CS231113B1 - Hydrogenation catalyst - Google Patents

Abstract

Hydrogenation catalyst of the general formula Rh(olefin)mL2(0^SR), where olefin is represented by an alkene with C2 to Cg, a cycloalkene with up to Cg, preferably ethylene, cyclooctene and further an alkadiene with up to C-L2, preferably 1,5-hexadiene, 1,5-cyclooctadiene and norbornadiene, the index m has a value of 0 to 1 in the case of dienes containing two 0=C bonds and a value of 0 to 2 in the case of alkenes, the index p is equal to 1 to 2, while the number of coordination bonds of the central metal to the olefin and the ligand L is equal to p four, L represents alkylene diphosphines of the general formula (0θΗ^)2Ρ0Η(Ε2)/ηΡ(0θΗ^)2 where R^sI^sH for n=1 to 4, R1=CH7or CNIU o i ■? ? and R =H for n=1 and R =R,-=CH^ for n=1, including 1,4-diphosphinobutane derivatives of the formula a/ \ 0-CH-CH2P(C6H5)2 i 0-CH-CH2P(C6H5)2 where A represents an isopropylidene, cyclopentylidene, cyclohexylidene and cyclooctylidene group and RSO^ represents a phenyl group of a styrene-divinylbenzene copolymer substituted with an SOj group. The hydrogenation catalyst according to the invention exhibits high catalytic activity in hydrogenation reactions and eliminates some of the disadvantages of previously known hydrogenation catalysts.

Description

The invention relates to hydrogenation catalysts based on rhodium complexes anchored on sulfonated styrene-divinylbenzene copolymers and a method for their production.

It is known that rhodium complexes are effective catalysts for the hydrogenation of unsaturated compounds containing C=C bonds. (For a review, see e.g. R.B. James: Homogeneous hydrogenation, Wiley 1973). Due to some disadvantages of soluble complexes, which mainly consist in their difficult isolation in the active state from the reaction solution and their reuse, rhodium complexes anchored on inorganic and organic polymer supports have also been used as catalysts. All types of heterogeneous rhodium complexes known so far are based on the central metal atom being bound to the support through a coordination bond between this metal and a suitable ligand containing phosphorus or nitrogen as a donor atom, with which the support is functionalized. For this purpose, styrene-divinylbenzene copolymers functionalized with diphenylphosphino groups (Adv. Organometal. Chem. 15, 189 (1977); 17, 319 (1979), J. Amer. Chem. Soc. 97, 1742 (1975), Chem. Lett. 1975, 203, Inorg. Chem. 14, 1419 (1975)), chelate bidentate ligands containing nitrogen and oxygen (J. Amer. Chem. Soc. 99, 7733 (1977), J. Org. Chem. 44, 234 (1979)) or phosphorus were used as organic carriers, the latter of which were particularly used as catalysts for asymmetric hydrogenation (J. Amer. Chem. Soc. 100, 268 (1978); 100, 264 (1978), Inorg. Chem. Nucl. Letters 15, 231 (1979), J. Amer. Chem. Soc. 95, 8295 (1973), NDR pat. 92 031 (1972)). In a similar way, various complexes were anchored on polyacrylic and polyvinyl chloride supports (J. Organometal. Chem. 87, 189 (1975), Brit. pat. 295 675 (1972)).

Although many of these catalysts exhibit high catalytic activity,

- 2 tic activity, in hydrogenation reactions, is not without disadvantages. One of them, which comes to the fore especially in the case of catalysts for asymmetric hydrogenation, is the necessary functionalization of the support with a group serving as a ligand. The preparation of these supports usually requires several steps and in the case of some chiral compounds, which show high asymmetric activity when used as ligands of soluble complexes, their anchoring on the surface of the support is impossible. This applies, for example, to bidentate phosphines of the type (S,S)-CHIRAPHOS and PROPHOS (J. Amer. Chem. Soc. 100, 5491 (1978)? 99, 6262 (1977)). This fact thus narrows the choice of catalysts suitable for anchoring.

This deficiency is eliminated by the catalysts according to the invention of the general formula

Rh(olefin) _m Lp(O^SR), where olefin represents an alkene with to Cg and a cycloalkene with C^ to Cg, preferably ethylene, cyclooctene and further alkadiene with C^ to C^ ₂ , preferably 1,5-hexadiene, 1,5-cyclooctadiene and norbornadiene, the index m has a value of 0 to 1 in the case of dienes containing two C=C bonds and a value

O to 2 in the case of alkenes, the index p is equal to 1 to 2, with the number o of coordination bonds of the central metal to the olefins and the ligand L being o , equal to four, L represents alkylenediphosphines of the general formula (C ₆ H ₅ ) ₂ jPCH(R ¹ )/CH(R ² )/ _n P(C ₆ H ₅ ) ₂ where R^=:R ² =H for η = 1 to 4, R^CH^ or CgH^ and R ² = H for η = 1 and R ¹ =R ² =CH^ for n = 1, including 1,4-diphosphinobutane derivatives of the formula o-ch-ch ₂ p(c ₆ h ₅ ) ₂ ¹ ' ^o-ch-ch ₂ p(c ₆ h ₅ ) ₂ where A represents an isopropylidene, cyclopentylidene, cyclohexylidene and cyclooctylidene group and RSO^ represents the phenyl group of the styrene-divinylbenzene copolymer substituted with an SO^H group.

Alkylenediphosphines defined by the above general formula also include derivatives in which the replacement of the hydrogen of the methylene group with a methyl or phenyl group results in a chiral carbon atom in the molecule. In the sense of the invention, the above formulas thus represent both the racemic mixture of both enantiomers and the respective optical antipodes.

In this sense, for example, the formula (c ₆ h ₅ ) ₂ kjh(ch ₅ )ch ₂ p(c ₆ h ₅ ) ₂

231 113 represents 1,2-bis(diphenylphosphino)propane, (R)-(+)-1,2-bis(diphenylphosphino)propane and (S)-(-)-1,2-bis(diphenylphosphino)propane.

The catalysts according to the invention form a group of substances in which the index m has a value of 0 to 1 in the case of dienes containing two C=C bonds and a value of 0 to 2 in the case of alkenes, the index p is equal to 1 to 2, and the number of coordination bonds of the central metal to the olefin and 2 ligands L is equal to four.

Catalysts of the above structure can be advantageously prepared by reacting (olefin)(pentadionato)-rich complexes with ligand L and sulfonated styrene-divinylbenzene copolymer, i.e. by a procedure analogous to the preparation of soluble (alkylediphosphine)arenesulfonate complexes*

The following examples characterize the catalysts and the process for their preparation according to the invention and illustrate their catalytic efficiency without limiting or delimiting the invention.

Example 1

2.6 parts of Lewatit SC 102/H (standard sulfonated styrene-divinylbenzene copolymer containing 2% divinylbenzene) were converted to the H form and dried at 80°C and 10 Pa for 16 hours. Then, a solution of 0.7 parts of Rh(1,5-C0D)(acac) (acac represents the 1,3-pentanedionate anion) and 0.9 parts of 1,2-bis(diphenylphosphino)ethane in 400 parts of an ethanol-benzene mixture (1:1 by volume) was added to the copolymer under argon. The polymer with the solution was shaken for 8 hours, the solution was drawn off, the polymer was washed with 2x 400 parts of solvent and allowed to shake with 400 parts of pure solvent for 4 hours.

After the solution was drawn off, the polymer was washed, allowed to shake for 3 to 4 hours with 400 parts of pure solvent, and after washing, allowed to stand overnight with 400 parts of pure solvent. Before use, the catalyst was transferred to the selected volume of solvent. In this way, catalyst No. 1 containing 5 wt% Rh was prepared.

Example 2

Example 1 was repeated except that 0.7 parts of Rh(1,5-C0D)(acac) was dissolved in 400 parts of solvent and added to the sulfonated copolymer. The polymer was shaken with the solution for 8 hours and left to stand overnight. Then 0.9 parts of 1,2-bis(diphenylphosphino)ethane was added to the mixture. After shaking for 8 hours and

231 113 After removing the solvent, the catalyst was further processed according to Example 1. A catalyst with identical properties and Rh content to the catalyst from Example 1 was obtained.

Example 3

Catalysts No. 2 to 7 were prepared according to the procedure of Example 1, using the polymer supports summarized in Table 1. The characteristics of the prepared catalysts are given in Table 2.

Table 1 and

Polymer

Exchange capacity mmol/g

Specific surface area m ² /g

SDVB-2 4.50 <0.1 SDVB-8 4.75 <0.1 SDVB-15 4.12 <0.1 SDVB-15M 3.83 35 SDVB-40M 2.97 110

^and SDVB - sulfonated styrene-divinylbenzene copolymer, the number after the designation indicates the divinylbenzene content in %, M indicates macroporous copolymer

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Example 4 231 113

Catalyst No. 1 from Example 1 (4 parts) was introduced into 1000 parts of a benzene-ethanol mixture (1:1 by volume) placed in a stationary hydrogenation reactor, 100 parts of 1-octene were added and after the introduction of hydrogen, hydrogenation was carried out at 40°C and a pressure of 180 kPa. After 2 hours, 100% conversion of 1-octene to n-octane was achieved. Similar results were also achieved with the catalyst from Example 2.

Example 5

Example 4 was repeated except that Catalyst No. 4 (8 parts) was used instead of Catalyst No. 1 and styrene (80 parts) was used as the substrate. The hydrogenation was completed after 2.5 hours.

Example 6

Hydrogenation of cyclooctene was carried out according to the procedure of Example 4 using catalyst No. 7. Complete saturation of the double bonds of the substrate was achieved after 3 hours.

Example 7

Catalyst No. 2 from Example 3 (12 parts) was introduced into 500 parts of benzene-ethanol (1:1 by volume), 95 parts of α-acetamidocinnamic acid dissolved in 1500 parts of the same solvent were added and hydrogenation was carried out at 40°C and a pressure of 180 kPa. The reaction was completed after 20 minutes. D-N-acetylphenylalanine was obtained in 95% chemical yield and 71% optical yield.

Example 8 Example 7 was repeated except that catalyst No. 3 was used instead of catalyst No. 2. After 80 minutes, L-N-acetylphenylalanine was obtained in 92% chemical yield and 85% optical purity. When catalyst No. 6 was used, L-N-acetylphenylalanine was obtained in 93% yield and 74% optical purity after 25 minutes.

Claims (1)

SUBJECT OF THE INVENTION Hydrogenation catalyst of formula Rh (olefin) _m L ² (O 2 SR), where 231113 olefin is an alkene having up Οθ, cycloalkene having up Οθ, preferably ethylene, cyclooctene, and further having up alkadiene C · ^, ^v y ^ ° UNE 1,5-hexadiene, 1,5-cyclooctadiene and norbornadiene, m has a value 0 to 1 in the case of dienes containing two C = C bonds and 0 to 2 in the case of alkenes, the index p being equal to 1 to 2, after p chat coordination bonds of the central metal to olefin ligand L is equal to four, is alkylendifosfiny formula (C ₆ H _{5) 2} PCH (R ¹⁾ / CH ^(R2) / _N P (C ₆ H _{5) 2} / R ¹ ^ ² ^ for η = 1 to 4, R ¹ = CH _3! or C, -H _c and R ² = H for η = 1 a 12 '· ® ·? R = R = CH 2 for n = 1, including the 1,4-diphosphinobutane derivative of formula o-ch-ch ₂ p (o ₆ h ₅ ) ₂ < ¹ / ^x o-ch-ch ₂ p (c ₆ h ₅ ) ₂ where a is isopropylidene, cyclopentylidene, cyclohexylidene and cyclooctylidene, and RSO is phenyl-styrene-divinylbenzene copolymer substituted with SO ^ H group.