PL210207B1 - The manner of obtaining esters (alkylo, arylo) silipropyl - Google Patents

Description

Description of the invention

The subject of the invention is a process for the preparation of (alkyl, aryl) silylpropyl ethers of the general formula I, in which R ¹ is an alkyl or phenyl group, by addition of triethoxysilane to alkyl and aryl allyl ethers catalyzed by rhodium (I) complexes.

The process of hydrosilylation of alkyl and aryl allyl ethers with trialkoxysilanes is known, carried out in the presence of platinum complexes: H2PtCl6 (hexachloroplatinic acid (IV) [Ger. (East) 144, 413] in the temperature range of 120-165 ° C after 1.4 h with a yield 50-65%; [Sultanov RA, Kadyrova MB, Khudayarov IA and Sadylch-Zade SI, Uch. Zap. Azerb. Univ., Ser. Khim. Nauk, 37 (1971); Ref. Zh. Khim., 24Zh730 (1971 )], H2PtCl6 (i-PrOH) + EtOH (hexachloroplatinic acid (IV) in a mixture of isopropanol and ethanol) with the yield of 62%, while PtCl2 (Me2C = CHCOMe) (Me2CO) (dichloro (4-methyl-3-pentene-2) -on) (propanone) platinum (II)) [Eur. Pat. Appl. EP 288,286] at 80 ° C after 3h with an efficiency of 88%; H2PtCl6 [Sultanov RA, Kadyrova MB, Khudayarov IA and Sadylch-Zade SI, Uch .

Zap. Azerbaijani. Univ., Ser. Khim. Nauk, 37 (1971); Ref. Zh. Khim., 24Zh730 (1971)] at an efficiency of 62%;

Pt ₂ l ₂ Me ₆ (py) ₆ (hexamethyl-di-Li-iodo-platinum (IV)) [German Patent No. 1,259,888] at a temperature of 150 ° C after 1 h with a yield of 97%. There is also a known method for the preparation of 3-glycidoxy (or butyloxy or phenyloxy) propylsilanes using rhodium siloxyl complexes (Marciniec B., Błażejewska-Chadyniak P., Walczak-Guściora E., Kujawa-Welten M., Pol. Pat. P-351449,2001;

In Organosilicon Chemistry V, Auner N., Weis J. (Ed.), Wiley-VCH Verlag GmbH & Co. KgaA, Weinheim, Marciniec B., Walczuk E., Błażejewska-Chadyniak P., Chadyniak D., Kujawa-Welten M., Krompiec S., 415, 2003; Marciniec B., Błażejewska-Chadyniak P., Kubicki M., Can. J. Chem., 81, 1292, 2003). The use of bis- (1,5-cyclooctadiene) -di-L-trimethylsiloxy) -dirodium (I) as a catalyst in this solution allows for obtaining products with high yields of 85-92%, at temperatures from 0 to 40 ° C C,

The subject matter of the invention, in which the triethoxysilane is added to the alkyl and aryl allyl ethers of the general formula 2, in which R ¹ is as defined above, consists in that the catalyst is a siloxy rhodium (I) complex immobilized on the surface silica having the general formula 3, wherein the diene is cyclooctadiene, norbornadiene or tetrafluorobenzobarrelen and L is a phosphine ligand of the general formula 4, wherein R ² represents an alkyl group or a phenyl or another unit HSiOX from the surface of the silica of the general formula 5, wherein X is a hydrogen or silicon atom, the reaction being carried out under an inert gas atmosphere at room temperature to 100 ° C.

The invention uses a new rhodium (I) complex as a catalyst, which is obtained as a result of an exchange reaction of siloxyl ligands in the metal coordination sphere between molecular siloxyl binuclear complexes of the general formula 6, in which the diene is as defined above, and R ³ is an alkyl group or phenyl or siloxy mononuclear complexes of general formula 7 in which diene, R ² , R ³ are as defined above, and with silanol groups located on the silica surface. The reaction according to the invention is carried out in an anhydrous, deoxygenated and non-rhodium-coordinating solvent and in a gas atmosphere.

The use of new catalysts, siloxyl complexes of rhodium (I) immobilized on the surface of silica, allows to combine the advantages of heterogeneous and homogeneous catalysis. With high efficiency and selectivity of catalytic reactions, we obtain the possibility of multiple use of the same portion of the catalyst and easy separation of the reaction product from the post-reaction mixture, for example by decanting.

In the process according to the invention, products are obtained with a conversion of 80-90% and yields of 80-98%.

The well-known 3-glycidoxypropyltriethoxysilane is used as an adhesion promoter and a polymer modifying agent.

The following examples illustrate the invention.

Example I - catalyst preparation

In a glass, two-necked, round-bottomed flask with a capacity of 50 ml, equipped with a magnetic stirrer, di-L-trimethylsiloxylsiloxide dicyclooctadiene-dirod (I) 1.2 g (2x10 ^-3 mol) and previously dried at 350 ° C were placed under an inert atmosphere. Aerosil 200 silica 6 g (7.6 x ^10-3 mol). 20 ml of benzene was added to the mixture, and it was stirred at room temperature for 24 hours. Then the benzene was evaporated under reduced pressure and 20 ml of pentane was added. The supernatant solution was decanted and the precipitate was washed three times with pentane and dried under reduced pressure. The catalyst [(HSiO) (HSiOX) Rh (cod)] (Aerosil 200) was obtained with the following rhodium content: 4.104 x 10 ^-4 mol Rh / g (data obtained by ICP-OES technique) ¹³ C MAS-NMR (ppm) = 75.19 (= CH-, cod); 31.02 (CH2, COD) ²⁹ Si MAS-NMR (ppm) = 99.68 (Q ^2), 106.88 (Q ^3), 110.38 (Q ^4).

P r z x l a d II

In a 50 ml glass two-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, the catalyst [(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.1 g ( 4.33 x 10 ⁵ mole) prepared as in example I, and then successively with 2 ml decane (internal standard) triethoxysilane 8 ml (4.34 x 10 ^-2 mol) and allyl glycidyl ether, 7.7 ml (6, 5 x ^10-2 moles). Reactions were carried out at room temperature for 1 hour. After a given reaction time, the triethoxysilane conversion and the yield of 3-glycidoxypropyltriethoxysilane were determined by gas chromatography. A yield of 96% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. At 99% conversion, 3-glycidoxypropyltriethoxysilane was obtained in 96% yield.

The structure of the obtained 3-glycidoxypropyltriethoxysilane was confirmed by spectroscopic analysis of ¹ H and ¹³ C NMR.

Example III - catalyst preparation

In a glass, two-neck, round-bottomed flask with a capacity of 50 ml, equipped with a magnetic stirrer, di-Li-trimethylsiloxylsiloxide dicycyclooctadiendirod (I) 1.3 g (2.2 x 10 ^-3 mol) and previously dried at 350 < 0 > C silica SBA-15 2 g (8.9 x ^10-3 mol). Then 20 ml of pentane was added to the mixture, the mixture was stirred at room temperature for 24 hours. The supernatant solution was decanted and the precipitate was washed three times with pentane and dried under reduced pressure. The catalyst [(HSiO) (HSiOX) Rh (cod)] (SBA-15) was obtained with the following rhodium content: 8.127 x 10 ^-4 mol Rh / g (data obtained by ICP-OES technique) ¹³ C MAS-NMR (ppm ) = 85.24, 75.19 (= CH-, cod); 29.28 (CH2, COD) ²⁹ Si MAS-NMR (ppm) = 101.02 (Q ^2), 105.73 (Q ^3), 108.87 (Q ^4).

P r x l a d IV

In a 100 ml glass two-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, the catalyst [(ESiO) (ESiOX) Rh (cod)] (SBA-15) 0.2 g was placed under an inert gas (argon) atmosphere. (1.63 x 10 ^-4 mol) prepared as in Example 3, followed by decane 6 ml (internal standard), triethoxysilane 30 ml (0.163 mol) and allyl glycidyl ether 28 ml (0.24 mol). Reactions were carried out at room temperature for 1 hour. After a given reaction time, the triethoxysilane conversion and the yield of 3-glycidoxypropyltriethoxysilane were determined by gas chromatography. The yield was 94% (GC). In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. In a 98% conversion, 3-glycidoxypropyltriethoxysilane was obtained in 94% yield.

P r z k ł a d V

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.01 g ( 4.33 x 10 ^-6 mol) obtained as in example 1, then decane 2 ml (internal standard), triethoxysilane 8 ml (4.34 x 10 ^-2 mol) and allyl glycidyl ether 7.7 ml (6.5 x ^10-2 moles). The reaction mixture was heated for one hour at 60 ° C. After a given reaction time, the triethoxysilane conversion and the yield of 3-glycidoxypropyltriethoxysilane were determined by gas chromatography. A yield of 95% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. At 99% conversion, 3-glycidoxypropyltriethoxysilane was obtained in 95% yield.

P r x l a d VI

In a 100 ml glass two-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, the catalyst [(ESiO) (ESiOX) Rh (cod)] (SBA-15) 0.02 g was placed under an inert gas (argon) atmosphere. (1.63 x 10 ^-5 mol) prepared as in Example 3, followed by decane 6 ml (internal standard), triethoxysilane 30 ml (0.163 mol) and allyl glycidyl ether 28 ml (0.24 mol). The reaction mixture was heated for one hour at 60 ° C. After a given reaction time, the triethoxysilane conversion and the yield of 3-glycidoxypropyltriethoxysilane were determined by gas chromatography. A yield of 95% (GC) was obtained. In order to delete 4

After removing the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. In a 97% conversion, 3-glycidoxypropyltriethoxysilane was obtained in 95% yield.

Example VII - catalyst preparation

In a glass, two-necked, round-bottomed flask with a capacity of 50 ml, equipped with a magnetic stirrer, cyclooctadientricycyclohexylphosphinatrimethylsiloxide (I) 1.9 g (3.3 x 10 ^-3 mol) and previously dried at 350 ° C were placed under an atmosphere of inert gas (argon) C Aerosil 200 silica 5 g (6.4 x ^10-3 mol). Then 20 ml of pentane was added to the mixture, the mixture was stirred at room temperature for 24 hours. The supernatant solution was decanted and the precipitate was washed three times with pentane and dried under reduced pressure. The catalyst [(HSiO) Rh (cod) (PCy ₃ )] (Aerosil 200) was obtained with the following rhodium content: 1.24 x 10 ^-4 mol Rh / g (data obtained by ICP-OES technique).

¹³ C MAS-NMR (ppm) = 26.63 (-CH2-, -Cy) ²⁹ Si MAS-NMR (ppm) = 103.79 (Q ³ ), 108.12 (Q ⁴ ) ³¹ P MAS-NMR ( ppm) = 23.42.

P r x l a d VIII

In a 50 ml glass two-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, the catalyst [(= SiO) Rh (cod) (PCy3)] (Aerosil 200) 0.08 g was placed under an atmosphere of inert gas (argon). (9.95 x 10 ^-6 mol) in Example 7, followed by 5 ml decane (internal standard), 26 ml triethoxysilane (9.95 x 10 ^-2 mol) and allyl glycidyl ether 18 ml (0.15 mol) ). The reaction mixture was heated for one hour at 60 ° C. After a given reaction time, the triethoxysilane conversion and the yield of 3-glycidoxypropyltriethoxysilane were determined by gas chromatography. A yield of 95% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. At 99% conversion, 3-glycidoxypropyltriethoxysilane was obtained in 95% yield.

P r x l a d IX

In a glass, two-necked, round-bottomed flask with a capacity of 50 ml, equipped with a reflux condenser and a magnetic stirrer, the catalyst [(HSiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.01 g ( 4.33 x 10 ^-6 mol) obtained as in example 1, then decane 2 ml (internal standard), triethoxysilane 8 ml (4.34 x 10 ^-2 mol) and allyl glycidyl ether 7.7 ml (6 , 5 x ^10-2 moles). The reaction mixture was heated for one hour at 100 ° C. After a given reaction time, the triethoxysilane conversion and the yield of 3-glycidoxypropyltriethoxysilane were determined by gas chromatography. A yield of 92% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. At 99% conversion, 3-glycidoxypropyltriethoxysilane was obtained in 92% yield. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction six times without a decrease in activity.

P r z k ł a d X

In a 100 ml glass two-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, the catalyst [(ESiO) (ESiOX) Rh (cod)] (SBA-15) 0.02 g was placed under an inert gas (argon) atmosphere. (1.63 x 10 ^-5 mol) prepared as in Example 3, followed by decane 6 ml (internal standard), triethoxysilane 30 ml (0.163 mol) and allyl glycidyl ether 28 ml (0.24 mol). The reaction mixture was heated for one hour at 100 ° C. After a given reaction time, the triethoxysilane conversion and the yield of 3-glycidoxypropyltriethoxysilane were determined by gas chromatography. The yield was 94% (GC). In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. In a 98% conversion, 3-glycidoxypropyltriethoxysilane was obtained in 94% yield. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction five times without a decrease in activity.

P r z x l a d XI

In a glass, two-necked, round-bottomed flask with a capacity of 50 ml, equipped with a reflux condenser and a magnetic stirrer, the catalyst [(HSiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.01 g ( 4.1 x 10 ^-6 mol) obtained as in Example 1, then decane 2 ml (internal standard), triethoxysilane 7.7 ml (4.1 x 10 ^-2 mol) and allyl phenyl ether 8.5 ml (6 , 1 x ^10-2 mole). The reaction mixture was heated for one hour at 25 ° C. After a given reaction time, the triethoxysilane conversion and the yield of 3-phenyloxypropyltriethoxysilane were determined by gas chromatography. The yield was 84% (GC). In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. With a conversion of 87%, 3-phenyloxypropyltriethoxysilane was obtained in 84% yield. The structure of the obtained 3-fenyloksypropylotrietoksysilanu confirmed by spectroscopic analysis of ¹ H and ¹³ C NMR.

P r x l a d XII

In a glass, two-neck, round bottom flask with a capacity of 50 ml, equipped with a reflux condenser and a magnetic stirrer, the catalyst was placed under an inert gas (argon) atmosphere.

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.018 g (7.38 x ^10-6 mol). Prepared as in Example I, and then successively with 3 ml decane (internal standard) triethoxysilane 19 ml (7.4 x 10 ^-2 mol) and allyl phenyl ether (15 mL, 0.11 mol). The reaction mixture was heated for one hour at 60 ° C. After a given reaction time, the triethoxysilane conversion and the yield of 3-phenyloxypropyltriethoxysilane were determined by gas chromatography. A yield of 98% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. At 99% conversion, 3-phenyloxypropyltriethoxysilane was obtained in 98% yield.

P r x l a d XIII

[(HSiO) Rh (cod) (PCy ₃ )] (Aerosil 200) 0.023 g (2 , 68 x 10 ^-6 mol) obtained as in Example 7, followed by 1 ml decane (internal standard), 7.5 ml triethoxysilane (2.7 x 10 ^-2 mol) and 6 ml allyl phenyl ether (4, 4 x ^10-2 moles). The reaction mixture was heated for one hour at 60 ° C. After a given reaction time, the triethoxysilane conversion and the yield of 3-phenyloxypropyltriethoxysilane were determined by gas chromatography. A yield of 95% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. At 99% conversion, 3-phenyloxypropyltriethoxysilane was obtained in 95% yield.

P r x l a d XIV

[(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.024 g (9.85 x 10 ^-6 mol) obtained as in Example 1, followed by decane 4 ml (internal standard), triethoxysilane 26 ml (9.8 x 10 ^-2 mol) and allyl phenyl ether 19.2 ml (0.14 mol) . The reaction mixture was heated for one hour at 100 ° C. After a given reaction time, the triethoxysilane conversion and the yield of 3-phenyloxypropyltriethoxysilane were determined by gas chromatography. A yield of 92% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. At 99% conversion, 3-phenyloxypropyltriethoxysilane was obtained in 92% yield. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction five times without any visible decrease in activity.

P r x l a d XV

In a glass, two-neck, round-bottomed flask with a capacity of 50 ml, equipped with a reflux condenser and a magnetic stirrer, the catalyst [(ESiO) (ESiOX) Rh (cod)] (Aerosil 200) 0.023 g (9, 44 x 10 ^-6 mol) obtained as in Example 1, then consecutively 4 ml decane (internal standard), triethoxysilane 17.8 ml (9.44 x 10 ^-2 mol) and allyl-butyl ether 20 ml (0.14 mole). The reaction mixture was heated for one hour at 60 ° C. After the given reaction time, the triethoxysilane conversion and the yield of 3-butyloxypropyltriethoxysilane were determined by gas chromatography. A yield of 88% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. In a 90% conversion, 3-butyloxypropyltriethoxysilane was obtained in 88% yield.

P r x l a d XVI

[(HSiO) Rh (cod) (PCy ₃ )] (Aerosil 200) 0.013 g (1 , 6 x 10 ^-6 mol) obtained as in Example 7, followed by 1 ml decane (internal standard), 3 ml triethoxysilane (1.6 x 10 ^-2 mol) and 3.5 ml allyl butyl ether (2, 4 x ^10-2 moles). The reaction mixture was heated for one hour at 60 ° C. After a given reaction time, the triethoxysilane conversion and the yield of 3-butyloxypropyltriethoxysilane were determined by gas chromatography. The yield was 80% (GC). In order to delete 6

After removing the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. In 81% conversion, 3-butyloxypropyltriethoxysilane was obtained in 80% yield.

E xample XVII

A 50 ml round bottom glass flask, equipped with a reflux condenser and a magnetic stirrer, was placed under an inert gas atmosphere [(HSiO) (HSiOX) Rh (cod)] (Aerosil 200) 0.016 g (6 , 56 x 10 ^-6 mol), followed by decane 2 ml (internal standard), triethoxysilane 12.1 ml (6.56 x 10 ^-2 mol) and allyl butyl ether 14.3 ml (9.8 x 10 ^-2 moles). The reaction mixture was heated for one hour at 100 ° C. After the given reaction time, the triethoxysilane conversion and the yield of 3-butyloxypropyltriethoxysilane were determined by gas chromatography. A yield of 90% (GC) was obtained. In order to remove the catalyst from the system, the reaction mixture was decanted, and then the product was distilled off. In a 95% conversion, 3-butyloxypropyltriethoxysilane was obtained in 90% yield. After decanting the post-reaction mixture, a new batch of reactants was introduced into the flask containing the catalyst and the reaction cycle was repeated, the catalytic system used made it possible to repeat the reaction three times without a decrease in activity.

Claims (1)

The method of obtaining (alkyl, aryl) silylpropyl ethers of the general formula 1, in which R ¹ is an alkyl or phenyl group, by the addition reaction of triethoxysilane to alkyl aryl allyl ethers of the general formula 2, in which R ¹ is as defined above, is catalyzed by rhodium (I) siloxy complexes, characterized in that the catalyst is a rhodium (I) siloxy complex immobilized on the surface of a silica of general formula 3, in which the diene is cyclooctadiene, norbomadiene or tetrafluorobenzobarrelene, and L is a phosphine ligand of general formula 4, wherein R ² is an alkyl or phenyl group or a further HSiOX unit from a silica surface of general formula 5, wherein X is hydrogen or silicon, the reaction being carried out under an inert gas atmosphere at room temperature to 100 ° C.