to be 500. The selectivity towards the amide product was 40%. The linear product (N-propyl nonanamide) of the amide produced was obtained-in 87%. The major by-product was N-propyl formamide.
Example 7
In the same way as described under example 1, an experiment was carried out, starting from 0,2 mmols of ruthenium tris acetylacetonate, 2 mmols of orthophosphoric, 50 ml of diglyme, 10 g of propionamide, ethylene with a partial pressure of 20 bar and carbon monoxide with a partial pressure of 20 bar. The propionamide conversion rate was found to be 65. The selectivity towards the product di-propionyl amine was 85%.
Example 8
The procedure outlined in example 1 was followed, now using 0,2 mmols or ruthenium tris acetylacetonate, 2 mmols of orthophosphoric acid, 50 ml of diglyme, 20 ml of
-octene, ammonia to a partial pressure of 4 bar and carbon monoxide to a partial pressure of 20 bar. The ammonia conversion rate was found to be 80. The selectivity towards the amide compound produced was 96%, whereas 63% of the amide compound was found to be the linear product nonanamide.
Example 9
According to the procedure described in example 1, an experiment was carried out, now using 0,2 mmols of ruthenium tris acetylacetonate, 2 mmols of orthophosphoric acid, 50 ml of diglyme, 10 ml of aniline, ethylene to a partial pressure of 20 bar, carbon monoxide to partial pressure of 20 bar.
The reaction was allowed to proceed for 2,5 hours. The aniline conversion was found to be 30%. The selectivity towards the product N-phenyl propionamide was 97%.
Comparative Example
The procedure outlined in example 1 was followed, except that no orthophosphoric acid was added. Only a trace of the desired product N,N-diethyl propionamide was found to be present in the product mixture. This comparative example shows, that the presence of a compound having an anion of an acid with a pKa value < 3,5 is essential for the carbo-amination or carbo-amidation of olefinically unsaturated compounds according to the present invention.
Claims (28)
1. A process for the carbo-amination or carbo-amidation of olefins, which process comprises contacting an olefinically unsaturated compound in the liquid phase with carbon monoxide or a carbon monoxide-containing fluid and a compound having the structure H-NR1R2, wherein R1 and R2 are each independently selected from hydrogen, a hydrocarbon 3 group or a group -C(o)-R3, in which R3 independently may be hydrogen or a hydrocarbon group, or R and R, together with the nitroaen atom to which they are attached, form a -heterocyclic group, the hydrocarbon moieties R1, R2 and/or
R optionally containing as further reactive groups one or more primary or secondary amino and/or aminocarbonyl groups, in the presence of a catalyst system obtainable by combining: component (a): - a ruthenium compound, and component (b): - a compound having an anion of an acid with
pKa value < 3,5 (measured at 25oC in
aqueous solution).
2. A process as claimed in claim 1 in which component (a) comprises ruthenium tris acetylacetonate.
3. A process as claimed in claim 1 or 2 in which component
(b) comprises a compound selected from orthophosphoric acid or a dibasic metal salt thereof, p-toluene sulphonic acid or hexafluoro phosphoric acid.
4. A process as claimed in claim 3 in which component (b)
comprises the dibasic alkali metal salt of orthophosphoric
acid.
5. A process as claimed in claim 4 in which the alkali
metal is sodium.
6. A process as claimed in any one of the preceding claims in which component (b) is present in a quantity in the range of from 0,1 to 100 equivalents per gram-atom of ruthenium.
7. A process as claimed in claim 6 in which component (b) is present in a quantity varying from 1 to 20 equivalents per gram-atom of ruthenium.
8. A process as claimed in any one of the preceding claims in which the olefinically unsaturated compound is an alkene or cycloalkene having from 2 to 20 carbon atoms, optionally containing reaction-inert substituent groups.
9. A process as claimed in claim 8 in which the olefinically unsaturated compound is an alkene having from 2 to 10 carbon atoms.
10. A process as claimed in any one of the preceding claims in which a compound having the structure H-NR1R2 is used, wherein R1, R2 and R3 each are independently selected from hydrogen, an alkyl or cycloalkyl group having from 1 to 20 carbon atoms, or an aromatic group.
11. A process as claimed in claim 10 in which R1, R2 and R3 each are independently selected from hydrogen, an alkyl group having from 1 to 4 carbon atoms or a phenyl group.
12. A process as claimed in any one of the preceding claims in which the molar ratio between the compound having structure H-NR1R2 and the olefinicallly unsaturated compound varies between from 10:1 to 1:10.
13. A process as claimed in any one of the preceding claims in which the molar ratio between carbon monoxide and the olefinically unsaturated compound lies in the range of from 1:10 to 10:1.
14. A process as claimed in any one of the preceding claims in which from 10-7 to 10-1 moles of the catalyst system are present per mole of olefinically unsaturated compound.
15. A process as claimed in any one of the preceding claims in which an aprotic solvent is used.
16. A process as claimed in claim 15 in which the aprotic solvent is the dimethyl ether of diethylene glycol.
17. A process as claimed in any one of the preceding claims which is carried out at a temperature in the range of from 50 to 250 C and at a pressure in the range of from 5 to 200 bar.
18. A process as claimed in claim 17 which is carried out at a temperature in the range of from 100 to 200 C and at a pressure in the range of from 10 to 80 bar.
19. Mono-, di- and triacyl amines whenever prepared by a process as claimed in any one of the preceding claims.
20. A composition suitable for use in the carbo-amination or carbo-amidation of an olefinically unsaturated compound obtainable by combining the following components: component (a) - a ruthenium compound, and component (b) - a compound having an anion of an acid with
a pKa value < 3,5 (measured at 25 OC in
aqueous solution).
21. A composition as claimed in claim 20 in which component
(a) comprises ruthenium tris acetylacetonate.
22. A composition as claimed in claim 20 or 21, in which component (b) comprises a compound selected from orthophosphoric acid or a dibasic metal salt thereof, p-toluene sulphonic acid or hexafluoro phosphoric acid.
23. A composition as claimed in claim 22 in which component
(b) comprises the dibasic alkali metal salt of orthophosphoric acid.
24. A composition as claimed in claim 23 in which the alkali metal is sodium.
25. A composition as claimed in any one of the claims 20 to 24 in which component (b) is present in a quantity in the range of from 0,1 to 100 equivalents, preferably from 1 to 20 equivalents, per gram-atom of ruthenium.
26. A composition as claimed in any one of the claims 20 to 25 which further comprises an aprotic solvent.
27. A composition as claimed in claim 20 substantially as hereinbefore described with reference to the examples. 28.
A process as claimed in claim 1, substantially as hereinbefore described with reference to the examples.
28. A process as claimed in claim 1 substantially as hereinbefore described with reference to the examples.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8807806A GB2216036A (en) | 1988-03-31 | 1988-03-31 | Process and catalyst for the carbo-amination or carbo-amidation of olefins |
| KR1019890004001A KR0128999B1 (en) | 1988-03-31 | 1989-03-29 | Process for separating hydroprocessed effluent streams |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8807806A GB2216036A (en) | 1988-03-31 | 1988-03-31 | Process and catalyst for the carbo-amination or carbo-amidation of olefins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8807806D0 GB8807806D0 (en) | 1988-05-05 |
| GB2216036A true GB2216036A (en) | 1989-10-04 |
Family
ID=10634495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8807806A Withdrawn GB2216036A (en) | 1988-03-31 | 1988-03-31 | Process and catalyst for the carbo-amination or carbo-amidation of olefins |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2216036A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0441445A2 (en) * | 1990-02-05 | 1991-08-14 | Shell Internationale Researchmaatschappij B.V. | Preparation of amides |
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|---|---|---|---|---|
| GB1451764A (en) * | 1974-04-05 | 1976-10-06 | Ube Industries | Process for preparing dialkyl oxalates |
| EP0048980A1 (en) * | 1980-09-26 | 1982-04-07 | Union Carbide Corporation | Continuous process for the manufacture of ethylene glycol |
| EP0073142A2 (en) * | 1981-08-21 | 1983-03-02 | Commonwealth Scientific And Industrial Research Organisation | Modified catalysts for the solar reduction of water |
| EP0117575A1 (en) * | 1983-02-17 | 1984-09-05 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of esters |
-
1988
- 1988-03-31 GB GB8807806A patent/GB2216036A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1451764A (en) * | 1974-04-05 | 1976-10-06 | Ube Industries | Process for preparing dialkyl oxalates |
| EP0048980A1 (en) * | 1980-09-26 | 1982-04-07 | Union Carbide Corporation | Continuous process for the manufacture of ethylene glycol |
| EP0073142A2 (en) * | 1981-08-21 | 1983-03-02 | Commonwealth Scientific And Industrial Research Organisation | Modified catalysts for the solar reduction of water |
| EP0117575A1 (en) * | 1983-02-17 | 1984-09-05 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of esters |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0441445A2 (en) * | 1990-02-05 | 1991-08-14 | Shell Internationale Researchmaatschappij B.V. | Preparation of amides |
| EP0441445A3 (en) * | 1990-02-05 | 1991-11-27 | Shell Internationale Research Maatschappij B.V. | Preparation of amides |
| US5128475A (en) * | 1990-02-05 | 1992-07-07 | Shell Oil Company | Preparation of amides |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8807806D0 (en) | 1988-05-05 |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |