JPS6045874B2 - Method for producing aromatic urethane compounds - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing aromatic urethane.

More specifically, the present invention relates to a method for producing an aromatic urethane by reacting an aromatic urea compound with carbon monoxide and an organic hydroxyl compound in the presence of an oxidizing agent to oxidatively carbonylate it. Aromatic urethanes are important compounds used in carbamate pesticides and the like, and recently there has been a demand for an inexpensive method for producing them as raw materials for producing aromatic isocyanates without using phosgene. As a method for producing aromatic urethane using carbon monoxide, aromatic nitro compounds, aromatic nitroso compounds, aromatic azo compounds, aromatic azoxy compounds, etc. are reductively produced in the absence of an oxidizing agent. A method of urethanizing an aromatic amino compound and a method of oxidatively urethanizing an aromatic amino compound are known.

Furthermore, a method of oxidatively converting N,N'-diarylurea into urethane has also been proposed (Japanese Patent Application Laid-Open No. 551-1205).
4th son gazette).

In this method, a Group I noble metal or its compound is used as the main catalyst, and a metal capable of carrying out a redox reaction in the reaction system, such as copper chloride, iron chloride, iron oxychloride, vanadium chloride, or vanadium oxychloride, is used as a co-catalyst. It is necessary to dissolve the chloride containing fluorine in the reaction system.
However, these dissolved metal chlorides are highly corrosive to metal materials such as reaction vessels, piping, and valves.
For this reason, there is an equipment problem in that expensive metal materials must be used. 5 Furthermore, in order to separate and recover these dissolved metal chlorides from high boiling point substances such as aromatic urethane products, there is a drawback that complicated operations and large costs are required.

In order to overcome these drawbacks, the present inventors have conducted intensive research on a method for producing aromatic urethane compounds by oxidatively urethanizing aromatic urea compounds, and as a result, we have discovered that this is the main cause of these drawbacks. The inventors discovered a new catalyst system that allows the reaction to proceed catalytically without using Lewis acids or chlorides of elements that perform redox reactions, and based on this knowledge, they completed the present invention.

That is, in the present invention, in producing an aromatic urethane by reacting an aromatic urea compound with carbon monoxide and an organic hydroxyl compound in the presence of an oxidizing agent, (4) containing a platinum metal group and a platinum group element. An aroma characterized by using a catalyst system comprising at least one selected from compounds and (B) at least one selected from alkali metal halides and alkaline earth metal halides. This paper provides a method for producing group urethanes.

As described above, a major feature of the present invention is that at least one kind selected from platinum group metals and compounds containing platinum group elements, and at least one kind selected from alkali metal halides and alkaline earth metal halides. By using a catalyst system in combination with at least one type of aromatic urea compound, aromatic urethane can be obtained with good selectivity and high yield from aromatic urea compounds.

This fact has not been known until now and is truly surprising, and is based on the prior art (Japanese Unexamined Patent Publication No.
5-12055), which could not have been predicted at all.

That is, in this prior art, a platinum group compound is used as the main catalyst, and an element capable of undergoing a redox reaction is chlorinated in the reaction system. A catalyst system using a substance as a co-catalyst, for example, a typical catalyst system in which palladium chloride and iron oxychloride are combined as seen in the examples is used. In such a system, divalent palladium is involved in the reaction, and as the reaction progresses, it is reduced to zero. This becomes valent palladium, which is reoxidized by trivalent iron oxychloride and returns to divalent palladium.At the same time, trivalent iron is reduced to divalent iron, and this divalent iron is then used as an oxidizing agent. It is thought that the main product, aromatic urethane, is produced through a so-called Watzker reaction-type catalytic cycle in which iron is reoxidized and returned to trivalent iron. As described above, in the prior art methods, it has been shown that the chloride of an element having a redox effect is essential as a reoxidizing agent for the main catalyst in the reaction system. Elements that have such a function are those that can undergo a redox reaction and are selected from the elements of Groups ■a-Va and Groups Ib to ■b of the periodic table. copper, zinc, mercury, thallium,
These include tin, titanium, arsenic, antimony, bismuth, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, and nickel, among which copper, vanadium, manganese, molybdenum, tungsten, antimony, and iron. Only those examples are described in the examples. On the other hand, the method of the present invention is based on 1 of the periodic table.
This method uses halides of alkali metals and alkaline earth metals, which are Group A and ■A elements, but Group 1A and ■A elements were thought to have no effect on redox reactions under normal reaction conditions. In fact, in the prior art mentioned above, the use of these compounds is not even considered.

Therefore, it is presumed that the reaction of the present invention proceeds by a completely different reaction mechanism from the reaction described in the prior art. Although it is not clear what mechanism the alkali metal halides and alkaline earth metal halides act in the reaction of the present invention, they may be used in combination with platinum group metals or compounds containing platinum group elements. It is clear that it plays an important role as a catalyst component in the oxidative urethanization reaction of aromatic urea compounds.

In other words, if only an alkali metal halide or an alkaline earth metal halide is used, the aromatic urethanization reaction of this reaction will not proceed quickly, and if only a platinum group metal or a compound containing a platinum group element is used. Even if the aromatic urethane formation reaction does not proceed under the conditions of this reaction, or even if it does proceed, only a small amount of aromatic urethane is produced, especially when only platinum group elements in the metallic state are used. Almost no aromatic urethane can be obtained. For example, palladium is one of the effective catalytic components for this reaction, but the reaction hardly progresses when only palladium black, which is O-valent metal palladium, is used alone. However, if an alkali metal halide or an alkaline earth metal halide, such as cesium iodide, is added to this, aromatic urethane can be obtained almost quantitatively. In this way, in the method of the present invention, a solid platinum group compound in a metallic state can also be used as one of the catalyst components, which means that the expensive platinum group compound can be separated from the reaction system by a simple method such as filtration. , indicating that it can be recovered.

In addition, alkali metal halides and alkaline earth metal halides are easy to separate and recover, unlike the heavy metal chlorides used in the prior art, and are used as sewage substances in the product. One of the major features of the present invention is that it does not mix.

The platinum group metal and platinum group element-containing compound used in the method of the present invention may contain at least one element selected from platinum group elements such as palladium, rhodium, platinum, ruthenium, iridium, and osmium. There are no particular limitations, and these elements may be in a metallic state or may be components forming a compound.

In addition, these catalyst components include activated carbon, graphite, silica, alumina, silica-alumina, silica titania,
Titania, zirconia, barium sulfate, calcium carbonate, asbestos, bentonite, diatomaceous earth, polymer,
It may be supported on a carrier such as ion exchange resin, zeolite, molecular sieve, magnesium silicate, gnesia, or the like. Examples of platinum group elements in the metallic state include metals such as palladium, rhodium, platinum, ruthenium, iridium, and osmium, these metal blacks, and catalyst components containing these metal ions on the above-mentioned carrier, and then hydrogen and reduced with formaldehyde,
Also, alloys or intermetallic compounds containing these metals are used.

In addition, the alloy or intermetallic compound may be one of these platinum group metals, or may contain other elements such as selenium, tellurium, sulfur, antimony, bismuth, copper) silver) gold to zinc) tin to vanadium). iron) cobalt, nickel,
It may contain mercury, lead, thallium, chromium, molybdenum, tungsten, etc. On the other hand, compounds containing platinum group elements include, for example, inorganic salts such as halides, sulfates, nitrates, phosphates, and borates; organic acid salts such as acetates, oxalates, and formates; cyanides; Hydroxides; oxides; sulfides; metal salts containing anions such as nitro groups, cyano groups, halogens, oxalate ions, and ammonia, amines, phosphines, carbon monoxide, chelate ligands, etc. metal complex compounds such as salts or complexes containing; organometallic compounds having organic ligands or organic groups; and the like.

Among these catalyst components, those containing palladium or rhodium or both are particularly preferred, such as Pd black; Pd-C, Pd-Al.

O3, Pd-SiO2, Pd-TiO2, Pd-ZrO
2. Supported palladium catalysts such as Pd-BaSO4, Pd-CaCO3, Pd-asbestos, Pd-zeolite, Pd-molecular sieve; Pd-Pb, Pd-Se
, Pd-Te, Pd-Hg, Pd-Tl, Pd-P, P
d-Cll, Pd-Ag, Pd-Fe, Pd-CO, P
Alloys or intermetallic compounds such as d-Ni, Pd-Rh;
and alloys or intermetallic compounds thereof supported on the above-mentioned carrier; PdCl. , PdBr2, Pdl. ，
Inorganic salts such as Pd(NO3)2, PdS04; Pd(
0C0CH3)2, organic acid salts such as palladium oxalate; Pd(CN)2; PdO; PdS; M2[PdX''
, ], palladate salts represented by M2[PdX″6] (M represents an alkali metal or ammonium ion, and X″ represents a nitro group, cyano group, or halogen) [Pd(NH3)4]X″2 , [Pd(En)
2] Palladium ammine complexes such as X″2 (X″ has the same meaning as above and En represents ethylenediamine); PdCl. (PhCN)2, PdCI2(PR(
)2, Pd(CO)(PRI)3, Pd(PPh3)4
,PdC1(R3)(PPh3)2,Pd(C2H4)
Complex compounds or organometallic compounds such as (PPh3)2, Pd(C3H5)2 (R3 represents an alkyl or aryl group); Complex compounds coordinated with chelate ligands such as Pd(Acac)2; Rh Black; Supported rhodium catalysts similar to Pd: Rh alloys or intermetallic compounds similar to Pd, and those supported on supports: RhCl3 and hydrates, RhBr3 and hydrates, RhI3 and hydrates, Rh2
(SO4)3 and inorganic salts such as hydrates; Rh2)(0
C0CH3)4;Rh2O3,RhO2;M3[RhX
"6" and hydrate (M, X" have the same meanings as above)
[Rh(NH3)5]X″3, [Rh(En)3]X″
Ammine complexes of rhodium such as 3; RFLl(CO)
1. , Rh6(CO)16; rhodium carbonyl clusters such as [RhCl(CO)2]2, RhCI3(
PR()3, RhC1(PPh3)3, RhX″(CO
) L2 (X'' has the same meaning as above, L is a ligand consisting of an organic phosphorus compound and an organic arsenic compound), Rh
Examples include complex compounds such as H(CO)(PPh3)3 and organometallic compounds. In the present invention, only one type of these platinum group metals or compounds containing platinum group elements may be used, or two or more types may be used as a mixture, and there is no particular restriction on the amount used. Usually, the component containing the platinum group element is 0.0001 to 5% relative to the aromatic urea compound.
A range of 0 mol % is desirable.

Furthermore, the alkali metal halides and alkaline earth metal halides used in the method of the present invention are:
For example, halides such as lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, and radium, specifically lithium cumulus fluoride, sodium fluoride, and potassium fluoride. , rubidium fluoride, cesium fluoride, francium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, radium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, chloride Cesium, francium chloride, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, radium chloride, lithium bromide, sodium bromide, rubidium bromide, cesium bromide, francium bromide, beryllium bromide, odor Magnesium chloride, strontium bromide, barium bromide, radium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, francium iodide, beryllium iodide, magnesium iodide, calcium iodide ．． Compounds of a single metal such as lithium, strontium iodide, barium iodide, and radium iodide and a single halogen: double salts such as sodium magnesium chloride, potassium magnesium chloride, potassium potassium chloride, magnesium bromide, and potassium Polyhalides such as potassium bromine fluoride, potassium iodine chloride, rubidium iodine chloride, cesium iodine chloride, cesium iodine chloride bromide, rubidium iodine chloride bromide, potassium iodine bromide, cesium iodine bromide, rubidium iodine bromide, etc. Examples include the following. These alkali metal and alkaline earth metal halides may be used alone or in combination of two or more.

Among these halides, those containing bromine or iodine are preferred, and iodides are particularly preferred. There are no particular limitations on the amount of the alkali metal and alkaline earth metal halides used in the present invention, but there are , usually in a range of 0.001 to 1000 mol. The aromatic urea compound used as a raw material in the present invention may be any compound in which the hydrogen atoms of urea are substituted with one or more aromatic groups.

Particularly preferred are N,N''-disubstituted aromatic urea compounds represented by the following general formula (1).
and N'' represent an aromatic group such as phenyl, naphthyl, pyridyl, furanyl, thiophenyl, etc., and Ar and N'' may be different or the same. In addition, in these aromatic groups, at least one hydrogen on the aromatic ring has another substituent, such as a halogen atom, a nitro group, an amino group, a cyano group, an alkyl group, an alicyclic group, an aromatic group,
It may be substituted with an aralkyl group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, or the like. Examples of such aromatic urea compounds include N,N-diphenylurea, N,N-di(p-tolyl)urea, and N,N''-di(0-tolyl).
Urea, N,N″-di(p-aminophenyl)urea, N
, N5-di(0-aminophenyl)urea, N,N″-
Di(p-nitrophenyl)urea, N,N″-di(0
-nitrophenyl)urea, N,N″-di(3-amino-2-methylphenyl)urea, N,N″-di(3-amino-4-methylphenyl)urea, N,N-di(5-
Amino-2-methylphenyl)urea, N,N″-G(
3-nitro-4-methylphenyl)urea, N,N″-di(5-nitro-2-methylphenyl)urea, N,N″
-di(3-nitro-2-methylphenyl)urea, N-
(3-amino-2-methylphenyl)-N2-(3-nitro-2-methylphenyl)urea, N-(3-amino-4-methylphenyl)-N'-(3-nitro-4-methylphenyl)urea, N -(5-amino-2-methylphenyl)-N''-(5-nitro-2-methylphenyl)urea, N-(3-amino-2-methylphenyl)-N''-(5-amino-2-methylphenyl)urea , N-(3-
Amino-2-methylphenyl)-N''-(3-amino-4-methylphenyl)urea, N-(3-amino-4-methylphenyl)-N''-(5-amino-2-methylphenyl)urea, N-( 3-nitro-2-methylphenyl)
-N″-(5-amino-2-methylphenyl)urea, N
-(3-nitro-2-methylphenyl)-N'-(5-
nitro-2-methylphenyl)urea, N,N″-di(
1-naphthyl) urea, N,N″-G(2-naphthyl)
Urea, N,N-di(6-amino-1-naphthyl)urea, N,N-di(4-amino-1-naphthyl)urea, N
,N″-di(6-nitro-1-naphthyl)urea, N,
Preferably used are N''-di(4-nitroamino-1-naphthyl)urea and polymeric ureas having a structural unit represented by the following formula.Particularly preferred are N,N''-diphenylurea and N,N'' -di(3-amino-2-methylphenyl)urea, N,N″-di(3
-amino-4-methylphenyl)urea, N,N''-di(5-amino-2-methylphenyl)urea and ureas having a naphthyl group.

The organic hydroxyl compound used in the present invention is a monohydric or polyhydric alcohol, or a monohydric or polyhydric phenol. Examples include chain monovalent or polyvalent alkanols and alkenols, monovalent or polyvalent cycloalkanols and cycloalkenols, and aralkyl alcohols.

Furthermore, these alcohols may contain other inert substituents, such as halogen atoms, cyano groups, alkoxy groups, sulfoxide groups, sulfone groups, carbonyl groups, ester groups, and amide groups. Specific examples of such alcohols include methanol, ethanol, propanol (each isomer), butanol (each isomer), pentanol (each isomer), hexanol (each isomer), and hebutanol (each isomer). , octanol (each isomer), nonyl alcohol (each isomer), decyl alcohol (each isomer), undecyl alcohol (each isomer), lauryl alcohol (each isomer), tridecyl alcohol (each isomer), Aliphatic alcohols such as tetradecyl alcohol (each isomer) and pentadecyl alcohol (each isomer);
Cycloalkanols such as cyclohexanol and cycloheptanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, Alkylene glycol monoethers such as propylene glycol monoethyl ether; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, hexanetriol, and trimethylolpropane; aralkyl alcohols such as benzyl alcohol etc. are used.

Examples of phenols include phenol, various alkylphenols, various alkoxyphenols, various halogenated phenols, dihydroxybenzene, 4,4''
-Dihydroxy-diphenylmethane, bisphenol-A1 hydroxynaphthalene, etc. are used.

As the oxidizing agent used in the present invention, ordinary oxidizing agents can be used, but molecular oxygen, organic nitro compounds, and mixtures thereof are preferred.

Particularly preferred is molecular oxygen. Molecular oxygen is pure oxygen or something containing oxygen, which may be air, or air or pure oxygen diluted with another gas that does not inhibit the reaction, such as nitrogen, argon, helium, carbon dioxide, or other inert gas. It may be something that has been done. In some cases, it may also contain gases such as hydrogen, carbon monoxide, hydrocarbons, and halogenated hydrocarbons. The organic nitro compound may be any of alicyclic, aliphatic and aromatic nitro compounds.

Examples of alicyclic nitro compounds include nitrocyclobutane, nitrocyclopentane, nitrocyclohexane, dinitrocyclohexane (each isomer), and bis(nitrocyclohexyl)-methane; examples of aliphatic nitro compounds include nitromethane, nitroethane, and nitrocyclohexane. Propane (each isomer), Nitrobutane (each isomer), Nitropentane (each isomer), Nitrohexane (each isomer)
, nitrodecane (each isomer), 1,2-dinitroethane, dinitropropane (each isomer), dinitrobutane (each isomer), dinitropentane (each isomer), dinitrohexane (each isomer), dinitrodecane (each isomer) ), phenylnitromethane, bis(nitromethyl)-cyclohexane, bis(nitromethyl)-benzene,
Examples of aromatic nitro compounds include nitrobenzene, dinitrobenzene (each isomer), nitrotoluene (each isomer), dinitrotoluene (each isomer), nitropyridine (dinitropyridine with each isomer (each isomer), dinitronaphthalene ( mononitro compounds and dinitro compounds of diphenyl compounds represented by the following 5 general formula (■). (In the formula, A is a simple chemical bond, or -0-, -S- , -SO2-, -CO-,
Represents a divalent group selected from -CONH-, -COO-, -C(R1)(R2)-, and -N(R1)-.

In addition, Rl, R2 represent an aromatic group and R, R'' represent an organic group. When only an organic nitro compound is used as an oxidizing agent, an aromatic urea compound The 4-mer ratio of the compound is 1 nitro group per 2 moles of urea group.
Although it is preferable to set the ratio to be a molar ratio, it is of course possible to perform the ratio at a value far from this stoichiometric ratio.
Generally, the equivalent ratio of an amino group to a nitro group is a Group 3 group or an alicyclic group. ) In addition, in these nitro compounds, at least one hydrogen has another substituent, such as a halogen atom, an amino group, a cyano group, an alkyl group, an alicyclic group, an aromatic group, a sulfone group, a carbonyl group, an ester group. , may be substituted with an amide group, etc.

Among these nitro compounds, aromatic nitro compounds are preferred, especially nitrobenzene, nitrotoluene (each isomer), nitroaniline (each isomer), 2,4-1 and 2-,
Preferred are 6-dinitrotonoleene, dichloronitrobenzene (each isomer), 4,4- and 2,4''-dinitrodiphenylmethane, 1,5-dinitronaphthalene, etc. In the present invention, the oxidizing agent is In this case, the reaction proceeds according to the following general reaction.

(Here, Ar and N'' represent an aromatic group and R represents an organic group) Molecular oxygen may be less or more than the equivalent amount, but a mixture of oxygen/carbon monoxide or oxygen/organic hydroxyl compound should be used outside the explosive limits.

In addition, when an organic nitro compound is used as an oxidizing agent, the organic nitro compound itself also participates in the reaction to form urethane, so if the structure of the organic group is different from the aromatic group of the aromatic urea compound, It goes without saying that if a urethane compound is obtained and both structures are the same, the same aromatic urethane compound will be obtained.

In this case, the urethanization reaction proceeds according to the following reaction formula, for example.

is 1.1:1 to 4:1, preferably 1.

It is carried out at a ratio of 5:1 to 2.5:1.

Of course, if molecular oxygen or other oxidizing agents are used at the same time, the amount of organic nitro compound may be less than the stoichiometric amount.

The most preferred organic nitro compounds in the method of the present invention are:
It is an aromatic nitro compound that has the same skeleton as the aromatic group of aromatic urea compounds.

In the method of the present invention, it is preferable to use an excess of the organic hydroxyl compound as the reaction solvent, but if necessary, a solvent that does not adversely affect the reaction can also be used.

Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; chlorobenzene, dichlorobenzene, trichlorobenzene,
Halogenated aromatic hydrocarbons such as fluorobenzene, chlorotoluene, chlornaphthalene, and bromnaphthalene; halogenated aliphatic hydrocarbons or halogenated fats such as chlorhexane, chlorocyclohexane, trichlorotrifluoroethane, methylene chloride, carbon tetrachloride, etc. Cyclic hydrocarbons; Nitriles such as acetonitrile and benzonitrile; Sulfones such as sulfolane, methylsulfolane and dimethylsulfolane: tetrahydrofuran, 1,4
- Ethers such as dioxane and 1,2-dimethoxyethane; Ketones such as acetone and methyl ethyl ketone;
Esters such as ethyl acetate and ethyl benzoate; N, N
Examples include amides such as -dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphoramide. In the method of the present invention, other additives may be added to the reaction system as necessary in order to carry out the reaction more efficiently.

Examples of such additives include zeolites, salts of nitrogen-containing compounds and hydrogen halides, quaternary ammonium salts, tertiary amines, and alkali acids such as boric acid, aluminic acid, carbonic acid, silicic acid, and organic acids. Metal salts and alkaline earth metal salts are preferred. In the method of the present invention, the reaction is usually 8
The temperature range is 0 to 300'C, preferably 120 to 220'C.

Also, the reaction pressure is 5-500k9/C! t1 preferably 2
The reaction time ranges from 0 to 300 k9/Clt, and the reaction time varies depending on the reaction system, catalyst system, and other reaction conditions, but is usually from several minutes to several hours. Further, the reaction of the present invention can be carried out either batchwise or continuously in which the reaction solution is continuously drawn out while continuously supplying the reaction components.

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

Example 1 N, N'-
Diphenylurea 201T1m0', ethanol 40ml
1 palladium black 0.5 m 9 at 0 m 1 cesium iodide 5
After adding n1m0e and replacing the inside of the system with carbon monoxide, 80 kg/Cfll of no oxide carbon and 6 kg/CT of oxygen were added.
1 was press-fitted to make the total pressure 86k9/Cfl.

After reacting at 160°C for 1 hour with stirring, the reaction mixture was passed through the mouth and the oral fluid was analyzed. As a result, the reaction rate of N,N''-diphenylurea was 100%, and the reaction rate of N,N''-diphenylurea was 100%. The yield was 98% and the selectivity was 98%.Examples 2 to 16 Various alkali metal halides or alkaline earth metal halides were used in place of cesium iodide.
Table 1 shows the results of the same reaction as in Example 1 except that m0' was used. Comparative Example 1 The same reaction as in Example 1 was carried out using only palladium black without using an alkali metal halide or an alkaline earth metal halide. As a result, the reaction rate of N,N''-diphenylurea was At 10%, ethyl N-phenylcarbamate was produced in only 3% yield.

Example 17 N, N in a stirring autoclave with an internal volume of 200 m1
- Add 25n1m0e1 of di(0-methylphenyl)urea, 50ml of ethanol, 6mm0e of Rh/Clgl cesium iodide with 5wt% rhodium supported on activated carbon, and replace the inside of the system with carbon monoxide, then remove 80kg of carbon monoxide.
Then, 5 kg/CTl of oxygen was injected under pressure.

After reacting at 160°C for 1 hour with stirring, the reaction mixture was filtered and the filtrate was analyzed. As a result, N,N-di(0
-Methylphenyl)urea reaction rate is 95%, N-(0-
The yield of ethyl (methylphenyl)carbamate was 88% and the selectivity was 93%. Comparative Example 2 The same reaction as in Example 17 was carried out without using cesium iodide, but the reaction rate of N,N''-di(0-methylphenyl)urea was 9%, and the reaction rate of N-(0-methylphenyl)carbamine was 9%. The yield of ethyl acid was less than 2%.

Example 18 Ru black 0.4 mg instead of Rh/C in Example 17
at0m and N,N″-diphenylurea 25rnm0e
The reaction was carried out in exactly the same manner as in Example 17, except for using
The selectivity was 90%.

Comparative Example 3 The same reaction as in Example 18 was carried out without using cesium iodide, but the reaction rate of N,N-diphenylurea was 8%, and N
-The yield of ethyl phenylcarbamate was 2% or less.

Example 19 In a stirring autoclave with an internal volume of 200 WLt,
N'-diphenylurea 30ml 1m0e1 Nitrobenzene 15mm0', Methanol 50ml 11 Paldium chloride 0
．． After adding 5mm0e1 cesium iodide (MOe) and replacing the inside of the system with carbon monoxide, 120kg/m of carbon monoxide was added.
Al was press-fitted.

After reacting at 180°C for 4 hours with stirring, the reaction solution was analyzed and the reaction rates of N,N''-diphenylurea and nitrobenzene were 25% and 30%, respectively, and N-
14 mmOe of ethyl phenylcarbamate was produced.

Examples 20 to 26 The same reactions as in Example 1 were carried out, except that various platinum group metals or compounds containing platinum group elements were used in place of palladium black in Example 1.

The results are shown in Table 2. In addition, in these Examples, the platinum group metal or platinum group compound is 0 as a metal element.

5m9at0m is used, and the % display indicates the weight % of the supported catalyst component.

Claims (1)

[Claims] 1. In producing an aromatic urethane by reacting an aromatic urea compound with carbon monoxide and an organic hydroxyl compound in the presence of an oxidizing agent, (A) containing a platinum group metal and a platinum group element; At least one selected from compounds, and (B)
A method for producing an aromatic urethane compound, comprising using a catalyst system comprising at least one selected from alkali metal halides and alkaline earth metal halides. 2. The method according to claim 1, wherein the oxidizing agent is molecular oxygen, an organic nitro compound, or both. 3. The method according to claim 1 or 2, wherein the platinum group metal and the compound containing the platinum group element are simple palladium, simple rhodium, palladium compounds, and rhodium compounds. 4. The method according to claim 1, 2, or 3, wherein the alkali metal halide and alkaline earth metal halide are iodides. 5. The method according to claim 1 or 2 or 3 or 4, wherein the oxidizing agent is molecular oxygen.