JPS6348586B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hydrogenation catalyst, a method for producing the same, and a hydrogenation method. Hydrogenation with small metal catalysts in homogeneous solution has no practical application either in the laboratory or in industry. This is because there are complex problems associated with separating reaction products and catalyst. Attempts have therefore been made to attach small molecule homogeneous catalysts to polymers containing phosphine groups.
The use of insoluble polymers results in heterogeneity. These polymer complexes having triphenylphosphine groups are
Like the small molecule complexes mentioned above, it has somewhat poor selectivity and stability. It is therefore an object of the present invention to provide catalysts that are soluble in common hydrocarbon solvents, that promote hydrogenation faster and more selectively than known catalysts, that are easily separated from the reaction products, and that It is an object of the present invention to provide a polymer hydrogenation catalyst that is sufficiently active over a period of time. Another object of the present invention is to provide a method for producing the above hydrogenation catalyst. Furthermore, an object of the present invention is to provide a method for hydrogenating organic compounds using the above hydrogenation catalyst. The hydrogenation catalyst of the present invention is a soluble polymer (which may be synthetic or semi-synthetic) that binds metals of subgroups of the periodic table or their salts through covalent bonds or secondary valence bonds. It is formed by combining. This hydrogenation catalyst is very effective in various hydrogenation reactions. The basic structure of the above polymer provides a soluble hydrogenation catalyst that can be used for hydrogenation in common solvents. The hydrogenation catalyst of this invention can be prepared from low molecular weight starting materials and from reaction products by conventional methods such as precipitation, distillation and extraction, as well as by diafiltration and gel chromatography, taking advantage of molecular weight differences. Can be separated. The problem of separation is thus simplified, while also preserving the homogeneous nature of the reaction. Among the hydrogenation catalysts of this invention, preferred ones are:
polyvinyl alcohol, polyvinylpyrrolidone,
polyacrylonitrile, polyacrylic acid, polyethylene glycol, polypropylene glycol,
These are derived from functionalized polystyrene, carboxymethylcellulose, polyurethane, polyvinylamine, polyethyleneimine, as well as synthetic and semi-synthetic polyamides, polypeptides and polymerized polyhydroxy compounds and mixtures thereof. The molecular weight of the above polymer can be selected within a wide range, for example from 1000 to 1000000, preferably about
5,000 to 300,000, more preferably 5,000 to 300,000
It is 100000. According to the invention, the polymer can be reacted directly with a salt or complex of a metal or metal ion of subgroup of the periodic table. These metal salts or metal complexes include Fe, Co, Ni, Ru, Rh, Pd, Os,
Advantageously, it is derived from Ir or Pt. The rate at which the metal or metal ion is bound to the functional polymer can vary within wide limits. Preferably, about 0.1-10% of the metal is bound to the polymer.
Increasing the metal bonding ratio beyond this does not increase the rate of hydrogenation. The metal-bonded polymers are generally produced in a very simple manner, namely by reacting at least one of the polymers with a metal from subgroup of the periodic table, an ion or a complex thereof, in aqueous solution or in an organic solvent. You can do it by setting it up. The metal or metal ion-containing polymer thus obtained can be separated from low molecular weight components by diafiltration, purified, and used in a hydrogenation reaction in solution without isolation. If desired, isolation can be achieved by precipitation, reprecipitation, evaporation of the solvent or lyophilization. Generally, metals from subgroups of the periodic table or ions thereof are reacted with polymers of the type described above and utilized as hydrogenation catalysts in accordance with the present invention. In addition to the above-mentioned polymers, as starting polymers for producing the polymer-based hydrogenation catalyst of the present invention,
Polymers modified by functionalization to incorporate other metal-binding groups can also be used. In addition to the aforementioned phosphine groups, sulfonic acid groups, carbonyl groups, carboxyl groups, amino groups, imino groups, hydroxyl groups, cyano groups, and/or acid amide groups can be introduced into the polymer as metal-binding functional groups. can. Metal compounds can also be bonded as pi complexes by olefins or aromatic compounds, or by carbon-metal bonds. Furthermore, in addition to directly bonding the metal or metal ion to the polymer as described above,
Coordination bonds or salt-forming bonds can also be bonded by means of small molecule ligands. For example, phosphines such as triphenylphosphine, carbon monoxide,
Halides are especially chlorides, cyanides, nitriles, alkenes, alkynes, especially acetylenes, and/or cyclopentadiene anions. Particularly preferred hydrogenation catalysts of the invention are metals of subgroups of the periodic table or metal salts, preferably metal palladium or palladium salts, which are covalently bonded and/or secondary to soluble synthetic or semisynthetic polymers. The metal is bonded by a valence bond, and at least one low molecular weight ligand is further bonded to the metal. These preferred hydrogenation catalysts can include the following small molecule ligands. (a) Amines. (b) Amino acids. (c) General formula R-(CHR ¹ ) _o -CN () (where R is a phenyl group, a naphthyl group, an anthracenyl group, or a phenanthrenyl group, and one or more straight-chain or branched C ₁ to _{C 6} alkyl The groups may be substituted, or R is a straight-chain or branched _C1 - _C6 alkyl group, ^R1 is hydrogen or a straight-chain or branched _C1 - _C6 alkyl group, and n is 0, 1 or 2) A nitrile represented by (d) General formula P(R ² ) ₃ ( ) (where R ² is the same or different group and is a straight chain or branched C ₁ -C ₆ alkyl group, a phenyl group, one or more straight chain chain or branch
Phosphines (including unsubstituted triphenylphosphine) represented by a phenyl group substituted by a _C1 - _C6 alkyl group or a C1 _{- C6} alkoxy group. (e) Olefins or alkynes (including cyclic olefins or alkynes). (f) Phosphoryl compounds. Particularly advantageous low molecular weight ligands of the type mentioned above are listed below. (a) primary with bulky aliphatic, cycloaliphatic or aromatic substituents, in particular branched aliphatic groups having from 4 to 16 carbon atoms, such as isopropyl, tert-butyl and neopentyl; Secondary or tertiary amines. (b) Amines having alicyclic groups (for example, cyclopentyl, cyclohexyl and adamantyl groups). (c) the alkyl radical contains from 1 to 6 carbon atoms and the aliphatic radical has at least one aromatic radical (in particular at least one phenyl radical) and/or at least one naphthyl radical; Araliphatic amines having an anthracenyl group or a phenanthrenyl group. Particularly preferred among this type of ligands are phenylethylamine (especially 1-phenylethylamine), diphenylethylamine (especially 1,1
-diphenylethylamine) and phenylpropylamine. In the aliphatic amines mentioned here, the bulky substituent, especially the aromatic group, is preferably located in the 1st or 2nd position with respect to the amino group bonded to the aliphatic group. Particularly preferred nitrile ligands of the above formula are those in which the cyano group is directly bonded to an aromatic group (particularly a phenyl group, a naphthyl group, an anthracenyl group or a phenanthrenyl group). In this case, the cyano group may be bonded to any position of the aromatic group. The aromatic radicals can also be substituted by one or two short-chain aliphatic branched or straight-chain radicals, especially by _C1 - _C6 alkyl radicals. This substituent is
Particularly bulky alkyl groups such as tert-butyl group, amyl group, neopentyl group and the like. Furthermore, nitriles in which the cyano group is separated from the aromatic group by 1 or 2 carbon atoms are also suitable. Such alkylene-bridged nitriles have a branched or straight chain C ₁ to
C ₆ alkyl group e.g. methyl group, ethyl group, n
-propyl group, isopropyl group, n-butyl group,
It may have a sec-butyl group, tert-butyl group, amyl group, neopentyl group or hexyl group. Preferred amino acids are those having bulky groups in the 1st to 3rd positions relative to the amino group. Preferred examples of this type include diphenylglycine, norleucine, leucine, isoleucine, tertiary leucine, and valine. Suitable phosphine-based ligands are, for example, arylphosphines, which may have one or more lower alkoxy or lower alkyl groups substituted on the aryl nucleus, especially on the phenyl nucleus.
Particularly preferred is triphenylphosphine, in which the phenyl group is substituted with the above groups. Suitable olefins are C2 to C12 cis or trans monoolefins which contain other groups in the carbon chain, such as C1 to C6 groups,
Halogen (e.g. F, Cl, Br, I), cyano group, carbonyl group, carboxyl group, amino group,
It may be substituted with an amide group or the like. Examples include ethylene, propylene, n-butene(1), n-
-butene (2), n-pentene (1), n-pentene (2),
n-pentene (3), n-hexene (1), n-hexene
(2), n-hexene (3), isopentene, isohexene, n- and iso-heptene, n- and iso-octene, n- and iso-nonene, n- and iso-decene, n- and iso-dodecene, Isobutylene, 2-methyl-butene (1), 3-methyl-butene (1), n-heptene (1), n-octene (1),
Allyl chloride, allyl bromide, etc., as well as cis or trans di- and polyolefins, such as di- and triolefins having 4 to 12 carbon atoms. These may be substituted with other substituents such as C ₁ -C ₆ alkyl groups, halogens, C≡N- groups, carbonyl groups, carboxyl groups, hydroxy groups, and the like. Examples of this type include butadiene (1,3), 2,3-dimethylbutadiene (1,3),
3), pentadiene, hexadiene, hexatriene, dodecatriene, etc. Examples of suitable alkynes include acetylene having 2 to 12 carbon atoms, methylacetylene, ethylacetylene, dimethylacetylene, pentyne (1), pentyne (2), 3-methylbutyne (1), hexyne (1). , hexine (2), hexine (3), 3,3-dimethylbutyne (1), etc. As in the case of the olefins described above, these alkynes may contain suitable functional groups such as carboxyl groups (in this case acetylene dicarboxylic acid), hydroxy groups, halogens,
It may be substituted with a _C1 - _C6 alkyl group or the like. Examples of suitable cyclic dienes are 1,3-cyclohexadiene, 1,4-cyclohexadiene and cyclooctadiene, especially 1,3-cyclooctadiene and 1,5-cyclooctadiene. Phosphoryl compounds are also suitable ligands. For example, methylenetriphenylphosphorane, whose methylene group contains an aliphatic group or an aromatic group, especially C ₁
It may be substituted with a ~ _C6 alkyl group, phenyl group, or benzyl group, and the methylene group may be a part of the ring of a cycloaliphatic group. Generally, the selectivity of the hydrogenation reaction increases as the bulk of the ligand increases. That is, when benzonitrile is used as a ligand, the selectivity is not very high, but when naphthonitrile is used,
Selectivity is greatly increased. When using cyanoanthracene, the selectivity is very high. Furthermore, the selectivity differs among amines. For example, the selectivity of 1,1-diphenylethylamine is much higher than that of 1-phenylethylamine. However, the latter compound itself also has very high selectivity. A drawback of conventional methods for hydrogenating fats has been that the desired unsaturated cis fatty acid esters are over hydrogenated. Furthermore, a large proportion of the esters were isomerized to the less desirable trans form. Compared to the above-mentioned conventional methods, the hydrogenation catalyst of the present invention, particularly one having a low molecular weight ligand, has the advantage that selective hydrogenation can be carried out when it is used for hydrogenation of fats. That is, it is possible to selectively hydrogenate only one double bond or only two double bonds in a fatty residue with several points of unsaturation. During this process, the cis conformation of the starting material is maintained to a large extent, often completely. In fact, no double bond isomerization occurs. In other words, no double bond transition occurs. The above observations clearly demonstrate that the hydrogenation catalyst of the present invention avoids the disadvantage of the prior art method, which is overhydrogenation of the fat to complete saturation. According to this invention, hydrogenation can be stopped to a desired degree of partial hydrogenation. The hydrogenation catalyst of the present invention having a low-molecular-weight ligand is a salt or complex of a metal from subgroup of the periodic table containing a low-molecular-weight ligand, preferably a palladium salt or a palladium complex, in an aqueous solution or an organic solvent. and optionally hydrogenation (reduction of the metal salt or metal complex with hydrogen).
It can be manufactured by The above reaction mixture can be used as a hydrogenation catalyst as it is, or it can be used as a hydrogenation catalyst after separating the low molecular weight starting material and the reaction product. The hydrogenation catalyst obtained as described above may be separated from low molecular weight components by diafiltration and purified, or may be subjected to the hydrogenation step as a solution without being isolated. If desired, the hydrogenation catalyst may be isolated by precipitation, reprecipitation, evaporation of the solvent or lyophilization. The hydrogenation catalyst of the present invention can be used for the hydrogenation of a wide variety of organic compounds in water or an organic solvent, at room temperature or at elevated temperature, and under pressure or normal pressure. The hydrogenation catalysts of the invention can also be used in suspensions, such as emulsions of fats or fatty acids in water. Thus, nitro, nitroso, and cyano groups can be hydrogenated to amines. Furthermore, the hydrogenation catalyst of this invention is an olefin,
Acetylene, aromatic compound, C=O- compound, C
It can be used for the hydrogenation of =N- and N=N-compounds. The type of metal or polymer makes the hydrogenation catalyst particularly suitable for a particular hydrogenation. That is, the structure of the polymeric metal complexes of this invention allows certain C≡C-triple bond compounds to be hydrogenated to cis or trans olefins, and also has several C≡C-double bonds. In organic compounds, certain individual double bonds can be hydrogenated at a greater rate than other double bonds.
The hydrogenation catalyst of this invention can be used in discontinuous or continuous processes and can be reused repeatedly. Examples of this invention will be described below. Example 1 1% of polyvinyl alcohol (molecular weight 72000)
Add 25 ml of the aqueous solution to 1 ml of a suspension of _PdCl2 in water (Pd
(equivalent to 10 mg), which was then treated with 4% Na ₂ CO ₃
0.5 ml of aqueous solution was added dropwise. Add water to this and 50ml
The mixture was reduced with H ₂ and subjected to diafiltration at a constant volume for 12 hours using a membrane that permeates substances with a molecular weight of less than 3000. This solution containing Pd at a rate of about 0.2 mg Pd/ml could be used directly for hydrogenation. Lyophilized for isolation. Yield is 0.23
g, which contained 3.9% Pd. According to the above steps, it was possible to produce a polymeric palladium compound having polyvinylpyrrolidone (for example Rubiscoll K70 manufactured by BASF) or carboxymethyl cellulose (Relatin manufactured by Henkel). The above palladium compounds were reacted in the same manner as with 25 ml of 1% solutions of these polymers. Example 2 1 ml of an aqueous suspension of PdCl ₂ (Pd content 10 mg) was added at room temperature to 25 ml of a 1% solution of polyvinyl alcohol (molecular weight 72000) in methanol (or propanol). Then, 1 ml of 2% triethylamine solution
was added dropwise, methanol (or propanol) was added to bring the total volume to 50 ml, the mixture was reduced with _H2 , and diafiltration was performed for 24 hours using a polyamide membrane (permeable to molecules with a molecular weight of less than 10,000). The residual liquid contains Pd at a rate of approximately 0.2mgPd/ml.
This could be used directly for hydrogenation. For isolation, the residual liquid (low molecular weights removed by diafiltration) was separated by evaporation of the solvent to dryness. The yield was 0.24 g (Pd content 3.8%). Example 3 1% methanol solution of polyvinylpyrrolidone25
ml was reacted with 38 mg of PdCl ₂ .2C ₆ H ₅ CN at room temperature under stirring. Then, 1 ml of a 2% methanol solution of triethylamine was added dropwise, methanol was added to make 50 ml, the mixture was reduced with hydrogen, and the mixture was diafiltered under constant volume for 24 hours. This residual liquid could be used directly for hydrogenation. The residual liquid was evaporated to dryness for isolation.
The yield was 0.22 g (Pd content 3.95%). Example 4 Following the procedure of Example 3, a 1% aqueous solution of polyvinylpyrrolidone was reacted with 1 ml of an aqueous solution of K ₂ [PtCl ₄ ] (platinum content 10 mg). The yield was 0.23g, Pt
The content rate was 3.7%. Example 5 25 ml of a 1% aqueous solution of polyvinylpyrrolidone was
React with 15mg of (OH) ₃ and add methanol to 50ml
and reduced with _H2 . This is then passed through a polyamide membrane (those with a molecular weight of less than 10,000 permeate) under a constant volume.
The mixture was diafiltered for 18 hours. The obtained rhodium polymer could be directly used for hydrogenation as a solution. For isolation, the dialysis residue was evaporated to dryness.
The yield was 2.2 g (Rh content 2.1%). Example 6 Following the steps of Example 5, 15 mg of Ru(OH) ₃ was reacted with 25 ml of a 1% solution of polyvinylpyrrolidone.
Yield was 2.05g and contained 3.5% Ru. Example 7 Following the steps of Example 1, 25 ml of an aqueous solution of polyvinylpyrrolidone was reacted with 1 ml of an aqueous solution of Na ₃ [IrCl ₆ ] (10 mg of iridium). The yield was 2.1 g (iridium content 3.5%). Example 8 1% methanol solution of polyvinylpyrrolidone25
ml was reacted with 13 mg of osmium tetroxide at room temperature, and acetylene was passed through the reaction solution for 30 minutes. Then, methanol was added to make up to 50 ml, and the mixture was diafiltered to a constant volume using a conventional method. This residual liquid could be used as it was for hydrogenation. For isolation, the residue was evaporated to dryness under reduced pressure. The yield was 2.1 g, and the osmium content was 4.0%. Example 9 (a) Chloromethylated linear non-crosslinked polystyrene (molecular weight 34000) was dissolved in dimethylformamide (DMF)
Triphenylphosphine 280mg dissolved in 50ml
and the solution was heated under reflux for 24 hours. After this reaction solution was cooled, it was introduced into 500 ml of ice-cooled petroleum ether (boiling point 30-50°C) to precipitate the produced polymer. The resulting polymer was filtered, dried, and dissolved in 50 ml of benzene, which was again poured into ice-cold petroleum ether and reprecipitated. The polymeric phosphonium salt thus obtained was dried under reduced pressure of P ₄ O ₁₀ . The P content was 1.63%. (b) 2 g of polymer phosphonium salt obtained in step (a) above
was suspended in 60 ml of dry benzene under N ₂ in a bifurcated tube and reacted with 0.17 ml of n-butyllithium. The suspension became clear and yellowish. After stirring for 1 hour, a small amount of lithium chloride was filtered off and the filtrate was reacted with 153 mg _{of PdCl2} .( _C6H5CN ) ₂ . When this solution was stirred at 60° C. for 3 days, it became dark and colored. After cooling, it was filtered, and the filtrate was poured into 500 ml of ice-cooled petroleum ether to precipitate the resulting polymer as a gray powder. The dissolution in benzene and precipitation in petroleum ether was repeated twice. It was then dried over P ₄ O ₁₀ under reduced pressure. For further purification, the resulting polymer was dissolved in benzene and diafiltered using a polyamide membrane that is permeable to molecules with molecular weights less than 10,000. Furthermore, ultrafiltration was performed until the filtrate became clear. The resulting polymer was again precipitated in ice-cold petroleum ether and dried in the same manner as above. The yield was 1.9g (Pd content 5.4%). Example 10 25 ml of a 1% solution of linear polyacrylonitrile (molecular weight ¹⁰⁶ daltons) in N-methylpyrrolidone (NMP) is reacted with 17 mg of solid PdCl ₂ at room temperature,
1 ml of a 2% solution of triethylamine in NMP was added and the mixture was made up to 50 ml with NMP. 10 ml of the above solution was charged into a hydrogenation reactor, flushed three times with H ₂ and stirred under H ₂ for 12 hours. Then 1 mmol of pentyne (2) was added and hydrogenated at room temperature and under 1 bar. After 20 to 60 minutes, gas chromatographic analysis showed that 96% of cispentene (2), plus 2% of transpentene (2) and 2% of n-pentane were obtained. Example 11 Polyacrylonitrile was prepared in the same manner as in Example 10.
A solution of 50 ml of palladium complex was prepared, and 10.5 mg of triphenylphosphine was added to this reaction solution. The above solvent was previously hydrogenated in the same manner as in Example 10.
Then, 1 mmol of pentyne (1) was added and hydrogenated. After 20 to 60 minutes, gas chromatographic analysis showed that 97% of pentene-(1) and 3% of n-pentane were obtained. After separation by distillation or ultrafiltration, the catalyst could be reused. Example 12 5 each of the catalyst solutions obtained in Examples 1, 2, 3 or 4
Hydrogenation was carried out as follows using ml. 5 ml of each catalyst solution was diluted with 30 ml of distilled water, rinsed three times with H ₂ and stirred under hydrogen for 30 min to prehydrate. 1 mmol of p-nitrophenol was then added and hydrogenated at room temperature and under 1 bar. Thereafter, it was filtered under constant volume at 2 bar using a polysulfone membrane that allows substances with a molecular weight of 10,000 to pass through. p-aminophenol was obtained in the filtrate with a yield of 97%. Hydrogenation times varied from 20 to 120 minutes depending on the catalyst used. The liquid retained by diafiltration contained a hydrogenation catalyst, which could be reused. Example 13 Hydrogenation catalyst solution 5 obtained in Example 5, 6 or 7
ml into a hydrogenation flask, diluted with 30 ml of distilled water, flushed with hydrogen three times, and heated under hydrogen at 60°C.
It was previously hydrogenated by stirring for 24 hours. Then, 1 mmol of p-nitrophenol was added,
Hydrogenation was carried out at room temperature and 1 bar. Hydrogenation times ranged from 20 minutes to 4 hours depending on the catalyst used. The yield of 4-aminocyclohexanol is 85~
It was 90%. Example 14 In a hydrogenation reaction vessel, 5 ml of the hydrogenation catalyst solution obtained in Example 2 was mixed with 12.5 ml of methanol and 7.5 ml of distilled water.
ml and flushed three times with _H2 . This was then preactivated under _H2 for 30 minutes. To this was added 1 mmol of maleic acid and hydrogenated for 2 hours at 20° C. and 1 bar. This reaction mixture was filtered using a membrane that allows molecules with a molecular weight of less than 10,000 to pass through. The filtrate contained succinic acid with a yield of 97%. Example 15 In a hydrogenation reaction vessel, 10 ml of the hydrogenation catalyst solution of Example 2 was diluted with 30 ml of methanol, flushed three times with H ₂ and preactivated for 30 minutes under H ₂ .
To this was added 1 mmol of linoleic acid and hydrogenated for 20 minutes. After diafiltration, stearic acid was removed.
Contained with a yield of 94%. Other unsaturated fatty acids could be hydrogenated under the same conditions as above. For example, oleic acid was hydrogenated to stearic acid. Example 16 In the same manner as in Example 14, 1 mmol of cyclohexene, pentyne or hexyne (2) was hydrogenated. Hydrogenation was completed in 20 minutes. In this way, cyclohexane, n-pentane or n-hexane were obtained quantitatively. Example 17 In a hydrogenation reaction vessel, the hydrogenation catalyst solution obtained in Example 2 was diluted with 20 ml of methanol and 20 ml of water,
Preactivation was performed by flushing three times with H ₂ and stirring for 30 minutes under H ₂ . Next, add this to the formula 1 g of a polyethylene glycol (PEG) polymer peptide having one benzyl ester group bound thereto was added and hydrogenated for 25 minutes (hydrogenation cleavage of benzyl ester). Then, the molecular weight is 10000
Diafiltration was performed using a membrane that allows less than The product peptide was obtained from the filtrate by freeze-drying. The yield was 98%. Example 18 In a hydrogenation reaction vessel, 100 mg of the hydrogenation catalyst solution from Example 9 was dissolved in 30 ml of dioxane, flushed three times with _H2 , and preactivated by stirring overnight under _H2 . . Then, 5 ml of cyclohexadiene (1,3) was added to this and hydrogenated for 30 minutes. 4 ml H ₂ /min was absorbed, and by stopping the reaction an additional 0.4 ml H ₂ /min was absorbed. The above reaction mixture was filtered using a membrane that allows substances having a molecular weight of 10,000 to pass therethrough. Gas chromatographic analysis showed that the filtrate contained 90% cyclohexene and 5% cyclohexane. Example 20 PdCl ₂ ×2 (9-cyano-anthracene) 5.5 mg
(approximately 1 mg Pd) was dissolved in 0.5 ml of N-methylpyrrolidone and diluted with 40 ml of a 1% solution of polyvinylpyrrolidone (molecular weight approximately 200,000) in n-propanol. Thereafter, 0.25 ml of a 2% solution of triethylamine in n-propanol was added and this was reduced with hydrogen.
With the air excluded, 5 ml of linseed oil was added using a pipette, and the mixture turned dark and colored within an hour. The mixture was hydrogenated at room temperature under 1 bar of hydrogen pressure while stirring. Absorbed 200ml of hydrogen (104
After 1 min), the hydrogenation was complete. The solvent was evaporated on a rotary evaporator and the hydrogenated oil was extracted from the residue with petroleum ether. After evaporating the petroleum ether, the resulting hydrogenated oil was saponified with alcoholic potassium hydroxide. The fatty acids thus obtained were esterified using diazomethane and analyzed by gas chromatography. Hydrogenation catalysts that are insoluble in petroleum ether are n
-Can be dissolved in propanol and reused for hydrogenation. (See table below). Example 20 The cyano-anthracene complex used in Example 19 was
PdCl ₂ ×2β-naphthonitrile 4.6mg (approximately 1mgPd)
The same operation as in Example 19 was performed except that . (See table below). Example 21 PdCl ₂ ×2 (1-phenylethylamine) instead of the cyano-anthracene complex used in Example 19
The same operation as in Example 19 was performed except that 4.0 mg (approximately 1 mg Pd) was used (see table below). Example 22 PdCl ₂ ×2 (1,1-diphenylethylamine)
5.4 mg was dissolved in 0.5 ml of N-methylpyrrolidone and diluted with 40 ml of a 1% solution of polyvinylpyrrolidone (molecular weight approximately 200,000). After adding 0.25 ml of a solution of triethylamine in n-propanol, this was reduced with hydrogen at room temperature. After 1 hour, while removing air, 5 ml of linseed oil was added using a pipette, and hydrogenation was carried out until hydrogen absorption was completed (approximately 250 ml). This solution was ultrafiltered, the filtrate was concentrated,
The remaining hydrogenated oil was saponified, esterified with diazomethane, and analyzed by gas chromatography. The residual liquid was diluted with n-propanol and could be reused for hydrogenation (see table below). Example 23 The same operation as in Example 19 was performed except that polyvinylpyridine was used in place of the polyvinylpyrrolidone used in Example 19. Example 24 The same procedure as in Example 19 was performed except that linolenic acid methyl ester was used as the oil.

【table】

【table】

【table】

[Table] As is clear from the above tables, the amounts of saturated fatty acids, ie, stearic acid and palmitic acid, contained in the linseed oil during hydrogenation of the linseed oil are substantially constant. In contrast, the amount of linolenic acid, which has three unsaturated bonds, disappears stepwise, and the amount of linoleic acid and oleic acid therefore increases. Trans isomerization has a hydrogen absorption capacity of 100 to 150 ml.
(equivalent to solid fat) does not occur much. That is, according to the hydrogenation in the table above, for example 100 ml of H ₂
Only 11% of the trans isomer was formed after absorption, and only 17% of the trans isomer was formed after absorption of 150 ml of _H2 . In contrast, in conventional methods, the trans isomer is produced during the hydrogenation step at a conversion rate of 60 to 80%. Example 25 48 mg of NiCl ₂ .6H ₂ O were dissolved in 20 ml of n-propanol in a flask. To this was added a 2% solution of polyvinylpyrrolidone (PVP) in n-propanol. The flask was connected to a hydrogenation reactor, evacuated and purged with nitrogen three times. After reduction with 10 mg of sodium borohydride, Becel Oil 5 was added at room temperature and 1 bar of hydrogen pressure.
ml was hydrogenated. The results are shown in the table. Example 26 Example except that the amount of NiCl ₂ 6H ₂ O was 24 mg.
Hydrogenation was carried out under the same conditions as in 25. The results are shown in the table.

【table】

[Table] Hydrogenation with the hydrogenation catalyst of the invention having low molecular weight ligands is preferably carried out in lower aliphatic alcohols, especially n-propanol.

Claims (1)

[Claims] 1 Metal-binding functional groups include phosphorylide, sulfonic acid, carbonyl, carboxyl, amino,
A soluble polymer having imino, hydroxyl, cyano or acid amide groups is bonded by covalent bonding or secondary valence bonding by the metal-binding functional group,
A hydrogenation catalyst directly bonded to a metal selected from group metals of the periodic table or a salt thereof,
A catalyst in which the soluble polymer is selected from the group consisting of polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, polyvinylpyrrolidone, carboxymethylcellulose, functionalized polystyrene, polyethylene glycol, polypropylene glycol, polyurethane, polyvinylamine, and polyethyleneimine. 2. Phosphorylide, sulfonic acid, carbonyl, carboxyl, amino,
A soluble polymer having imino, hydroxyl, cyano or acid amide groups is bonded by covalent bonding or secondary valence bonding by the metal-binding functional group,
A hydrogenation catalyst directly bonded to a metal selected from Group metals of the periodic table or a salt thereof, and containing a low molecular weight ligand, in which the approved soluble polymer is polyvinyl alcohol, polyacrylonitrile, etc. , polyacrylic acid, polyvinylpyrrolidone, carboxymethylcellulose, functionalized polystyrene, polyethylene glycol, polypropylene glycol, polyurethane, polyvinylamine and polyethyleneimine. 3. The hydrogenation catalyst according to claim 2, wherein the low molecular weight ligand is phosphine, carbon monoxide, halide, cyanide, nitrile, alkene or alkyne. 4 The low molecular weight ligand is (a) amine, (b) amino acid, (c) formula R-(CHR ¹ ) _o -CN (where R is a phenyl group,
Naphthyl group, anthracenyl group, phenanthrenyl group or linear or branched C ₁ to C ₆
one or more substituted alkyl groups, or linear or branched _C1 - _C6 alkyl groups,
R ¹ is hydrogen or a linear or branched C ₁ -C ₆ alkyl group, and n is 0, ¹ or ² _. Branched _C1 - _C6 alkyl groups, phenyl groups, and linear or branched _C1 - _C6 alkyl groups or _C1 - _C6
the same or different groups selected from the group consisting of phenyl groups substituted with one or more alkoxy groups),
The hydrogenation catalyst according to claim 2, which is (e) an olefin or alkyne, or (f) a phosphoryl compound. 5. The hydrogenation catalyst according to claim 4, wherein the metal is palladium or a palladium salt having a valence of zero. 6. The hydrogenation catalyst according to claim 5, wherein the low molecular weight ligand is a primary, secondary or tertiary amine having a bulky aliphatic, alicyclic or aromatic group. 7. The hydrogenation catalyst according to claim 6, wherein the low molecular weight ligand is an amine having a branched aliphatic group having 4 to 6 carbon atoms. 8. The hydrogenation catalyst according to claim 6, wherein the low molecular weight ligand is a primary, secondary or tertiary amine having a cyclopentyl group, cyclohexyl group or adamantyl group. 9 The low molecular weight ligand has 1 to 6 alkyl groups.
7. The hydrogenation catalyst according to claim 6, which is an allylaliphatic amine containing at least one aromatic group bonded to its alkyl group. 10 The low molecular weight ligand has the formula H ₂ N―R ³ (where R ³ is a 1-phenylethyl group, 1,
1-diphenylethyl group, 1-phenylpropyl group, 1,1-diphenylpropyl group, 2-phenylethyl group, 1,2-diphenylethyl group, 2,
2-diphenylethyl group, 1,2-diphenylpropyl group or 2,2-diphenylpropyl group)
The hydrogenation catalyst according to claim 9, which is an amine represented by: 11. The hydrogenation catalyst according to claim 4, wherein the low molecular weight ligand is an amino group having a bulky group at the 1st to 3rd positions relative to the amino group. 12. The hydrogenation catalyst according to claim 1, wherein the low molecular weight ligand is diphenylglycine, norleucine, leucine, isoleucine, tert-leucine or valine. 13. The hydrogenation catalyst according to claim 4, wherein the low molecular weight ligand is 9-cyanoanthracene or β-naphthonitrile. 14 Phosphorylide as a metal-binding functional group,
It is characterized by reacting a soluble polymer having a sulfonic acid, carbonyl, carboxyl, amino, imino, hydroxyl, cyano or acid amide group with a metal selected from group metals of the periodic table or a complex or salt thereof in a solution. A method for producing a hydrogenation catalyst, the soluble polymer comprising:
polyvinyl alcohol, polyacrylonitrile,
A method for producing a hydrogenation catalyst selected from the group consisting of polyacrylic acid, polyvinylpyrrolidone, carboxymethylcellulose, functionalized polystyrene, polyethylene glycol, polypropylene glycol, polyurethane, polyvinylamine and polyethyleneimine. 15 Claim 14 in which the solution is an aqueous solution
Manufacturing method described in section. 16. The manufacturing method according to claim 14, wherein the solution is a solution in an organic solvent. 17. The manufacturing method according to claim 14, wherein the metal is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, or platinum. 18 A metal salt or a metal complex formed by a salt or complex of a group metal of the periodic table and at least one low molecular weight ligand is reacted with a polymer in an aqueous solution or an organic solvent, and then, if necessary, 15. Process according to claim 14, characterized in that the product is hydrogenated accordingly. 19. The manufacturing method according to claim 18, characterized in that a palladium salt or a palladium complex is used as the metal salt or metal complex. 20 A process for the hydrogenation of organic compounds in solution, suspension or homogeneous phase, in which the hydrogenation is carried out using phosphorylide, sulfonic acid, carbonyl, carboxyl, amino, imino, hydroxyl, cyano or acid amide groups as metal-binding functional groups. A hydrogenation catalyst in which a soluble polymer having a soluble polymer is directly bonded to a metal selected from group metals of the periodic table or a salt thereof through a covalent bond or a secondary valence bond through the metal-binding functional group. and the soluble polymer is a catalyst selected from the group consisting of polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, polyvinylpyrrolidone, carboxymethylcellulose, functionalized polystyrene, polyethylene glycol, polypropylene glycol, polyurethane, polyvinylamine, and polyethyleneimine. A hydrogenation method characterized by being carried out in the presence of. 21. The hydrogenation method according to claim 20, wherein the hydrogenation is carried out under normal pressure. 22. The hydrogenation method according to claim 20, wherein the hydrogenation is carried out under pressure. 23. The hydrogenation method according to claim 20, wherein the organic compound is a nitro compound or a nitroso compound, and the organic compound is hydrogenated to an amine. 24. The hydrogenation method according to claim 20, wherein the organic compound is an alkyne or an alkene, and the organic compound is hydrogenated to an alkane. 25. The hydrogenation method according to claim 20, wherein the organic compound is a cycloolefin or an aromatic compound, and the organic compound is hydrogenated to an alicyclic compound. 26 Claim 20 that cleaves ester
Hydrogenation method described in section. 27. The hydrogenation method according to claim 20, wherein an alkyne is selectively hydrogenated to a cis or trans alkene. 28 Organic compound is polyolefin, unsaturated acid,
21. The hydrogenation method according to claim 20, wherein the hydrogenation is an alcohol, a ketone or a fat. 29 The hydrogenation catalyst has palladium or a palladium salt as the metal or its salt, and (a) amine, (b) amino acid, (c) formula R-(CHR ¹ ) _o -CN (where R is a phenyl group) , naphthyl, anthracenyl, phenanthrenyl or these substituted with one or more linear or branched C1 _{- C6} alkyl groups, or linear or branched _C1 - _C6 alkyl groups, R ¹ is hydrogen or a linear or branched C ₁ -C ₆ alkyl group, and n is 0,1
or nitrile represented by 2), formula (d) P(R ² ) ₃
(where R ² is a linear or branched C ₁ -C ₆ alkyl group, a phenyl group, and a linear or branched C 1 -C 6 alkyl group, a _phenyl group,
1 of C ₆ alkyl group or C ₁ to C ₆ alkoxy group
(e) olefins or alkynes; and (f) phosphoryl compounds. 21. The hydrogenation method according to claim 20, wherein the hydrogenation is carried out in a homogeneous phase. 30. The hydrogenation method according to claim 29, wherein a fatty acid or fatty acid ester having two or more double bonds is hydrogenated to a fatty acid or fatty acid ester having one double bond. 31. The hydrogenation method according to claim 30, wherein the fatty acid or fatty acid ester is in the cis form.