JPH02718A - Production of aromatic alcohol - Google Patents

Abstract

PURPOSE:To stably obtain the objective compound in high yield for a long period using a specific catalyst having properties of a solid acid and base in producing the subject compound by intermolecular catalytic hydrogen transfer reaction in the vapor phase of an aromatic aldehyde or ketone with a primary or secondary alcohol. CONSTITUTION:A compound expressed by formula I or II [R<1> to R<3> are H or 1-2C alkyl; R<4> is H or 1-4C alkyl or alkoxy; n is an integer of 0-3; X<1> and X<2> are formula III or H (provided that X<1> and X<2> are not H)] and a compound expressed by formula IV (R<5> and R<6> are H, alkyl, hydroxyalkyl, etc.; the total number of carbon atoms of R<5> and R<6> is 0-8) are subjected to intermolecular catalytic hydrogen transfer reaction in the vapor phase in the presence of a catalyst expressed by formula V (X is Ca, Sr, Ba, La, Ce, yttrium or Zr; Y is Si, B, Al, Nb, Ti or P; Z is alkaline metal; a to d are atomic ratios; when a is 1, b is 0-0.5; c is 0-0.1; d is a numerical value determined by the valences and atomic ratios of the respective elements) to advantageously afford the objective compound expressed by formula VI or VII useful as an intermediate for perfumes, coatings, medicines, agricultural chemicals, etc.

Description

Detailed Description of the Invention (Industrial Application Field) (In the formula, R1, R2 and R3 are the same or different and each represents hydrogen or an alkyl group having 1 to 2 carbon atoms, and R4 is hydrogen or represents an alkyl group or alkoxyl group having 1 to 4 carbon atoms, n represents an integer in the range of 0 to 3, and Xl and x2 are not hydrogen at the same time. R6-Cto10to1 (wherein, R5 and R6
are each selected from the group of hydrogen, an alkyl group, a hydroxyalkyl group, an alkenyl group, a phenyl group, and a benzyl group, and the sum of the carbon numbers of R5 and R6 is 0 to 8. This invention relates to a method for producing the corresponding aromatic alcohol using a catalyst having solid acid-base properties in an intermolecular catalytic gas phase hydrogen transfer reaction with a primary or secondary alcohol represented by

The reaction is shown by the following formula.

I X2 Aromatic alcohols have a wide range of applications and are useful compounds that are used as important raw materials or intermediates in fields such as perfumes, paints, and pharmaceuticals.

(Prior Art) Conventionally, as a method for producing a corresponding aromatic alcohol from an aromatic aldehyde or an aromatic ketone, for example,
A method for producing aromatic alcohols by hydrogenation using a palladium catalyst in a liquid phase reaction (Japanese Patent Laid-Open No. 51-8
6432 Tan, Japanese Patent Application Laid-open No. 57-26634), and a method for producing an aromatic alcohol by subjecting an aromatic aldehyde and formalin to a cross-force nitzaro reaction using a ruthenium catalyst (Japanese Patent Application Laid-open No. 136533-1982). Also disclosed are methods for producing the corresponding aromatic alcohols from aromatic carboxylic acids and their derivatives. For example, methods for producing aromatic alcohols by hydrogen reduction using a rhenium catalyst (Japanese Unexamined Patent Publication No. 57-32237) and methods for producing aromatic alcohols by electrolytic reduction (Japanese Unexamined Patent Publications No. 117887-1988) are popular. has been done.

These manufacturing methods generally produce 10-80 K'J/c
Although the high-pressure reaction conditions of iG are applied, it is necessary to separate the solvent or additives from the aromatic alcohol produced after the reaction. On the other hand, a method for producing a corresponding aromatic alcohol by a hydrogen transfer reaction between an aromatic aldehyde or an aromatic liquid ketone and an alcohol, which is in the same field as the invention, is a method using hydrous zirconium oxide as a catalyst in the liquid phase or gas phase. JP-A No. 61-204143) or a method using a hydrous oxide of one or more metals selected from titanium, tin, iron, aluminum, cerium and niobium (JP-A No. 62-252737). ing. Two or more elements including magnesium (excluding oxygen) in the gas phase by a hydrogen transfer reaction in the same sphere.
A method for producing an aromatic alcohol using a catalyst (Japanese Unexamined Patent Publication No. 62-30552) has been disclosed.

(Problems to be Solved by the Invention) When producing aromatic alcohols, a catalyst containing an expensive metal is used in the liquid phase hydrogenation reaction, and the catalyst needs to be separated and recovered from the solvent, products, etc. There is also the danger of reacting hydrogen under high pressure.

On the other hand, synthesizing aromatic alcohols by gas phase reaction does not require multi-step processes like liquid phase reaction, and is very advantageous for industrial production.

However, as far as the method for producing aromatic alcohol is concerned, catalysts used in conventional intermolecular catalytic gas phase hydrogen transfer reactions, such as hydrous zirconium oxide catalysts (Japanese Unexamined Patent Publication No. 61-2012)
04143) is used at a low temperature of 75 to 110°C, and the raw material aromatic aldehyde is generally a high-boiling substance, so it is difficult to improve the raw material concentration, and in that case, there are problems with the yield of the aromatic liquid alcohol produced and the catalyst life. be.

Further, although the magnesium-based catalyst disclosed in JP-A-62-30552 has excellent initial activity, there is still room for improvement in terms of catalyst life.

(Objective of the Invention) The object of the present invention is to convert an aromatic aldehyde into a corresponding aromatic alcohol in high yield and stably for a long period of time by an intermolecular catalytic gas phase hydrogen transfer reaction using a primary or secondary alcohol as a hydrogen source. The objective is to provide a method for manufacturing the same.

(Means for Solving the Problems) The present inventors took into consideration the shortcomings of conventional catalysts for intermolecular catalytic gas phase hydrogen transfer reactions and endeavored to develop a new catalyst. the result,
It has been discovered that at least one metal oxide selected from the group consisting of calcium, strontium, barium, lanthanum, cerium, yttrium, and zirconium is effective in producing the desired aromatic alcohol. Furthermore, if necessary, at least one selected from the group consisting of silicon, boron, aluminum, niobium, titanium, and phosphorus may be added as an acidic component, and an alkali metal may be added as a base component to increase the acid base of the catalyst. and optimization of acid-base strength, which could improve the mechanical strength and surface area of the catalyst.

They succeeded in developing a catalyst that can supply the raw material aromatic aldehyde or aromatic ketone at a high concentration and also produce the corresponding aromatic alcohol in a high yield and stably over a long period of time, and completed the present invention. It happened. Furthermore, according to the present invention, useful aldehydes or ketones can also be produced at the same time by changing the type of primary or secondary alcohol used as a raw material, and this method is also very advantageous from an industrial perspective. be.

The aromatic aldehyde or aromatic liquid ketone used in this reaction has the general formula (wherein R1, R2 and R3 are the same or different, each represents hydrogen or an alkyl group having 1 to 2 carbon atoms, and R4 is a carbon represents an alkyl group or alkoxyl group of numbers 1 to 4, n is selected from the range of 0 to 3 and the group of hydrogen, but is not hydrogen at the same time), and specific examples thereof include (a ) benzaldehyde, (b)
Anisaldehyde, (C) phenylacetaldehyde,
(d) m-tolualdehyde, (e) cuminaldehyde,
Examples include (f) cinnamaldehyde, (Q) atrobaldehyde, and (h) acetophenone. These are (a') benzyl alcohol, (b') anis alcohol, (a') β-phenylethyl alcohol, (
d') 3-methylbenzyl alcohol, (e') cumyl alcohol, (f') cinnamyl alcohol, (g')
2-phenyl-2-propen-1-ol and (h'
) It is converted into α-phenylethyl alcohol, etc.

On the other hand, the primary or secondary alcohol used as a hydrogen source has the general formula R6-CHOH (wherein R5 and R6 are each selected from the group of hydrogen, an alkyl group, a hydroxyalkyl group, an alkenyl group, a phenyl group, and a benzyl group). Re, R5
The sum of the carbon numbers of and R6 is 0 to 8. ), and specific examples thereof include monoalcohols such as methanol, ethanol, propatool, isopropanol, n-butyl alcohol, benzyl alcohol, and β-phenylethyl alcohol; and ethylene glycol.
Examples include glycols such as 1,4-butanediol.

According to the present invention, the above-mentioned conventional problems in such an intermolecular catalytic gas phase hydrogen transfer reaction are fully solved, and the desired aromatic alcohol can be produced stably in high yield over a long period of time. As a possible catalyst, -form XaYbZcOd
(Here, X represents one or more elements selected from the group of calcium, strontium, barium, lanthanum, cerium, yttrium, and zirconyl, and Y represents one or more elements selected from the group of silicon, boron, aluminum, niobium, titanium, and phosphorus. Z represents one or more elements selected from the group of alkali metal rots. alb.

C and d represent the atomic ratio of each element, when a=1, b=o~0.5, preferably 0~0.1, C=O~
0.1, preferably 0-0.02, and d does not represent a numerical value determined by the valence and atomic ratio of each element. ) is provided.

To prepare the catalyst of the present invention, raw materials such as oxides, hydroxides, nitrates, oxynitrates, carbonates, etc. of each fence addition element (X1Y and Z component) can be used.

The method for preparing the catalyst according to the present invention includes, for example, dissolving or suspending various raw materials in water, heating and stirring, concentrating, drying, molding, and further calcination to obtain a catalyst; or dissolving various raw materials in water. After making it into hydroxide by adding ammonia water, filtering and washing with water, and drying,
A method of molding and rough calcination to make a catalyst: Furthermore, oxides or hydroxides of various elements are mixed in powder form, and after adding an appropriate molding aid (e.g., water, alcohol, etc.),
Examples include molding, drying, and calcination to use as a catalyst.

The firing temperature of the catalyst may vary widely from 300 to 800°C, preferably from 400 to 700°C, depending on the type of raw material used.

When the catalyst of the present invention is used in an intermolecular contact gas phase hydrogen transfer reaction between an aromatic aldehyde or a mono-aromatic ketone and a primary or secondary alcohol, the catalyst is very strong even if the raw material aldehyde or ketone concentration is high. It showed high activity and also had an extremely high selectivity to the target aromatic alcohol. Moreover, even when this reaction is continuously carried out for a long period of time, no deterioration in the activity of the catalyst is observed, and both the activity and selectivity are stable, and therefore the yield of the target aromatic alcohol is extremely high.

Note that the catalytic performance was determined using a known hydrogen transfer reaction catalyst, such as JP-A-11F? No. 62-30552 Mg1Sio, 1Nb
When compared with o, olKo, and olox, the catalyst performance according to the present invention was clearly superior after 1000 hours.

When using the catalyst of the present invention, either a fixed bed flow type reactor or a fluidized bed type reactor can be used.

The raw material gas has a molar ratio of raw material aromatic aldehyde or aromatic ketone to primary or secondary alcohol of 1:0.5.
~20, preferably in the range of 1:1 to 10, is diluted with an inert gas such as nitrogen, helium, or argon as necessary to obtain a raw material gas concentration of 1 to 1.
00% by volume, preferably 2 to 80% by volume.

The reaction is usually carried out at normal pressure, but can also be carried out under increased pressure or reduced pressure if necessary.

The reaction temperature is 200 to 450°C, preferably 250 to 40°C.
It is in the range of 0°C. The space velocity of the raw material gas varies depending on the raw material gas concentration, but is 100 to 5000 h "-1, preferably 5
A range of 00 to 3000 hr-1 is suitable.

Hereinafter, the present invention will be specifically described in Examples, and the conversion rate and selectivity in the Examples shall be in accordance with the following definitions.

Conversion rate (χ) = Number of moles of consumed raw material aromatic aldehyde or aromatic ketone Selectivity (%) Number of moles of aromatic alcohol produced Example 1 225 g of calcium hydroxide Ca (OH) was mixed with 100 d of water
Suspend it in , heat and concentrate at 90°C while stirring thoroughly,
After drying this in a warm bath, the outer diameter was 5M and the height was 5In.
It was molded into a cylindrical shape of In and fired at 600° C. for 2 hours in an air atmosphere to obtain a catalyst.

This catalyst 30- was filled in a stainless steel O-tube with an inner diameter of 20a++, and a continuous reaction was carried out at a reaction temperature of 300°C and a raw material gas of benzaldehyde: isobutylene: nitrogen = 10:0:20 at a space velocity of 1500 hr-1 (STP). I did it. The reaction product was analyzed by gas chromatography, and the results shown in Table 1 were obtained.

Example 2 Using the catalyst of Example 1 and using anisaldehyde and isopropanol as reaction raw materials, a continuous reaction was carried out under the same reaction conditions as in Example 1, and the results shown in Table 1 were obtained.

Example 3 Calcium hydroxide 22.5g, barium hydroxide Ba (
10.64 g of OH)2-8820 was suspended in 100 d of water and prepared in the same manner as in Example fIi41 to obtain a catalyst having an atomic ratio of Cao, 9Bao, and t excluding oxygen.

Using this catalyst, the reaction temperature was 350°C, and the ratio of phenylacetaldehyde:n-butyl alcohol:nitrogen was 5:30.
: Raw material gas with a volume ratio of 65 at a space velocity of 1000 hr
"(STP)t', continuous reaction was carried out, and the results shown in Table 1 were obtained.

Example 4 Calcium hydroxide 25g, anhydrous silicon its i 020
, 40 g and potassium hydroxide KOf-10,19 g
was suspended in 100% of water and prepared in the same manner as in Example 1,
In terms of atomic ratio excluding oxygen, Ca1. oSio, 02K o,
A catalyst having a composition of al was obtained.

Using this catalyst, a reaction temperature of 300°C and a raw material gas with a volume ratio of anisaldehyde:ethanol:nitrogen-10nia 0:20 were passed at a space velocity of 1500 hr-1 (STP).
Continuous reactions were carried out, and the results shown in Table 1 were obtained.

Example 5 Using the catalyst of Example 4, the reaction temperature was 300°C, m-tolualdehyde=1,4-butanediol:nitrogen-5:20
The raw material gas with a volume ratio of near 5 is heated to a space velocity of 1500 hr-1.
A continuous reaction was carried out, and the results shown in Table 1 were obtained.

Example 6 Strontium hydroxide 3r (OH)2 ・8H202
5 g was suspended in 100 ml of water, and prepared in the same manner as in Example 1 to obtain a catalyst.

Using this catalyst, continuous reactions were carried out under the same reaction conditions as in Example 2, and the results shown in Table 1 were obtained.

Example 7 Strontium hydroxide 26.58 g, boron oxide 8
2030.07SF, sodium hydroxide NaOH0,0
8g of water 10011! l! It was prepared in the same manner as in Example 1, with an atomic ratio of S r i, excluding oxygen.

A catalyst having a composition of 8 o, cn Na 0.02 was obtained.

Using this catalyst, a continuous reaction was carried out at a reaction temperature of 350°C and a raw material gas with a volume ratio of cuminaldehyde:2-butanol:nitrogen-5:30:65 passed through at a space velocity of 1500 hr.The results are shown in Table 1. I got it.

Example 8 Strontium hydroxide 26.58g, silicic anhydride 0.1
2g, cesium nitrate CsNO30, 19g in water 100#
! i! It was prepared in the same manner as in Example 1, and the atomic ratio excluding oxygen was 3 rl, o Si o, o2cso,
A catalyst having the composition ol was obtained.

Using this catalyst, a continuous reaction was carried out at a reaction temperature of 300°C and a raw material gas having a volume ratio of anisaldehyde:methanol:nitrogen = 5:30:65 at a space velocity of 1500 hr'', and the results shown in Table 1 were obtained. ,Ta.

Example 9 Strontium hydroxide 26.58g, aluminum oxide Aj 20s O, 15g, potassium hydroxide 0.06
g was suspended in 100 d of water, prepared in the same manner as in Example 1, and S i t in the atomic ratio excluding oxygen.

Catalysts having the following compositions were obtained: AJo, o3Ko, and ol.

Using this catalyst, a continuous reaction was carried out using m-tolualdehyde and isopropanol as reaction materials under the same reaction conditions as in Example 3, and the results shown in Table 1 were obtained.

Example 10 Ni'tt Lanthanum La (NO3) 3 ・6 days 205 (1
, 85% phosphorus MO, 27 g was dissolved in 200 te of water, and 1 lll was prepared in the same manner as in Example 1, and the atomic ratio excluding oxygen was L.
a1. A catalyst having the composition oPo, o2 was obtained.

Using this catalyst, a continuous reaction was carried out under the same reaction conditions as in Example 3, and the results shown in Table 1 were obtained.

Example 11 Lanthanum nitrate 43.30g, calcium hydroxide 7°41
1.60 g of titanium oxide TiO2 was suspended in 200 Id of water and prepared in the same manner as in Example 1 to obtain a catalyst having an atomic ratio of Lao, s C80,5T + o, 1, excluding oxygen.

Using this catalyst, a continuous reaction was carried out using phenylacetaldehyde and benzyl alcohol as reaction materials under the same reaction conditions as in Example 3, and the results shown in Table 1 were obtained.

Example 12 In Example 11, cerium was used instead of lanthanum to obtain a catalyst having a composition of TCe0.5 Cao, s T i 0.1.

Using this catalyst, continuous reactions were carried out under the same reaction materials and reaction conditions as in Example 11, and the results shown in Table 1 were obtained.

Example 13 Zirconyl nitrate ZrO(NO3)2 2H205C1
was dissolved in 200 d of water and hydrolyzed with 28% aqueous ammonia to obtain a precipitate. This precipitate was filtered, washed with water,
After drying at 20°C, the outer diameter is 5 mm.

It was molded into a cylindrical shape with a height of 5 gates and fired at 600° C. for 3 hours in an air atmosphere to obtain a catalyst. Using this catalyst, the repulsion degree was 350°C, anisaldehyde: n-butyl alcohol:
Nitrogen = 5:50:45 volume ratio raw material gas with space velocity 1
500 hr" (3TP) to carry out continuous reaction.
The results shown in 1 were obtained.

Example 14 50 g of zirconyl nitrate, 0.139 g of boron oxide, and 0.159 g of sodium hydroxide were dissolved in 200 d of water and prepared in the same manner as in Example 13 to obtain Z r in an atomic ratio excluding oxygen.
1. A catalyst having a composition of OBo, 02N ao, and o2 was obtained. Using this catalyst, a continuous reaction was carried out using benzaldehyde and ethanol as raw materials under the same reaction conditions as in Example 1, and the results shown in Table 1 were obtained.

Example 15 Calcium hydroxide 22.5 g, yttrium trioxide Y
2O33, 81g, niobium pentoxide Nb2050, 90
g Lithium hydroxide L10 days - H2C0,14g water 10 days
Cao, 9Yo, 1Nbo, o2Lio, o
A catalyst having a composition of 1 was obtained.

Using this catalyst, a continuous reaction was carried out using anisaldehyde and ethylene glycol as reaction raw materials under the same reaction conditions as in Example 1, and the results shown in Table 1 were obtained.

Example 16 A continuous reaction was carried out using the catalyst of Example 1 and acetophenone and isopropanol as reaction materials under the same reaction conditions as in Example 1, and the results shown in Table 1 were obtained.

Example 17 Using the catalyst of Example 4 and using cinnamaldehyde and isopropanol as reaction raw materials, a continuous reaction was carried out under the same reaction conditions as in Example 1, and the results shown in Table 1 were obtained.

Example 18 Using the catalyst of Example 4 and using atrobaldehyde and isopropanol as reaction raw materials, a continuous reaction was carried out under the same reaction conditions as in Example 1, and the results shown in Table 1 were obtained.

Comparative Example 1 225 g of magnesium hydroxide MO (OH) and 0.6 g of boron oxide were suspended in 100 g of water, prepared in the same manner as in Example 1, and had a composition of MQl, 0BO, Ofl in atomic ratio excluding oxygen. I got a catalyst.

This catalyst has the same composition as the catalyst disclosed in the Examples of JP-A-62-30552. Using this catalyst, the same reaction as in Example 1 was carried out, and the results shown in Table 2 were obtained.

Comparative Example 2 Magnesium hydroxide 25g, anhydrous silicon! 2.59 g, niobium pentoxide 0.57 g and potassium hydroxide 0.24
g to 100 ai of water! W4 in the same manner as in Example 1.
and remove oxygen (in atomic ratio MOl, 03io, 1N b
Catalysts having the following compositions were obtained: o, olKo, and ol. The Kono catalyst has the same composition as the catalyst disclosed in JP-A-62-30552. Using this catalyst, the same reaction as in Example 4 was carried out, and the results shown in Table 2 were obtained.

Comparative Example 3 In Comparative Example 2, except for niobium pentoxide, the atomic ratios of fvll, osio, o2K o
A catalyst having the following composition was obtained. This catalyst was published in Japanese Patent Application Publication No. 62
It has the same composition as the catalyst disclosed in the Examples of No.-30552. Using this catalyst, the same reaction as in Example 5 was carried out, and the results shown in Table 2 were obtained.

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, are R^1, R^2 and R^3 the same?
or different, each represents hydrogen or an alkyl group having 1 to 2 carbon atoms, R^4 represents hydrogen or an alkyl group or alkoxyl group having 1 to 4 carbon atoms, n represents an integer in the range of 0 to 3, and ^1 and X^2 are ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ and is selected from the group of hydrogen, but it is not hydrogen at the same time. ) aromatic aldehyde or aromatic ketone, and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula R^5
and R^6 are each selected from the group of hydrogen, an alkyl group, a hydroxyalkyl group, an alkenyl group, a phenyl group, and a benzyl group, and the sum of the carbon numbers of R^5 and R^6 is 0 to 8. ) In the intermolecular catalytic gas phase hydrogen transfer reaction with a primary or secondary alcohol, the general formula XaYbZcOd (wherein Y represents one or more elements selected from the group consisting of silicon, boron, aluminum, niobium, titanium, and phosphorus; Z represents one or more elements selected from the group of alkali metals; a, b, c and d represent the atomic ratio of each element, when a=1, b=0
~0.5, c=0~0.1, d represents a numerical value determined by the valence and atomic ratio of each element. ) A method for producing an aromatic alcohol, characterized by using a catalyst represented by: