CS242004B1 - Anchored hydrogenation catalysts and method of their production - Google Patents

Description

BACKGROUND OF THE INVENTION The present invention relates to anchored hydrotreating catalysts based on rhodium complexes coordinated to sulfopropylated glycidyl methacrylate copolymers and a process for their preparation.

Random complexes are known to be effective catalysts for the hydrogenation of unsaturated compounds containing C = C bonds (for review see, e.g., R. B. James: Homogeneous hydrogenation; Wiley, New York 1973). Due to some disadvantages of the soluble complexes, which mainly consist in their difficult isolation in the active state from the reaction mixture and their reuse, attempts have been made to heterogeneize them by anchoring them to the surface of inorganic or organic polymeric carriers. All known types of anchored rhodium complexes are based on the fact that the central metal atom of the complex is bound to the support via a coordination bond between the metal and a suitable phosphorus or nitrogen containing ligand as the donor atom through which the support is functionalized. In particular, styrene-divinylbenzene copolymers functionalized with diphenylphosphino groups have been used as organic carriers for this purpose [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)], nitrogen-oxygen chelated bidentate ligands (Amer. Chem. Soc. 99, 7,723 (1977), J. Org. Chem. 44, 234 (1979)), or P-atorne chelates , the latter in particular being used as catalysts for asymmetric hydrogenation. Amer. Chem. Soc. 100, 263 (1978); 100, 264 (1978); Inorg. Chem. Nucl. Letters

15, 231 (1979); J. Amer. Chem. Soc. 95, 8 295 (1973); 92,031 (1972)]. Similarly, the random complexes were anchored on polyacrylic and polyvinyl chloride supports [J. Organometal. Chem. 87: 189 (1975); Brit. U.S. Pat. 295,675 (1972)).

Although many of these catalysts exhibit high catalytic activity in hydrogenation reactions, this type is not without disadvantages, one of which is particularly prominent in the case of asymmetric hydrogenation catalysts is the functionalization of the support with a ligand group. The preparation of these carriers usually requires several steps, and for some chiral compounds which exhibit high asymmetric activity when used as soluble complexes, their anchoring to the carrier surface is impossible. This is particularly true for bidentate (S, S) -CHIRAPHOS and PROPHOS-type phosphines [J. Amer. Chem. Soc. 100, 5,491 (1975); 99, 6262 (1977) j. This reduces the choice of catalysts to be anchored.

This problem is overcome by the catalysts of the present invention

Rh (L _m olefin j ² P (O3SR), wherein the olefin is an alkene of C2 to Cs and a cyclo C₅ to C₈, preferably ethylene, cyclooctene and further Ci-C12 alkadiene, preferably 1,5-hexadiene, and 1,5-cykooktadien norbornadien, L ² represents alkylenediphosphines of formula (C 6 H 5) 2 PCH (R 1) / CH (R ² ) / P (C ⁶ H 5) ² where R ¹ = R ² = H for η = 1 to 4, R ¹ = CH 3, C ⁶ H 11 C6H5CH2, or Ph, and R ² = H n - 1, and R ¹ --- R ² = CH 3 n = 1, including derivatives of 1,4-difosfinobutanu (n = 3) of formula

O - CCP (O ₆ Hifa

o-ch-ch _of P (c ₆ h ₅ ) _of wherein

A is isopropylidene (D1OPj, cyclopentylidene, cyclohexylidene and cyclooctylidene group and RSO3 is sulfopropyl group of glycidyl methacrylate copolymer.

Alkylenediphosphines as defined above also include derivatives in which the replacement of the hydrogen of a methylene group with a methyl or phenyl group results in a chiral carbon atom in the molecule. For the purposes of the invention, the formulas thus represent both a mixture of both enantiomers and the respective optical antipodes. In this sense, for example, the formula (C6H5) 2PCH (CH3) CH2P (C3H5) 2 represents 1,2-bis (diphenylphosphino) propane, (S) - (-) -1,2-bis (diphenylphosphino) propane, or a mixture of both enantiomers in any ratio different from the racemic composition.

The alkylenediphosphines of the above structure are known ligands of soluble rhodium complexes and their preparation is described in the above literature (for 1,4-diphosphinobutane derivatives see further, cf. author, vol. 178 227 and 178 228).

The sulfopropylated glycidyl methacrylate copolymers useful in the present invention have been prepared by sulfopropylating the hydrolysed suspension copolymers of glycidyl methacrylate with ethylenedimethacrylate in an alkaline medium [Angew. Makromol. Chem. 87, 119 (1980); Polymer Bulletin 6, 565 (1982). This procedure provides cationic copolymers having a sulfo group content of up to 1.47 mmol / g. In view of the porosity which is particularly important for the catalytic effect of these polymers, it is possible to prepare polymers which are only porous in the swollen state or polymers permanently porous - macroporous copolymers which retain even non-polar solvents up to 1.4 g per gram. In the case of macroporous copolymers, the choice of reaction conditions can place the sulfopropyl groups and hence the catalytically active groups on the inner surface of the polymer, favoring them by a higher reaction rate of the catalytic reaction due to the reduction of the negative effect of diffusion processes. Suspension copolymers have a regular spherical shape, which favors them when used in a column type catalyst bed. The use of these polymers is evident from the examples which illustrate the invention without limiting it.

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. to olefin and ligand L ² is equal to four.

Catalysts of the above structure can be advantageously prepared by reacting (olefin) (pentadione) rhodium complexes with 11gand L ² and a sulfopropylated glycidyl methacrylate copolymer, i.e. a process analogous to the preparation of the soluble (alkylenediphosphine jarsene sulfonate complexes described in US author, certificates 224 134 and 240 663).

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

Example 1 parts of a macroporous sulfopropylated copoly (glycidyl methacrylate - ethylene dimethacrylate) containing 0.69 mmol SO3H groups per g copolymer and a 20% crosslinking component (ethylene dimethacrylate) [Angew. Makromol. Chem. 87, 119 (1980)] was converted to H form in a conventional manner and dried at 90 ° C and 10 ^-2 Pa for 20 hours. Then a solution of 2 parts of 1,3-pentanedione (1,5-cyclooctadiene-iodine, Rh (1,5-COD) (acac) and 3.2 parts of (--DIOP) in 400 parts of ethanol- The reaction mixture was shaken for 8 hours, the solution was withdrawn, the polymer was washed with 2 XX 400 parts of solvent and allowed to shake with 400 parts of pure solvent and after washing left to stand overnight with 400 parts of the same solvent. The catalyst was transferred to a selected volume of solvent to prepare catalyst # 1 containing 1.2 wt% Rh.

Example 2 of the propylene copolymers summarized in Table 1. The characteristics prepared by the procedure of Example 1 were prepared as catalysts from Table 2.

Vena Catalysts No. 2-6 using SulTable 1

Copolymer ³ Replaceable capacity mmol / g ° / 0 N Retention, g / g of water cyclohexane Specific surface area m ² / g MA - 2.5 1 25 3.23 0.80 0.00 <0.1 MA-20 M 0.69 2.61 1.42 1,02 0.84 72.5 MA-60 M 1.43 4.71 0.56 16.5

³ MA - sulfopropylated kopaly (giycidyl methacrylate-ethylenedimethacrylate), the number after the label indicates the ethylenedimethacrylate content, M stands for macroporous copolymer

Table 2

Catalyst- Default Rh L ² · ³ (parts) Carrier ^b (parts) hm. % Rh in the supported catalyst tor č. complex (parts) 2 Rh (1,5-COD) (acac) (2S, 3S) -buphos MA - 20 M 1,2 (2.0) (2.7) (40) 3 Rh (norbornadien) (R) -phosphophos MA - 60 M 2.3 (acacj (2.7) (19.3) (1.9) 1,4-bis (diphenylphosphine- 4 Rh (ethylene) 2 (acac) nojbutan MA - 2.5 2.1 (IN) (2.7) Italy (22) 5 Rr (cyclooctene) 2 (-j -) - DIOP MA - 60 M 1.3 (acac) (3.2) (19.3) (2.7) 1,2-bis (diphenylphosphi- 6 Rh (δ, 5-COD) (acac) no) ethane MA - 2.5 1.15 (2.0) (2.6) Italy (22)

^and prophos - 1,2-bis (diphenylphosphino) propane, buphos - 2,3-his (diphenylphosphino) butane, ³ see Table 1

Example 3

Catalyst No. 1 of Example 1 (12 parts) was charged to 500 parts of benzene-ethanol (1: 1 v / v), then 95 parts of α-acetamidocinnamic acid dissolved in 1000 parts of the same solvent was added and hydrogenation was performed in a stationary hydrogenation reactor at The reaction was complete after 180 minutes, the catalyst was separated and DN-acetylphenylalanine was recovered in a known manner in 97% yield and 73% optical yield.

Example 4

Example 1 was repeated except that catalyst # 5 of Example 2 was used instead of Catalyst 1. After reaction under the same conditions, L-N-acetylphenylalanine was obtained in 94% yield and 71% optical purity.

Example 5

According to the procedure of Example 3, hydrogenation of α-acetamidocinnamic acid was carried out using catalysts. 2 and 3 of Example 2. The reaction conditions and the yield of the hydrogenation product are summarized in Table 3.

Table 3

Catalyst No. Reaction temperature Reaction time D-N-acetylphenylalanine (parts) ° C / pressure H2, MPa min chemical yield opt.

2 (17) 40 0.3 80 92 89 25 2 120 95 85 3 (22) 40 0.2 120 92 89 Example 6 100% conversion

nu to n-octane.

Catalyst No. 4 of Example 2 (10 parts) was charged to 500 parts of a 1: 1 v / v benzene-ethanol mixture placed in a stirred stationary hydrogenation reactor. Then 100 parts of 1-octene were added and hydrogen was introduced at 40 degrees Celsius and 180 kPa pressure after hydrogen introduction. After 4 hours 1 and d 7

Example 6 was repeated except that catalyst # 6 of Example 2 was used instead of catalyst # 4, and the hydrogenated substrate was cyclooctene instead of 1-octene. After 5 hours, 98% conversion of cyclooctene to cyclooctane was achieved.

Claims (2)

SUBJECT VYNALEZU Anchored hydrogenation catalysts of the general formula Rh (olefin) _m L ² p (O 3 SR), wherein the olefin is an alkene C 2 -C 6, cycloalkene C 5 -C 8, preferably ethylene, cyclooctene and further alkadiene C 4 -C 12, preferably 1,5-hexadiene, 1,5-cyclooctadiene and norbornadiene , L ² represents alkylenediphosphines of general formula (C 6 H 5) and PCH (R ¹¹ / CH (R ² ) / _n P (C 6 H 5) 2 where R ¹ = R ² = H for η = 1 to 4, R ¹ = CH 3, CeHu , C6H5CH2, or Ph, and R ² = H for η = 1, and R ¹ - R ² - CH 3 n = 1, including derivatives of 1,4-diphenylphosphinobutane (n = 3) of formula O-CH-CH2p (G ₆ H _s ) _z • A o-ch- _z p (c ₆ h _s ) _z wherein A represents isopropylidene, cyclopentylidene, cyclohexylidene and cyclooctylidene group and RSO3 represents sulfopropyl group of glycidyl methacrylate or hydroxyethyl methacrylate suspension copolymer with ethylene dimethacrylate containing 97.5 to 40 wt. % glycidyl methacrylate or hydroixyl methacrylate and 2.5 to 60 wt. % of ethylene dimethacrylate, index m having a value of 0 to 1 for dienes and a value of 0 to 2 for alkenes, the index p being 1 to 2, the number of coordinating bonds of the central metal atom to the olefins and the ligand L ² being four. 2. A process for the preparation of hydrogenation catalysts according to claim 1, characterized in that it is reacted (Rh (olefin) (acac), wherein 0lefin represents the unsaturated compounds according to claim 1 and acac represents a pentanedionate anion and diphosphine L ² in the presence of a sulfopropylated glycidyl methacrylate copolymer in an organic solvent medium, preferably a mixture of ethanol-benzene at a temperature of 10 to 60 ° C.