RU2591954C1 - Method of producing o-alkenyl phenols and catalyst for its implementation - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing o-alkenyl phenols, which are promising initial compounds for synthesis of medicinal preparations and fragrance compounds in cosmetic and food industries. Method involves reaction of phenol or substituted phenol with aliphatic aldehyde in presence of catalyst, which has general formula: xM¹ _αO_β·yM² ₂O·zM³O₂·qM⁴ / carrier, where: M¹ is transition metal selected from row: Co, Cu, Ni, V, Mn, Cr; M² is metal of first group from row: Li, Na, K, Rb, Cs; M³ is metal of third or fourth group from row: Zr, Ti, Ge and/or Ce, and/or U; M⁴ is noble metal from row: Pt, Pd, Ru, Rh, Ag, Au; x, y, z, q are weight fractions of corresponding components, where x=0.0-0.50; y=0.0-0.05; z=0.0-0.05; q=0.0-0.2, by reaction:

,

where: X₁-X₄=-H, -Alc, -OH, -OAlc, -Hal; R=-H, hydrocarbon radical. Invention also relates to catalyst for producing o-alkenyl phenols.

EFFECT: presented invention enables to obtain desired products with high output using simple technology.

7 cl, 20 ex

Description

The invention relates to a method for producing o-alkenylphenols, including substituted o-alkenylphenols, more specifically, to a method for their preparation by condensation of hydroxyl-containing aromatic compounds with aliphatic aldehydes in the presence of a catalyst.

Among alkenylphenols, vinylphenols are most used. These substances are promising starting compounds for the synthesis of drugs and fragrances in the cosmetic and food industries. Polyvinylphenols are used in the production of polymer photosensitive materials, liquid crystals, antibacterial polymers, etc. [M. Yamaguchi, M. Arisawa, K. Omata, K. Kabito, M. Hirama, T. Uchimaru. J. Org. Chem. 1998, 63, 7298-7305].

Several methods are known for preparing o-vinyl phenol. Historically, one of the first methods for producing o-vinylphenol was the decarboxylation of 2-hydroxycinnamic acid [Fries, K .; Fickewirth, G. Chem. Ber. 1908, 41, 367]. In the patent of Kumar et al, this reaction is proposed to be carried out under the influence of microwave radiation [US 7759527, C07C 37/00, 07/20/2010]. The disadvantages of the method include the inaccessibility of the starting compound, the complexity of the technology and the low yield of the product (58%).

The method of direct vinylation of phenol and its derivatives using acetylene in the presence of SnCl ₄ [Yamaguchi, M; Flayashi, A .; Hirama, M. J. Am. Chem. Soc. 1995, 117, 1151]. The reaction proceeds with a yield of up to 80%.

The possibility of producing o-vinyl phenol by reacting phenol with ethylene oxide in the presence of sulfuric acid as a catalyst has been reported [Smith R.A., Niederl J. B. J. Amer. Chem. Soc, 1931, v. 53, p. 806]. However, all later attempts to reproduce these results have been unsuccessful [Bader, A.R. J. Am. Chem. Soc. 1955, 77, 4155; Williams, J.L. R .; Borden, D.G .; Laakso, T.M. J. Org. Chem. 1956, 21, 1461; Dale, W. J., Hennis, H.E. J. Am. Chem. Soc. 1958, 80, 3645; Sovish, R.C. J. Org. Chem. 1959, 24, 1345].

The present invention solves the problem of obtaining o-alkenylphenols in high yield using simple technology and available starting compounds. According to this invention, o-alkenylphenols are obtained by reaction between an aliphatic aldehyde and phenol or substituted phenols (see equation 1) in the presence of a catalyst. The reaction can be carried out in a flowing mode in the gas phase, for which phenol is evaporated and mixed with gaseous acetaldehyde. If necessary, a certain amount of an inert diluent gas (nitrogen, argon, saturated hydrocarbons, etc.) can also be added to the mixture. The resulting gas mixture is fed into a flow reactor with a catalyst bed temperature of 200-500 ° C. The contact time of the mixture with the catalyst is 0.1-10 seconds. After passing through the catalyst bed, the mixture is separated, reaction products (o-alkenylphenols) are isolated, for example, by distillation, and unreacted starting materials are recycled.

(1)

(one)

where: X ₁ —X ₄ = —H, —Alc, —OH, —OAlc, —Hal; R = —H, hydrocarbon radical.

The process can be carried out in a static mode in the liquid phase, for which an aldehyde is placed in the autoclave in such a quantity that it is present in the liquid phase at the test temperature, phenol or substituted phenol and, if necessary, an inert solvent (liquid aliphatic hydrocarbons, benzene) are added. After this, the catalyst is added, the reactor is closed and heated to 100-350 ° C. The reaction time can vary from several tens of minutes to tens of hours.

As a catalyst, transition metals and their oxides supported on a carrier selected from a number of simple and complex inorganic oxides, for example, SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , aluminosilicates, clays, zeolites, or a mechanical mixture thereof can be used. The catalyst can be used in the form of a powder of 5-100 microns or fractions with a diameter of 0.25-5.00 mm. Before carrying out the reaction, the catalyst is dried at 110 ° C and calcined at 500 ° C in a stream of air and / or inert gas and / or hydrogen-containing gas and / or a mixture of water vapor with air.

You can use a catalyst of the General formula:

/ носитель, где: М¹ - переходный металл, М² - металл первой группы, М³ - металл третьей или четвертой группы, М⁴ - благородный металл, x, y, z, q - массовые доли соответствующих компонентов; x=0.0-0.50; y=0.0-0.05; z=0.0-0.05; q=0.0-0.2; М¹ выбран из ряда: Со, Cu, Ni, V, Mn, Cr; М² выбран из ряда: Li, Na, K, Rb, Cs; М³ выбран из ряда: Zr, Ti, Ge и/или Ce, и/или U; М⁴ выбран из ряда: Pt, Pd, Ru, Rh, Ag, Au; носитель выбран из ряда простых и сложных неорганических оксидов, например SiO₂, TiO₂, ZrO₂, Al₂CO₃, алюмосиликаты, глины, цеолиты или их механическая смесь. $${\text{xM}}_{\alpha }^{\text{one}}{O}_{\beta }\cdot y{M}_2^{2}O\cdot z{M}^3{O}_2\cdot q{M}^{\mathrm{four}}$$

/ carrier, where: M ¹ is a transition metal, M ² is a metal of the first group, M ³ is a metal of the third or fourth group, M ⁴ is a noble metal, x, y, z, q are mass fractions of the corresponding components; x = 0.0-0.50; y = 0.0-0.05; z = 0.0-0.05; q = 0.0-0.2; M ^{1 is} selected from the series: Co, Cu, Ni, V, Mn, Cr; M ^{2 is} selected from the series: Li, Na, K, Rb, Cs; M ^{3 is} selected from the series: Zr, Ti, Ge and / or Ce, and / or U; M ^{4 is} selected from the series: Pt, Pd, Ru, Rh, Ag, Au; carrier is selected from a number of simple and complex inorganic oxides such as SiO _2, TiO _2, ZrO _2, Al ₂ CO _3, aluminosilicates, clays, zeolites or a mechanical mixture.

/ носитель, где: М¹ - переходный металл, М² - металл первой группы, М³ - металл третьей или четвертой группы, М⁴ - благородный металл, x=0.0-0.50; y=0.0-0.05; z=0.0-0.05; q=0.0-0.2.The reaction is carried out in gas or liquid phases at a temperature of 100-500 ° C, a pressure of 1-30 atm in the presence of a catalyst of the general formula: $${\text{xM}}_{\alpha }^{\text{one}}{O}_{\beta }\cdot y{M}_2^{2}O\cdot z{M}^3{O}_2\cdot q{M}^{\mathrm{four}}$$

/ carrier, where: M ¹ is a transition metal, M ² is a metal of the first group, M ³ is a metal of the third or fourth group, M ⁴ is a noble metal, x = 0.0-0.50; y = 0.0-0.05; z = 0.0-0.05; q = 0.0-0.2.

The molar ratio of aliphatic aldehyde to phenol or substituted phenol is from 0.01 to 99.9.

The initial gas mixture may contain gases inert in this reaction, such as nitrogen, helium, saturated hydrocarbons, etc.

The proposed method for producing o-vinyl phenol and its derivatives is new and based on a previously unknown reaction between phenols and aldehydes, which shows the non-obviousness of this method.

The advantages of the proposed approach are the availability and low price of raw materials, the fundamental simplicity of the technology, the absence of harmful effluents.

The invention is illustrated by the following examples.

Example 1

Phenol gas at 200 ° C is mixed with acetaldehyde and helium so that the mixture contains 2.0 mol. % acetaldehyde, 8.0 mol. % phenol, the rest is helium. The mixture at a pressure of 1 atm is passed through a quartz reactor, in which 0.5 ml of a fraction of a catalyst containing (mass fraction): 0.16 Cr ₂ O ₃ , 0.015 K ₂ O, 0.01 ZrO ₂ , 0.815 Al ₂ O _{3 are} placed. The reactor is maintained at a temperature of 300 ° C and a contact time of 1 s. The conversion of acetaldehyde is calculated according to equation (2), the selectivity for o-WF according to equation (3). Under these conditions, the conversion of acetaldehyde is 14%, the selectivity for o-WF 86%. The formation of o-WF is confirmed by NMR and chromatography-mass spectrometry.

Examples 2-4

The reaction is carried out analogously to example 1 with the difference that the temperature in the reactor is set to 350 ° C (example 2), 375 ° C (example 3) and 400 ° C (example 4). With an increase in temperature from 350 to 400 ° C, the conversion of acetaldehyde increases from 19 to 40%, the selectivity for o-WF decreases slightly - from 84 to 80%.

Example 5

The reaction is carried out analogously to example 3 with the difference that the catalyst has a composition (mass fraction): 0.15 Cr ₂ O ₃ , 0.02 K ₂ O, 0.83 Al ₂ O ₃ . The conversion of acetaldehyde is 36%, the selectivity for o-WF is 70%.

Example 6

The reaction is carried out analogously to example 3 with the difference that the catalyst has a composition (mass fraction): 0.30 Cr ₂ O ₃ -0.70 Al ₂ O ₃ . The conversion of acetaldehyde is 21%, the selectivity for o-WF 61%.

Example 7

The reaction is carried out analogously to example 3 with the difference that they use a catalyst composition (mass fraction): 0.15 Cr ₂ O ₃ -0.85 Al ₂ O ₃ . The conversion of acetaldehyde is 47%, the selectivity for o-WF 57%.

Example 8

The reaction is carried out analogously to example 3 with the difference that the catalyst has the composition (mass fraction): 0.10 NiO-0.90 α-Al ₂ O ₃ . The conversion of acetaldehyde is 22%, the selectivity for o-WF 3%.

Example 9

The reaction is carried out analogously to example 3 with the difference that the catalyst has the composition, (mass fraction): 0.20 V ₂ O ₅ -0.80 SiO ₂ . The conversion of acetaldehyde is 14%, the selectivity for o-WF 5%.

Example 10

The reaction is carried out analogously to example 3 with the difference that they use a composition catalyst, (mass fraction): 0.04 Cr ₂ O ₃ -0.96 aluminosilicate. The conversion of acetaldehyde is 17%, the selectivity for o-WF 39%.

Example 11

The reaction is carried out analogously to example 3 with the difference that the catalyst has the composition, (wt. Shares): 0.04 CoO-0.96 SiO ₂ . The conversion of acetaldehyde is 4%, the selectivity for o-WF 65%.

Example 12

The reaction is carried out analogously to example 11 with the difference that they use a composition catalyst, (mass fraction): 0.04 CoO-0.96 SiO ₂ , previously reduced in a mixture of 25% hydrogen in helium for 1 h at 500 ° C. The conversion of acetaldehyde is 4.5%, the selectivity for o-WF 58%. A comparison of these results with the results of experiment 11 suggests that the reduction of the catalyst has little effect on the reaction parameters.

Example 13

The reaction is carried out analogously to example 3 with the difference that they use a composition catalyst, (mass fraction): 0.04 MnO-0.96 SiO ₂ . The conversion of acetaldehyde is 5.0%, the selectivity for o-WF 55%.

Example 14

The reaction is carried out analogously to example 3 with the difference that they use a composition catalyst, (mass fraction): 0.01 Pt-0.99 SiO ₂ . The conversion of acetaldehyde is 12%, the selectivity for o-WF 3%.

Example 15

The reaction is carried out analogously to example 3 with the difference that they use a composition catalyst, (mass fraction): 0.01 Pt-0.99 MgO. The conversion of acetaldehyde is 6%, the selectivity for o-WF 32%.

Example 16

The reaction is carried out analogously to example 3 with the difference that they use a composition catalyst, (mass fraction): 0.01 Ru-0.99 ZSM-5 (zeolite structure MFI aluminosilicate composition). The conversion of acetaldehyde is 42%, the selectivity for o-WF 27%.

Example 17 (comparative)

The reaction is carried out analogously to example 3 with the difference that the catalyst is not used. In this case, the conversions of acetaldehyde and phenol are equal to zero.

Example 18

A mixture of 1.81 g (0.0193 mol) of phenol, 13.95 g (0.166 mol) of cyclohexane, 0.158 g (0.00357 mole) acetaldehyde and 0.6 g of a catalyst comprising (weight fraction.): 0.16 Cr ₂ O _3, 0.015 K ₂ O, 0.01 ZrO ₂ and 0.815 Al ₂ O ₃ , kept in an autoclave at 200 ° C for 5 hours. The pressure in the reactor is 10.3 atm. The composition of the products is analyzed on a gas chromatograph. The conversion of acetaldehyde is 15.3%, the selectivity for o-vinyl phenol is 10.2%.

Example 19

The reaction is carried out analogously to example 18 with the difference that instead of phenol, p-cresol is used. The conversion of acetaldehyde was 5.4%, the selectivity for 2-vinyl, 4-methylphenol 5.6%.

Example 20

The reaction is carried out analogously to example 18 with the difference that butanal is used instead of acetaldehyde. The butanal conversion was 3.6%, and the selectivity for 2-uten-1-enylphenol was 7.1%.

Claims (7)

1. A method of producing o-alkenylphenols, characterized in that o-alkenylphenols are obtained by reacting phenol or substituted phenol with an aliphatic aldehyde in the presence of a catalyst, which is characterized by the general formula: xM ¹ _α O _β · yM ² ₂ O · zM ³ О ₂ · qM ⁴ / carrier, where: M ¹ is a transition metal from the series: Co, Cu, Ni, V, Mn, Cr; M ² is a metal of the first group from the series: Li, Na, K, Rb, Cs; M ³ is a metal of the third or fourth group from the series: Zr, Ti, Ge and / or Ce, and / or U; M ⁴ is a noble metal from the series: Pt, Pd, Ru, Rh, Ag, Au; x, y, z, q are mass fractions of the corresponding components, with x = 0.0-0.50; y = 0.0-0.05; z = 0.0-0.05; q = 0.0-0.2, according to the reaction:

,
where: X ₁ —X ₄ = —H, —Alc, —OH, —OAlc, —Hal; R = —H, hydrocarbon radical. 2. The method according to p. 1, characterized in that the reaction is carried out in the gas or liquid phases at a temperature of 100-500 ° C, a pressure of 1-30 atm. 3. The method according to p. 1, characterized in that the molar ratio of aliphatic aldehyde to phenol or substituted phenol is from 0.01 to 99.9. 4. The method according to p. 1, characterized in that the source gas mixture may contain inert gases in this reaction, such as: nitrogen, helium, saturated hydrocarbons. 5. The method according to p. 1, characterized in that the liquid-phase reaction is carried out in the presence of solvents. 6. A catalyst for producing o-alkenylphenols by reacting phenol or substituted phenol with an aliphatic aldehyde according to claim 1, characterized in that it has the general formula: xM ¹ _α O _β · y M ² ₂ O · zM ³ O ₂ · qM ⁴ / carrier, where: M ¹ is a transition metal from the series: Co, Cu, Ni, V, Mn, Cr; M ² is a metal of the first group from the series: Li, Na, K, Rb, Cs; M ³ is a metal of the third or fourth group from the series: Zr, Ti, Ge and / or Ce, and / or U; M ⁴ - noble metal from the series: Pt, Pd, Ru, Rh , Ag, Au; x, y, z, q are mass fractions of the corresponding components, with x = 0.0-0.50; y = 0.0-0.05; z = 0.0-0.05; q = 0.0-0.2. 7. The catalyst according to claim 6, characterized in that the carrier is selected from a number of simple and complex inorganic oxides, for example SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , aluminosilicates, clays, zeolites or a mechanical mixture thereof.