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
- Authority
- CA
- Canada
- Prior art keywords
- alpha
- catalyst
- clay
- prochiral
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 title claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 title abstract description 5
- 239000011707 mineral Substances 0.000 title abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 title description 4
- 150000003624 transition metals Chemical class 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000010948 rhodium Substances 0.000 claims abstract description 11
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 230000003100 immobilizing effect Effects 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 230000006872 improvement Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 11
- 229910000271 hectorite Inorganic materials 0.000 abstract description 6
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 abstract description 5
- 239000000440 bentonite Substances 0.000 abstract description 2
- 229910000278 bentonite Inorganic materials 0.000 abstract description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- XODAOBAZOQSFDS-UHFFFAOYSA-N 2-acetamido-3-phenylprop-2-enoic acid Chemical compound CC(=O)NC(C(O)=O)=CC1=CC=CC=C1 XODAOBAZOQSFDS-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UFDFFEMHDKXMBG-UHFFFAOYSA-N 2-acetamidoprop-2-enoic acid Chemical compound CC(=O)NC(=C)C(O)=O UFDFFEMHDKXMBG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 3
- 229910052621 halloysite Inorganic materials 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VFUFIIXSVCSRBQ-NSHDSACASA-N (2S)-2-acetamido-3-(3-acetyloxy-4-methoxyphenyl)propanoic acid Chemical compound COC1=CC=C(C[C@H](NC(C)=O)C(O)=O)C=C1OC(C)=O VFUFIIXSVCSRBQ-NSHDSACASA-N 0.000 description 1
- CBQJSKKFNMDLON-JTQLQIEISA-N N-acetyl-L-phenylalanine Chemical compound CC(=O)N[C@H](C(O)=O)CC1=CC=CC=C1 CBQJSKKFNMDLON-JTQLQIEISA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- -1 alpha-methyl-benzyl Chemical group 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- QIIDJGRNOPDQIC-UHFFFAOYSA-N cyclohexylmethyl-[(2-methoxyphenyl)methyl]phosphane;rhodium Chemical compound [Rh].COC1=CC=CC=C1CPCC1CCCCC1 QIIDJGRNOPDQIC-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- HZPZCHFYBJYZKQ-UHFFFAOYSA-N n,n'-bis(diphenylphosphanyl)ethane-1,2-diamine Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)NCCNP(C=1C=CC=CC=1)C1=CC=CC=C1 HZPZCHFYBJYZKQ-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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 NO NO783492A patent/NO148778C/en unknown
- 1978-10-16 CS CS786724A patent/CS208483B2/en unknown
- 1978-10-16 FR FR7829446A patent/FR2405911A1/en active Granted
- 1978-10-16 CH CH1070078A patent/CH636589A5/en not_active IP Right Cessation
- 1978-10-16 DK DK461478A patent/DK461478A/en not_active Application Discontinuation
- 1978-10-16 SE SE7810776A patent/SE435923B/en unknown
- 1978-10-16 HU HU78SA3141A patent/HU181953B/en unknown
- 1978-10-16 LU LU80370A patent/LU80370A1/en unknown
- 1978-10-16 DD DD78208480A patent/DD139251A5/en unknown
- 1978-10-17 DE DE2845216A patent/DE2845216C2/en not_active Expired
- 1978-10-17 BE BE191166A patent/BE871320A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5466615A (en) | 1979-05-29 |
| DD139251A5 (en) | 1979-12-19 |
| HU181953B (en) | 1983-11-28 |
| CS208483B2 (en) | 1981-09-15 |
| CH636589A5 (en) | 1983-06-15 |
| DE2845216A1 (en) | 1979-04-19 |
| NL7810236A (en) | 1979-04-19 |
| YU237578A (en) | 1983-01-21 |
| NO148778B (en) | 1983-09-05 |
| SE7810776L (en) | 1979-04-18 |
| LU80370A1 (en) | 1979-03-19 |
| FR2405911B1 (en) | 1981-03-20 |
| IL55733A0 (en) | 1978-12-17 |
| NO783492L (en) | 1979-04-18 |
| GB2006770A (en) | 1979-05-10 |
| IL55733A (en) | 1981-11-30 |
| SE435923B (en) | 1984-10-29 |
| AU4025178A (en) | 1980-04-03 |
| IT1087963B (en) | 1985-06-04 |
| FR2405911A1 (en) | 1979-05-11 |
| DK461478A (en) | 1979-04-18 |
| GB2006770B (en) | 1982-03-17 |
| NO148778C (en) | 1983-12-14 |
| ZA785486B (en) | 1979-09-26 |
| AU520574B2 (en) | 1982-02-11 |
| BE871320A (en) | 1979-04-17 |
| DE2845216C2 (en) | 1984-05-10 |
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