JPS58146548A - Preparation of urethane - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a preparation raw material of isocyanates, in high selectivity and yield, without using a metal chloride, by the catalytic reaction of a primary amine, etc. with CO and an organic hydroxyl compound in the presence of a specific catalyst system and an oxidizing agent. CONSTITUTION:A urethane is prepared by reacting a primary amine or secondary amine (e.g. NH3, methylamine, dimethylamine, dipropylamine, etc.) with CO and an organic hydroxyl compound (e.g. methanol, ethanol, phenol, etc.) in the presence of an oxidizing agent (e.g. molecular oxygen, organic nitro compound, etc.). The reaction is carried out in the presence of a catalyst selected from platinum group metals and compounds containing platinum group element (e.g. Pd, Rh, etc.) and a cocatalyst selected from Cl, Br and I. The cocatalyst promotes the activity of the main catalyst, and gives the objective compound almost quantitatively. The process is economical because a metallic solid platinum group compound can be used and the compound can be recovered easily.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing urethane, and more particularly, to oxidative carbonylation by reacting a primary amine or a secondary amine with carbon monoxide and an organic hydroxyl compound in the presence of an oxidizing agent. The present invention relates to a method for producing urethane by.

Urethanes are important compounds used in carbamate-based pesticides, and recently there has been a demand for an inexpensive method for producing them as raw materials for producing incyanates without using phosgene.

Conventionally, the following two methods have been mainly proposed as methods for producing urethane compounds using -glyzed carbon.

The first method is a method in which a nitro compound is reductively urethanized in the presence of an alcohol. For example, nitrobenzene is represented by the following formula.

(R represents an organic group) However, in this reaction, for 1 mole of nitrobenzene, 3 moles of -carbon oxide are required, of which 2
Moles of carbon monoxide become worthless carbon dioxide, so −
Carbon oxide has the disadvantage that only a small amount of it is used effectively, and in order to carry out this reaction continuously, carbon dioxide must be separated from the mixed gas of carbon oxide and carbon dioxide. This is also a drawback in industrial implementation.

The second method is a method in which a primary amine compound is reacted with carbon monoxide and alcohol in the presence of an oxidizing agent such as oxygen or an organic nitro compound to oxidatively form a urethane,
This method uses carbon monoxide more effectively than the above-mentioned methods, and can be said to be a more preferable method. However, Lewis acids such as copper chloride, iron chloride, iron oxychloride, sodium chloride, and vanadium oxychloride are used as cocatalysts, but these introduce chlorides of elements that can undergo redox reactions into the reaction system. Because it is necessary to dissolve it (JP-A-55-120551, JP-A-55-1)
24750), these dissolved chlorides are highly corrosive to metal materials such as reaction vessels, piping, pulp, etc., and this poses an equipment problem in that expensive metal materials must be used.

Furthermore, in the production of aromatic urethanes, complicated operations are required to separate and recover these dissolved chlorides from aromatic urethanes or high-boiling products such as diarylurea, which is a reaction by-product. In addition to being expensive, these cocatalysts are also susceptible to reoxidation in the reaction system, since the hydrogen chloride produced in the reduced state by the redox reaction becomes hydrochloride of unreacted amine. Since it does not completely return to the original chloride, and therefore some partially reduced chloride is present when recovered, these cocatalysts must also be re-prepared when the reaction is repeated. The disadvantage is that it does not.

In order to overcome these drawbacks, the present inventors have conducted intensive research on a method of oxidatively converting primary amines or secondary amines into urethanes, and as a result, we have found that Lewis, which is the main cause of these drawbacks, We have discovered a completely new catalyst system that allows the reaction to proceed catalytically without using acids or chlorides of elements that perform redox reactions, and based on this knowledge, we have completed the present invention.

In other words, the present invention reacts carbon monoxide and an organic hydroxyl compound with a primary amine or a secondary amine in the presence of an oxidizing agent! In producing urethane, (a) at least one selected from platinum group metals and compounds containing platinum group elements, and (b) at least one halogen selected from chlorine, bromine, and iodine. or (C) at least one selected from oxides and hydroxides of alkali metals and alkaline earth metals.
The present invention provides a method for producing urethane characterized by using a seeded catalyst system.

As described above, a major feature of the present invention is that at least one selected from platinum group metals and compounds containing platinum group elements is combined with at least one selected from chlorine, bromine, and iodine. A catalyst system, or at least one selected from platinum group metals and compounds containing platinum group elements, at least one selected from chlorine, bromine, and iodine, and oxidation of alkali metals and alkaline earth metals. By using a catalyst system which is a combination of at least one selected from hydroxides and hydroxides, by using this catalyst system, it is possible to achieve high selectivity from primary amines or secondary amines, and The reason is that urethane can be obtained in high yield.

This is a truly surprising fact that was completely unknown until now.
120551, Japanese Unexamined Patent Application Publication No. 124750/1983) and beards were completely unexpected. That is, in this prior art, a catalyst system in which a platinum group compound is used as a main catalyst and a chloride of an element that can undergo a redox reaction in a reaction system is used as a co-catalyst, such as palladium chloride as a typical example, is used. ferric chloride,
Alternatively, a catalyst system combining trivalent iron such as iron oxychloride is used. In such a system, divalent palladium participates in the reaction, and as the reaction progresses, it is reduced to zero-valent palladium, which is reoxidized by trivalent iron and returned to divalent palladium. At the same time, trivalent iron is reduced to divalent iron, and then this divalent iron is reoxidized by an oxidizing agent and returned to trivalent iron.
It is thought that the main product, urethane, is produced through a so-called Waraker reaction type catalytic cycle.

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 with such functions include [[
l a % Va An element that can undergo a redox reaction selected from the elements of group a and group ■b to group ■b, specifically copper, zinc, mercury, thallium, tin, titanium, and arsenic. Among them, only copper, vanadium, manganese and iron are mentioned in the examples. .

In contrast, the method of the present invention uses a compound selected from alkali metal and alkaline earth metal acid arsenides and hydroxides in combination with... The ions of alkali metals and alkaline earth metals, which are the metal components, cannot undergo a redox reaction under normal conditions. Therefore, it is presumed that the reaction of the present invention proceeds by a completely different reaction mechanism from the reactions described in the prior art.

What mechanism does the halogen or the combination of halogen and a compound selected from oxides and hydroxides of alkali metals and alkaline earth metals act in this reaction? Although unknown, when combined 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 amine compounds. That is,
When only a platinum group metal or a compound containing a platinum group element is used, under the conditions of this reaction, the urethanization reaction hardly progresses, or even if it does proceed, only a small amount of urethane is produced. When only platinum group elements are used, hardly any urethane can be obtained. For example, palladium is one of the effective catalyst components for this reaction, but the reaction hardly progresses if only palladium black, which is zero-valent metal palladium, is used alone. However, when a halogen, such as iodine, is added to this, the reaction proceeds catalytically, and when an alkali metal or alkaline earth metal oxide or hydroxide, such as cesium hydroxide, is added to this system, the reaction progresses almost quantitatively. urethane can be obtained.

In this way, in the method of the present invention, solid platinum group compounds in the metallic state can also be used as one of the catalyst components, and this means that expensive platinum group compounds can be removed from the reaction system by simple methods such as filtration. This shows that it can be separated and recovered by this method, which is industrially advantageous.

Furthermore, when a solid platinum group compound in a metallic state is used, if a Lewis acid such as ferric chloride used in the prior art coexists, the platinum group compound may be eluted into the solution by these acids. Another major feature of the present invention is that these platinum group compounds are not substantially eluted in the reaction system of the present invention.

Another major feature of the present invention is the use of oxides or hydroxides of halogens and alkali metals or alkaline earth metals. It can be easily recovered, and unlike conventionally used heavy metal chlorides, it does not mix into the product as a contaminant.

The platinum group metal and platinum group element-containing compound used in the method of the present invention may contain at least one component 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, liquid titania,
Titania, zirconia, barium sulfur, carbonate, asbestos, bentonite, diatomite, polymer, ion exchange resin, zeolite, molecular ＞
It may be supported on a carrier such as -F, Madanium silicate, Macnesia, 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 Those reduced with formaldehyde, alloys or intermetallic compounds containing these metals, etc. are used. Alloys or intermetallic compounds may also be between these platinum group metals and other elements such as selenium, tellurium, sulfur, antimony, bismuth, copper, silver, gold, zinc, tin, vanadium, iron. , cobalt, nickel, 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; and cyanides. ; Hydroxides; Oxides; Sulfides; Metal acid salts containing anions such as nitro groups, /ano groups, halogens, oxalate ions, and ammonia, amines, phosphines, -carbon oxide chelate ligands Metal complex compounds such as salts or complexes containing the like; organometallic compounds having an organic ligand or an organic group, and the like.

Among these catalyst components, those containing palladium or rhodium or both are particularly preferred, such as P(l black; Pd-C, Pd-Al).
2O3, Pd-8i02, Pd-TiO2, Pd-Zr
Supported palladium catalysts such as O2, Pd-BaSO4, Pd-CaCO3, Pd-asbestos, Pd-zeolite, Pd-molecular sheep: Pd-Pb.

Pd-8e, Pd-Ts, Pa-Hg,
Pd-Tl, Pd-P.

Pd-Cu, Pd-Ag, Pd-Fe,
Pd-Co, Pd-Ni.

Alloys such as Pd-Rh or intermetallic It compounds; and those in which these alloys or intermetallic compounds are supported on the above-mentioned carriers: PdO12, PdBr2, Pd-2, pa(
No. 5) Inorganic salts such as 2, Pd5Oa; Pd (
QC! OCH3) 2, organic acid salts such as palladium oxalate: Pd(ON)2: PdO: PdS:
Palladate salts represented by M2[PdXa,], M2[PdX6] (M represents an alkali metal, ammonium ion, nitro group, or cyan group, and X represents a halogen); [Pd(NH3)4]X2, [Pd(en)
2] Ammine complexes of palladium such as X2 (X has the same meaning as above and represents ethylenediamine); PdCl2 (Ph0N) 2, PdCl
2(PRs)2, pa(co)(pa3)Pd(PPh
3) A, Pd01(R)(PPJ)2, Pd(C2
H4) (PPh3)2, complex compounds or organometallic compounds such as Pd(C3H5)2 (R represents an organic group):
Complex compounds coordinated with chelate ligands such as Pd(acac)2; Rh black; supported rhodium catalysts similar to Pd; Rh alloys or intermetallic compound hydrates similar to Pd;
RhBr3 and hydrate, Rhl3 and hydrate, Rh2
(804) 5 and inorganic salts such as hydrates; Rh2(
OCOCH3)a; Rh20M, Rha2: M
5 [RhX6J and hydrate (M, X have the same meanings as above); [Rh(Na3)s]Xx, [Rh(en)s
) X3 and other ammine complexes of rhodium: Rha
Rhodium carbonyl clusters such as (Go)12, Rh6(CO)16: (Rhal(co)2:12, R
hal5 (PH1)s, RhC! 1 (PPJ)
5, RhX(Co)L2 (X has the same meaning as above,
L is a ligand derived from an organic phosphorus compound and an organic arsenic compound), a complex compound such as RhH(co)(ppb4)x, or an organic metal compound.

31 In the present invention, these platinum group metals or compounds containing platinum group elements may be used alone or in a mixture of two or more, and there is no particular restriction on the amount used. Generally, it is desirable that the amount of the component containing the platinum group element is in the range of 0,000 to 50 moles based on the amine.

The oxides and hydroxides of alkali metals and alkaline earth metals used in the present invention include, for example, lithium oxide, lithium peroxide, monoarsenic acid, sodium peroxide, sodium superoxide, potassium oxide, potassium peroxide, Dipotassium trioxide, potassium superoxide, rubidium oxide, rubidium peroxide, dirubidium trioxide, rubidium superoxide, ruby/ium ozonide, cesium oxide, cesium peroxide,
oxides of alkali metals, such as dicesium trioxide, cesium superoxide, and cenium ozonide; beryllium oxide,
Alkaline earth metal oxides such as magnesium oxide, calcium oxide, calcium peroxide, strontium oxide, strontium peroxide, barium oxide, barium peroxide; lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, Examples include cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.

These oxides or hydroxides may be used alone or in combination of two or more. Further, as for the halogen, only one type of chlorine, bromine, and iodine may be used, or two or more types may be used as a mixture. Among the halogens, bromine and iodine are preferred, with iodine being particularly preferred.

There are no particular limitations on the amount of halogen and alkali metal or alkaline earth metal oxides or hydroxides used in the present invention, but the amount of halogen and alkali metal or alkaline earth metal oxide or hydroxide is not particularly limited. Usually o for the amount of
It is preferable to use the oxide or hydroxide of an alkali metal or alkaline earth metal in an amount of 0.01 to 10,000 times the halogen.
It is preferable to use it in a range of 1.000 to 1.000 times the mole.

The primary amine or secondary amine used as a raw material in the present invention refers to at least 1 amine group in one molecule as represented by the following formula %.
A compound that contains Here, one or two lines bonded to the nitrogen atom represent a bond between the nitrogen atom and another atom or group, and examples of such atoms or groups include hydrogen, halogen, alkali metal, and hydroxyl group. , amine group, aliphatic group, alicyclic group, aromatic group, araliphatic group, heterocyclic group, etc. In secondary amines, the nitrogen atom itself may be an element constituting a ring, such as in virol, piperidine, piperazine, morpholine, and the like.

Examples of such scale-grade amines include ammonia,
Aliphatic primary monoamines such as methylamine, ethylamine, propylamine (each isomer), butylamine (each isomer), pentylamine (each isomer), hexylamine (each isomer), dotesylamine (each isomer) Classes: Ethylenediamine, diaminopropane (each isomer), diaminobutane (each isomer), diaminopentane (each isomer),
Aliphatic-primary diamyl compounds such as diaminohexane (each isomer), cyami□notecan (each isomer); 1.2゜3
- Aliphatic primary triamines such as triaminopropane, triaminohexane (each isomer), triaminononane (each isomer), triaminododecane (each isomer); cyclopropylamine, cyclobutylamine, cyclopentylamine , cyclohexylamine, diaminocyclobutane, diaminocyclohexane (each isomer), triaminocyclohexane (each isomer), alicyclic primary mono- and polyamines, benzylamine, di(aminomethyl)-
Benzene (each isomer), aminomethylpyridine (each isomer), di(aminomethyl)-pyridine (1 isomer of each isomer)
, aminomethylnaphthalene (each isomer), di(aminomethyl)-naphthalene (each isomer), etc., aromatic aliphatic primary mono- and polyamines; aminofuran (each isomer),
Heterocyclic primary amines such as aminotetrahydrofuran (all isomers), aminothiophene (all isomers), aminovirol (all isomers), and aminopyrrolidine (all isomers) are preferably used.

Examples of aromatic primary amines include aniline, diaminobenzene (isomers), triaminobenzene (isomers), tetraaminobenzene (isomers), aminetoluene (isomers), and diaminotoluene (isomers). each isomer)
, aminopyridine (each isomer), diaminopyridine (each isomer), triaminopyridine (each isomer), aminonaphthalene (each isomer), diaminonaphthalene (each isomer), triaminonaphthalene (each isomer) , tetraaminonaphthalene (isomers), and monoamine, diamine, triamine, and tetraamine isomers of the diphenyl compound represented by the following general formula (i).

(In the formula, A is a simple chemical bond, -〇-, -S-.

-5o2-, -co-, -coNH-, -coo-.

Represents a divalent group selected from -C(R1)(R2)- and -N(R')-. In addition, in these aromatic primary amines, at least one hydrogen on the aromatic ring is substituted with another substituent, such as a halogen atom or a nitro group. , 77 groups, alkyl groups, alicyclic groups, aromatic groups, aralkyl groups, alkoxy groups, sulfoxide groups, sulfone groups, carbonyl groups, ester groups, amide groups, and the like.

Among these aromatic amine compounds, particularly preferred are aniline, 2,4- and 2,6-diaminotoluene, chloroaniline (each isomer), dichloroaniline (each isomer), 4,4'- and They are 2,4'-diaminodiphenylmethane and 1,5-diaminonaphthalene.

In addition, examples of secondary amines include dimethylamine,
dibutylamine, dipropylamine, dibutylamine,
Aliphatic secondary amines such as dibentylamine, dibutylamine, ethylmethylamine, ethylhexylamine, butylmethylamine, and ethylhexylamine Alicyclic secondary amines such as dicyclopropylamine, dicyclohexylamine, and methylcyclohexylamine Classes; N-methylaniline, N-ethylaniline, N-) lutoluidine (each isomer), diphenylamine, N,N'-diphenylmethanediamine, N,N'-dimethylphenylenediamine (each isomer), N- Aromatic secondary amines such as methylnaphthylamine (each isomer), dinaphthylamine (each isomer); Aroaliphatic secondary amines such as diben/luamine, ethylbenzylamine, dinaphthylamine; dinaphthylamine, dithio Secondary amines such as phenylamine; pyrrolidine, virol, 3-pyrrolidone, indole, carbazole, piperidine, piperazine, β-piperidone, γ-piperidone, imidazole, pyrazole, triazole, benzimidazole, morpholine, 1 , 3-oxylidine and other cyclic secondary amines are preferably used.

Furthermore, in these primary amines and secondary amines, one or more hydrogen atoms in the organic group bonded to nitrogen may be substituted with other substituents, such as lower aliphatic groups, amino groups, carboxyl groups, ester groups, alkoxy groups, cyano groups, etc. It may be IN-substituted with a halogenitro group, a urethane group, a sulfoaromatic group, an araliphatic group, or the like. Furthermore, these primary amines and secondary amines may have an unsaturated bond.In addition, the above-mentioned amino group is directly bonded to an organic group having a nitrogen atom through N-N. It may also be a hydrazine type compound 0 Also, a compound having an amine group and a hydroxyl group in the molecule, such as ethanolamine, globanolamine, 0-
Aminobenzyl alcohol can also be used in the main reaction, and in such cases, a concessionary urethane can be produced.

One or more of these primary amines and secondary amines may be used.

The organic hydroxyl compound used in the present invention is a monohydric or polyhydric alcohol, or a -hydric or polyhydric phenol, and such alcohols include, for example, linear or Examples include branched monovalent or polyvalent alkanols and alkenols, -valent or polyvalent cycloalkanols, cycloalkanols, and aralkyl alcohols. Furthermore, these alcohols may contain other substituents, such as a rogen atom, a cyano group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, and the like.

Specific examples of such alcohols include methanol,
Ethanol, glopanol (each isomer), butanol (
each isomer), pentanol (each isomer), hexanol (each isomer), hexanol (each isomer), octatool (each isomer), nonyl alcohol (each Xt1 unit)
, f sol alcohol (each isomer), undecyl alcohol (each isomer), lauryl alcohol (each isomer), tridecyl alcohol (each isomer), tetradecyl alcohol (each isomer), pentadenyl alcohol ( Aliphatic alcohols such as each 14-mer) = 7 clohexanol,
7-chloroalkanols such as cycloheptatool; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, JETEL monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Alkylene glycol monoethers such as propylene glycol 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 are used.

Examples of phenols include phenol, various alkylphenols, and various alkoxyphenols/L/%
Each t#z rogogenated phephenol hydroxybenzene,
4.4'-dihydroxy-diphenylmethane, bisphenol-A1 hydroxynaphthalene, etc. are used.

As the oxidizing agent used in the present invention, conventional oxidizing agents can be used, but preferred are molecular oxygen, organic nitro compounds, or mixtures thereof. Particularly preferred is molecular oxygen.

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 oxide, hydrocarbons, and halogenated hydrocarbons.

Further, the organic nitro compound may be any of alicyclic, aliphatic, and aromatic nitro compounds. Examples of alicyclic nitro compounds include nitrocyclobutane, nitrocyclopentane, nitrocyclohexane, dinitrocyclohexane (container aK), and bis-cyclohexyl)-methane; examples of aliphatic nitro compounds include nitromethane, Nitroethane, nitropronoζ
(each isomer), nitrobutane (each isomer), nitropentane (each isomer), nitrohexane (each isomer), nitrodeca/ (each isomer), 1,2-dinitroethane, dinitroethane ( each isomer), dinitrobutane (each isomer), dinitropentane (each isomer), dinitrohexane (each isomer), dinitrodecane (each isomer), phenylnitromethane 1 bis-(nitromethyl)-cyclohexane, bis- Examples of aromatic nitro compounds include nitrobenzene, dinitrobenzene (each isomer), nitrotoluene (each isomer), dinitrotoluene (each isomer), nitropyridine (each isomer), and dinitrobenzene. Examples include pyridine (each isomer)% nitronaphthalene (each isomer), dinitronaphthalene (each isomer), and isomers of the mononitro compound and dinitro compound of the diphenyl compound represented by the general formula (I).

In addition, in these nitro compounds, at least one hydrogen is substituted with another substituent, such as a nitrogen atom, an amino group, a cyano group, an alkyl group, an alicyclic group, an aromatic group, an aralkyl group, an alkoxy group, or a sulfoxide group. group, sulfone group,
It may be substituted with a carbonyl group, an ester group, an amide group, etc. In the present invention, when the oxidizing agent is molecular oxygen, for example, the urethanization reaction of a primary amine is carried out according to the following general reaction formula. Proceeding OR' (NH2)n+0.5n-02+n-Co+n
-ROH→ R' (NHCOOR)n+ n-H2O
(Here, R' and R represent organic groups, and n represents the number of amine groups in one molecule of the amino compound.) The molecular oxygen may be less than or more than the equivalent amount, but
Oxygen/carbon oxide or oxygen/organic hydroxyl compound mixtures 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 and becomes urethane, so if the structure is different from the amino compound used, a urethane compound corresponding to each structure can be obtained. It goes without saying that if both structures are the same, the same urethane compound can be obtained.In this case, the urethanization reaction, for example, the reaction of a primary amine, proceeds according to the following reaction formula.

2R' (NH2)n+ R'' (NO2)n+ 3n
-co +3n-ROH→2R' (NHCOOR)n
10R"(NHCooR)n+ 2n HH-(R', R
, n have the same meanings as above, and R" represents a residue other than the nitro group of the organic nitro compound.) When only the organic nitro compound is used as an oxidizing agent, the organic nitro The quantitative ratio of the compounds is preferably such that 1 mole of dinitro group per 2 moles of amine group, but of course it may be carried out at a value deviating from this stoichiometric ratio.In general, the ratio of amino group to nitro group is Equivalent ratio is 1.1:1 to 4:11 preferably 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.

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, and mesitylene; chlorobenzene, dichlorobenzene, trichlorobenzene,
Halogenated aromatic hydrocarbons such as fluorobenzene, chlorotoluene, chlornaphthalene, and bromnaphthalene; halogenated aliphatic hydrocarbons or halogens such as chlorhexane, chlorocyclohexane, trichlorotrifluoroethane, saltwater methylene, and carbon tetrachloride; Polycyclic alicyclic hydrocarbons; Nitriles such as acetonitrile and benzonitrile; Sulfones such as sulfolane, methylsulfolane, dime, and thylsulfolane; Tetrahydrofuran, 1,
Ethers such as 4-dioxane and 1,2-dimethoxyethane; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate and ethyl benzoate; N,
N-dimethylformamide % Amides such as NJJ-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, and the like can be mentioned.

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.

Suitable examples of such additives include zeolites, salts of nitrogen-containing compounds and hydrogen halides, and onium halide compounds.

In the method of the present invention, the reaction is usually carried out at a temperature range of 80 to 300°C, preferably 120 to 220°C.

In addition, the reaction pressure is 5 to 500 Kf/, d, preferably 2
The reaction time ranges from 0 to 3 ooKp/ffl, 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 1 740 mmol of anili, 40 ml of ethanol, 0.519 atoms of palladium black, 1 ml of iodine, 1 ml of TI01, and 1 mmol of rubidium hydroxide were placed in a stirring autoclave with an internal volume of 140 ml, and after replacing the inside of the system with carbon monoxide, -carbon oxide was added. 8 odor/ct/l - Then 6~/Ca of oxygen was injected to make the total pressure 86 kg/i. After incubating the reaction mixture at 160°C for 1 hour with stirring, the reaction mixture was filtered and the filtrate was analyzed. The reaction rate of aniline was 85%, and the yield of ethyl N-phenylcarbamate was 82%.
%, the selectivity was 97%. Note that palladium was not detected in the solution.

Examples 2 to 1゜In place of rubidium hydroxide in Example 1, hydroxides or oxides of various alkali metals and alkaline earths (
The reaction was carried out in exactly the same manner as in Example, except that 1 mmol) was used. As a halogen, iodine (1 mmol
) was used. The results are shown in Table 16 Table 1 Comparative Example 1 The same reaction as in Example 1 was carried out using only palladium black without using iodine and rubidium hydroxide.As a result, the reaction rate of aniline was 8%. Ethyl sN-phenylcarbamate was produced with a yield of only 1.9%.

Example 11 The same reaction as in Example 1 was carried out using 40 mmol of aniline, 40 mmol of ethanol, 0.5 μatom of radium black, and 2 mmol of iodine. As a result, the reaction rate of aniline was 42% and N-phenylcarbamine The yield of ethyl acid was 28% and the selectivity was 67%.

Example 12 As a result of adding 1 mmol of potassium hydroxide to the system of Example 11 and conducting a reaction exactly the same as in Example 11, aniso/
The reaction rate was 90%, the yield of ethyl N-phenylcarbamate was 86%, and the selectivity was 96%.

Example 13 The same reaction as in Example 11 was carried out except that 1 mmol of bromine was used instead of iodine in Example 11. The reaction rate of aniline was 38% and the yield of ethyl N-phenylcarbamate was was 21% and the selectivity was 55%.

Example 14 1 mmol of rubidium hydroxide was added to the system of Example 13 and the reaction was carried out in exactly the same manner as in Example 13. As a result, the reaction rate of aniline was 68% and the yield of ethyl N-phenylcarbamate was 60%. The selectivity was 88%.0 Example 15 The reaction was exactly the same as in Example 1, except that an ethanol solution of chlorine (containing about 1 ml of chlorine) was used instead of iodine in Example 1. As a result, the reaction rate of aniline was 55%, the yield of ethyl N-phenylcarbamate was 39%, and the selectivity was 71%. Example 16 Cyclohexylamine 40 mmol, methanol 5
0-, palladium black 0.51q atOm s As a result of carrying out the same reaction as in Example 1 using 1 mmol of iodine and 1 mmol of potassium hydroxide, the reaction rate of cyclohexylamine was 88%, and the reaction rate of methyl N-cyclohexylcarbamate was 88%. The yield was 83% and the selectivity was 94%.

Example 17 The same reaction as in Example 1 was carried out using 40 mmol of benzylamine, 40 mmol of ethanol, 111 Iyatom of palladium black, 1 mmol of iodine, and 1 mmol of sodium hydroxide. As a result, the reaction rate of benzylamine was 87%,
The yield of N-benzylcarbamic acid was 79% and the selectivity was 91%.

Example 18 Di(n-butyl)amine 30 mmol, methanol 4
0m7! , palladium black 0.5119 atOms iodine 1 m m 01 s cesium hydroxide] As a result of performing the same reaction as in Example 1 using mmol, the reaction rate of di(n-butyl)amine was 70%, N, N'- The yield of methyl di(n-butyl)carbamate was 56% and the selectivity was 8.
It was 0%.

Example 19 Internal volume 200mj! Aniline 30 mn1o1b nitrobenzene 15 mmo in a stirring autoclave
l, methanol 50-1 palladium chloride 0.5 mmol
, 3 mmol of iodine, 3 mmol of hirubigilum hydroxide
After replacing the inside of the system with carbon monoxide, -carbon oxide was injected at 12 oKy/cr/. 180 while stirring
The reaction was carried out at ℃ for 5 hours. As a result of analyzing the reaction solution, the reaction rates of aniline and nitrobenzene were 20% and 28%, respectively, and methyl N-phenylcarbamate was
1 was generated.

Examples 20 to 27 Reactions were carried out in exactly the same manner as in Example 1, 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.

Table 2 In these examples, platinum group metal or platinum group compound uses -0,5rIIgatom as the metal element.

The % display indicates the weight % of the supported catalyst component.

pa-TClo is produced by co-supporting palladium chloride and tellurium dioxide on activated carbon at a molar ratio of 1O to 3.
It is hydrogen-reduced at ℃.

In an autoclave with an internal volume of 300 m, 30 mmol of 2,4-diaminotoluev,
s Palladium black 1 atom% iodine 2 mmol
, rubidium hydroxide (2 mmo, 1) were introduced into the system, and the inside of the system was replaced with carbon monoxide. After that, -carbon oxide was injected into the system at a rate of 9/i to 100, and then 7 kg/i of oxygen was injected under pressure. 160 while stirring
After reacting at ℃ for 1 hour, the reaction mixture was filtered and the filtrate was analyzed. As a result, the reaction rate of 2,4-diaminotoluene was 8.
9% tolylene-2,4-dicarbami/diethyl acid in 74% yield and also in mixture with ethyl-3-amino-4-methylcarbanilate-doethyl-2-methyl-5-aminocarbanilate. Ruru amino monourethane yield 1
It was found that it was generated at 2%. The total selectivity in urethanization was 97%.

Example 29 n-octylamine 40 mmol, ethanol 407!
As a result of carrying out the same reaction as in Example 1 using 0.5 mmol of rhodium iodide and 1 mmol of iodine, the reaction rate of n-octylamine was 53% and the yield of ethyl N-n-octylcarbamate was 34%. The selectivity was 65%.

Example 30 Cyclohexylamine 40mm 01% Ruthenium black 0
．． 5■atOms Chlorine methanol solution (approx. 1mm
As a result of carrying out the same reaction as in Example 1 using 40- (containing chlorine of 01), the reaction rate of 7 chlorhexylamine was 34
%, the yield of N-cyclohexylcarno(methyl mate) was 17% and the selectivity was 50%.

Example 31 7-? -lj y 30 mmo: 1% nitrobenzene 15 mm 01 m ethanol 50-, potassium tetrapromonoradiate 0.5 mmol, iodine 1 mm
As a result of carrying out the reaction in the same manner as in Example 19 using ol, the reaction rate of aniline and nitrobenzene was 14%, respectively.
19% and 1 mm of N-phenylcarbaminated ethyl
It was producing ol.

Claims (1)

[Claims] ■ A method for producing urethane by reacting a primary amine or a secondary amine with -m carbon and an organic hydroxyl compound in the presence of an oxidizing agent, comprising (al) a platinum group metal and a platinum group metal; A method for producing urethane, characterized by using a catalyst system comprising at least one kind selected from compounds containing elements and (1) at least one kind of halogen selected from chlorine, bromine and iodine. 2. The method according to claim 1, wherein the oxidizing agent is molecular chlorine, an organic nidro compound, or both. 3. The method according to claim 2, wherein the oxidizing agent is molecular oxygen. The method according to claim 1, 2 or 3, wherein the platinum group metal and the compound containing the platinum group element are palladium, rhodium, a palladium compound and a rhodium compound. 5. A patent in which the halogen is bromine or iodine. 6. The method according to claim 1, 2, 3 or 4. 6. The method according to claim 5, wherein the halogen is iodine. 7. The amine is an aromatic primary amine. The method according to claim 1, 2, 3, 4, 5 or 6. 8. Monoxidizing a primary amine or a secondary amine in the presence of an oxidizing agent. In a method for producing urethane by reacting carbon and an organic hydroxyl compound, (a) at least one selected from platinum group metals and compounds containing platinum group elements; and (1) chlorine, bromine, and iodine. (c) at least one halogen selected from the group consisting of oxides of alkali metals and alkaline earth metals and hydroxides; Urethane manufacturing method. 9. The method according to claim 8, wherein the 9r11-forming agent is molecular oxygen, an organic nitro compound, or both. 10. The method according to claim 9, wherein the oxidizing agent is molecular oxygen. 11. The method according to claims 8 to 10, wherein the platinum group metal and the compound containing the platinum group element are palladium, rhodium, a palladium compound, and a rhodium compound. 12. The method according to claim 8, 9, 10 or 11, wherein the halogen is bromine or iodine. 13. The method according to claim 12, wherein the halogen is iodine. 14. The method according to claim 8, 9, 10, 11, 12 or 13, wherein the amine is an aromatic primary amine.