JP3036935B2 - Method for producing phenol and aldehydes or ketones - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel process for producing at least one aldehyde and ketone and phenol.

[0002]

2. Description of the Related Art Conventionally, as a method for producing phenol from benzene and oxygen in one step, a method is known in which benzene and oxygen are reacted in a gas phase or a liquid phase in the presence of a catalyst.
However, in the case of a gas phase reaction, complete oxidation of benzene occurs and the selectivity of phenol is very low (Japanese Patent Application Laid-Open No. 56-87).
No. 527). In the case of a liquid phase reaction, there is a method of oxidizing benzene using a copper salt and oxygen, but the conversion of benzene is low and the yield of phenol is low (see Organic Synthetic Chemistry 41,
839 (1983)).

Further, using a palladium-based catalyst,
There is a method of oxidizing benzene in the presence of 0-phenanthroline and carbon monoxide, but the yield of phenol is low (JP-A-2-19809). Therefore, a method of producing phenol by direct oxidation of benzene has been desired,
It is not yet industrialized.

On the other hand, as a method for producing aldehydes or ketones, a so-called Wacker method has been conventionally known. That is, a method is known in which an olefin, water and oxygen are reacted in the presence of palladium ion and copper ion to produce aldehydes or ketones in a liquid phase (An method).
gew. Chem. 71, 176 (1959)).

In this method, for example, if ethylene is used as an olefin, acetaldehyde is generated. If propylene is used as the olefin, acetone is generated. For aldehydes or ketones formed from other olefins, see Angew.
6 (1959).

[0006] Therefore, the present inventors have provided a process for producing at least one aldehyde and ketone and phenol together (Japanese Patent Application No. 2-406712). However, the selectivity and yield of phenols and aldehydes or ketones are not sufficiently high.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for simultaneously producing phenol, aldehyde or ketone from benzene and olefins in a single step. The purpose is to provide a way to:

[0008]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have found that a method for simultaneously producing phenol, aldehyde or ketone in a single step from benzene and olefins with a higher yield and a higher selectivity. Was found.
That is, the present invention provides a liquid phase oxidation reaction using an oxidizing agent in the presence of copper ions and palladium as catalysts with olefins and benzene to produce at least one type of aldehyde and ketone and phenol. The presence of at least one member of the group consisting of quaternary ammonium ions and crown ethers in the liquid allows the product to be produced in high yield and high selectivity, and the presence of water as the liquid phase By making the reaction solution acidic, it is possible to provide a method for producing the product with higher yield and higher selectivity.

The olefins used in the present invention include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, butadiene-1,3. , Pentadiene-1,
4, cyclopentene, cyclohexene, styrene, allylbenzene, acrylic acid, crotonic acid, methacrylic acid,
Allyl alcohol, crotonaldehyde, vinyl chloride, etc.
All unsaturated compounds shown in Table 1 of Angew. Chem. 71, 176 (1959) are included.

[0010] The copper ion as a catalyst used in the present invention can be obtained by adding at least one of the group consisting of metallic copper, a monovalent copper compound and a divalent copper compound to a reaction solution. The monovalent copper compound used as the catalyst in the present invention is Cu ₂ Cl ₂ , Cu ₂ F ₂ , Cu ₂ Br ₂ , Cu ₂ l ₂ , Cu ₂ O, Cu
₂ CO ₃ , Cu ₂ (CN) ₂ , Cu ₂ SO ₃ , Cu ₂ OH, Cu ₂ S, Cu ₃ Fe (CN) ₆ ,
Cu ₄ Fe (CN) _{6 and the} like. The divalent copper compound used as a catalyst in the present invention is CuCl ₂ , CuF ₂ , CuBr ₂ , CuO, Cu (O
_{H) 2, Cu (CH 3} COO) 2, CuSO 4, CuCO 3, Cu (ClO 4) 2, Cu
CrO ₄ , Cu (CN) ₂ , CuCr ₂ O ₇ , Cu ₃ (Fe (CN) ₆ ) ₂ , Cu ₂ Fe (C
H) ₆ , Cu (HCO ₂ ) ₂ , Cu (NO ₃ ) ₂ , Cu ₃ (PO ₄ ) ₂ , CuS, naphthenic acid, copper stearate and the like. The amount of metallic copper and copper compound used in the present invention is usually 100 g of benzene.
0.001 to 10 g, preferably 0.01 to 1 g per
It is.

Palladium as a catalyst used in the present invention can be obtained by adding a palladium salt, metal palladium, palladium oxide, palladium with a carrier, organic palladium, or the like to a reaction solution. The palladium salt as a catalyst used in the present invention is PdF ₂ , PdCl ₂ , PdBr ₂ , Pd
I ₂ , Pd (NO ₃ ) ₂ , PdSO ₄ , Pd (CH ₃ COO) ₂ , PdS, palladium acetyl acetate, PdCl ₂ (PPh ₃ ) _{2 and the} like. The amount of the metal palladium and the palladium compound used in the present invention is usually 0.001 to 10 per 100 g of benzene.
g, preferably 0.01 to 1 g.

In the present invention, the addition of quaternary ammonium ions to the reaction system has a good effect on the yield of phenol. The quaternary ammonium ion used in the present invention is usually added to the reaction system as a quaternary ammonium salt. The quaternary ammonium salt used in the present invention is benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltri-n-butylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, decyltrimethylammonium chloride, decyltrimethylammonium iodide, phenyl Trimethylammonium chloride, phenyltrimethylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, trimethylstearylammonium chloride and the like.
In addition, those obtained by substituting a counter anion of these ammonium salts with a hydroxy anion are also used. The quaternary phosphonium ion used in the present invention is usually added to the reaction system as a quaternary phosphonium salt. The quaternary phosphonium salt used in the present invention is benzyltriethylphosphonium chloride, benzyltriethylphosphonium bromide, benzyltri-n-butylphosphonium chloride, cetyltrimethylphosphonium chloride, cetyltrimethylphosphonium bromide, decyltrimethylphosphonium chloride, decyltrimethylphosphonium iodide, phenyl Trimethylphosphonium chloride, phenyltrimethylphosphonium bromide,
Tetra-n-butylphosphonium chloride, tetra-
n-butylphosphonium bromide, trimethylstearylphosphonium chloride and the like. In addition, those in which the counter halogen anion of these phosphonium salts is substituted with a hydroxy anion are also used. The amount of the quaternary ammonium salt and the phosphonium salt used in the present invention is not particularly limited, but is preferably 0.001 to 0.1 mol per 1 mol of benzene.

In the present invention, if a crown ether is added to the reaction system, by-products are reduced, which has a good effect on phenol selectivity and yield. The crown ether used in the present invention is crown ether / 12-crown-
4, crown ether / 15-crown-5, crown ether / 18-crown-6, 18-crown-6 acetonitrile complex, crown ether /
(+)-18-crown-6-tetracarboxylic acid, crown ether / dibenzo-18-crown-6, crown ether / dibenzo-24-crown-8, crown ether / dibenzoviridino-18-crown-6, crown ether / Dicyclohexyl-18-crown-
6, crown ether / N-phenol aza-15-crown-5, crown ether / dicyclohexyl-2
4-crown-8 and the like. The amount of the crown ether used in the present invention is not particularly limited, but is preferably 0.001 to 0.1 mol per 1 mol of benzene. In the method of the present invention, the yield and selectivity of phenol are improved by adding a surfactant to the reaction system. These surfactants usually emulsify the heterogeneous two or multi-liquid phase by reducing the interfacial tension between these different liquid phases in the non-uniform two-liquid or multi-liquid phase,
It can be formed into micelles, highly dispersed or emulsified, and specifically, any commercially available surfactants can be used. More specifically, fatty acid soda soaps, fatty acid potassium soaps, alkyl sulfonates, alkyl ether sulfonates, alkylbenzene sulfonates, N-methyltaurates, acylalkyl taurates, dialkyl sulfosuccinates , Anionic surfactants such as polycarboxylates, amide ether sulfates, and alkyl sarcosinates; alkylamine acetates, long-chain alkylammonium salts, oxyalkylenealkylamines, and polyoxyalkylenealkylamines. Ionic surfactants, polyoxyalkylene alkyl ethers, alkyl phenols, polyoxyalkylene alkylates, sorbitan alkyl esters, oxyethylene oxypropylene block polymers, alkyl alkylo Amides, nonionic surfactants such as glycerol esters, alkyl glycines are illustrated and amphoteric surfactants such as dimethyl alkyl lauryl betaines. Of course,
The method of the present invention is not limited to only these surfactants. The use amount of these surfactants is not particularly limited, but preferably, benzene 1
0.001 to 20 g per 00 g, more preferably,
It is 0.01 to 2 g.

The iron ion used in the present invention is metallic iron, 2
It is obtained by adding at least one member of the group consisting of a trivalent iron compound and a trivalent iron compound to the reaction solution.
The divalent iron compound used in the present invention is FeCl ₂ , FeF ₂ , F
eBr ₂ , FeI ₂ , FeO, Fe (OH) ₂ , Fe (CH ₃ COO) ₂ , FeSO ₄ ,
FeCO ₃ , Fe (ClO ₄ ) ₂ , Fe ₃ (CN) ₆ , Fe (NO ₃ ) ₂ , Fe ₃ (P
O ₄ ) ₂ , FeS, etc. Trivalent iron compounds used in the present invention is _{FeCl 3, FeF 3, FeBr 3} , Fe 2 O 3, Fe (OH) 3, Fe
(OH) (CH ₃ COO) ₂ , Fe ₂ (SO ₄ ) ₃ , Fe ₄ [Fe (CN) ₆ ] ₃ , Fe (NO ₃ )
₃ , FePO ₄ , Fe ₂ S _{3 and the} like. The amount of metallic iron and iron compound used in the present invention is usually 0.001 to 10 g, preferably 0.01 to 1 g per 100 g of benzene.

The lithium ions used in the present invention can be obtained by adding lithium metal or lithium salt to the reaction solution. The lithium salt used in the present invention is LiC
l, LiNO ₃ , Li ₂ SO ₄ , LiBr, LiI, Li (CH ₃ COO), LiHCO ₃ ,
LiCO ₃ , LiClO ₃ , LiHCO ₂ , LiOH, LiNO ₂ , Li ₂ S, Li ₂ SO ₃
And so on. The amount of lithium metal and lithium compound used in the present invention is usually 0.00
It is 1 to 10 g, preferably 0.01 to 1 g.

The reaction solution according to the present invention is acidic. This acidic reaction solution is obtained by adding an acid to the reaction solution. As the acid added to the reaction solution, usually, hydrochloric acid, sulfuric acid,
Acetic acid, nitric acid, formic acid, acidic salts and the like are used. The acidity of the reaction solution used in the present invention is generally carried out at a pH of 6 or less, preferably at a pH of 4 or less.

The reaction solution according to the present invention can be carried out in a solution state, a two-layer separation state, a two-liquid mixed state, a colloidal state, a slurry state, a gas-phase mixed phase state, a gas-liquid mixed phase state and the like.
The reaction temperature according to the present invention is usually from 0 to 300 ° C, preferably from 10 to 200 ° C. When the reaction temperature is lower than 0 ° C., the conversion of benzene or olefin is low, and the productivity may be low. On the other hand, when the reaction temperature is higher than 300 ° C., by-products increase, and the selectivity of phenol and aldehyde or ketone may decrease. The reaction pressure according to the present invention is generally 0 to 300 kg / cm ² , preferably ^{2 to} 300 kg / cm ² .
It is 150 kg / cm ² . This reaction pressure can be adjusted by the pressure of oxygen, nitrogen, carbon monoxide or the like. The reaction time according to the invention is generally between 0.05 and 30 hours, preferably between 0.1 and 10 hours. In addition, in the present invention, the reaction can theoretically be performed until any of the raw materials, benzene, olefin, and oxygen, disappears. Therefore, if the raw material is continuously supplied and the product is continuously extracted, it takes a longer time. Is possible. In particular, the intercalation of additional olefins improves the yield of phenols and aldehydes.

The reaction according to the invention can be carried out in batch, semi-batch,
It can be carried out by various reaction methods and reaction operations such as a continuous method. The catalyst may be used in any of a solution state, a two-phase separation state, a two-liquid mixed state, a slurry state, a fixed bed, a moving bed, and a fluidized bed. In the present invention, there is no particular limitation on the order of addition of each component of the reaction raw materials to the reactor and the order of contact with the catalyst. After the reaction according to the present invention, the reaction product can be separated and recovered from the catalyst or the like by a usual separation method such as filtration, extraction, and distillation.
Solvent extraction, distillation, alkali treatment, sequential treatment such as acid treatment, etc., of the recovered material containing the phenol and aldehyde or ketone which are the target products according to the present invention, or an operation in which these are appropriately combined, etc. Phenol and aldehyde and / or ketone as target products can be separated and purified by ordinary separation and purification methods. Unreacted raw materials such as benzene, olefins and oxygen can be recovered and recycled to the reaction system. When the reaction according to the present invention is carried out by a batch operation method, after the reaction, a catalyst recovered by separating a reaction product may be used as it is, or after regenerating part or all of the catalyst, and repeatedly used as a catalyst in the reaction. Can be.

When the reaction according to the present invention is carried out continuously, part or all of the catalyst is deactivated or reduced in activity by subjecting it to the reaction, and the catalyst can be regenerated after the reaction is interrupted and used for the reaction. Alternatively, a part of the catalyst may be continuously or continuously withdrawn from the reactor, regenerated, recycled to the reactor, and used for the reaction. Also,
Fresh catalyst can also be added to the reactor continuously or intermittently.

[0020]

【Example】

Example 1 4.0 g of benzene, 15 g of 0.1N hydrochloric acid, 0.05 g of PdCl _2, 0.05 g of copper powder, 0.1 g of FeCl ₂ .4H ₂ O, 0.1 g of FeCl ₃ .6H ₂ O in a 50 ml Hastelloy C autoclave.
0.1 g, LiCl 0.05 g, were charged to crown ether / dicyclohexyl-18-crown -6 0.1 g, replace this autoclave with oxygen gas, oxygen pressure 15 Kg / cm ² and ethylene pressure in the autoclave 15 kg / cm ² was charged. After the reaction temperature was set to 100 ° C. and the reaction time was 3 hours, the autoclave was stirred, and the reaction solution was extracted with benzene, and the reaction product in benzene was analyzed by gas chromatography. As a result, the phenol yield was 8.6%. And acetaldehyde yield 28.7%
I got No by-product of p-benzoquinone was observed.

Example 2 FeCl ₂ .4H ₂ O, FeCl _2
3 · 6H not charged with ₂ O and LiCl, the method results in the same manner as in Example 1 to obtain a 6.8% phenol yield and 12.6% acetaldehyde yield. P as a by-product
-1.0% of benzoquinone was obtained.

Comparative Example 1 In the same manner as in Example 1, the crown ether /
The same operation as in Example 1 was carried out except that dicyclohexyl-18-crown-6 was not charged. As a result, a phenol yield of 7.8% and an acetaldehyde yield of 25.8% were obtained. No by-product of p-benzoquinone was observed.

Comparative Example 2 In the same manner as in Example 1, FeCl ₂ .4H ₂ O, FeCl
₃ · 6H ₂ not charged O and LiCl and crown ether / dicyclohexyl-18-crown-6, others were carried out in the same manner as in Example 1 results, 5.6% phenol yield and 9.4% acetaldehyde yield Obtained. 1.2% of p-benzoquinone was obtained as a by-product.

Example 3 The procedure of Example 1 was repeated, except that 8 kg / cm ² of propylene was charged instead of ethylene.
As a result, a phenol yield of 7.6% and an acetone yield of 24.7% were obtained. No by-product of p-benzoquinone was observed.

Example 4 After carrying out Example 5, a further 8 kg / c of propylene was added.
m ² , and then the same procedure as in Example 5 was carried out.
Phenol yield 10.8% and acetone yield 31.7
%. No by-product of p-benzoquinone was observed.

Example 5 After using Example 6, an additional 8 kg / c of propylene was used.
m ² , and then the same procedure as in Example 6 was carried out.
Phenol yield 13.9% and acetone yield 38.5
%. No by-product of p-benzoquinone was observed.

Example 6 In Example 1, 4 parts of benzene were added to the autoclave.
g, 0.1 g of CuCl, 0.05 g of palladium acetate and crown ether / dicyclohexyl-18-crown-6, the inside of the autoclave was replaced with oxygen gas, and oxygen gas with an oxygen pressure of 15 kg / cm ^{2 was} introduced into the autoclave. And an ethylene gas having an ethylene pressure of 15 kg / cm ^{2 and} a carbon monoxide gas having a carbon monoxide pressure of 15 kg / cm ² . The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 180 ° C. and the reaction time was 1 hour. As a result, the phenol yield was 6.7%, the acetaldehyde yield was 12.3%, and the phenyl acetate yield was 1.2%.

Comparative Example 3 The procedure of Example 6 was repeated, except that dicyclohexyl-18-crown-6 was not used. As a result, the phenol yield was 4.8%, the acetaldehyde yield was 8.1%, and the phenyl acetate yield was 1.0%.

Example 7 Example 1 was repeated except that 0.01 g of tetrabutylammonium chloride was added instead of crown ether / dicyclohexyl-18-crown-6.
Was performed in the same manner as described above. As a result, the phenol yield was 8.5.
%, The acetaldehyde yield was 27.3%, and no by-product of p-benzoquinone was observed.

Example 8 The procedure of Example 1 was repeated, except that 0.01 g of benzyltriethylammonium chloride was used instead of crown ether / dicyclohexyl-18-crown-6. As a result, the phenol yield was 8.5.
%, Acetaldehyde yield of 27.1% and by-product of p-benzoquinone were not observed.

Example 9 Example 8 was carried out in the same manner as in Example 8, except that 0.01 g of tetrabutylammonium chloride was used instead of crown ether / dicyclohexyl-18-crown-6. As a result, the phenol yield was 6.6%,
The acetaldehyde yield was 12.0% and the phenyl acetate yield was 0.9%.

Example 10 In Example 1, crown ether / dicyclohexyl-18-crown-6 was used instead of crown ether / dicyclohexyl-18-crown-6.
Example 1 except that 0.1 g of 12-crown-4 was used.
Was performed in the same manner as described above. As a result, the phenol yield was 8.5.
%, Acetaldehyde yield 28.1%, and by-products of p-benzoquinone were not observed.

Example 11 The same procedure as in Example 1 was repeated except that 4.2 g of butene-1 was charged instead of ethylene, and the same procedure as in Example 1 was carried out. As a result, the phenol yield was 6.4% and the methyl ethyl ketone yield was as follows. A rate of 22.1% was obtained. No by-product of p-benzoquinone was observed.

Comparative Example 4 The procedure of Example 13 was repeated, except that crown ether / dicyclohexyl-18-crown-6 was not used.
Other than that, it carried out similarly to Example 13 and obtained the phenol yield 6.0% and the methyl ethyl ketone yield 20.2%. No by-product of p-benzoquinone was observed.

Example 12 The procedure of Example 1 was repeated, except that 4.0 g of cyclohexene was charged instead of ethylene, and the other procedures were the same as in Example 1. As a result, a phenol yield of 6.2% and a cyclohexanone yield of 10. 3% was obtained. No by-product of p-benzoquinone was observed.

Comparative Example 5 The procedure of Example 12 was repeated except that no crown ether / dicyclohexyl-18-crown-6 was charged.
Other than that, it carried out similarly to Example 12 and obtained phenol yield 5.8% and cyclohexanone yield 8.7%. No by-product of p-benzoquinone was observed.

[0037]

According to the present invention, the following effects can be obtained. (1) Phenol and aldehyde or ketone can be co-produced. (2) Phenol can be produced with good selectivity by directly oxidizing benzene, and the phenol yield can be increased by adding an olefin. (3) Aldehydes or ketones can be produced with good selectivity and high yield. (4) mutually increase the phenol yield and the aldehyde or ketone yield. (5) Compared with the conventional method, phenol can be directly oxidized and produced under mild conditions of low temperature and low pressure. (6) Phenol and aldehyde or acetone, which are industrially important, can be produced with excellent safety, process, and economy. As described above, the present invention can provide a novel method for co-production of phenols and aldehydes or ketones which is industrially remarkably excellent.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 27/12 350 C07C 27/12 350 37/58 37/58 39/04 39/04 47/06 47/06 B 49/08 49/08 A 49/10 49/10 49/403 49/403 A // C07B 61/00 300 C07B 61/00 300 (56) References JP 5-85973 (JP, A) JP 4-273836 (JP JP-A-56-87527 (JP, A) JP-B-40-11368 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 27/00 340 C07C 27/12 350 C07C 37/58 C07C 39/04 C07C 47/06 C07C 49/08 C07C 49/10 C07C 49/403 C07B 61/00 300

Claims (8)

(57) [Claims] 1. A liquid phase reaction using an oxidizing agent in the presence of copper ions and palladium using olefins and benzene as catalysts, wherein the reaction solution contains at least one of the group consisting of a phase transfer catalyst and a surfactant. At least one aldehyde and ketone characterized by the presence of at least one species;
A method for producing seeds and phenol. 2. The method according to claim 1, wherein the reaction system further comprises at least one of the group consisting of iron ions and lithium ions as a catalyst. 3. The method according to claim 1, wherein water is present as a liquid phase. 4. The method according to claim 1, wherein the phase transfer catalyst is a quaternary ammonium ion, a quaternary phosphonium ion or a crown ether. 5. The method according to claim 1, wherein the surfactant is a substance that emulsifies, micelles or emulsifies the reaction solution system. 6. The method according to claim 1, wherein the oxidizing agent is oxygen gas or water diluted with an inert gas and water. 7. The method according to claim 1, further comprising adding an acid to the reaction solution. 8. The process according to claim 1, wherein the olefins are added intermittently.