CA1148564A - Asymmetric hydrogenation of prochiral olefines by complexes of transition metals immobilized in clay-like minerals - Google Patents
Asymmetric hydrogenation of prochiral olefines by complexes of transition metals immobilized in clay-like mineralsInfo
- Publication number
- CA1148564A CA1148564A CA000311978A CA311978A CA1148564A CA 1148564 A CA1148564 A CA 1148564A CA 000311978 A CA000311978 A CA 000311978A CA 311978 A CA311978 A CA 311978A CA 1148564 A CA1148564 A CA 1148564A
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- Prior art keywords
- alpha
- catalyst
- clay
- prochiral
- acid
- Prior art date
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- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- 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
- B01J31/1855—Triamide derivatives thereof
-
- 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
- B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
- B01J31/187—Amide derivatives thereof
-
- 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
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
- B01J31/188—Amide derivatives thereof
-
- 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
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of 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
- B01J2531/822—Rhodium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
For the asymmetrical hydrogenation of prochiral olefines, a catalyst system is proposed which is a Rhodium cationic complex immobilized on a clay-like mineral such as hectorite, bentonite and haloysite.
For the asymmetrical hydrogenation of prochiral olefines, a catalyst system is proposed which is a Rhodium cationic complex immobilized on a clay-like mineral such as hectorite, bentonite and haloysite.
Description
~8564 This invention relates to a method for the hydrogena-tion of prochiral olefines with induction of asymmetry by the agency of complexes of transition metals immobilized in clay-like minerals.
More exactly, the present invention relates to a method for the asymmetric hydrogenation of a prochiral olefin selected from the group consisting of alpha-acrylamide acrylic acids, alpha-acetoamino-cinnamic acid, alpha-acetoamino-acrylic acid, and 3-acetoxy-4-methoxy alpha-acetoaminocinnamic acid, comprising contacting said olefin with a catalyst composed of a cationic complex of rhodium with aminic derivatives of phosphorus, the improvement comprising immobilizing said catalyst on a silicate clay material selected from the group consisting of smectites and kaolin.
The scrutiny~of the technical literature of these last years shows a considerable interest in the use of the asymmetric catalytic systems for the preparation of optica~lly active compounds by reactions of hydrogenation, hydrosilylation and hydroformylation.
In reactions of hydrogenation of alpha-acylamidoacrylic acids, for example, catalyzed by chiral complexes of rhodium o-anisylcyclohexylmethylphosphine, optical yields are reported as high as 95%-96% which are virtually near those experienced in enzymic processes.
However, the use of homogeneous catalysts involves a great number of problems, including the difficulty of separating the reaction product and the recovery of the catalyst; this becomes especially cumbersome when traces of the catalyst are retained in the reaction product. To overcome these difficulties, the homogeneous catalysts have been insolubilized by covalent bonds with substrates which are predominantly of an organic nature.
The polymers which are most frequently used are ~ ' ~1~8~i6'~
polystyrene which has been cross-linked with divinylbenzene and functionalized with phosphine bonds to which transition metal are co-ordinated. Also copolymers of the same fun-ctionalized polystyrene are used.
We are proposing, that which is the subject matter of the present invention, to use clay-like minerals, more particularly of the class of smectites and kaolin~ as sub-strates for homogeneous catalysts of asymmetric hydrogenation reactions.
Smectites are fillosilicates the structural unit of which is composed by a tetrahedral layer, an octahedral layer and another tetrahedral layer with a layer charge of 0.25 0.60 per formula uni~due to isomorphic substitutions which a~e distributed in the tetrahedral and the octahedral layers:
such a charge is balanced by easily exchangeable interlayer cations. The exchange capacity is comparatively high and varies from 80 and 150 milliequivalents per 100 grams.
In addition, particularly interesting are a few minerals of the clay type in the group of serpentine kaolin such as halloysite which is the most hydrous variety a~d has an exchange capacity of about 40 milliequivalents per 100 grams.
The catalysts the subject of the present invention are obtained by simple exchange reaction between the cationic complex of the transition metal and the clay-like matexials.
Such catalytic systems have the considerable advantage of the simplicity of preparation and cheapness, especially when compared with the conventional heterogeneization systems which employ modified organic polymeric matrices.
The cationic complex which is catalytically active in the asymmetric hydroger:ation reaction can be selected among th e having the formula P R'x (NR2R3)3_X, detail in the Ca~adian Patent Application No. 275 . 775 of 6 .4. 1977 85~4 Tlle catalysts in ~uestion can be used in the form of a fine powder or granules or can have any shape which is appropriate to the contact procedure to be used.
The process of asymmetric reduction is carried out at a temperature comprised between -70C and +200C, preferably between 0C and 50C at a hydrogen pressure up to 200 atnl, preferably between 1 and 50 atm, and with a molar ratio of the substrate to the catalyst variable between 10 and 10,000.
A few operative characteristics are described in the ensuing examples, which are no limitation and are given only to illustrate the invention.
E X A M P L E
One gram of Hectorite slurried in anhydrous methanol has been exchanged with rhodium by placing them to reach equilibrium overnight with 0.475 g of [Rh COD L]~ CL04 in 50 mls methanol.
COD - cyclooctadiene: L = N-N' bis (R(+) alpha-methyl-benzyl) N-N' bis (diphenylphosphino) ethylenediamine.
- Hectorite takes an intense yellow color and is carefully washed with anh.methanol and then dried. The Rhodium contents is 1.6% by wt.
Such compound has been slurried in anh.ethanol and hydrogenated in an autoclave at a pressure of 20 atm. of hydrogen: there is obtained a product colored in dark red which is characteristic of the hydride species of the Rhodium complex, which has been used in the hydrogenation of the alpha-acetaminocinnamic acid.
A glass flask has been charged with 0.942 g of sub-strate in 25 mls anh.ethanol and 0.450 g of previously hydrogenated catalyst. The flask has been connected to a hydrogenation apparatus working under atmospherical pressure.
The progress of the reaction has been monitored with the conventional pressure-check-ng procedures. After 8 hours, the reaction has been stopped: the catalyst has been filtered off and the solution e~aporated to dryness. The product, characterized through NMR analysis was R(+)N-acetylphenylalanine with[~]2D = 21.5 (c = 1 anh.ethanol).
With the same catalyst of the previous example there have been performed hydrogenation cycles of the alpha-acetaminocinnamic acid: the data which have been obtained are collected in Table 1.
The catalyst is recovered after each cycle by filtration of the reaction mixture, washed with anh.ethanol and reused under the same conditions.
Cycles [c] Reaction [~]
substrate :time 1% Soln.
% hrs. anh.ethanol e.e.
1 4.4 2 + 0.170 37
More exactly, the present invention relates to a method for the asymmetric hydrogenation of a prochiral olefin selected from the group consisting of alpha-acrylamide acrylic acids, alpha-acetoamino-cinnamic acid, alpha-acetoamino-acrylic acid, and 3-acetoxy-4-methoxy alpha-acetoaminocinnamic acid, comprising contacting said olefin with a catalyst composed of a cationic complex of rhodium with aminic derivatives of phosphorus, the improvement comprising immobilizing said catalyst on a silicate clay material selected from the group consisting of smectites and kaolin.
The scrutiny~of the technical literature of these last years shows a considerable interest in the use of the asymmetric catalytic systems for the preparation of optica~lly active compounds by reactions of hydrogenation, hydrosilylation and hydroformylation.
In reactions of hydrogenation of alpha-acylamidoacrylic acids, for example, catalyzed by chiral complexes of rhodium o-anisylcyclohexylmethylphosphine, optical yields are reported as high as 95%-96% which are virtually near those experienced in enzymic processes.
However, the use of homogeneous catalysts involves a great number of problems, including the difficulty of separating the reaction product and the recovery of the catalyst; this becomes especially cumbersome when traces of the catalyst are retained in the reaction product. To overcome these difficulties, the homogeneous catalysts have been insolubilized by covalent bonds with substrates which are predominantly of an organic nature.
The polymers which are most frequently used are ~ ' ~1~8~i6'~
polystyrene which has been cross-linked with divinylbenzene and functionalized with phosphine bonds to which transition metal are co-ordinated. Also copolymers of the same fun-ctionalized polystyrene are used.
We are proposing, that which is the subject matter of the present invention, to use clay-like minerals, more particularly of the class of smectites and kaolin~ as sub-strates for homogeneous catalysts of asymmetric hydrogenation reactions.
Smectites are fillosilicates the structural unit of which is composed by a tetrahedral layer, an octahedral layer and another tetrahedral layer with a layer charge of 0.25 0.60 per formula uni~due to isomorphic substitutions which a~e distributed in the tetrahedral and the octahedral layers:
such a charge is balanced by easily exchangeable interlayer cations. The exchange capacity is comparatively high and varies from 80 and 150 milliequivalents per 100 grams.
In addition, particularly interesting are a few minerals of the clay type in the group of serpentine kaolin such as halloysite which is the most hydrous variety a~d has an exchange capacity of about 40 milliequivalents per 100 grams.
The catalysts the subject of the present invention are obtained by simple exchange reaction between the cationic complex of the transition metal and the clay-like matexials.
Such catalytic systems have the considerable advantage of the simplicity of preparation and cheapness, especially when compared with the conventional heterogeneization systems which employ modified organic polymeric matrices.
The cationic complex which is catalytically active in the asymmetric hydroger:ation reaction can be selected among th e having the formula P R'x (NR2R3)3_X, detail in the Ca~adian Patent Application No. 275 . 775 of 6 .4. 1977 85~4 Tlle catalysts in ~uestion can be used in the form of a fine powder or granules or can have any shape which is appropriate to the contact procedure to be used.
The process of asymmetric reduction is carried out at a temperature comprised between -70C and +200C, preferably between 0C and 50C at a hydrogen pressure up to 200 atnl, preferably between 1 and 50 atm, and with a molar ratio of the substrate to the catalyst variable between 10 and 10,000.
A few operative characteristics are described in the ensuing examples, which are no limitation and are given only to illustrate the invention.
E X A M P L E
One gram of Hectorite slurried in anhydrous methanol has been exchanged with rhodium by placing them to reach equilibrium overnight with 0.475 g of [Rh COD L]~ CL04 in 50 mls methanol.
COD - cyclooctadiene: L = N-N' bis (R(+) alpha-methyl-benzyl) N-N' bis (diphenylphosphino) ethylenediamine.
- Hectorite takes an intense yellow color and is carefully washed with anh.methanol and then dried. The Rhodium contents is 1.6% by wt.
Such compound has been slurried in anh.ethanol and hydrogenated in an autoclave at a pressure of 20 atm. of hydrogen: there is obtained a product colored in dark red which is characteristic of the hydride species of the Rhodium complex, which has been used in the hydrogenation of the alpha-acetaminocinnamic acid.
A glass flask has been charged with 0.942 g of sub-strate in 25 mls anh.ethanol and 0.450 g of previously hydrogenated catalyst. The flask has been connected to a hydrogenation apparatus working under atmospherical pressure.
The progress of the reaction has been monitored with the conventional pressure-check-ng procedures. After 8 hours, the reaction has been stopped: the catalyst has been filtered off and the solution e~aporated to dryness. The product, characterized through NMR analysis was R(+)N-acetylphenylalanine with[~]2D = 21.5 (c = 1 anh.ethanol).
With the same catalyst of the previous example there have been performed hydrogenation cycles of the alpha-acetaminocinnamic acid: the data which have been obtained are collected in Table 1.
The catalyst is recovered after each cycle by filtration of the reaction mixture, washed with anh.ethanol and reused under the same conditions.
Cycles [c] Reaction [~]
substrate :time 1% Soln.
% hrs. anh.ethanol e.e.
1 4.4 2 + 0.170 37
2 4.4 2~: ~ 0.218 47
3 4.3 20 + 0.230 50
4 4.3 4 + 0.144 31 4.5 20 + 0.184 40 catalyst : Hectorite (RhCODL) g = 0.~10 substrate : alpha-acetaminocinnamic acid pressure : 20 atm of H2 temperature : room temp. 23C
sol~ent : anhydrous ethanol E X A M P T, E S 7-12 Hectorite, prior +o ba-ancing with the cationic complex of Rhodium, has been treated with diluted acetic acid to
sol~ent : anhydrous ethanol E X A M P T, E S 7-12 Hectorite, prior +o ba-ancing with the cationic complex of Rhodium, has been treated with diluted acetic acid to
5~
remove the carbonatcs wllich were present and then thoroughly washed until the washing waters were ne~tral~ The catalyst has been prepared with the same procedure as described in the previous example.
Table 2 reports the data as obtained in successive cycles of reduction of the alpha-aceta~inoacrylic acid.
Cycles ~c] Reaction L ~ ~ %
substrate time c = 1,H20 % hrs. e.e.
I 1.9 1.1/2 - 0.355 53 2 2.0 1.1/4 - 0.425 64 3 2.0 1.0 _ -43 65 4 2.0 1.3/4 - 0.44 66 2.1 1.1/4 - 0.437 66
remove the carbonatcs wllich were present and then thoroughly washed until the washing waters were ne~tral~ The catalyst has been prepared with the same procedure as described in the previous example.
Table 2 reports the data as obtained in successive cycles of reduction of the alpha-aceta~inoacrylic acid.
Cycles ~c] Reaction L ~ ~ %
substrate time c = 1,H20 % hrs. e.e.
I 1.9 1.1/2 - 0.355 53 2 2.0 1.1/4 - 0.425 64 3 2.0 1.0 _ -43 65 4 2.0 1.3/4 - 0.44 66 2.1 1.1/4 - 0.437 66
6 2.0 2.1/2 - 0.~12 6z Hydrogenation of alpha-acetaminoacrylic acid Catalyst : Hectorite (RhCODL) g 0.550 Room temperature : 23C
Pressure : 1 atm H2 Solvent : anhydrous ethanol With the catalyst prepared as in example 7 there have been reduced 0.725 g of 3-acetoxy, 4-methoxy, alpha-acetamino cinnamic acid dissolved in 25 mls of anh.ethanol. The reaction has been carried out in an autoclave (glass) with a hydrogen pressure of 2 atm at room temperature. There has been obtained 3-acetoxy, 4-methoxy, N-acetylphenylalanine with an optical yield of 58%. ~d] 2D2 = + 12.8 (c = 1, acetonej the[~ D (c = 1~ acetone) of enantiomerically pure 3-acetoxy, 6.
~8~i4 4-methoxy N-acetylphenyialanine is -- 22.
In the following examples there are reported the data obtained (Table 3) in tests of asy~netric hydrogenation with a cata]yst obtained by immobilizing the cationic complex of Rhodium on bentonite. The preparation of the catalyst has been made as described in example 1. The reduction cycles have been carried out as in example 2.
Cycles [c] Reaction r ~ 3 %
substrate time c = 1,H20 % hrs. e.e.
I 1.95 3 - 0.272 41 2 1.95 6 - 0.348 52 3 1.95 8 - 0.375 56 4 2.0 10 - 0.352 53 2.0 24 _ 0,416 62 Hydrogenation of alpha-acetaminoacrylic acid.
Catalyst s Benton~te (Rh COD L) g 0.450 Room temperature : 23C
Pressure : 1 atm H2 Solvent : anh.ethanol There are reported data obtained in reduction tests with a catalyst obtained by immobilizing the cationic complex of Rhodium on Halloysite. The preparation of the catalyst has been effected as described in example 1. The reduction cycles have been performed as described in example 2.
1 1~856'~
T ~ B L E 4 Cycles ~c] Reaction [ ~ ] %
substrate time c = l,H20 e.e.
% hrs.
1 1.8 3 - 0.495 74 2 2.0 3 - 0.515 77 3 2.0 24 - 0.500 75 Hydrogenation of alpha-acetaminoacrylic acid.
. Catalyst : Halloysite (P~C0~ L) g 0.500 Room temperature : 23C
Hydrogen pressure : 1 atm Solvents : anh.ethanol.
Pressure : 1 atm H2 Solvent : anhydrous ethanol With the catalyst prepared as in example 7 there have been reduced 0.725 g of 3-acetoxy, 4-methoxy, alpha-acetamino cinnamic acid dissolved in 25 mls of anh.ethanol. The reaction has been carried out in an autoclave (glass) with a hydrogen pressure of 2 atm at room temperature. There has been obtained 3-acetoxy, 4-methoxy, N-acetylphenylalanine with an optical yield of 58%. ~d] 2D2 = + 12.8 (c = 1, acetonej the[~ D (c = 1~ acetone) of enantiomerically pure 3-acetoxy, 6.
~8~i4 4-methoxy N-acetylphenyialanine is -- 22.
In the following examples there are reported the data obtained (Table 3) in tests of asy~netric hydrogenation with a cata]yst obtained by immobilizing the cationic complex of Rhodium on bentonite. The preparation of the catalyst has been made as described in example 1. The reduction cycles have been carried out as in example 2.
Cycles [c] Reaction r ~ 3 %
substrate time c = 1,H20 % hrs. e.e.
I 1.95 3 - 0.272 41 2 1.95 6 - 0.348 52 3 1.95 8 - 0.375 56 4 2.0 10 - 0.352 53 2.0 24 _ 0,416 62 Hydrogenation of alpha-acetaminoacrylic acid.
Catalyst s Benton~te (Rh COD L) g 0.450 Room temperature : 23C
Pressure : 1 atm H2 Solvent : anh.ethanol There are reported data obtained in reduction tests with a catalyst obtained by immobilizing the cationic complex of Rhodium on Halloysite. The preparation of the catalyst has been effected as described in example 1. The reduction cycles have been performed as described in example 2.
1 1~856'~
T ~ B L E 4 Cycles ~c] Reaction [ ~ ] %
substrate time c = l,H20 e.e.
% hrs.
1 1.8 3 - 0.495 74 2 2.0 3 - 0.515 77 3 2.0 24 - 0.500 75 Hydrogenation of alpha-acetaminoacrylic acid.
. Catalyst : Halloysite (P~C0~ L) g 0.500 Room temperature : 23C
Hydrogen pressure : 1 atm Solvents : anh.ethanol.
Claims (4)
1. In a method for the asymmetric hydrogenation of a prochiral olefin selected from the group consisting of alpha-acrylamide acrylic acids, alpha-acetoamino-cinnamic acid, alpha-acetoamino-acrylic acid, and 3-acetoxy-4-methoxy alpha-acetoami-nocinnamic acid, comprising contacting said olefin with a catalyst composed of a cationic complex of rhodium with aminic derivatives of phosphorus, the improvement comprising immobilizing said catalyst on a silicate clay material selected from the group consisting of smectites and kaolin.
2. The method of claim 1, characterized in that the reaction takes place at a temperature between 0°C and 50°C.
3. The method of claim 1, characterized in that the hydrogen pressure is between 1 to 50 atmospheres.
4. The method of claims 1, 2 or 3, characterized in that the molar ratio of the substrate to the catalyst is from 10 to 10,000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT28666A/77 | 1977-10-17 | ||
| IT28666/77A IT1087963B (en) | 1977-10-17 | 1977-10-17 | ASYMMETRICAL HYDROGENATION OF PROCHIRAL OLEFINS BY COMPLEX OF TRANSITION METALS IMMOBILIZED IN CLAY MINERALS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1148564A true CA1148564A (en) | 1983-06-21 |
Family
ID=11223981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000311978A Expired CA1148564A (en) | 1977-10-17 | 1978-09-25 | Asymmetric hydrogenation of prochiral olefines by complexes of transition metals immobilized in clay-like minerals |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS5466615A (en) |
| AU (1) | AU520574B2 (en) |
| BE (1) | BE871320A (en) |
| CA (1) | CA1148564A (en) |
| CH (1) | CH636589A5 (en) |
| CS (1) | CS208483B2 (en) |
| DD (1) | DD139251A5 (en) |
| DE (1) | DE2845216C2 (en) |
| DK (1) | DK461478A (en) |
| FR (1) | FR2405911A1 (en) |
| GB (1) | GB2006770B (en) |
| HU (1) | HU181953B (en) |
| IL (1) | IL55733A (en) |
| IT (1) | IT1087963B (en) |
| LU (1) | LU80370A1 (en) |
| NL (1) | NL7810236A (en) |
| NO (1) | NO148778C (en) |
| SE (1) | SE435923B (en) |
| YU (1) | YU237578A (en) |
| ZA (1) | ZA785486B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU190864B (en) * | 1983-12-08 | 1986-11-28 | Alkaloida Vegyeszeti Gyar | Process for production of phenil-alanin derivatives |
| GB8519008D0 (en) * | 1985-07-27 | 1985-09-04 | British Petroleum Co Plc | Chemical process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4008281A (en) * | 1973-12-03 | 1977-02-15 | Monsanto Company | Asymmetric catalysis |
| CA1109074A (en) * | 1976-04-26 | 1981-09-15 | Mario Fiorini | Asymmetrical hydrogenation and related means for this purpose |
-
1977
- 1977-10-17 IT IT28666/77A patent/IT1087963B/en active
-
1978
- 1978-09-25 CA CA000311978A patent/CA1148564A/en not_active Expired
- 1978-09-27 ZA ZA00785486A patent/ZA785486B/en unknown
- 1978-09-27 AU AU40251/78A patent/AU520574B2/en not_active Expired
- 1978-10-09 JP JP12370578A patent/JPS5466615A/en active Pending
- 1978-10-10 YU YU02375/78A patent/YU237578A/en unknown
- 1978-10-11 GB GB7840114A patent/GB2006770B/en not_active Expired
- 1978-10-11 NL NL7810236A patent/NL7810236A/en not_active Application Discontinuation
- 1978-10-13 IL IL55733A patent/IL55733A/en unknown
- 1978-10-16 DD DD78208480A patent/DD139251A5/en unknown
- 1978-10-16 NO NO783492A patent/NO148778C/en unknown
- 1978-10-16 HU HU78SA3141A patent/HU181953B/en unknown
- 1978-10-16 FR FR7829446A patent/FR2405911A1/en active Granted
- 1978-10-16 CS CS786724A patent/CS208483B2/en unknown
- 1978-10-16 DK DK461478A patent/DK461478A/en not_active Application Discontinuation
- 1978-10-16 CH CH1070078A patent/CH636589A5/en not_active IP Right Cessation
- 1978-10-16 LU LU80370A patent/LU80370A1/en unknown
- 1978-10-16 SE SE7810776A patent/SE435923B/en unknown
- 1978-10-17 BE BE191166A patent/BE871320A/en not_active IP Right Cessation
- 1978-10-17 DE DE2845216A patent/DE2845216C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NO148778C (en) | 1983-12-14 |
| JPS5466615A (en) | 1979-05-29 |
| ZA785486B (en) | 1979-09-26 |
| NO783492L (en) | 1979-04-18 |
| DD139251A5 (en) | 1979-12-19 |
| AU520574B2 (en) | 1982-02-11 |
| NO148778B (en) | 1983-09-05 |
| DE2845216C2 (en) | 1984-05-10 |
| FR2405911A1 (en) | 1979-05-11 |
| GB2006770B (en) | 1982-03-17 |
| IL55733A0 (en) | 1978-12-17 |
| NL7810236A (en) | 1979-04-19 |
| IT1087963B (en) | 1985-06-04 |
| DE2845216A1 (en) | 1979-04-19 |
| SE435923B (en) | 1984-10-29 |
| SE7810776L (en) | 1979-04-17 |
| CH636589A5 (en) | 1983-06-15 |
| DK461478A (en) | 1979-04-18 |
| CS208483B2 (en) | 1981-09-15 |
| YU237578A (en) | 1983-01-21 |
| HU181953B (en) | 1983-11-28 |
| BE871320A (en) | 1979-04-17 |
| GB2006770A (en) | 1979-05-10 |
| IL55733A (en) | 1981-11-30 |
| FR2405911B1 (en) | 1981-03-20 |
| AU4025178A (en) | 1980-04-03 |
| LU80370A1 (en) | 1979-03-19 |
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