JPS61191665A - Production of aryl aromatic carbamate - Google Patents

Abstract

PURPOSE:The reaction between an aromatic nitro compound, an aromatic hydroxy compound and carbon monoxide is carried out in the presence of a novel catalyst to enable high-yield production of the titled compound which is used as a feedstock for agricultural chemicals, isocyanates and polyurethanes with good operability. CONSTITUTION:The reaction between an aromatic nitro compound, an aromatic hydroxy compound and carbon monoxide is carried out in the presence of a catalyst of metallic palladium or its compound and, in addition, a cocatalyst of a specific catalyst containing a phosphorus halide, a vanadium compound and a tertiary amine, in a solvent such as benzene at 160-220 deg.C under a carbon monoxide partial pressure of 100-500kg/cm<2>G for 10min-10hr to give the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an aromatic carbamic acid aryl ester useful as a raw material for agricultural chemicals, isocyanates, or polyurethanes.

More specifically, the present invention relates to a method for producing an aromatic carbamic acid aryl ester from an aromatic nitro compound, an aromatic hydroxy compound, and carbon monoxide using a novel catalyst system.

[Conventional technology]

Aromatic isocyanates are generally produced by reacting aromatic amines obtained by reducing aromatic nitro compounds with phosgene. In recent years, new methods for producing isocyanates have been developed due to the lack of raw material resources, soaring prices, and the strong toxicity of intermediate raw materials such as phosgene.

One of these methods involves reacting an organic nitro compound with carbon monoxide and an organic hydroxy compound to produce the corresponding carbamic acid ester, which is then decomposed into an isocyanate and an organic hydroxy compound.

In this case, when an alcohol is used as the organic hydroxy compound, an aromatic carbamic acid alkyl ester can be obtained.

Aromatic carbamic acid alkyl esters generally have a high decomposition temperature, and when attempting to obtain aromatic butocyanate by thermal decomposition, a high temperature of 250°C or higher is usually required to obtain an effective reaction rate for efficient implementation. This causes many problems such as deterioration of raw materials and products, decrease in yield, and increase in utility costs.

On the other hand, aromatic carbamic acid aryl esters obtained using aromatic hydroxy compounds as organic hydroxy compounds can be thermally decomposed at relatively low temperatures, which alleviates the above-mentioned problems in the thermal decomposition process. This is extremely advantageous compared to using it as a raw material.

However, the conventional method for producing aromatic carbamic acid aryl ester from an aromatic nitro compound, an aromatic hydroxy compound, and carbon monoxide has various problems.

For example, Japanese Patent Publication No. 56-12.632 describes a method for producing aromatic carbamic acid esters using a catalyst consisting of palladium, ruthenium, or rhodium, a Lewis acid, and a tertiary amine; however, phenol is used as the hydroxy compound. The reaction rate is lower and the yield is lower than when alcohol is used.

Moreover, the reaction liquid becomes a slurry, making separation and purification of the catalyst and reactants troublesome.

In addition, Japanese Patent Publication No. 43-23-939 describes a method for producing aromatic carbamic acid esters in the presence of a carbonyl-containing derivative of a group I metal of the periodic table such as rhodium as a catalyst and a co-catalyst such as ferric chloride. However, when phenol is used as the hydroxy compound, the yield is significantly lower than when alcohol is used.

In addition, U.S. Pat. No. 3,531,512 (1970) proposes a method using palladium and a Lewis acid as a catalyst, but this method also has a low yield when phenol is used, and it is also difficult to use a Lewis acid such as No. It is extremely corrosive to diferrous iron, stainless steel, etc., making it difficult to put it into practical use.

Furthermore, as a method for producing an aromatic carbamic acid ester with an improved catalyst system, a method using a catalyst consisting of metal palladium or a palladium compound, vanadium oxytrichloride, and a tertiary amine (Japanese Patent Application Laid-Open No. 54-22-339), #A method using a gold group metal and/or its compound as a main catalyst and a Lewis acid and an oxide of a group Va or VIa metal of the periodic table such as vanadium as a co-catalyst (Japanese Patent Application Laid-Open No. 128-550 1982)
, a method using a catalyst consisting of metallic palladium or a palladium compound, an iron compound, a bicyclic amidine, and a halogen compound has been reported (Japanese Patent Application Laid-open No. 57-32-251), and phenols are used as usable hydroxy compounds. Although they are listed, specific examples are not mentioned.

The present inventors investigated the production of aromatic carbamic acid aryl esters from aromatic nitro compounds, aromatic hydroxy compounds, and carbon monoxide, and found that the conventional method using alcohol could be used as is in place of aromatic hydroxy compounds. However, even if a highly active catalyst is used to produce aromatic carbamic acid alkyl esters, many problems arise, such as a decrease in reaction rate and yield of the desired product, and deterioration in the operability of the catalyst-reaction solution. I understand.

[Problem that the invention seeks to solve]

The present invention was made from the viewpoint of ridge production, and uses a new catalyst system to produce aromatic carbamic acid aryl esters from aromatic nitro compounds, aromatic hydroxy compounds, and carbon monoxide in good yields. Another object of the present invention is to provide a manufacturing method with good operability.

[Means to solve the problem]

The present inventors have completed the present invention as a result of intensive studies to achieve the above object. That is, the present invention provides a method for producing an aromatic carbamic acid ester by reacting an aromatic nitro compound, an aromatic hydroxy compound, and carbon monoxide in the presence of a catalyst. This is a method for producing an aromatic carbamic acid aryl ester, which is characterized by carrying out the reaction at high temperature and high pressure using a catalyst system consisting of a phosphorus compound, a vanadium compound, and a tertiary amine.

According to the method of the present invention, aromatic carbamic acid aryl esters, which can be easily thermally decomposed under mild conditions to obtain the corresponding isocyanate in high yield, can be produced at a high reaction rate and high yield compared to conventional methods. It can be produced with high yield.

Furthermore, since the catalyst metal component is extremely small compared to conventional methods, the catalyst component is well dissolved, and the reaction liquid does not substantially become a slurry, making it easy to handle.

The aromatic nitro compound used as the main raw material in the method of the present invention is an aromatic compound having at least one nitro group as a nuclear substituent, and the number of nitro groups may be one or two or more. . That is, it may be a mononitro compound or a polynitro compound. Further, the aromatic compound may contain a substituent other than a nitro group.

For example, these include nitrobenzenes, dinitrobenzenes, dinitrotoluenes, nitronaphthalenes, nitroanthracenes, nitrobiphenyls, bis-trophenyl) alkanes, bis-trophenyl) ethers, bis-trophenyl) ) thioethers, bistrophenyl) sulfones, nitrodiphenoxyalkanes,
Examples include nitrophenothiazines and heterocyclic compounds such as 5-nitropyrimidine. Specific compounds include nitrobenzene, o-, m- and p-nitrotoluene, O-nitro-p-t-silene, 1-nitronaphthalene, m- and p-dinitrobenzene, 2,4- and 2 .6-sinitrotoluene, dinitromesitylene, 4
．． 4'-dinitrobiphenyl/2,4-dinitrobiphenyl, 4,4'-dinitrodibenzyl, bis(4-nitrophenyl)methane, bis(4-nitrophenyl)ether, bis(2,4-dinitrophenyl) Ether, bis(4-nitrophenyl)thioether, bis(4-nitrophenyl)sulfone, his(4-nitrophenoxy)ethane, α, α′-dinitro p-xylene, α, α
'-dinitro m-xylene, 2,4,6-dolinitrotoluene, 0-, m- and p-chloronitrobenzene,
2.3-13.4- and 2,5-dichloronitrobenzene, 1-chloro-2,4-'; nitrobenzene, l-furomo-4-nitrobenzene, 1-fluoro-2,4-dinitrobenzene, 〇- + m- and p-nitrophenyl carbamate, o-, m- and p-nitroanisole, 2
．． Examples include 4-dinitrophenylur, ethyl p-nitrobenzoate, m-nitrobenzenesulfonyl chloride, 3-nitrophthalic anhydride, 3,3'-dimethyl-4,4'-dinitrobiphenyl, 1,5-dinitronaphthalene, etc. Furthermore, isomers or mixtures of these aromatic nitro compounds can also be used, and homologs can also be used. Further, aromatic nitroso compounds, azo, and azoxy compounds can also be used in the same manner as aromatic nitro compounds.

The aromatic hydroxy compounds used in the present invention include monovalent and polyvalent monocyclic and polycyclic aromatic hydroxy compounds. Further, these aromatic hydroxy compounds may be substituted with a substituent inert to this reaction, such as a monovalent substituent such as an alkyl group, a halogen atom, or a carboxylic acid ester group, or may be substituted with an alkylene group, an oxy group, It may be crosslinked with a divalent group such as a sulfinyl group, a sulfonyl group, or a carbonyl group.

For example, phenol, chlorophenol, cresol, ethylphenol or alkylphenols such as linear or branched propylphenol, butyl and higher nonylphenols, catechol, resorcinol, pyrogallol, phloroglucinol, α-naphthol, β-
Naphthol, anthranol, phenanthrol, 4.
Examples include 4'-dihydroxydiphenylmethane and 2,2'-isopropylidene diphenol.

The amount of these aromatic hydroxy compounds used must be at least in an equimolar ratio to the nitro group of the aromatic nitro compound. If the molar ratio is less than the equimolar ratio, the reaction will be slow and the yield of the target aromatic carbamic acid aryl ester will decrease.Also, it is not economical to use a large excess of the aromatic hydroxy compound relative to the aromatic nitro compound. Considering this, it is not only not a good idea but also tends to reduce the yield.Usually, the molar ratio is 1 to 10 to the nitro group of the aromatic nitro compound.
It is preferably used in a molar ratio of 1 to 5. In addition, the amount of aromatic hydroxy compound used in the total raw material liquid is 5 to 8.
5wt%, preferably 10-75%1t%.

In the method of the present invention, metal palladium or palladium compounds are used as the main catalyst, including simple metals such as palladium black, halides, cyanides, thiocyanides,
Addition compounds or complexes with isocyanides, oxides, sulfates, nitrates, organic acid salts such as acetic acid, carbonyl compounds, tertiary amines such as triethylamine, pyridine, isoquinoline, or organic phosphorus compounds such as triphenylphosphine. Examples include complexes, divalent or zero-valent palladium complexes coordinated with neutral ligands such as carbon monoxide, and the like. Reactions also occur with noble metals other than palladium, such as platinum, ruthenium, rhodium, and iridium, and aromatic carbamic acid aryl esters are produced, but in very small quantities, making industrial use difficult.

If these can be used as they are in the reaction, they can be used as carriers such as alumina, silica, silica alumina, carbon, barium sulfate, calcium carbonate, asbestos, bentonite, diatomaceous earth, Fuller's earth, organic ion exchange resin, inorganic ion exchange resin, silicic acid. It may also be supported on magnesium, ammonium silicate, molecular sieve, zeolite, or the like.

Furthermore, these carriers may be charged into the reactor separately from palladium or their compounds.

The amount of palladium used for the nitro compound can vary widely depending on the type and other reaction conditions;
1 to I in weight ratio as a single metal to the nitro compound
X 10-5, preferably 5 X 10-1 to 5 X
Used in the range 10-'.

The process of the present invention is characterized by the use of a co-catalyst system consisting of a combination of a special compound consisting of a halogenated phosphorus compound, a vanadium compound and a tertiary amine in addition to the main catalyst palladium or its compound.

In order to carry out the method of the present invention effectively, the use of each catalyst component is essential, but the addition of halogenated phosphorus compounds is particularly effective, increasing the activity of the catalyst system and promoting the reaction. Suppresses the formation of by-products and increases the selectivity of the target product.

Examples of the halogenated phosphorus compounds used in the method of the present invention include phosphorus trifluoride, phosphorus trichloride, phosphorus tribromide, phosphorus triiodide, phosphorus pentafluoride, phosphorus pentachloride, phosphorus pentabromide, and phosphorus tetrabromide. Phosphorus halide compounds such as niline chloride and niline tetrachloride; alkyl- or aryl-substituted phosphorus halide compounds such as dimethylbromophosphine, diphenylchlorophosphine, and ethylphosphorus tetrachloride; phosphoryl fluoride, phosphoryl chloride, phosphoryl bromide, -F Phosphorus oxyhalides such as phosphoryl difluoride, phosphoryl dichloride, pyrophosphoryl chloride, and phosphorus oxyhalide; Quaternary phosphonium halides such as tetraethylphosphonium chloride; Phosphonyl halides such as ethylphosphonate dichloride ; Examples include alkyl phosphate halogenides such as methyl phosphate dichloride.

These halogenated phosphorus compounds are used in an amount of 0.05 to 20 gram atoms, preferably 0.1 to 10 gram atoms of phosphorus per 1 gram atom of palladium. Also, for 1 mole of raw material nitro compound, I x 10
-3 mol or more, the concentration in the reaction solution is 1 k of the total reaction solution
It is preferable to use it at a concentration of 1 x 10-4 g or more.

Any vanadium compound can be selected as the vanadium compound. In addition, in the method of the present invention, the valence of the vanadium compound may change during the reaction, or it may have a certain distribution (it is considered to exist in a temporary valence state), and the valence of vanadium in the vanadium compound that can be used is particularly limited. Not done.

Specific examples of vanadium compounds that can be used in the method of the present invention include chlorides such as vanadium trichloride and vanadium tetrachloride, salts of chlorides such as vanadium (IV) potassium chloride, vanadium dichloride oxide, and vanadium trichloride oxide. chloride oxides such as vanadium oxide (■), vanadium oxide (■), vanadium (V) oxide, vanadic acids such as pyrovanadic acid, metavanadate, sodium orthovanadate, ammonium metavanadate, potassium metavanadate. vanadate, vanadium sulfate (
DI) Ammonium, vanadium salts of acids such as potassium vanadium(III) oxalate, vanadium oxysulfate (■)
, vanadyl salts of acids such as vanadium oxyoxalate, acetylacetone salts such as oxybis(acetylacetone)vanadium (IV), and complex compounds coordinated with neutral ligands such as hexacarbonylvanadium.

These vanadium compounds contain 0.05 to 20 gram atoms of vanadium per 1 gram atom of palladium.
Preferably 01 to 10 gram atoms are used. 0.
If less than 0.5 gram atoms are used, the activity is low, and if more than 20 gram atoms are used, the selectivity decreases. Also, for 1 mole of raw material nitro compound, 1 x 10-4 to I x 10
-1 mol, preferably I X 10-3 to 5 x 10-2
It is preferable to use it in a molar range.

As the tertiary amine, aliphatic, aliaromatic, alicyclic, aromatic tertiary amines and nitrogen-containing heterocyclic compounds are used. If these may be in unsubstituted form, suitable substituents inert to this reaction may be used, such as halogen atoms, alkyl groups, aryl groups, alkenyl groups, cyano groups, aldehyde groups, alkoxy groups, phenoxy groups, alkylthio groups, It may have a substituent such as a phenylthio group, a carbamyl group, a carbalkoxy group, or a thiocarbamyl group.

These include, for example, aliphatic tertiary amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine, N,N-dimethylaniline, N,N-
Fatty aromatic amines such as diethylaniline, N,N-diisopropylaniline, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine,
N,N-diisopropylcyclohexylamine, 1.4
-Alicyclic tertiary amines such as diazabicyclo(2,2,2)octane, aromatic tertiary amines such as triphenylamine
These include nitrogen-containing heterocyclic compounds such as class amines, pyridine, quinoline, and isoquinoline. Among these, nitrogen-containing heterocyclic compounds are particularly effective in improving the yield of urethane and the reaction rate. Further examples of effective nitrogen-containing heterocyclic compounds other than those mentioned above include 1-methylpyrrole, 1-phenylpyrrole, 1-methylimidazole, l
-Methylindole, 1-phenylindole, indolenine, 2-isobenzazole, indolizine, 1-methylcarbazole, 2-chloropyridine, 2-bromopyridine, 2-fluoropyridine, 4-phenylpyridine, 2-, 3-, and 4-methylpyridine, 2-methyl-
5-ethylpyridine, 2,8-dimethylpyridine, 2,
4.6-1-dimethylpyridine, 2-vinylpyridine,
2-styrylpyridine, 3-chloropyridine, 2.6-
dichloropyridine, 2-chloro-4-methylpyridine,
4-phenylthiopyridine, 2-methoxypyridine, 4
-dimethylaminopyridine, α-picolinate phenyl ester, γ-picolinate methyl ester, 2,6-dichloropyridine, α-picolinaldehyde, α-picolinamide, 5,6.7.8-tetrahydroquinoline, 2
．． 2'-dipyridyl, 2-chloroquinoline, acridine, phenanthridine, benzoquinoline, benzisoquinoline, naphthyridine, pyrazine, 4.6-dimethylpyridine, 2,6-dimethylpyridine, pyridazine, pyrimidine, quinoxaline, 2.3- dimethylquinoxaline,
Examples include quinazoline, phthalazine, phenazine, cinnoline, and pteridine. They can also be used as polymers such as polyvinylpyridine. These tertiary amines may be added to the reactor separately from the raw materials and other catalyst components, or a portion of them may be treated in advance with a portion of the other components of the catalyst system to form appropriate complexes, adducts, etc. It can also be used in place of other compounds. - For example, palladium chloride and pyridine can be added separately to a reactor and reacted, but a palladium chloride-pyridine complex can be prepared in advance, and the complex, other raw materials, and catalyst components can be reacted. It is also possible to additionally add and react with an amine.

The amount of tertiary amine used is at least 0.05 molar ratio, preferably at least 0.1 molar ratio, based on the nitro group of the nitro compound used as a raw material.

If the molar ratio is less than 0.05, the reaction becomes extremely slow and the selectivity decreases.

Although the process of the present invention can be carried out without the presence of a solvent, the use of a solvent is preferred in order to effectively carry out the invention.

Examples of solvents include aromatic solvents such as benzene, toluene, and xylene, nitriles such as acetonitrile and benzonitrile, sulfolane solvents such as sulfolane, and 1.1.2-trichloro-1゜2.2-trifluoro. Aliphatic halogenated hydrocarbons such as ethane, halogenated aromatic hydrocarbons such as monochlorobenzene, dichlorobenzene and trichlorobenzene, ketones, esters, tetrahydrofuran, 1.4-dioxane, 1.2-
Dimethoxyethane or the like can be used as a solvent.

The solvent is generally used in a weight ratio of 1 or more, preferably 3 or more, relative to the aromatic nitro compound.

Even if the amount used is large, there is no problem with the reaction, and the upper limit of the amount used is determined mainly from an economic standpoint. If a solvent is not used, the reaction rate will be slow and the yield of the target product will be poor.

In carrying out the method of the present invention, there are no particular limitations on the method of charging, but it is desirable to add the nitro compound and the catalyst component after dissolving or partially dissolving them in the aromatic hydroxy compound or a suitable solvent.

The order of addition is also not limited, but can be varied within the constraints of the equipment used. For example, a suitable pressure reactor such as an autoclave is charged with a catalyst, an aromatic nitro compound, and an aromatic hydroxy compound, carbon monoxide is introduced under pressure, and the mixture is heated and stirred until the desired reaction is completed. Carbon monoxide can also be supplied intermittently or continuously by exhausting carbon dioxide gas generated as the reaction progresses. The reaction may be carried out batchwise, semi-continuously or continuously. Excess carbon monoxide after the reaction can be recycled.

The reaction temperature is generally maintained in the range of 100 to 250°C, with a range of 140 to 240°C being particularly preferred. Although the reaction proceeds faster at higher temperatures, a temperature of 160 to 220°C is usually sufficient.

The reaction pressure is 50 to 1000 kg as the partial pressure of carbon monoxide.
/aG, more preferably 100 to 500 kg/c
d is in the range of G.

The reaction time varies depending on the nature of the nitro compound used, the reaction temperature, the reaction pressure, the type and amount of the catalyst, the reaction apparatus, etc., but is generally carried out in the range of 10 minutes to 10 hours. After the reaction is complete, the reaction mixture is cooled and evacuated, and the reaction product is processed by conventional methods including filtration, distillation, or other suitable separation methods to free the carbamide from unreacted materials, impurities, solvents, catalysts, etc. Separation of acid aryl esters is carried out.

〔Example〕

The present invention will be specifically explained using Examples or Comparative Examples.

In the following Examples and Comparative Examples, an electromagnetic stirring autoclave made of stainless steel (5O3-316L) was used for all reactions.

Further, the conversion rate and yield were calculated from the results of gas chromatography analysis and liquid chromatography analysis.

In addition, the following abbreviations of compounds were used. That is, dinitrotoluene is abbreviated as DNT,) lylene dicarbamic acid diphenyl ester is abbreviated as TDC-P, trotolyl) carbamic acid phenyl ester is abbreviated as TNC-P, and when it is necessary to indicate the position of a substituent, e.g. 2,4-DNT for 2,4-dinitrotoluene,) rylene-2,4
-2.4 for dicarbamic acid diphenyl ester
A number indicating the position was added in front, such as -T D C-P.

Example-1 2.4-D in an autoclave with an internal volume of 500 m It
N T 15.0 g 1 phenol 17.1 g, dichlorobis(pyridine) palladium 0.189 g, phosphoryl chloride 0.345 g.

Vanadium trichloride oxide 0.048g, quinoline 4.9
g.

A solution consisting of 164 g of O-dichlorobenzene was charged. This solution was a homogeneous solution containing no insoluble matter. The inside of the autoclave was replaced with carbon monoxide at 10 kg/aaG twice and then pressurized to 160 kg/aaC. The temperature was raised to 200℃ while stirring, and the reaction pressure was 250~2.
After reacting at 00 kg/cd G for 180 minutes, the reaction mixture was cooled to 70°C, the pressure was released, and the reaction solution was analyzed by liquid chromatography. The reaction solution was a substantially homogeneous solution containing almost no insoluble matter at 70°C.

As a result of the analysis, the reaction solution did not contain the raw material 2.4-D N T or the intermediate heptanonitro compound, and 24.8 g of 2,4
-TDC-P was contained. The yield based on 2.4-DNT was 83%.

Example-2 7625 g of crude DN obtained by nitration of toluene (2,4-DNT 48
0 g, 120 g of 2.6-DNT, including small amounts of nitrotoluene and 2,3-13,4- and 2.5-DNT isomers), 1240 g of phenol, dichlorobis (
pyridine) palladium 7.57 g, phosphoryl chloride 13
．． 84 g of vanadium trichloride oxide, 3.91 g of quinoline, and 2337 g of o-dichlorobenzene were charged, and the system was replaced with carbon monoxide at 10 kg/ctl (2 times) and pressurized to 180 kg/ai G. Stirring. At the same time, the temperature was raised to 190°C in about 1 hour, and the reaction was carried out at the same temperature for 180 minutes at a reaction pressure of 260 to 240 kg/cd G.

After cooling to room temperature and releasing the pressure, the reaction solution was analyzed by liquid chromatography. As a result, the reaction solution did not contain DNT or the mononitro intermediate, and was 2.4-T D C-P 782.
7g and 2.6-T D C-P 20B, Og.
65.6% and 17.4 respectively for the total amount of NT.
% (total 83%).

Comparative Examples 1 to 4 In order to clearly demonstrate the effect of the promoter system of the present invention, Comparative Example-1
In Comparative Example-2, no phosphoryl chloride was used, and in Comparative Example-2, vanadium trichloride oxide was not used.
In Comparative Example 3, diethyl phenylphosphonate was used as a phosphorus compound without a halogen, and in Comparative Example-4, triphenyl phosphate and hydrochloric acid at a molar ratio of 3 to it were used, and the reactions were performed for the reaction times listed in Table 1. The reaction was carried out in the same manner as in Example-1. The results are shown in Table 1 again together with the results of Example-1. If any of the promoter components of the present invention is omitted or a compound that does not fall within the scope of the present invention is used instead, the reaction rate will decrease and the yield of the target product, TDC-P, will decrease, and it will not contain halogen. The yield decreased with phosphorus compounds.

Comparative Example-5 194g of phenol without using 0-dichlorobenzene
The reaction was carried out in the same manner as in Example-1 except that the following components were used. Although unreacted DNT was not detected, the TDc-p yield was 10
%, the TNC-P yield was 55%, and the reaction results were significantly inferior to Example-1.

Examples 3 to 6 Using 0.234 g of phosphorus pentachloride as a phosphorus compound, 0.109 g of vanadium tetrachloride as a vanadium compound, and using the compounds listed in Table 2 as raw material nitro compounds,
Example-1 except that the reaction was carried out at the reaction temperature and time listed in the table.
The reaction was carried out in the same manner.

The results are shown in Table 2. In all cases, the desired products were obtained in good yields.

Examples 7 to 13 Reactions were carried out in the same manner as in Example 1, except that the compounds listed in Table 3 were used as catalysts and the reactions were carried out under the described reaction conditions.

The results are shown in Table 3. In all cases, the desired products were obtained in good yields.

Examples 14 to 15 Nitrobenzene, phenol, and carbon monoxide were reacted in the same manner as in Example 3, except that isoquinoline or pyridine was used as the tertiary amine instead of quinoline.

N-phenylcarbamic acid phenyl ester was obtained in the same yield as in Example-3.

〔Effect of the invention〕

According to the method of the present invention, aromatic carbamic acid aryl esters can be produced from aromatic nitro compounds, aromatic hydroxy compounds, and carbon monoxide in good yield and with good operability.

Claims (1)

[Claims] 1) In a method for producing an aromatic carbamic acid aryl ester by reacting an aromatic nitro compound, an aromatic hydroxy compound and carbon monoxide in the presence of a catalyst, metallic palladium or a palladium compound or a halogenated phosphorus compound is used. , a method for producing an aromatic carbamic acid aryl ester, which comprises reacting at high temperature and pressure using a catalyst system consisting of a vanadium compound and a tertiary amine.