JPS636542B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing N.N-disubstituted aminophenyl isocyanates. Conventionally, isocyanates have been produced industrially by reacting the corresponding primary amine with phosgene, but this method requires the use of highly toxic phosgene and produces a large amount of corrosive hydrogen chloride as a by-product. Furthermore, products may contain hydrolyzable chlorine compounds, and it is extremely difficult to remove this byproduct.Therefore, it is difficult to produce isocyanates relatively easily without using phosgene. A method is desired. In addition, isocyanates having a tertiary amino group, which is the target substance of the present invention,
Production from the corresponding amine and phosgene resulted in low yields and was not a preferred method. Therefore, the present inventors conducted extensive studies on an easy method for producing N·N-disubstituted aminophenyl isocyanate using N·N-disubstituted aminoaniline as a raw material, and as a result, they were able to complete the present invention. Ivy. That is, the present invention provides an oxidizing agent, at least one selected from palladium and a compound containing palladium, and at least one selected from bromine, iodine, or a compound containing these.
In the presence of a urethanization catalyst consisting of species, the general formula

[Formula] (However, R′ and R″ represent an aliphatic group, an alicyclic group, an aromatic group, and an araliphatic group, and each may be the same group. Y represents an aliphatic group, and n is 0 or 1), by reacting N.N-disubstituted aminoaniline with carbon monoxide and an organic hydroxyl compound.
N/N consisting of producing a disubstituted aminocarbanilate compound and then separately recovering the isocyanate and organic hydroxyl compound produced by thermally decomposing the carbanilate compound at a temperature of 100 to 350°C. An object of the present invention is to provide a method for producing -disubstituted aminophenyl isocyanate. The method of the present invention can be simply illustrated using a reaction formula as follows. (1) Oxidative urethanization reaction When molecular oxygen is used as the oxidizing agent When using an organic nitro compound as an oxidizing agent (2) Pyrolysis reaction (Here, R' and R'' are as described above, R represents an aliphatic group, an alicyclic group, an aromatic group, and an araliphatic group, and R', R'', and R are each the same group. As described above, the N·N-disubstituted aminoaniline used as a raw material in the present invention has the general formula (R' and R'' are as described above and may be the same group. Y represents an aliphatic group, and n is 0 or 1), which has a tertiary amino group. ,
Substituted aniline at the ortho, meta, or para position, such as N・N-dimethylaminoaniline (each isomer), N・N-diethylaminoaniline (each isomer), N-methyl-
N・N-dialkylaminoanilines such as N-ethylaminoaniline (each isomer); N・N-
Diphenylaminoaniline (each isomer), N-methyl-N-phenylaminoaniline (each isomer)
Aromatic substituted aminoanilines such as N・N-dicyclohexylaminoaniline (each isomer), N
-Alicyclic ring-substituted aminoanilines such as methyl-N-cyclohexylaminoaniline (each isomer); furthermore, N・N-dimethylaminotoluidine (each isomer), N・N-diethylaminotoluidine (each isomer) N・N- where the hydrogen of the aromatic ring of aniline is substituted with another substituent, such as
Examples include disubstituted aminoaline derivatives. In the first step of the present invention, a urethane compound is produced by an oxidative carbonylation reaction in which N.N-disubstituted aminoaniline is reacted with carbon monoxide and an organic hydroxyl compound in the presence of an oxidizing agent. However, in this case, the urethanation catalyst is (1) at least one selected from palladium or a compound containing palladium, and (2) at least one selected from bromine, iodine, or a compound containing these. It is characterized by using a catalyst system consisting of, and by using this catalyst system, high yield,
It has been found that N.N-disubstituted aminocarbanilate compounds can be obtained with high selectivity. Palladium and palladium-containing compounds used as the catalyst system of the present invention are not particularly limited as long as they contain the palladium element as a component, and may be in a metallic state or as a component forming a compound. good. In addition, these palladium components include activated carbon, graphite, silica, alumina, silica-alumina, silica-titania, titania, zirconia, barium sulfate, calcium carbonate, asbestos, bentonite, diatomaceous earth,
It may be supported on a carrier such as a polymer, ion exchange resin, zeolite, molecular sieve, magnesium silicate, or magnesia. Palladium in a metallic state can be obtained, for example, by supporting palladium metal, palladium black, or a catalyst component containing palladium ions on the above-mentioned carrier.
Those that have been reduced with hydrogen or formaldehyde, and alloys or intermetallic compounds containing palladium metal are used. The alloy or intermetallic compound may also be of palladium and other platinum group metals, or of other elements such as selenium,
tellurium, sulfur, antimony, bismuth, copper,
It may contain silver, gold, zinc, tin, vanadium, iron, cobalt, nickel, mercury, lead, thallium, chromium, molybdenum, tungsten, and the like. On the other hand, palladium-containing compounds include, for example, inorganic salts such as halides, sulfates, nitrates, phosphates, and borates; organic acid salts such as acetates, oxalates, and formates; cyanides; Oxides; 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 Examples include organometallic compounds having groups. In the present invention, these palladium or palladium-containing compounds may be used alone or in a mixture of two or more, and there is no particular restriction on the amount used, but palladium-containing compounds usually include palladium. It is desirable that the component is in a range of 0.0001 to 50 mol % based on the amino group of the aliphatic primary amine. The compound containing bromine or iodine, which is another important catalyst component used in the present invention, may be organic or inorganic, such as metal halides where the halogen is bromine or iodine, and onium halides. Preferably used are compounds or compounds capable of producing these compounds in a reaction system, halogen oxoacids or salts thereof, complex compounds containing halogen ions, organic halides, and halogen molecules. Examples of metal halides include alkali metals, alkaline earth metals, copper, silver, zinc, cadmium, mercury, aluminum, potassium, thallium, germanium, tin, lead, antimony, bismuth, titanium, zirconium, vanadium, and niobium. , tantalum, tellurium, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rare earth metals, and other halides are used. Particularly preferred are alkali metal and alkaline earth metal bromides or iodides. An onium halide compound is a compound containing an element with a lone pair of electrons, in which a proton or other cationic reagent is bonded to these lone pairs, and the element with a lone pair of electrons forms a covalent bond with a valence of 1.
increases and becomes a cation,
It has a halogen anion as a counter ion. Such onium compounds include ammonium compounds ([R ¹ R ² R ³ R ^{4 N} ]X), phosphonium compounds ([R ¹ R ² R ³ R ^{4 P} ] ^{R 3} R ⁴ As ^〕 X), stibonium compounds ([ ^{R 1 R 2 R 3 R 4 Sb} ) ³ S]X) ^, oxysulfonium compounds ^{([R 1 R 2 R 3 S ( O ) ]} Examples include a stannonium compound ([R ¹ R ² R ³ Sn] X), an iodonium compound ([R ¹ R ² I] X), and the like. Here, R ¹ , R ² , R ³ , and R ⁴ represent hydrogen or a group selected from an aliphatic group, an aromatic group, an alicyclic group, and an araliphatic group, and each may be the same or , or in some cases, may be a constituent element of a ring containing an element having a lone pair of electrons. Further, X represents a halogen selected from Br and I. Of course, it may be a compound having two or more such onium groups in its molecule, or it may be a polymer containing such onium groups in its main chain or side chain. Such halogenated onium compounds, which are onium compounds whose anion is a halogen, include amines or nitrogen-containing compounds, phosphine compounds, arsine compounds, stibine compounds, oxy compounds,
It is easily obtained by reaction with sulfide compounds, sulfoxide compounds, selenide compounds, telluride compounds, etc. These can be produced outside the reaction system, or they can be produced within the reaction system. You may let them. Of course, it may be produced by other methods, or may be produced within the reaction system by other methods. Among these, preferred are halogenated ammonium compounds, halogenated phosphonium compounds,
Among the halogenated arsonium compounds and halogenated sulfonium compounds, particularly preferred are halogenated ammonium compounds. Halogenated ammonium compounds can be easily obtained by reacting a corresponding nitrogen-containing compound with hydrogen halide, or by reacting a nitrogen-containing compound with an alkyl halide or an aryl halide. For example, ammonia; 1
Amines such as primary amines, secondary amines, and tertiary amines;
Hydroxylamines; hydrazines; hydrazones; amino acids; oximes; imidoesters; amides and various nitrogen-containing heterocyclic compounds. Halogen oxyacids and their salts refer to halogen oxyacids and their salts with positive oxidation numbers of 1, 3, 5, and 7, and specifically include hypobromous acid, bromic acid, and perbromic acid. , hypoiodic acid, iodic acid, iodic acid, orthoperiodic acid, metaperiodic acid, and salts of these acids. The cations of the salts may be any ions such as ammonium ions and various metal ions, but alkali metal ions and alkaline earth metal ions are particularly preferred. A halogen-containing complex compound may contain either a cationic or anionic halogen; for example, polyhalogenated halogenated salts such as ammonium dichlorobromate and tetramethylammonium tetrabromoiodate; hexaiodine; Metal halides such as potassium tellurate, tetraethylammonium tetraiodomercurate, potassium tetraiodobismuthate, sodium tetrabromocuprate, cesium tetrabromoferrate, barium hexaiodostannate, potassium tetraiodoleadate, potassium hexabromotellurate; Complexes having a ligand such as octate (N·N-dimethylformamide) lanthanum triiodide, iodopentaammine chromium triiodide, bis(2,2'-pipyridine) copper diiodide, etc. are used. In addition, organic halides have the general formula R ⁶ (X)m (wherein R ⁶ is an m-valent organic group, X is Br or I, m
means an integer greater than or equal to 1. ), and when m is 2 or more,
X may be a different halogen species. Furthermore, the halogen X may be bonded to a heteroatom other than carbon, such as nitrogen, phosphorus, oxygen sulfur, selenium, or the like. Such organic halides include, for example, aliphatic mono- and polyhalides such as methyl halide, ethyl halide, methylene halide, haloform, and tetrahalogenomethane;
Aromatic mono- and polyhalides such as halogenobenzene, dihalogenobenzene (each isomer), iodosobenzene, iodoxybenzene; alicyclic halides such as halogenated cyclohexane and halogenated cyclobutane; halogenated benzyl,
Aroaliphatic halides such as halogenated phenethyl; heterocyclic halides such as halogenated furan, halogenated tetrahydrofuran, halogenated thiophene, halogenated imidazole, and halogenated piperidine; acids such as halogenated acetyl and halogenated benzoyl Halides: N-halides such as N-halogenosuccinimide, N-halogenoalkylamine, N-halogenoacetamide, and N-halogenobenzamide are preferably used. Furthermore, these organic groups can be substituted with various substituents, such as nitro groups, lower alkyl groups, cyano groups, alkoxy groups, aryloxy groups, aromatic groups, sulfoxide groups, sulfone groups, carbonyl groups, ester groups, amide groups, etc. or may have an unsaturated group. Bromine molecules or iodine molecules can also be used. Furthermore, as a compound containing bromine or iodine, hydrogen halides such as hydrogen bromide and hydrogen iodide, or hydrohalic acids can be used, but in this case, the raw materials N,N-disubstituted aminoaniline and ammonium salt are However, these salts are difficult to urethanize, resulting in lower reaction rates and yields. Therefore, in this case, it is preferable to use a substance that is more basic than the raw material N·N-disubstituted aminoaniline in an amount equal to or more than the hydrogen halide. Such bromine, iodine, or compounds containing these may be used alone or in combination of two or more. Among bromine, iodine, or compounds containing these used in the method of the present invention, those containing iodine are particularly preferred catalyst components. The catalyst system for the oxidative urethanization reaction in the present invention is characterized by a combination of a catalyst component made of palladium or a palladium compound and a catalyst component made of bromine, iodine or a compound containing these. It is also a preferred method to add a basic substance as an additional co-catalyst, if necessary, for the purpose of increasing selectivity or reaction rate. In particular, when an organic halide or halogen molecule is used as one of the catalyst components, the effect of adding a basic substance is large. Such basic substances may be either inorganic or organic, such as alkali metals, alkaline earth metals, and oxides, hydroxides, carbonates, and hydrogen carbonates of these metals. Salts, carbides, hydrides, sulfides, organic acid salts, alcoholates, phenolates, amides, etc.; quaternary ammonium hydroxide compounds; quaternary phosphonium hydroxide compounds; tertiary amines and cyclic nitrogen-containing compounds (but N -H groups); crown compounds, etc. are used. Furthermore, there may be two or more of these basic groups in the molecule, or it may form part of a polymer such as an anion exchange resin having a quaternary ammonium hydroxide group. . Further, these basic substances or groups having basicity may be supported on a solid or chemically bonded. These basic substances may be used alone or
Alternatively, two or more types may be mixed and used. The amount of bromine, iodine, or a compound containing these used in the urethanization reaction is preferably in the range of 0.001 to 10,000 times the amount of palladium used. When used in combination, it is preferable that the amount used is usually 0.01 to 1000 times the molar amount of the halogen. The organic hydroxyl compound used in the present invention is a monohydric or polyhydric alcohol, or a monohydric or polyhydric phenol, and examples of such alcohol include linear or branched alcohols having 1 to 20 carbon atoms. monohydric or polyhydric alkanols or alkenols in the chain,
Examples include monovalent or polyvalent cycloalkanols, cycloalkenols, and aralkyl alcohols. Furthermore, these alcohols have other substituents,
For example, halogen atoms, cyano groups, alkoxy groups,
It may contain a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, etc. Specific 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 pendadecyl 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, proprene glycol Alkylene glycol monoethers such as monomethyl ether and 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 that can be used include phenol, various alkylphenols, various alkoxyphenols, various halogenated phenols, dihydroxybenzene, 4,4'-dihydroxy-diphenylmethane, bisphenol-A, and hydroxynaphthalene. The oxidizing agent used in the present invention may be any conventional oxidizing agent, but preferred are molecular oxygen, organic nitro compounds, or mixtures thereof. This molecular oxygen is pure oxygen or a substance containing oxygen, which may be air, or air or pure oxygen may be mixed with other gases that do not inhibit the reaction, such as nitrogen, argon, helium, carbon dioxide, or other inert gases. In addition, it may be diluted.
In some cases, it may also contain gases such as hydrogen, carbon monoxide, hydrocarbons, and halogenated hydrocarbons. Further, the organic nitro compound may be any of alicyclic, aliphatic, and aromatic nitro compounds. Preferred are aromatic nitro compounds such as nitrobenzene, and particularly preferred is N.N-disubstituted aminonitrobenzene having the same skeleton structure as the raw material N.N-disubstituted aminoaniline. In this case, the raw amine and the nitro compound can be reacted to produce a urethane compound having the same structure. Molecular oxygen may be used in less or more than equivalent amounts, but mixtures of oxygen/carbon monoxide or oxygen/organic hydroxyl compounds should be used outside the explosive limits. When only an organic nitro compound is used as an oxidizing agent, it is preferable that the ratio of the raw material N·N-disubstituted aminoaniline to the organic nitro compound is 1 mole of nitro group per 2 moles of primary amino group. Of course, it may be carried out at a location far from this stoichiometric ratio. Generally, the equivalent ratio of primary amino groups to nitro groups is carried out from 1.1:1 to 4:1, preferably from 1.5:1 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 urethanization reaction can be carried out without using any solvent other than the organic hydroxyl compound, but
It is also a preferred method to carry out the reaction in a suitable solvent. Examples of such solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and dicane; alicyclic hydrocarbons such as cyclohexane, tetralin, and decalin; and aromatic solvents such as benzene, toluene, xylene, and mesitylene. Nitriles such as acetonitrile and benzonitrile; Sulfones such as sulfolane, methylsulfolane and dimethylsulfolane; tetrahydrofuran, 1,4-dioxane, 1,2-
Ethers such as dimethoxyethane; acetone,
Ketones such as methyl ethyl ketone; Esters such as ethyl acetate and ethyl benzoate; N/N-
Amides such as dimethylformamide, N·N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, and the like can be mentioned. Furthermore, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, chlorotoluene, chlornaphthalene, and bromnaphthalene; chlorhexane, chlorocyclohexane, trichlorotrifluoroethane, methylene chloride, and tetrachloride; Halogenated aliphatic hydrocarbons such as carbon or halogenated aliphatic hydrocarbons are also used as solvents. In the urethanization reaction of the present invention, other additives may be added to the reaction system as necessary in order to carry out the reaction more efficiently. Suitable examples of such additives include zeolites, orthoesters, ketals, acetals, enol ethers, and trialkylorthoborates. Further, the urethanization reaction is usually carried out at a temperature range of 80 to 300°C, preferably 120 to 250°C. The reaction pressure is 1 to 500Kg/cm ² , preferably 20 to 300Kg/cm 2 .
^cm2 , and the reaction time varies depending on the reaction system, catalyst system, and other reaction conditions, and is usually from several minutes to several hours. This urethanization reaction can be carried out either batchwise or continuously in which the reaction solution is continuously extracted while continuously supplying the reaction components. In the second step of the present invention, the N·N-disubstituted aminocarbanilate compound produced in the first step is heated to 100 to 350°C to decompose it into isocyanate and an organic hydroxyl compound,
Each is separated and collected to produce the desired N·N-disubstituted aminophenyl isocyanate. This thermal decomposition reaction of the N·N-disubstituted aminocarbanilate compound can be carried out without a solvent, but it is more preferably carried out in a solvent that is inert to the isocyanate produced. Such solvents include aliphatic, cycloaliphatic or aromatic substituted or unsubstituted hydrocarbons or mixtures thereof, and also certain oxygenated compounds such as ethers, ketones and esters. . Preferred solvents include hexane, heptane,
Octane, nonane, decane, n-hexadecane,
Alkanes such as n-octadecane, eicosane, squalane, and alkenes corresponding to these;
Aromatic hydrocarbons and alkyl-substituted aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, diisopropylbenzene, dibutylbenzene, naphthalene, lower alkyl-substituted naphthalene, dodecylbenzene; chlorobenzene, dichlorobenzene, bromobenzene, Aromatic compounds substituted with nitro groups and halogens such as dibromobenzene, chlornaphthalene, bromnaphthalene, nitrobenzene, nitronaphthalene; diphenyl, substituted diphenyl, diphenylmethane, terphenyl, anthracene, phenanthrene, various isomers of dibenzyltoluene , polycyclic hydrocarbons such as triphenylmethane; alicyclic hydrocarbons such as cyclohexane and ethylcyclohexane; ketones such as methyl ethyl ketone and acetophenone; esters such as dibutyl phthalate, dihexyl phthalate, and dioctyl phthalate; Examples include ethers and thioethers such as enyl ether and diphenyl sulfide; sulfoxides such as dimethyl sulfoxide and diphenyl sulfoxide; nitriles such as benzonitrile; and silicone oil. When performing a thermal decomposition reaction, the N·N-disubstituted aminocarbanilate compound is
Although it is converted into a disubstituted aminophenyl isocyanate and an organic hydroxyl compound, it is necessary to remove one of the components from the reaction system in order to prevent these from recombining and returning to the original carbanilate compound. In this case, it is preferable to remove and separate low boiling point components by distillation or the like among these components that are generated as the reaction progresses. In order to promote this separation, it is also a preferred method to introduce an inert gas such as nitrogen, helium, argon, carbon dioxide, methane, ethane, propane, etc., singly or in combination, into the reaction system. Organic solvents with a similar effect include low boiling point organic solvents, such as halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, lower hydrocarbons such as pentane, hexane, heptane, and benzene, and tetrahydrofuran and dioxane. Ethers can also be used. The thermal decomposition reaction can be carried out either batchwise or continuously. The reaction temperature is usually preferably 100 to 350°C, more preferably 120 to 270°C. A thermal decomposition catalyst can also be used for the purpose of lowering the temperature of the thermal decomposition reaction or increasing the reaction rate. Such catalysts include, for example, rare earth elements, antimony, bismuth, and their oxides, sulfides, and salts; elemental boron and boron compounds; copper group, zinc group of the periodic table,
Metals from the aluminum group, carbon group, and titanium group, and oxides and sulfides of these metals; carbides and nitrides of elements from the carbon group, titanium group, vanadium group, and chromium group excluding carbon in the periodic table are preferably used. . When using a catalyst, the ratio of these catalysts to the N·N-disubstituted aminocarbanilate compound may be arbitrary, but it is preferable to use the catalyst in an amount of usually 0.0001 to 100 times the weight of the carbanilate compound. The reaction time for thermal decomposition varies depending on the type of N/N-disubstituted aminocarbanilate compound used, the type of solvent and catalyst, the reaction temperature, etc.
The duration ranges from several minutes to several tens of hours. Further, although this thermal decomposition reaction is usually carried out at normal pressure, it may be carried out under increased pressure or reduced pressure if necessary. The N·N-disubstituted aminophenyl isocyanates produced by the method of the present invention can be used as raw materials for various insecticides, agricultural chemicals, and dyes, or as raw materials for color formers. As an application of the coloring agent, for example, it can be used as a raw material for thermal recording paper which is thermally colored by coating it on a paper-like material together with a heterocyclic compound having active hydrogen. 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 A P-
(N・N-dimethylamino)aniline 200 mmol,
Add 200ml of ethanol, 2mgatom of palladium black, and 4mmol of cesium iodide, and after replacing the inside of the system with carbon monoxide, 80Kg/cm ² of carbon monoxide and then 6Kg/cm ² of oxygen are introduced to bring the total pressure to 86Kg/cm. I made it ² . After reacting for 1 hour at 160-170°C with stirring, oxygen 5
Kg/cm ² was added and reacted for 30 minutes, and then 5 Kg/cm ² of oxygen was added and reacted for 30 minutes. After filtering the reaction solution, analysis showed that the reaction rate of p-(N/N-dimethylamino)aniline was 98%, and the yield of ethyl-p-(N/N-dimethylamino)carbanilate was 93%. It was generated with a selectivity of 95%. After ethanol was distilled off from the reaction solution, it was washed with water and dried to obtain light brown crystals. By recrystallizing this crystal from n-hexane, 35 g of white needle crystals with a melting point of 74 to 76°C were obtained. Note that when cesium iodide was not used, the urethanization reaction hardly proceeded. Next, in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet extending below the liquid level, and an air cooler, 20 g of ethyl p-(N N-dimethylamino)carbanilate was added as a solvent. Add 200ml of 1-chlornaphthalene and add 30N of nitrogen into the solution.
The decomposition reaction was carried out at 240° C. for 3 hours with stirring while introducing the solution at a rate of 100° C./hour. The generated ethanol was led from the top of the condenser to a trap cooled to -50°C and collected. Analysis of the reaction solution by gas chromatography and infrared absorption spectroscopy revealed that unreacted ethyl-p-(N/N-dimethylamino)
There are no carbanilates, all p-(N・N-
It had decomposed into phenyl isocyanate (dimethylamino). By distilling this solution under reduced pressure, 1-
Distill chlornaphthalene, then 108-110
p-(N.N-dimethylamino)phenyl isocyanate was obtained in a yield of 90%, which was distilled off at .degree. C./2 mmHg. Example 2 p-(N·N-diethylamino)aniline 200 instead of p-(N·N-dimethylamino)aniline
The reaction was carried out in the same manner as in Example 1 except that 5 mmol of tetramethylammonium iodide was used instead of cesium iodide.
The reaction rate of p-(N·N-diethylamino)aniline was 99%, and ethyl-p-(N·N-diethylamino)carbanilate was produced in a yield of 92% and a selectivity of 93%. Note that when tetramethylammonium iodide was not used, the urethanization reaction hardly proceeded. Next, ethyl-p-(N・N-diethylamino)
Using 20 g of carbanilate, a thermal decomposition reaction was carried out at 240°C for 3 hours in exactly the same manner as in Example 1, and then 1-chlornaphtaryline was first distilled off by distilling the reaction solution under reduced pressure. then
p-(N・N-
Diethylamino,) phenyl isocyanate was obtained in a yield of 92%. Example 3 In a 500ml stirring autoclave, p-(N・N
230 mmol of -dimethylamino)aniline, 200 ml of methanol, 2 mg of palladium black, and 4 mmol of potassium iodide were added, and after purging the system with carbon monoxide, it was heated under pressure of carbon monoxide. After reaching 160℃, carbon monoxide 80Kg/cm ² and air 30Kg/cm ²
As a result, methyl-p-(N・N-dimethylamino)carbanilate was obtained with a yield of 94% and a selectivity of 94%. It was done. A thermal decomposition reaction was carried out in the same manner as in Example 1 to obtain p-(N·N-dimethylamino)phenyl isocyanate in a yield of 88%. Example 4 p-(N・N-dimethylamino)aniline 20m
10 mmol of p-(N・N-dimethylamino)nitrobenzene, 1 mmol of palladium chloride, 2 mmol of cesium iodide, and 50 ml of ethanol were placed in a 200 ml stirring autoclave, and after replacing the inside of the system with carbon monoxide, 120 kg of carbon monoxide/ cm ² was press-fitted.
After reacting at 170 to 180°C for 6 hours with stirring, the reaction solution was analyzed, and the reaction rate of p-(N・N-dimethylamino)aniline was 65%, and p-(N・N-
The reaction rate of dimethylamino)nitrobenzene is 73%
17 mmol of ethyl p-(N·N-dimethylamino)carbanilate was produced. After ethanol was distilled off from the reaction solution, it was washed with water to remove unreacted p-(N·N-dimethylamino)aniline and cesium iodide. Next, recrystallization was repeated with n-hexane to obtain 2.5 g of ethyl p-(N·N-dimethylamino)carbanilate. The thermal decomposition reaction was carried out in the same manner as in Example 1, and p-(N·N-dimethylamino)phenyl isocyanate was obtained with a yield of 90%. Examples 5 to 10 200 mmol of p-(N・N-dimethylamino)aniline and ethanol were prepared in the same manner as in Example 3.
200ml, palladium metal or a compound containing palladium (2mgatom as palladium metal), iodine molecule or a compound containing bromine or iodine 4m
mol was used to produce ethyl-p-(N·N-dimethylamino)carbanilate. The results are shown in Table 1.

[Table] In the table, % indicates the weight % of palladium supported on the carrier. (Pd-Te)/C is a product in which palladium chloride and tellurium dioxide are co-supported on activated carbon at a molar ratio of 10:3, and then subjected to hydrogen ring reduction at 350°C. The thus obtained ethyl-p-(N.
N-dimethylamino)carbanilate Example 1
By a method similar to the decomposition method of p-
Decomposed to (N.N-dimethylamino)phenyl isocyanate. Example 11 In the same manner as in Example 1 except that p-(N-methyl-N-phenylamino)aniline was used instead of p-(N·N-dimethylamino)aniline in Example 1, p- (N-methyl-N-phenylamino) phenyl isocyanate was obtained in a yield of 80%. Example 12 Example 1 except that p-(N-methyl-N-cyclohexylamino)aniline was used instead of p-(N·N-dimethylamino)aniline in Example 1.
p-(N-methyl-N-
Cyclohexylamino)phenyl isocyanate was obtained in a yield of 82%. Example 13 p-(N·N-dimethylamino)- in place of p-(N·N-dimethylamino)aniline in Example 1
2-Methyl-4-(N·N-dimethylamino)phenyl isocyanate was produced in a yield of 80% by the same method as in Example 1 except for using θ-toluidine.
I got it from )

Claims (1)

[Scope of Claims] 1. The presence of an oxidizing agent and a urethanization catalyst comprising at least one type selected from palladium or a compound containing palladium, and at least one type selected from bromine, iodine, or a compound containing these. Below is the general formula [Formula] (where R' and R'' represent an aliphatic group, an alicyclic group, an aromatic group, or an araliphatic group, and each may be the same group. Y is an aliphatic group. and n is 0 or 1) is reacted with carbon monoxide and an organic hydroxyl compound to produce an N.N-disubstituted urethane compound. An N.N-dimeryl compound comprising producing an aminocarbanilate compound and then separately recovering the isocyanate and organic hydroxyl compound produced by thermally decomposing the carbanilate compound at a temperature of 100 to 350°C. Method for producing substituted aminophenyl isocyanate. 2. Patent for using at least one type selected from palladium or a compound containing palladium and at least one type selected from iodine or a compound containing iodine as a urethanization catalyst. The method according to claim 1. 3. The method according to claim 1, wherein the oxidizing agent is molecular oxygen or/and an organic nitro compound. 4. The method according to claim 1, wherein the oxidizing agent is molecular oxygen. The method according to claim 3. 5. The method according to claim 1, 2, 3 or 4, wherein the N·N-disubstituted aminoaniline is N·N-dialkylaminoaniline. Method. 6 N.N-dialkylaminoaniline is p-
The method according to claim 5, wherein (N.N-dialkylamino)aniline is used.