JPS61286342A - Production of acyloxynaphthoic acid - Google Patents

Abstract

PURPOSE:To obtain the titled compound in high yield, by reacting an acylnaphthalene compound with hydrogen peroxide, etc., in a solvent containing specific amounts of formic acid and water, and carrying out a specific oxidization reaction using the resultant acyloxy alkylnaphthalene compound as a raw material. CONSTITUTION:The compound of formula I (R1 is 1-3C alkyl; R2 is H or 1-4C alkyl) is oxidized with molecular oxygen in an organic solvent in the presence of a cobalt and/or manganese compound and a bromine compound to obtain an acyloxynaphthoic acid useful as a raw material of synthetic resin and synthetic fiber (e.g. high-tenacity polyester fiber). In the above process, the compound of formula I produced by oxidizing the compound of formula II with hydrogen peroxide or an organic peracid in the presence of a solvent having a formic acid concentration of 45-95wt% and a water concentration of >=5wt% is used as the raw material. The objective compound can be easily produced in high selectivity and yield.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a corresponding acyloxynaphthoic acid compound by oxidizing an acyloxyalkylnaphthalene compound represented by the following general formula with molecular oxygen.

General formula: (In the formula, R1 is an alkyl group having 1 to 3 carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a mixture of glacial acetic acid is used, and at least one compound of cobalt or manganese compounds is used. This relates to a method for producing acyloxy and naphthoic acids in which an oxidation reaction is carried out in the presence of a catalyst containing a bromine compound.

The acyloxynaphthoic acid compound obtained by the method of the present invention is used as it is or in the form of hydrolyzing the acyloxy group to form a hydroxyl group, and is a compound useful as a raw material for synthetic resins or as a raw material for synthetic fibers.

[Conventional technology and its problems]

As a method for oxidizing alkylbenzenes having an acyloxy group in the presence of an oxidation catalyst, for example,
-8'49, Japanese Patent Publication No. 50-55066, etc. The former is a method in which p-cresyl acetate is oxidized at 100 to 140° C. in the presence of a cobalt catalyst to obtain 1, p-acetoxybenzoic acid. However, in this method p
-The reaction rate of cresyl acetate is only 12 mo1%. The latter invention is an improvement on the former, and is a method in which an organic carboxylic acid or its anhydride is used as a solvent and a three-component system of a bromine compound, a cobalt compound and a manganese compound is used as a catalyst.

It is also known to oxidize alkylnaphthalene compounds such as methylnaphthalene and dimethylnaphthalene with molecular oxygen in the presence of a heavy metal catalyst to obtain naphthoic acid or naphthalene dicarboxylic acid.

In addition, the applicant has previously prepared an alkylnaphthalene compound having an acyloxy group obtained by reacting an acylalkylnaphthalene with a peroxide in an organic solvent, and a bromine compound.
Cobalt compound or bromine compound - Cobalt compound -
We have developed a method for producing acyloxy and naphthoic acid compounds by oxidizing them with molecular oxygen in the presence of manganese compounds.

(Japanese Patent Application Nos. 59-145183 and 59-163402) Although this method efficiently yields the corresponding acyloxy naphthoic acids, the reaction rate of acyloxy and alkylnaphthalenes is still insufficient.

[Means for solving problems]

For this reason, various studies have been conducted to increase the reaction rate of acyloxy and alkylnaphthalenes, and as a result, acyloxy and alkylnaphthalene compounds, which can be obtained by reacting an acylnaphthalene compound with a peroxide such as hydrogen peroxide in a solvent containing formic acid and water at specific concentrations, have been developed. It has been discovered that by using an alkylnaphthalene compound as a raw material for the oxidation reaction, the reaction rate of acyloxy and alkylnaphthalene can be improved and acyloxy and naphthoic acids can be obtained in high yields, leading to the present invention.

That is, the present invention is based on the following general formula (1) (wherein R1 has 1 carbon number)
~3 alkyl group, R2 is a hydrogen atom or has 1 to 4 carbon atoms
is an alkyl group. ) When oxidizing an acyloxy naphthalene compound with molecular oxygen in the presence of at least one cobalt or manganese compound and a moxibustion compound in an organic solvent, acyl represented by the following general formula (2), Alkylnaphthalene (R1 and R2 in the formula are the same as above) An acyloxy, alkylnaphthalene compound is used in which the compound is prepared in the presence of a solvent having a formic acid concentration of 45 to 95% and a water concentration of at least 5%. This is a method for producing acyloxy and naphthoic acids.

The acyloxy and alkylnaphthalene compounds used in the present invention are obtained by reacting acyl/alkylnaphthalenes with peroxides such as hydrogen peroxide, and the reaction temperature at this time can be in the range of 0°C to 100°C. However, it is usually carried out at a temperature in the range of 10"C to 70C.

Further, the reaction is carried out in a solvent containing specific amounts of formic acid and water, and the amount of formic acid used can be generally in the range of 0.1 to 100 in weight ratio to the raw material acyl/alkylnaphthalene compound. A suitable value is 0°3 to 60°.

Furthermore, in the nuclear reaction, formic acid and water bodies function as reaction solvents, so there is no particular need for a reaction solvent, but any solvent can be used as long as it does not adversely affect the reaction. can.

Examples of such solvents include organic fatty acids and their esters, and aromatic hydrocarbons.

The organic fatty acids are lower fatty acids having 2 to 4 carbon atoms, such as acetic acid, propionic acid, and acetic acid. Examples of organic fatty acid esters include methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate. Examples of aromatic hydrocarbons include benzene, toluene, xylene, and ethylbenzene.

One of hydrogen peroxide or organic peracids or mixtures thereof is used in the reaction. Industrially, it is preferable to use hydrogen peroxide. Organic peracids are percarboxylic acids synthesized from hydrogen peroxide and lower fatty acids, and examples include peracetic acid and perpropionic acid.

In the reaction, hydrogen peroxide can be supplied as it is, or as a formic acid solution, or as an organic fatty acid solution used as a solvent or other solvent. A solution of hydrogen peroxide in formic acid or an organic fatty acid solution may produce some percarboxylic acid if the residence time is long, but it can be used without any problem. Hydrogen peroxide is usually used at a concentration of 30 to 95 wt96.

Hydrogen peroxide is used in a molar ratio of 1.00 to 2.0 with respect to the raw material acyl-furkylnaphthalene. If the amount exceeds this range, there is no particular advantage, and in some cases, side reactions may occur, resulting in disadvantages.

In this reaction, organic peracids such as peracid and perpropionic acid are also used in the same manner as hydrogen peroxide.

After the reaction is completed, the reaction product is cooled to precipitate crystals,
Obtain crystals of acyloxy alkylnaphthalene. Further, if necessary, the crystals are rinsed with the same solvent used in the reaction.

Specific examples of the acyloxyalkylnaphthalene compound represented by the general formula (1) obtained in the following manner include 2-methyl-6-acetyloxynaphthalene, 2-methyl-6-propyloxynaphthalene, 2
-Methyl-6-isobutyryloxynaphthalene, 2-methyl-7-7cetyloxynaphthalene, 2-methyl-7
-p pionyloxynaphthalene, 2-methyl-7-isobutyryloxynaphthalene, 2-ethyl-6-7cetyloxynaphthalene, 2-ethyl-6-propionyloxynaphthalene, 2-ethyl-6-isobutyryl Oxynaphthalene, 2-ethyl-7-7cetyloxynaphthalene, 2-ethyl-7-7t-pionyloxynaphthalene, 2-ethyl-7-isobutyryloxynaphthalene, 2
-isopropyl-6-fucetyloxynaphthalene, 2-
Isopropyl-6-bu pionyloxynaphthalene, 2
-isoprobyl-6-ybutyryloxynaphthalene,
2-isopropyl-7-7cetyloxynaphthalene, 2
-Inpropyl-7-propionyloxynaphthaleneruoxynaphthalene, 1-methyl-6-7cetyloxynaphthalene, 1-methyl-6-propionyloxynaphthalene, 1-methyl-6-isobutyryloxynaphthalene, 1- Methyl-7-acetyloxynaphthalene, 1-
Examples include methyl-7diprobionyloxynaphthalene and 1-methyl-7-isobutyryloxynaphthalene. ' Next, the acyloxy-alkylnaphthalene compound obtained by the reaction is oxidized with molecular oxygen in the presence of an organic solvent.

As the solvent used in the oxidation reaction, a lower organic carboxylic acid having 2 to 4 carbon atoms or a mixture of the organic carboxylic acid and acetic anhydride is used.

The amount of solvent to be used is at least 2 times or more, preferably 3 to 100 times the amount of the reaction raw material.

It is preferable that the amount of water in the reaction medium be as small as possible. Although it varies depending on the concentration of the catalyst and the amount of solvent used relative to the reaction raw material, it may be normally commercially available, and is generally 1 wt% or less, preferably 0.5 wt% or less. If too much water is present, some side reactions may occur, which is undesirable.

When a mixture of an organic carboxylic acid and acetic anhydride is used, the amount of acetic anhydride is desirably 100 times or less, preferably 60 times or less, relative to the reaction raw material.

If the amount of acetic anhydride is too large, the selectivity of acyloxy naphthoic acid tends to decrease, which is not preferable.

Next, the catalyst used in the present invention is a two-component system consisting of a bromine compound and a cobalt compound, or a three-component system in which a manganese compound is further added to the catalyst. , sodium bromide, manganese bromide, ammonium bromide, etc. are used, and the amount used is 100wt as Br based on the solvent.
ppm or more, preferably 200 to 10000 wtpp
It is m.

Examples of the cobalt compound include cobalt bromide and cobalt acetate, and the amount used is 10 wtppm or more as Co, preferably 50 to 500 wtppm based on the solvent.
It is pm. Furthermore, manganese compounds include manganese bromide, manganese acetate, etc.
Used at concentrations below 0.00 wtppm.

In the present invention, the reaction temperature is preferably in the range of 100 to 200°C. If the temperature is too high, decomposition of dV::Y''5 will occur, which is undesirable, and if the temperature is lower than 100°C, the reaction will not proceed sufficiently, which is undesirable.

In addition, for reaction H2, a normal pressure to 200 Ky/iG1 acid cumulative ratio of 40 Kg/iG or less is adopted, and although it is not preferable if the oxygen partial pressure is zero, the reaction will proceed satisfactorily even if the oxygen partial pressure is 2 Kg/αIG or less. . As the molecular oxygen of the present invention, either pure oxygen gas or an oxygen-containing gas diluted with an inert gas, such as air, can be used.

〔Effect of the invention〕

According to the present invention, a naphthoic acid compound having an acyloxy group can be easily obtained with good selectivity and high yield. The naphthoic acid compound is used as it is or by hydrolyzing the acyloxy group to form a hydroxyl group, as a raw material compound for synthetic resins or synthetic fibers. Naphthoic acid compounds obtained by the method of the present invention, such as 2-7cetoxy-6-naphthoic acid, have recently attracted attention as a raw material for high-strength polyester fibers, and the present invention is directed to the industrial supply of such naphthoic acids. This is extremely significant.

〔Example〕

Next, examples of the present invention will be described.

Example 1 12.4 g of water, 40 g of formic acid, and 29.29 g of 2-methyl-6-7 cetylnaphthalene were added to a reaction vessel equipped with a stirrer, a reflux condenser, and a dropping q-), and the mixture was heated on a water bath while stirring. Maintain at 29°C.

Formic acid 30.12g, water 10.04. ! 9 and 9
49.8 g of a mixture prepared with 0% hydrogen peroxide aqueous solution 9,649 was added dropwise from the dropping funnel over 3 minutes while stirring. (Formic acid concentration: 74.7 wt%) Heat generation is observed during the dropping, but the temperature of the water-cooled liquid is maintained at 29°C as necessary. After the dropwise addition was completed, the reaction was carried out at 29°C for about 5 hours.

After the completion of the reaction, the desired product 2-methyl-
Crystals of 6-7 setoxynaphthalene were separated, rinsed with an aqueous formic acid solution, and dried under reduced pressure at 60°C.

Then 2-methyl-6-7 setkinnaphthalene 75, FJ
, acetic acid (water content 0.2wt%) 100g, acetic anhydride
10,9, Cobalt acetate tetrahydrate 1.16g (Cobalt 2500wtpl'1m) Manganese acetate hydrate 1,
259 (manganese 250 mouths wtpp...), ammonium bromide 0°384, zo (bromine 2850 wL pp...)
m) into a titanium autoclave with an internal volume of 500 mg equipped with an oval machine, and 2.6 to 3. OKp/ff1G
After pressurizing with air, it is heated to 117-126°C.

Air was blown at a rate of 501/hr, and the reaction was continued until no oxygen was absorbed. The reaction time was 2.5 hours.

The contents were taken out and analyzed by high performance liquid chromatography. As a result, the conversion rate of 2-methyl-6-7cetoxynaphthalene was 97.2%, and the yield of 6-7cetoxy-2-naphthoic acid was 88.8mol% (selectivity 91.3 rnol
Ly5).

Example 2 In a reaction vessel equipped with a stirrer, a reflux condenser, and a dropping funnel, 1.14 g of water, 11.46 g of giso, and 2-
Add 8.58g of methyl-6-acetylnaphthalene,
Keep at 20°C on a water bath with stirring.

Formic acid 10g, 90% hydrogen peroxide aqueous solution 2.6
12.64 g of a mixture of 4 g and 4 g was added dropwise from the dropping funnel over a period of 82 minutes while stirring. (Formic acid concentration 9
3.9wt%) Although heat generation is observed during dropping, the liquid temperature is maintained at 17 to 20°C by cooling with water as necessary. After the dropwise addition was completed, the reaction was carried out at 17 to 26°C for about 5 hours.

After the completion of the reaction, the desired product 2-methyl-
Crystals of 6-7 setoxynaphthalene were separated, rinsed with an aqueous solution, and then dried under reduced pressure at 60°C.

Then 2-methyl-6-7cetoxynaphthalene 5.5
g, acetic acid (water content 0.2wt96) 100g, anhydrous vinegar #110g, cobalt acetate tetrahydrate 0,047g (cobalt 100wtpp (Co.), manganese acetate tetrahydrate klA
O,4429 (manganese 9 [10wt T)pm
), ammonium bromide 0.384g (bromine 28
50 wtppm) into a titanium autoclave with an internal volume of 500 ml and an agitator and 1.7 to 2.2K.
After pressurizing with air to g/iG, 118. Heat to ~124°C.

Air was flowed at a rate of 271/hr IW, and the reaction was continued until no oxygen was absorbed. The reaction time was 2.5 hours.

The contents were taken out and analyzed by high performance liquid chromatography.The results showed that the conversion rate of 2-methyl-6-7cetoxynaphthalene was 96.2%, and the yield of 6-acetoxy-2-naphthoic acid was 80.3mol% (selected). Rate 83.4+no1
%)Met.

Example 3 Water 14,649. 22.28 g of formic acid and 2-
Add 77.86 g of methyl-6-7 cetylnaphthalene and maintain at 40° C. on a water bath while stirring.

Formic acid in advance 7.31. j9. A mixture of 5.0 g of water and 2.469 90% hydrogen peroxide aqueous solution 1
4.77 g was added dropwise over a period of 30 minutes while stirring. (Formic acid concentration: 59.8 wt%) Heat generation is observed during dropping, but if necessary, cool with water to maintain the liquid temperature at 40°C. After the dropwise addition was completed, the reaction was carried out at 40° C. for about 5 hours.

After the completion of the reaction, the desired product 2-methyl-
Crystals of 6-7 setoxynaphthalene were separated, rinsed with an aqueous formic acid solution, and then dried under reduced pressure at 60°C.

Then 2-methyl-6-7cetoxynaphthalene v5.59
, acetic acid (water content 0.2wt%) 100g, acetic anhydride
10g, cobalt acetate tetrahydrate 0,349g (cobalt 750 wt ppm), manganese acetate tetrahydrate 0.
125g (Ma/Ga/25o wtppm), ammonium bromide 0.684g (bromine 2850wtppm)
was charged into a titanium autoclave with an internal volume of 500 ml and equipped with a stirrer, pressurized with air to 1.7-2.1 kg/-〇, and then heated to 118-123°C.

Air was flowed at a rate of 401/hr, and the reaction was continued until no oxygen was absorbed. The reaction time was 2.5 hours.

The contents were taken out and analyzed by high-performance liquid chromatography. As a result, the conversion rate of 2-methyl-6-acetoxynaphthalene was 100%, and the yield of 6-7cetoxy-2-naphthoic acid was 86.0 mo1% (selectivity 86. Omo1%).

In addition, the selectivity of 6-hydroxy-2-naphthoic acid is 0.5
The mo was 1%.

Example 4 5.04 g of ethyl acetate and 2-methyl-
Add 7°39g of 6-7 cetylnaphthalene and maintain at 30°C on a water bath while stirring.

A mixture prepared in advance of 5.05 g of formic acid, 0.5 g of water, and 2.27 r of 90% aqueous hydrogen peroxide solution 7.8
9 was added dropwise from the dropping funnel over a period of 19 minutes while stirring. (Formic acid concentration: 46°6 wt%) Heat generation is observed during dropping, but if necessary, cool with water to maintain the liquid temperature at 30°C. After the dropwise addition was completed, the reaction was carried out at 30° C. for about 10 hours.

After the completion of the reaction, the desired product 2-methyl-
Crystals of 6-acetoxynaphthalene were separated, rinsed with an aqueous formic acid solution, and then dried under reduced pressure at 60°C.

Then 2-methyl-6-acetoxynaphthalene 5.5
t, acetic acid (water content 0.2wt%) 100? , acetic anhydride
10t1 cobalt acetate tetrahydrate 0,244tC cobalt 525 wtppm>, manganese acetate tetrahydrate 0.
244t (manganese 500wtppm), ammonium bromide 0.384f (bromine 2Bsowtppm)
) into a titanium autoclave with an internal volume of 500 ml and equipped with a stirrer to make 2kl. /iG with air and then heated to 115-116°C.

Air 71. ．． The reaction was continued at a rate of 13/hr until no oxygen was absorbed. The reaction time was 2.5 hours.

The contents were taken out and analyzed by high performance liquid chromatography. As a result, the conversion rate of 2-methyl-6-acetoxynaphthalene was 100%, and the yield of 6-acetoxy-2-naphthoic acid was 88.2 mo1% (selectivity 88.2 mo1%). )
Met.

Examples 5 to 10 A reaction was carried out under the same conditions as the first stage reaction in Example 1, and the second stage was carried out in the same manner as in Example 1 using the obtained 2-methyl-6-acetoxynaphthalene under the conditions shown in Table 1. The reaction was carried out.

The results obtained are shown in Table-1.

In addition, the water concentration in the reaction solvent before the reaction in Example 8 was approximately 0.
．． It becomes 2wt%.

Example 11 In a reaction vessel equipped with a stirrer, a reflux condenser, and a dropping funnel, 3.1 r of water, 10 of formic acid, and 2-methyl-
Add 6-imbutyrylnaphthalene 12.1F and maintain at 29°C on a water bath while stirring.

A mixture prepared in advance of formic acid 7.55F, water 2.51F, and 9096 hydrogen peroxide aqueous solution 2.41F 1
Add 2.45r of the solution dropwise from the dropping funnel over 3 minutes while stirring. (Formic acid concentration: 74.7 wt%) Heat generation is observed during dropping, but if necessary, cool with water to maintain the liquid temperature at 29°C. After the dropwise addition was completed, the reaction was carried out at 29°C for about 5 hours.

After the completion of the reaction, the desired product 2-methyl-
Crystals of 6-inbutyloxynaphthalene were separated, rinsed with an aqueous formic acid solution, and then dried under reduced pressure at 60°C.

Next, 2-methyl-6-imbutyryloxynaphthalene 10f1 acetic acid (water content 0.2 wt%) 1 (I
IQ? , acetic anhydride IQ f , vinegar 9 , :7
Baltic tetrahydrate 0', 244f (cobalt 525 w
t ppm), manganese acetate tetrahydrate 0.2442 (
Manganese 5o OWt I)pm) and ammonium bromide 0.3849 (bromine 2850Wtppm) were charged into a titanium autoclave with an internal volume of 500m1 equipped with a stirrer, and after pressurizing with air to 25kg/dG, heated to 120℃. do.

Air was flowed at a rate of 25-#/hr and the reaction continued until no oxygen was absorbed. The reaction time was 2.5 hours.

The contents were taken out and analyzed by high-performance liquid chromatography. As a result, the conversion rate of 2-methyl-6-imbutyryloxynaphthalene was 100%, and the yield of 6-imptyryloxy-2-naphthoic acid was 78.5 mo1%. (Selection rate 7
8.5 molL36).

Example 12 In a reaction vessel equipped with a stirrer, a reflux condenser and a dropping funnel, water jIF, formic acid 1°2 and 2-ethyl-6 were added.
- Add 10.69 g of acetylnaphthalene and keep at 29° C. on a water bath with stirring.

Preliminary amount of formic acid 7.56, water 2.51? and 90% hydrogen peroxide aqueous solution 2.41F mixture 12
．． 45F was added dropwise from the dropping funnel over a period of 3 minutes while stirring. (Formic acid concentration: 74.7 wt%) Heat generation is observed during dropping, but if necessary, cool with water to maintain the liquid temperature at 29°C. After the dropwise addition was completed, the reaction was carried out at 29°C for about 5 hours.

After the completion of the reaction, the desired product 2-ethyl-
Crystals of 6-acetoxynaphthalene were separated, rinsed with an aqueous formic acid solution, and then dried under reduced pressure at 60°C.

Then 2-ethyl-6-acetoxynaphthalene 10f
1 acetic acid (water content 0.2 wt%) 100t1 acetic anhydride 10v1 cobalt acetate tetrahydrate o, 244r (cobalt s 2 s wt ppm).

Vinegar 6? Manganese tetrahydrate salt 0.2449 (manganese 500w
t ppm ), ammonium bromide 0.3842 (bromine 2850 wt ppm) were charged into a titanium autoclave with an internal volume of 500 ml equipped with a stirrer, pressurized to 25 to 9/cdG with air, and then heated to 120°C.

25. Air. The reaction was continued at a flow rate of g/hr until no oxygen was absorbed. The reaction time was 2.5 hours.

Remove the contents 1. As a result of analysis by high performance liquid chromatography, the conversion rate of 2-ethyl-6-acetoxynaphthalene was 10096. (The yield of S-acetoxy-2-naphthoic acid is 76.3 mo1% (selectivity 76.3 mo
1%).

Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Agent: Patent Attorney Sadafumi Kohori Continuation of the handbook (written by Hosei (spontaneous)) August 13, 1985

Claims (1)

[Claims] The acyloxy, alkylnaphthalene compound represented by the general formula (1) has numerical formulas, chemical formulas, tables, etc. (1) (In the formula; R_1 is an alkyl group having 1 to 3 carbon atoms, R_2 is (It is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) When oxidized with molecular oxygen in the presence of at least one cobalt or manganese compound and a bromine compound in an organic solvent, the following general formula (2) is used. The acyl/alkylnaphthalenes expressed are ▲Mathematical formulas, chemical formulas, tables, etc.▼(2) (R_1 and R_2 in the formula are the same as above) Formic acid concentration of 45 to 95% by weight and water concentration of at least 5% by weight An acyloxy-alkylnaphthalene compound represented by the general formula (1) obtained by oxidation with hydrogen peroxide, an organic peracid, or a mixture thereof in the presence of a certain solvent. Method for producing naphthoic acid