JPS639505B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing aromatic urethane. Aromatic urethanes are important substances as carbamate-based pesticides, and have recently attracted attention as raw materials for the production of aromatic isocyanates that do not use phosgene, and are expected to be in wide demand. Regarding the production of aromatic urethane,
Although there are several proposals, the following two manufacturing methods are known as representative methods. One method is to reductively urethanize an aromatic nitro compound using carbon monoxide in the presence of an alcohol. For example, in the case of nitrobenzene, the following reaction formula () An aromatic urethane is obtained. As can be seen from this formula, 3 moles of carbon monoxide are required for 1 mole of nitrobenzene, of which 2 moles become worthless carbon dioxide gas that does not directly participate in the formation of the target product and disappear from the system, leaving only 1 mole. Only the actual amount is used effectively. Moreover, in order to carry out this reaction continuously, it is necessary to separate the introduced carbon monoxide and the produced carbon dioxide gas, which makes the process complicated and extremely disadvantageous industrially. Another method is to react an aromatic amino compound with carbon monoxide and alcohol in the presence of an oxidizing agent such as oxygen or an organic nitro compound to oxidatively convert it into a urethane. (For example, JP-A-54-
Publication No. 24854, Japanese Unexamined Patent Publication No. 1984-84550, Japanese Patent Unexamined Publication No. 1983
-7227 Publication, JP-A-55-120551, JP-A-Sho
Publication No. 55-124750. ) This method is preferable to the former method in that carbon monoxide is used more effectively, but when oxygen is used as the oxidizing agent, the explosive limit of carbon monoxide is wide, so it is not suitable for industrial use. is highly dangerous and difficult to implement. In addition, when using an organic nitro compound as an oxidizing agent, the following reaction formula () 2Ar (NH ₂ ) m + Ar′ (NO ₂ ) _n + 3 m・CO + 3 m・ROH→2Ar (
NHCOOR) _n +Ar′(NHCOOR) _n +2m・H ₂ O
() (In the formula, Ar and Ar' are aromatic groups, m is the number of amino groups or nitro groups in one molecule of the amino compound and nitro compound, and R is an organic group.) Urethane is formed by the reaction of In particular, all of the carbon monoxide is effectively utilized only when the equivalent ratio of nitro groups to amino groups is 1:2, but when the amount of nitro groups is greater than this ratio, as expressed by the above formula (), Reductive urethanization of nitro compounds occurs, and the effective utilization rate of carbon monoxide decreases. In addition, in the above urethanization reaction, it is necessary to use carbon monoxide with the highest possible purity, and it is not possible to use synthesis gas containing a mixture of carbon monoxide and hydrogen, which can be obtained industrially at low cost. , hydrogen and other impurities must be separated and purified, and the practical disadvantage of this is extremely large. In view of the fact that the previously proposed methods for producing aromatic urethanes as described above are not industrially satisfactory, the present inventors conducted various studies on industrially advantageous and easy production methods. By reacting aromatic amino compounds and aromatic nitro compounds with organic hydroxyl compounds, hydrogen and carbon monoxide in the presence of catalysts containing the above-mentioned elements, aromatic He discovered that urethane could be manufactured and proposed it earlier. (Japanese Unexamined Patent Publication No. 57-185253.) However, in this method, metal halides such as copper chloride, iron chloride, iron oxychloride, and vanadium chloride are used as cocatalysts, and good results have been obtained.
These metal halides are highly corrosive to metal materials, corroding metal materials such as reaction vessels, piping, and valves, so they have the disadvantage of requiring the use of expensive, corrosion-resistant special metal materials for reaction system equipment. Furthermore, it has been found that it is necessary to separate and recover these metal halides dissolved in the reaction system from the high-boiling aromatic urethane product, which requires complicated operations and a large amount of cost. As a result of repeated research to overcome these defects in particular co-catalysts, the present inventors found that when these metal halides are used as co-catalysts in the form of intercalation compounds with graphite, the above-mentioned defects can be advantageously overcome. It has been found that this problem can be solved and an extremely excellent catalyst system can be provided. The present invention provides (a) a catalyst containing a platinum group metal, and (b) a catalyst containing a copper group metal, a zinc group metal, a nitrogen group metal, a vanadium group metal, a chromium group metal,
An aromatic amino compound and an aromatic nitro compound are combined into an organic compound in the presence of a cocatalyst consisting of at least one intercalation compound of graphite and a metal halide selected from halides of metal elements belonging to the manganese group and the iron group. The gist of this invention is a method for producing urethane, which is characterized by reacting with a hydroxyl compound, hydrogen, and carbon monoxide. The intercalation compound of a metal halide and graphite used in the method of the present invention is a compound in which a metal halide is infiltrated between the layers of graphite having a layered structure, and is a lamellar compound.
These compounds are also called intercalation compounds. In these intercalation compounds,
Metal halides mainly exist as a monomolecular layer between the layers of graphite, and are thought to exchange electrons with graphite, and are physically different from the original metal halides.・
It is known that they have different chemical properties.
Therefore, it is an essentially different compound from one in which a metal halide is adsorbed and supported on graphite as a carrier. Such intercalation compounds are described by RCCroft [Australian Journal of Chemistry, Vol. 9,
184, 1956] and E. Stumpp [Materials Science and Engineering, No. 31]
Vol., p. 53, 1977], for example, by heating a mixture of anhydrous metal halide and graphite either neat in a sealed tube or in a sealed tube filled with fluorine, chlorine or bromine. Therefore, it can be easily manufactured. The amount of metal halide in graphite is usually 1 to 70% by weight. Also, certain metal halides, e.g.
Intercalation compounds of graphite with CuCl ₂ , SbF ₅ , CrCl ₃ , FeCl ₃ , CoCl ₂ , NiCl ₂ etc. are Alfa
It is commercially available from Products Inc. (Thiokol/Ventron Division) as "Graphimet (registered trademark)". The cocatalyst used in the present invention is an interlayer compound of graphite and a metal halide selected from halides of metal elements belonging to the copper group, zinc group, nitrogen group, vanadium group, chromium group, manganese group, and iron group. It is. These metallic elements include
Cu, Ag, Au, Zn, Cd, Hg, Sb, Bi, V,
Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe,
Co, Ni, and halides of such metal elements include, for example, CuCl ₂ , AuCl ₃ ,
_ZnCl2 , _CdCl2 , _HgCl2 , _SbCl5 , _VCl3 , _NbCl5 ,
_TaCl5 , _CrCl3 , _CrO2Cl2 , _MoCl5 , _{WCl6 ,}
Examples include MnCl ₂ , ReCl ₄ , FeCl ₂ , FeCl ₃ , CoCl ₂ , NiCl ₂ and corresponding bromides. Among these, CuCl ₂ , FeCl ₂ , FeCl ₃ , and CoCl ₂ are preferably used, and among them, CuCl ₂ and FeCl ₃ are particularly preferred metal halides. Such intercalation compounds of metal halides and graphite are used alone or in combination of two or more as cocatalysts. The amount of these co-catalysts to be used is not particularly limited, but it is usually conveniently used in the range of 0.01 to 1000 g atoms as metal atoms per 1 g atom of the main catalyst metal. The first feature of the present invention is the use of such a solid graphite intercalation compound as a cocatalyst, and one major feature of the reaction is:
A method for converting a mixture of an aromatic amino compound and an aromatic nitro compound into urethane using hydrogen and carbon monoxide. These two gas components are contained as a mixed gas in synthesis gas, which can be obtained industrially at low cost, and can be used as is, which is extremely advantageous industrially. Furthermore, another feature of the present invention is that the ratio of aromatic amino compound to aromatic nitro compound can be selected more freely than when hydrogen is not used. That is, when hydrogen is not used, the equivalent ratio of nitro group to amino group is limited to around 1/2, but
The method of the present invention is superior in that aromatic urethane can be effectively obtained at any value as long as this ratio is 1/2 or more, so it is advantageous in that it has a large degree of operational freedom. In the method for producing aromatic urethane using a mixture of aromatic nitro compounds as a raw material, the use of hydrogen allows the use of more aromatic nitro compounds, which are obtained at a lower cost than aromatic amino compounds. It is also advantageous. In addition, when using a mixture of an aromatic nitro compound and an aromatic amino compound in which the equivalent ratio of nitro group to amino group is greater than 1/2 as a raw material, if the reaction is performed with only carbon monoxide without using hydrogen, partial reduction can be achieved. When urethanization occurs, carbon dioxide gas is produced as a by-product, and carbon monoxide is not used effectively.However, according to the method of the present invention, which uses a mixed gas of hydrogen and carbon monoxide, less carbon dioxide gas is produced and carbon monoxide is effectively used. available for use. The reaction of the present invention is a reaction formula () that does not use hydrogen.
Unlike the case of , the reaction proceeds according to the following reaction formula (). a・Ar(NH ₂ ) _x + b・Ar′(NO ₂ ) _y + (2by−ax)・H
₂ +(ax+by)・CO+(ax+by)・ROH→ a・Ar(NHCOOR) _x +b・Ar′(NHCOOR) _y +2by・H
₂ O () (Here, Ar and Ar' represent aromatic groups, x represents the number of amino groups in 1 mol of aromatic amino compound, and y represents the number of nitro groups in 1 mol of aromatic nitro compound. (In addition, a and b are numbers proportional to the respective molar amounts of the aromatic amino compound and the aromatic nitro compound used in the reaction.) Of course, even if the equivalent ratio of the nitro group to the amino group is 1/2 or less, Although some aromatic amino compounds remain, the reaction proceeds smoothly. The aromatic amino compound used as a raw material in the method of the present invention may be any compound in which an amino group or a monosubstituted amino group is directly bonded to an aromatic ring, but aromatic primary amines are particularly suitable. preferable. Such aromatic primary amines include aniline, diaminobenzene (each isomer), triaminobenzene (each isomer), tetraaminobenzene (each isomer), aminopyridine (each isomer), and diaminopyridine. (each isomer), triaminopyridine (each isomer), aminonaphthalene (each isomer), diaminonaphthalene (each isomer),
Triaminonaphthalene (each isomer), tetraminonaphthalene (each isomer) and the following general formula ()
Monoamine, diamine, triamine, and tetraamine isomers of the diphenyl compound represented by: [X is a simple bond of phenyl group, -O-, -
S-, _-SO2- , -CO-, -CONH-, -COO-,
-C(R ¹ )(R ² )-, and -N(R ¹ )- (where R ¹ ,
R ² represents a divalent group selected from H, an aliphatic group and an alicyclic group] Furthermore, in these aromatic primary amines, one or more groups bonded to the aromatic ring hydrogen is replaced by other substituents, such as halogen atoms, nitro groups,
It may be substituted with a cyano group, an alkyl group, an alicyclic group, an aromatic group, an aralkyl group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, or the like. Among these aromatic amino compounds, particularly preferred are aniline, 2,4- and 2,6-diaminotoluene, chloroaniline (each isomer), dichloroaniline (each isomer), 4,4'- and 2,
4'-diaminodiphenylmethane and 1,5-diaminonaphthalene. Further, the aromatic nitro compound may be any compound in which a nitro group is directly bonded to an aromatic ring. Examples of such aromatic nitro compounds include nitrobenzene, dinitrobenzene (each isomer), nitropyridine (each isomer), dinitropyridine (each isomer), nitronaphthalene (each isomer), and dinitronaphthalene (each isomer). Examples include isomers of mononitro compounds and dinitro compounds of the diphenyl compound represented by the general formula () and the above-mentioned general formula (). Furthermore, in these aromatic nitro compounds, one or more hydrogens bonded to the aromatic ring may be substituted with other substituents, such as halogen atoms, amino groups, cyano groups, alkyl groups, alicyclic groups, aromatic groups. , an aralkyl group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, etc. Among these aromatic nitro compounds, particularly preferred are nitrobenzene, nitrotoluene (each isomer), nitroaniline (each isomer), 2,4-
and 2,6-dinitrotoluene, dichloronitrobenzene (each isomer), 4,4'- and 2,4'-dinitrodiphenylmethane, and 1,5-dinitronaphthalene. In the method of the present invention, the aromatic nitro compound acts as a reaction agent and an oxidizing agent. Therefore, when the aromatic nitro compound and the aromatic amino compound used differ in structure other than both groups, at least two types of aromatic nitro compounds are used. aromatic urethane will be obtained. When manufacturing only one type of aromatic urethane, the aromatic nitro compound may be structurally the same as the aromatic amino compound. The organic hydroxyl compound used in the present invention refers to monohydric or polyhydric alcohols or monohydric or polyhydric phenols. Such alcohols include linear or branched monohydric or polyhydric alkanols or alkenols having 1 to 20 carbon atoms, or monohydric or polyhydric cycloalkanols;
There are cycloalkenols or 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. Examples of such alcohols include methanol, ethanol, propanol (each isomer),
Butanol (each isomer), pentanol (each isomer), hexanol (each isomer), heptanol (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), tetradecyl alcohol (each isomer), and aliphatic alcohols such as 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 Alkylene glycol monoalkyl ethers such as ether and propylene glycol monoethyl ether; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, hexanetriol, and trimethylolpropane; aralkyl such as benzyl alcohol, etc. Alcohols etc. are used. Examples of phenols that can be used include phenol, various alkylphenols, various alkoxyphenols, various halogenated phenols, dihydroxybenzene, 4,4'-dihydroxy-diphenylmethane, bisphenol-A, and hydroxynaphthalene. The catalyst used in the method of the present invention contains a platinum group metal as a catalyst component, and such a component includes one or more platinum group metals consisting of palladium, rhodium, platinum, ruthenium, iridium, and osmium. Any type of material containing more than this may be used. These metals may be in a metallic state or may be a compound component.
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, polymers, ion exchange resins, zeolites, and more. It may be supported on a carrier such as cyular sieve, magnesium silicate, or magnesia. Platinum group metals in the metallic state include palladium,
Metals such as rhodium, platinum, ruthenium, iridium, and osmium are included, and catalyst components containing these metal ions are supported on the above-mentioned carrier, and then reduced with hydrogen or formaldehyde. Alternatively, alloys or intermetallic compounds containing these metals may be used. The alloy or intermetallic compound may be of these platinum group metals, or of these platinum group metals and other metals, such as selenium, tellurium, sulfur, antimony, bismuth, copper, silver, gold, and zinc. ,
It may be an alloy or intermetallic compound with tin, vanadium, iron, cobalt, nickel, mercury, lead, thallium, chromium, molybdenum, tungsten, etc. Compounds containing platinum group metals include inorganic salts of these metals such as halides, sulfates, nitrates, phosphates, and borates; organic acid salts such as acetates, oxalates, and formates; and cyanides. ; Hydroxides; Oxides; Sulfides; Nitro group, cyano group,
Complex compounds of metals such as metal salts containing anions such as halogens and oxalate ions, and salts or complexes containing ammonia, amines, phosphines, carbon monoxide, chelate ligands, etc.; organic ligands or organic This includes organometallic compounds having groups. Among these catalyst species, those containing palladium or rhodium are particularly preferred. Catalyst species containing palladium and rhodium include, for example, Pd.
Black; Pd-C, Pd- _Al2O3 , _Pd - _SiO2 , Pd-
_TiO2 , Pd- _ZrO2 , Pd- _BaSO4 , Pd- _CaCO3 ,
Supported palladium catalysts such as Pd-asbestos, Pd-zeolite, Pd-molecular sieve; Pd
−Pb, Pd−Se, Pd−Te, Pd−Hg, Pd−Tl,
Pd-P, Pd-Cu, Pd-Ag, Pd-Fe, Pd-Co,
Alloys or intermetallic compounds such as Pd-Ni and Pd-Rh; and these alloys or intermetallic compounds supported on the above-mentioned carriers; PdCl ₂ , PdBr ₂ ,
Inorganic salts such as PdI ₂ , Pd(NO ₃ ) ₂ , PdSo ₄ ; Organic acid salts such as palladium acetate and palladium oxalate; Pd(CN) ₂ ; PdO; PdS; M ₂ [PdX′ ₄ ], M ₂
Palladate salts represented by [PdX′ ₆ ] (where M represents an alkali metal or ammonium ion, and X′ represents a nitro group, cyano group, or halogen); [Pd(NH ₃ ) ₄ ]X′ ₂ , Palladium ammine complexes such as [Pd(en) ₂ ]X′ ₂ (X′ is as above,
en represents ethylenediamine); PdCl ₂
(PhCN) ₂ , PdCl ₂ (PR ³ ₃ ) ₂ , Pd(CO) (PR ³ ₃ ) ₃ ,
Pd( _PPh3 ) ₄ , PdCl( ^R3 )( _PPh3 ) ₂ , Pd( _{C2H4 )}
Complex compounds or organometallic compounds such as (PPh ₃ ) ₂ , Pd(C ₃ H ₅ ) ₂ (R ³ represents an alkyl or aryl group); coordinated with chelate ligands such as Pd(acac) ₂ Complex compounds; Rh black; Supported rhodium catalysts similar to Pd; Rh alloys or intermetallic compounds similar to Pd, and these supported on carriers; RhCl ₃
and hydrates, RhBr ₃ and hydrates, Rh ₂ (So ₄ ) ₃ and inorganic salts such as hydrates; Rh ₂ (OCOCH ₃ ) ₄ ;
Rh ₂ O ₃ , RhO ₂ ; M ₂ [RhX′ ₆ ] and hydrates (M,
X′ is as above); [Rh(NH ₃ ) ₅ ]X′ ₃ , [Rh
Rhodium ammine complexes such as (en) ₃ ]X′ ₃ ;
Rhodium carbonyl clusters such as Rh ₄ (CO) ₁₂ , Rh ₆ (CO) ₁₆ ; [RhCl(CO) ₂ ] ₂ , RhCl ₃
(PR ³ ₃ ) ₃ , RhCl(PPh ₃ ) ₃ , RhX′(CO)L ₂ (X′ is as described above, L represents a ligand consisting of an organic phosphorus compound and an organic arsenic compound), RhH( CO)
Complex compounds such as (PPh ₃ ) ₃ or organometallic compounds can be mentioned. One or more types of these platinum group metal or compound catalysts can be used. These platinum group metal-containing catalysts used as catalysts usually contain 0.0001% of the total amount of aromatic amino compounds and aromatic nitro compounds as metal components.
It is used in a range of 50 mol%, preferably 0.001 to 10 mol%. In the method of the present invention, other additives can also be added to the reaction system in order to carry out the reaction more efficiently. Preferred examples of such additives include tertiary amines; zeolites; alkali metal salts or alkaline earth metal salts of boric acid, aluminate, carbonic acid, silicic acid, and organic acids. In the reaction of the present invention, it is preferable to use an excess of the organic hydroxyl compound so that it also serves as a solvent.
Other solvents that are inert to the reaction can also be used. Examples of such inert solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; halogenated solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, chlorotoluene, chlornaphthalene, and bromnaphthalene; Aromatic hydrocarbons; halogenated aliphatic hydrocarbons or halogenated alicyclic hydrocarbons such as chlorhexane, chlorocyclohexane, trichlorotrifluoroethane, methylene chloride, and carbon tetrachloride; nitriles such as acetonitrile and benzonitrile; Sulfones such as sulfolane, methylsulfolane, dimethylsulfolane;
Tetrahydrofuran, 1,4-dioxane, 1,
Examples include ethers such as 2-dimethoxyethane; ketones such as acetone and methyl ethyl ketone; and esters such as ethyl acetate and ethyl benzoate. Since the compound is a solid, there is little corrosion of equipment, separation and recovery from the reaction solution can be carried out by simple methods such as filtration, and the compound can be recycled and reused, which is extremely advantageous. In the method of the present invention, some diarylureas may be produced as by-products, but these diarylureas are converted to the target aromatic urethane under the conditions of this reaction, so they cannot be recycled to the reaction system. The yield of urethane can be increased by The reaction is generally carried out at 80-300°C, preferably 120-220°C.
It is carried out in a temperature range of ℃. Pressure is 5~500Kg/
cm ² , preferably in the range of 20 to 300 Kg/cm ² . The reaction time varies depending on the reaction system, catalyst system, and other reaction conditions, but is usually from several minutes to several hours. The reaction of the present invention can be carried out either batchwise or continuously, in which reaction components are continuously supplied and a reaction solution is continuously withdrawn. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 200ml stirring autoclave (SUS316
), 30 mmol of aniline, 30 m of nitrobenzene
mol, methanol 60ml, Pd black 0.8mgatom, black powdery intercalation compound of ferric chloride and graphite containing about 15% by weight _FeCl3 (Graphimet _FeCl3
-15) After 4g of carbon monoxide was added and the inside of the system was replaced with carbon monoxide, 130Kg/cm ² of carbon monoxide and 10Kg/cm ² of hydrogen were introduced under pressure. After reacting at 160°C for 2 hours with stirring, the reaction mixture was filtered and the filtrate was analyzed, and it was found that 7 mmol of aniline and 3 m of nitrobenzene.
mol, methyl N-phenylcarbamate is 43m
It was found that mol was present. The yield of methyl N-phenylcarbamate from aniline and nitrobenzene was 72%, and the selectivity was 86%. The filtrate was placed in an autoclave as it was, 30 mmol of aniline, 30 mmol of nitrobenzene, and 60 ml of methanol were added, and carbon monoxide and hydrogen were injected under pressure. As a result of repeating the same experiment, methyl N-phenylcarbamate was recovered from aniline and nitrobenzene. The rate was 70% and the selection rate was 85%, showing similar results. It should be noted that almost no corrosion of the container or stirrer rod was observed after the reaction. Example 2 30 mmol of aniline, 40 mmol of nitrobenzene,
60ml of ethanol, 1mgatom of Pd black, about 15% by weight
Interlayer compound of cupric chloride and graphite containing CuCl ₂ [Graphimet (registered trademark name) CuCl ₂ -15]
5 g was placed in the same autoclave as in Example 1, and after replacing the system with carbon monoxide, 120 g of carbon monoxide was added.
Kg/cm ² and hydrogen 12Kg/cm ² were pressurized. After reacting at 170°C for 2 hours while stirring, the reaction mixture was filtered and the filtrate was analyzed.
mol, 4 mmol of nitrobenzene, and 48 mmol of ethyl N-phenylcarbamate were found to be present. N- from aniline and nitrobenzene
The yield and selectivity of ethyl phenylcarbamate were 69% and 80%, respectively. The filtrate was returned to the autoclave as it was, 30 mmol of aniline, 40 mmol of nitrobenzene and 60 ml of ethanol were added, and carbon monoxide and hydrogen were injected under pressure and the same experiment was repeated. As a result, ethyl N-phenylcarbamate was recovered from aniline and nitrobenzene. rate and selection rate were 72% and 83%, respectively.
The results were almost the same. It should be noted that almost no corrosion of the container or stirrer rod was observed after the reaction. Example 3 25 mmol of aniline, 45 mmol of nitrobenzene,
Intercalation compound with graphite containing 50 ml of ethanol, 1 mmol of palladium chloride, and 15% by weight of ferric chloride [Graphimet (registered trademark) FeCl ₃ -15] 5
After placing g in an autoclave and replacing the inside of the system with carbon monoxide, carbon monoxide was 120 kg/cm ² and hydrogen was 15 kg/cm 2 .
cm ² was injected under pressure and reacted at 160°C for 2 hours. Analysis of the reaction solution revealed 8 mmol of aniline, 2 mmol of nitrobenzene, and ethyl N-phenylcarbamate.
It was found that 50 mmol was present. Examples 4 to 12 Aniline 30 was added to the autoclave used in Example 1.
mmol, nitrobenzene 30 mmol, ethanol 60
ml of carbon monoxide and hydrogen at room temperature using various catalysts shown in the table below and intercalation compounds of various metal halides and graphite as cocatalysts at 130 Kg/cm ² and 10 Kg/cm ² , respectively. The reaction was carried out in the same manner as in Example 1 by injecting the mixture under initial pressure. The results of each experiment are summarized in the table below. In each of these examples, the intercalation compound contained approximately 5 mmol as metal halide and the catalyst contained approximately 1 mmol as metal atom.
mgatom was used. In addition, G means graphite, and the % expression represents the approximate weight % of the metal halide in the intercalation compound.

【table】

[Table] Example 13 2,4-diaminotoluene 25 mmol, 2,4-
Dinitrotoluene 25 mmol, ethanol 50 ml, Pd
2 mg of black, 5 g of an intercalation compound with graphite containing 15% by weight of cupric chloride [Graphimet (registered trademark) CuCl ₂ -15] was placed in an autoclave.
After replacing the system with carbon monoxide, carbon monoxide 130
Kg/cm ² and hydrogen at 20 Kg/cm ² were injected under pressure, and the mixture was reacted at 170°C for 2 hours. As a result of analyzing the obtained reaction product liquid by high performance liquid chromatography, it was found that tolylene-2,
28 mmol of diethyl 4-dicarbamate, 8 mmol of aminomonourethane, which is a mixture of ethyl-3-amino-4-methylcarbanilate and ethyl-2-methyl-5-aminocarbanilate, and ethyl-3-nitro- 3 mmol of nitromonourethane, which is a mixture of 4-methylcarbanilate and ethyl-2-methyl-5-nitrocarbanilate.
I found out that it was generated.

Claims (1)

[Scope of Claims] 1 (a) A catalyst containing a platinum group metal; and (b) a halide of a metal element belonging to the copper group, lead group, nitrogen group, vanadium group, chromium group, manganese group, and iron group. It is characterized by reacting an aromatic amino compound and an aromatic nitro compound with an organic hydroxyl compound, hydrogen and carbon monoxide in the presence of a cocatalyst consisting of at least one intercalation compound of a selected metal halide and graphite. A method for producing urethane. 2. The method according to claim 1, wherein the catalyst component is at least one selected from palladium, rhodium, palladium compounds, and rhodium compounds. 3. The method according to claim 2, wherein the promoter is at least one intercalation compound of graphite and a halide selected from halides of copper group metals and halides of iron group metals. 4. The method according to claim 3, wherein the promoter is an intercalation compound of cupric chloride and graphite and/or an intercalation compound of ferric chloride and graphite.