JPS58126855A - Preparation of aromatic urethane compound - Google Patents

Abstract

PURPOSE:To obtain industrially advantageously the titled compound useful as a carbamate-based agricultural chemical, by reacting an aromatic urea compound with carbon monoxide and an organic hydroxyl compound in the presence of an oxidizing agent using a specific catalytic system. CONSTITUTION:In preparing an aromatic urethane by reacting an aromatic urea compound (e.g., N,N'-diphenylurea) with carbon monoxide and an organic hydroxyl compound (e.g., mono- or polyhydric alcohol) in the presence of an oxidizing agent[e.g., molecular oxygen, organic nitro compound (e.g., nitrocyclobutane)], at least one selected from platinum group metals and platinum group metal- containing compounds (e.g., Pb-C) and at least one selected from salts of nitrogen-containing compounds shown by the formulasIan dII (X is halogen) with hydrogen halides and quaternary ammonium halides (e.g., tetramethylammonium halides) are used as a catalytic system.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aromatic urethanes. More specifically, the present invention relates to a method for producing an aromatic urethane by reacting an aromatic urea compound with carbon monoxide and an organic hydroxyl compound in the presence of an oxidizing agent to oxidatively carbonylate it.

Aromatic urethanes are important compounds used in carbamate pesticides, etc., and recently there has been a demand for an inexpensive method for producing them as raw materials for producing aromatic isocyanates that do not use phosgene.

A method for producing such an aromatic urethane using carbon monoxide is an aromatic nitro compound.

Aromatic nitroso compounds, aromatic azo compounds, aromatic-f
A method of reductively urethanizing an aromatic amine compound in the absence of any oxidizing agent such as a chlorine compound, and a method of reductively urethanizing an aromatic amine compound are known.

Furthermore, a method of converting N+N'-diaryl urea into urethane by total oxidation has been proposed (% opening/closing 55-120552
Publication No.). In this method, Group Ⅰ precious metals or their compounds are used as the main catalyst, copper chloride, iron chloride, iron oxychloride, vanadium chloride, vanadium oxychloride, etc. are used as co-catalysts, and the entire redox reaction can be carried out in the reaction system. It is necessary to dissolve the chloride containing the metal in the reaction system.

However, these dissolved metal chlorides are highly corrosive to metal materials such as reaction vessels, fittings, and pulp.
For this reason, there is an equipment problem in that expensive metal materials must be used. Furthermore, in order to separate and recover these dissolved metal chlorides from high boiling point materials such as aromatic urethane, there is a drawback that complicated operations and large costs are incurred.

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

That is, the present invention provides a method for producing an aromatic urethane by reacting an aromatic urea compound with t-m carbon and an organic hydroxyl compound in the presence of an oxidizing agent, the method comprising: (a) a platinum group metal and a compound containing a platinum group element; and (b) at least one kind selected from salts of nitrogen-containing compounds and hydrogen halides, quaternary ammonium halides, or compounds that can be produced in all of these reaction systems. An object of the present invention is to provide a method for producing an aromatic urethane, which is characterized by using a catalyst system consisting of the following.

As described above, the major features of the present invention are essentially platinum, at least one selected from platinum group metals and platinum group element-containing compounds, a nitrogen-containing compound, a hydrogen halide, and a quaternary ammonium halide. By using this catalyst system, aromatic urethane can be obtained with high selectivity and yield from aromatic urea compounds.

These facts are completely unknown until now and are truly surprising.
This was completely unexpected from the publication (No. 552).

That is, in the prior art, a catalytic thread is used in which a platinum group compound is used as a main catalyst and a chloride of an element capable of carrying out a redox reaction is used as a co-catalyst in the reaction thread. He is a combination of palladium chloride and iron oxychloride. In such threads, divalent palladium is involved in the reaction, and as the reaction progresses, it is reduced to zero-valent palladium, which is reoxidized by trivalent iron oxychloride to form divalent ζradium. At the same time as the iron returns to It is thought that a certain aromatic urethane is provided.

As described above, it has been shown that in the prior art method, a chloride of an element having a redox action is essential as a reoxidizing agent for the main catalyst in the reaction system.

Elements with such functions include Ia-V in the periodic table.
This is a book that can undergo redox reactions selected from the elements of Group A and Groups 1b to 1b, specifically copper, zinc, mercury, thallium, tin, titanium, arsenic,
Antimony, bismuth, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, and nickel are listed, among which only copper, vanadium, manganese, molybdenum, tungsten, and antimony iron are mentioned in the examples. Not too K.

On the other hand, the method of the present invention uses a salt of a nitrogen-containing compound and a hydrogen halide, or a quaternary ammonium halide, or a compound capable of producing these in a reaction thread, and these compound barrels are It does not contain any metal components, and of course the cation S cannot undergo a redox reaction under normal reaction conditions.

It can be concluded that the reaction of the present invention proceeds with a completely different reaction pattern than the reactions described in the prior art.

Of course, in the case of redox reaction (JP-A-55-120
552), tertiary amine hydrochloride, or chloride such as *rs salt of amine having the same aromatic group 1Et as the aromatic urea compound used in dioxidation, but this is only for redox purposes. Chlorine ions are necessary to make the metal (ti) active, and its effect is manifested when combined with these metal compounds.

Therefore, it is natural that the effect of the amine hydrochloride when VC, the redox metal #I, is not used as in the method of the present invention was not predicted at all. Much less,
Nothing is known about the special young fruits of quaternary ammonium halides or quaternary ammonium halides which are sometimes preferably used in the present invention. There wasn't.

Although it is unclear what mechanism the quaternary ammonium salt or quaternary ammonium salt or quaternary ammonium salt used in the method of the present invention acts on platinum group metals, It is clear that when combined with a compound containing a platinum group element, it plays an important role as a catalyst component in the oxidative urethanization reaction of an aromatic urea compound.

That is, the unreacted aromatic urethane-forming reaction does not proceed at all with a nitrogen-containing compound and a salt of 7-rogeno-1 dihydrogen or a quaternary ammonium halide alone.

Under the conditions of this reaction, the aromatic urethane-forming reaction hardly progresses even if only the platinum group metal or platinum group element "A" functional compound is present, or even if it does proceed, a small amount of aromatic urethane is produced. If only metal-state platinum group elements are used in the material, aromatic urethane will hardly be obtained.For example, vanadium is one of the non-reactive catalyst components, but 0 Vanadium black, which is a valent metal vanadium, alone does not make much progress in terms of nonreaction, but
When a salt of amide/hydrogenide or a quaternary ammonium halide, such as sulfur tetramethylammonium, is added to this, aromatic urethane can be obtained almost quantitatively.

As described above, in the method of the present invention, a solid platinum group compound in a metallic state can also be used as one of the catalyst components. This means that the separation of flat platinum group compounds from anti-LC)
This shows that recovery can be carried out by a simple method such as filtration, which is industrially advantageous.

Another major feature of the present invention is the use of a salt of a nitrogen-containing compound and hydrogen chloride or a quaternary ammonium chloride, and 1m of these compounds is mostly water-soluble. Therefore, it can be easily separated and recovered from the product, and unlike the conventionally used heavy metal chlorides, it does not mix into the product as contamination.

The platinum group metal and platinum group element-containing compound barrel used in the present invention refers to at least 1 m of platinum group elements selected from platinum group elements such as radium, rhodium, platinum, ruthenium, iridium, and osmium. ,
These elements are in a metallic state or are components forming a compound. In addition, these catalyst components include activated carbon, graphite, silica, alumina, silica-alumina, silica-titania, titania, zirconia, barium sulfate, calcium carbonate, asbestos, bentonite, diatomite, polymer, ion exchange resin, zeolite, Molecular sieve, magnesium silicate,
Preferably, it is supported on a carrier such as magnesia.

Examples of platinum group elements in the metallic state include metals such as sodium, rhodium, platinum, ruthenium, iridium, and osmium, these metal islands, and catalytic components containing these metal ions supported on a carrier as described in 1 above. Afterwards, those subjected to reduction treatment with hydrogen or formaldehyde, and their alloys or intermetallic compounds containing gold are used.

In addition, alloys or intermetallic compounds may be of these platinum group metals, or may be of other elements such as seleno, tellurium, sulfur, antimony, bismuth, steel, button, gold, lead, tin, vanadium. , iron, cobalt, nickel,
It may be rich in mercury, lead, thallium, chromium, (nybdenum, tungsten, etc.).

- Compounds rich in platinum group elements include, for example, unscrupulous salts such as chlorine/chemical salts, sulfur clk salts, nitrates, phosphates, and porcelain; Organic acid salts; 7-anides; hydroxides; oxides; sulfides; nitro group, cyano group,...Rogge/, anion such as soylic acid ion Kanakuram W Im acid m and ammonia, amine Complex compounds of metals, such as mounds or @ rods, which refer to groups, phosphine rivers, -carbon oxides, L/-) ligands, etc.; organometallic compounds having organic ligands or arrogant groups, etc. .

Among these catalyst components, palladium or ronrum or both are particularly preferred, such as palladium black; Pd 0%P.
d Al2O5, Pd-8i02, PdTi0t, P
d-Zr0□, Pd-BaSO4, Pd-0aOU3
, Pd-asbestos.

Supported palladium catalysts such as pd-zeolite, Pd-molecular sheep: pd-pb, Pd-8e, Pd
-Te, Pd-Hg%Pd-Tl, Pd-P,
Pd-Ou, Pd-Ag.

PdFe, Pd-0o%Pd-Ni%Pd-Rh
Alloys or intermetallic compounds such as; and these alloys or intermetallic compounds supported on the above-mentioned supports; Pd
011+PdBr, l Pd I, l Pd (N
O, )xl Inorganic salts such as Pd804; Pd (OO
OOH8), organic acid salts such as palladium oxalate;
Pd(ON); PdO; Pd8; M, (
Palladate salts represented by PdX), νu, (pdx,) (M represents an alkali metal, ammonium ion, nitro group, cyanAk, and X represents a halogen.)
; (Pd(NHs)t)Xtt(pd(on)Jx
Ammine complexes of palladium such as t (XFi has the same meaning as above, end ethylenediamine Th)
; Pd0I, (PbON), t Pd01. (Pf
'L:)t *pc+(oo)(p bow)s t P d
(P P b 3)4νpdo+(Rs(PPhs)
t'Pd (O1H4XPPbs) ttsuP d (03
Complex compounds or organometallic compounds such as Hs)t (R1 represents an alkyl or aryl group 1) *Pd
Complex compound steels coordinated with chelate ligands such as (acac); rhodium black; compatible rhodium catalysts similar to Pd; l'Lb alloys similar to pd or all 1! b 1 (hol, and hydrate, I'LbBr, and hydrate,
Inorganic clays such as Rh, (SO4)n and hydrates: Rh
2(ocooH,), ;leh201lehO,: M3
(fthX,) and hydration @ (M + X has the same characteristics as above);
Ammine complexes of rhodium such as ()Lh(en)3)xl HRh+(00)t2 + R11@(Co)1
Rhodium carbonyl clusters such as 6: 1, 1th
Cl (C0)Jz t Rh OIs()'R',
)3r Rh 01”(PP bs)sνhhx(D(
J) R2 (all have the same meaning as Xr'i deletion, L is organic) Compound 4N: A ligand consisting of J& and an organic arsenic compound6) Complex with RhH(CO)(PPhx)s Compounds or organometallic compounds are discussed.

These platinum group metals or platinum group element-containing compounds can be used alone or in combination of two or more.

Also used in the present invention is a compound having a group represented by the general formula (1), the IQ of a nitrogen compound and a hydrogen hydride, and a quaternary ammonium compound. . Here, the - of 3 or 4 consecutively connected to N represents the bond between the nitrogen atom and another atom or group, and X is the same as above and Fν
0hBrtI.

In the formula (+), examples of atoms or groups bonded to nitrogen include hydrogen, alkali metal llI4 atoms, hydroxyl group, aliphatic group, alicyclic group, aromatic group, araliphatic group, heterocyclic group, etc. . Further, in formula (1), nitrogen itself may be a capital constituting a ring, as in, for example, piperidine, viridi/quinoline.

Further, it may be a hydrogen salt or a quaternary ammonium salt of a nitrogen-rich compound in which two or more groups represented by formula (1) are present in the molecule.

In the salt of a nitrogen-containing compound and a hydrogen chloride used in the present invention and the quaternary ammonium ride, the reaction of a corresponding nitrogen-containing compound with a nitrogen-containing compound and a hydrogen hydride; It can be easily obtained by reaction with an alkyl compound or a hyaryl compound.

Examples of nitrogen-containing compounds that can be formed in a salt or quaternary ammonium halide association with hydrogen halides, alkyl halides, or aryl halides include ammonia; primary amines; Amine compounds such as tertiary amines; hydroxyl/luamines; hydrazines;
These include hydrazones; amino acids; oxidants, imidoesters, amides, and continuous nitrogen heterocyclic compounds.

In addition, these secondary amines, tertiary amines, and quaternary ammonium halides include symmetrical amines and symmetrical ammonium halides in which the groups bonded to nitrogen are the same, or symmetrical ammonium halides in which the groups bonded to nitrogen are 1-. It may also be a mixed amine and a mixed ammonium...ride.

Preferred hydrogen halide salts of nitrogen compounds include salts of ammonia such as ammonium chloride, ammonium bromide, and monomonium iodide; salts of amines having the same aromatic group as the aromatic urea compound used as the raw material of the present invention. Salts of aromatic amines such as diphenylamine and triphenylamine: methylamine, ethylamine, globylamine, butylamine, hexylamine, octylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, diethylamine, tripropylamine, dibutylamine, tripropylamine , methylethylamine, dimethylethylamine, diethylmethylamine, etherbutylamine, dibutylmethylamine,
Salts of aliphatic amines such as tributylamine, trihexylamine, ethylenediamine, hexamethylenediamine; cyclopropylamine, cyclohexylamine, N-
Salts of alicyclic amines such as methylcyclohexylamine;
Benzylamine, N-methylbenzylamine 7, NνN-
Salts of aromatic aliphatic amines such as diethylbenzylamine and dibenzylamine; piperidine, piperazine, morpholine, pyridine, quinoli! /, hexamethylenetetramine, oxazole, thiazole, imidazole,
Examples include salts of cyclic compounds such as triazole, benztriazole, and azabicycloundecene; salts of dimethylacetamide and N-methylpyrrolidone amide.

Examples of quaternary ammonium halides include ). Aliphatic quaternary ammonium halides such as Rum, trimethylbutylammonium halide, diethylsifthylammonium halide; halogenated NνNtN) Alicyclic quaternary ammonium halides such as dibutyl/lylohexylammonium; halogenated Tetrabenzylammonium, no.
Aromatic fats of trimethylbenzylammonium chloride i Quaternary soft ammonium rides; chloride N+
N+N-t')l tylphenylammonium, halogenated NtN+N-) ethylphenylammonium aromatic quaternary ammonium halides; halogenated N-
Methylpyridinium, halogenated N-ethylpyridinium, halogenated N-methylquinolinium, halogenated N-ethylquinolinium, halogenated NUN-dimethylpiperidinium, halogenated NsN'-dimethylimidazolinium, etc. Heterocyclic quaternary ammonium rides and the like are preferably used.

These salts of nitrogen-containing compounds and hydrogen halides and quaternary ammonium halides can be used alone or in combination of two or more.

When carrying out the method of the present invention, such a salt of a nitrogen-containing compound and a hydrogen halide and a quaternary ammonium halide may be harmonized outside the reaction system, or they may be harmonized within the reaction system. Alternatively, a compound *' may be produced.

Among such salts of nitrogen-containing compounds and hydrogen halides and quaternary ammonium halides, those containing bromine or iodine are preferred, and those containing iodine are particularly preferred.

The aromatic urea compound used as the base material of the present invention may be any compound in which one or more hydrogen atoms are directly connected to an aromatic group.

% is preferably a NIN•-diwIL substituted aromatic urea compound as represented by the following general formula (1).

ArNHONHAr' (1)1 Here, A, r, and A r l are all aromatic groups such as phenyl, naphthyl, hiridyl, nolanyl, and thiophenyl, and Ar and A r l may be different from each other,
They may be the same. In addition, in these aromatic groups,
At least one hydrogen on the aromatic ring has another substituent, for example,
・Roge/Hara-f, nitro group, amino group, cyan group, alkyl group, alicyclic group, aromatic group, aralkyl group, alkoxy group, sulfoxide group, sulfo/4, carbonyl group, ester group, amide group, etc. It is okay for VC to show off their arrogance.

Examples of such aromatic urea compounds include NνN'
-/phenylurea, 89N'-di(p-tolyl)urea, NUN〆-di(o-tolyl)urea, NtN'-di(p-aminophenyl)urea, NrN'-di(0-aminophenyl)urea , NUN'-di(p-nitrophenyl)urea, NνN'-no(0-nitrophenyl)
Urea, NνN'-di(3-amino-2-methylphenyl) WJA, N I NI-di(3-amino-
4-methylphenyl)urea, N? N'-di(5-amino-2-methylphenyl)urea, N+N'-di(3-
nitro-4-methylphenyl)urea, NνN'-di(
5-nitro-2-methylphenyl)urea, NtN'-di(3-nitro-2-)phenyl)urea, N-
(3-7mino-2-methylphenyl)-N'-(3-nitro-2-methylphenyl)urea, N-(a-7mino-4-methylphenyl)-N'-(3-nitro-4- methylphenyl)urea, N-(s-7minor-2-methylphenyl)-Nl-(s-nitro-2-methylphenyl)urea J, N-(a-amino-2-methylphenyl)-N
'-(s-amino-2-methylphenyl)urine 1 to-(
3-ami)-2-1fk7el) -NI-(3-
Amino-4-methylpheny+1. ．． )Urine J, N-(
3-amino-4-methylphenyl)-N'-(5-amino-2-methylphenyl)urine J, N-(3-nitro-2
-methylphenyl)-NI-(5-amino-2-methylphenyl)urea, N-(3-nitro-2-methylphenyl)-N'-(5-nitro-2-methylphenyl)urea, N*N '-di(l-naphthyl)urea, N+N'-di(2-naphthyl)urea, NνN'-di(6-amino-1-naphthyl)urea, NtN'-di(4-amine-
1-naphthyl) urea, N+N'-di(6-nitro-1
-naphthyl)urea, N2N'-di(4-nitroamino-1-naphthyl)urea, and polymeric ureas having a structural unit represented by the following formula are preferably used.

Particularly preferred FiN+N'-diphenyluria t, N
IN'-di(3-amino-2-methylphenyl)urea, NUN'-di(3-amino-4-methylphenyl)
Urea, N+N'-di(5-amino-2-methylphenyl)urea and ureas having a 7-methyl group.

The organic hydroxyl compound used in the present invention is a -valent or polyhydric alcohol, or a -valent or polyhydric phenol. Examples include monohydric or polyhydric alkanols and alkanols, -hydric or polyhydric cycloalkanols, cycloalkanols, and aralkyl alcohols. Furthermore, these alcohols may also include other inert substituents, such as halogen atoms, cyan groups, alkoxy groups, sulfoxide groups, sulfone groups, carbonyl groups, ester groups, and amide groups.

Specific examples of such alcohols include methanol,
Ethanol, glopanol (Tani heterocolloid), butanol (Each isomer), pentanol (Tani heterocolloid), hexanol (Each isomer), heptatool (Each isomer), octatool (Tani Xe isomer), nonyl alcohol ( each A column)
, decyl alcohol (each isomer), undefuryl alcohol (6 isomers), furyl alcohol (14 isomers each),
Aliphatic algol such as tridecyl alcohol (each X8 isomer), tetradecyl alcohol (each isomer), pentadecyl alcohol (tani isomer +); 7-chloroalkanol such as cyclohexanol, nochlohebutanol; ethylene glycol monomethyl Ether, pear/glycol 7-ethyl ether, diethin glycol 7-methyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Alkylene glycol monoethers of ethyl ether; ethylene glycol, propylene glycol,
Polyhydric alcohols such as diethylene glycol, cyglobylene glycol, glycerin, hexanetriol, and trimethylolpropane; and aralkyl alcohols such as benodyl alcohol are used.

Examples of phenol fists include phenol, each alkyl phenol, each alkyl phenol, % halogenated phenol, dihydroxybenzene, 4+
4'-dihydroxy-diphenylmethane, bisphenol, hydroquinaphthalene, etc. are used.

As the oxidizing agent used in the present invention, ordinary oxidizing agents can be used, but preferred are molecular filaments, organic nitro compounds, and mixtures thereof. Sometimes preferred is molecular #1.

Molecular element is pure oxygen or oxygen-rich gas, which may be air, or air or a gas that does not inhibit the pure acid ILt-reaction, such as fj1 element, argon, helium, carbon dioxide gas, etc. It may be diluted with active gas. 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.

stomach. Examples of alicyclic nitro compounds include nitrocyclohexane, nitrocyclopentane, nitrocyclohexane, nitrocyclohexane (note by Taninori), and bis-nitrohexyl)-methane; examples of aliphatic nitro compounds include , nitromethane, nitroethane, nitropropane (volume column), nitrobutane (each isomer),
Nitropentane (each isomer), nitrohexane (each isomer), nidrotican (each *6 isomers), t + 2
- Dinitroethane, dinitroethane (volume column), sinitrono'tane (tanika injection), dinitrobe/li/ (volume column), dinitrohexane (volume column), dinitroethane (volume column), phenylnitromethane , bis-(nitromethane)-7chlorohexa/, bis-(nido[J methyl)
~benzene, and examples of aromatic nitro compounds include nitrobenzene, dinitrobenzene (MX compound),
Nitrotoluene (each isomer), dinitroethane/(each isomer), nitropyridine (each isomer), dinitropyridine (% square), nitronaphthalene/(each isomer), dinitroethane (each isomer) and the following Mononitro compounds and dinitro compounds of the diphenyl compounds represented by the general formula (1) are included.

(The person in the formula is just a chemical bond, or -〇 + 8-ν
802 +-00-t-0ONHt coo-C〇(1'L') (R- and -N(-R-). Also, R1 sil2 is H% aliphatic basis,
In addition, in these nitro compounds, at least 4i hydrogen atoms are substituted with other substituents, such as rogen atoms, amino groups, cyano groups, alkyl groups, alicyclic groups, aromatic groups, etc. group group, aralkyl group, alkokino group, sulfoki7
It may be substituted with a do group, a sulfone group, a carbonyl group, an ester group, a tamide group, etc.

Among these nitro compounds, aromatic nitro compounds are preferable, especially nitrobenzene, nitrotoluene (Koden Hashira), nitroaniline (Tanino Hashira), 2 r 4 &
Preferred are U296-dinitrotoluene, dichloronitrobenzene (each isomer), 4+4'- and 2+4'-sinitrodiphenylmethane, 1t5-'; nitronaphthalene, and the like.

In the case where the oxidizing agent is molecular oxygen in 2 of the present invention, also in 1-
It progresses according to general reactions such as 1.

A r NHCONHA r' + 0.50. t
+ 00 + 2 ROH--→ArNH000+A
r'NHOOOI'L+H10 (where Ar and Ar
' is an aromatic group, 几 is an organic group) Molecular acid JAμ can be less or more than -, but mixtures of oxygen/- carbon oxide or oxygen/organic hydrogyryl compound are explosive. It should be used outside the limits.

In addition, m8, which is used as an organic nitro compound sonic oxidant, and the organic nitro compound itself participate in the reaction and become ureta/, so if the structure of the organic group is the same as the aromatic group of the aromatic urea compound, the respective structures If the structures of the two are the same, it goes without saying that the same aromatic urethane compound can be obtained.

In this case, the urethanization reaction proceeds using the following old method.

2ArNHOONHAr'+R'NO! +300+5R
OH-1→2 A r NHCOOl'L+2A r'
NHOoo R+ R'NH(joo R+ 2
8,0 (ArνAr' represents an aromatic group, and 1. represents an organic group) When only an organic nitro compound is used as the 't-oxidizing agent, the quantitative ratio of the aromatic urea compound and the organic nitro compound is:
One mole of nitro groups per two moles of urea groups is preferred, but it is of course possible to carry out this chemistry away from the weight ratio. In general, the equivalent ratio of amine 7 groups to nitro groups is carried out from 1.1 2l to 4:11, preferably from 1,s:t to 2.5:1.

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

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

In the method of the present invention, it is preferable to use an excess of the organic hydroxyl compound 4J as a reaction solvent, but an inert solvent for the reaction can also be used if necessary. Examples of such solvents include 1, for example, pen, toluene, xylene, menothylene and hydrocarbons; halogenated aromatic carbons such as chlorobenzene, dichloropenozene, trichlorobenzene, fluorobenzene, chlorotoluene, chlornaphthalene, and bromonaphthalene. Hydrogen #i: chlorohexane, chlorocyclohexane, trichlorotrifluoroethane, methine chloride, carbon tetrachloride, etc., rogogenated aliphatic hydrocarbons or non-logenated alicyclic hydrocarbons; acetonitrile, benzonitrile sodium Nitriles; sulfonate such as sulfolane, methylsulfola/, trimethylsulfolane; tetrahydrofuran, l
Ethers such as ν4-dioxane and 112-dimethoxy7ethane; ahito/, keto/ such as methyl ethyl ketone
Class; esters such as ethyl acetate and ethyl zoate; N
yN--dimethylformamide, NUN-dimethylacetamide, N-methylpyrrolidone, tetramethylurea,
Examples include amide compounds such as hexamethylphosphoramide.

Any amount of violet may be used in the catalyst used in the present invention, but the platinum group element-containing component is
Usually, the range of 0-0001 to 50 mol% is preferable. In addition, a salt of a Kotodama element compound and a hydrogen halide, and a hydrogen compound selected from quaternary ammonium halides, are effective against metal elements in the platinum group element-containing components used.
Usually, it is preferably used in a range of 0,001 to 10,000 times the mole.

Further, it is preferable to use the oxidizing agent violet in an amount equal to or more than the amount ki relative to the aromatic urea compound, but it is of course preferable to use the amount less than that.

In the method of the present invention, other additives can be added to the reaction yarn as necessary in order to carry out the reaction more efficiently. Such additives include, for example, tertiary amines, zeolite) M, and alkali metal salts and alkaline earth acids such as boric acid, alumines, carbonic acid, silicic acid, and organic acids. Metal salts are preferred.

In the method of the present invention, the reaction is generally carried out at a temperature range of 80 to 300°C, preferably 120 to 220°C. The reaction pressure is 5 to 500Q/32, preferably 20 to 300
111/cIR'', and the reaction time varies depending on the reaction yarn, catalyst yarn, and other reaction conditions, but ranges from several minutes to several hours.

The primary, 4:8 reaction can be carried out either batchwise or continuously, in which reaction components are continuously supplied while reaction liquid is continuously withdrawn.

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

Example 1 N+N' in a stirring autoclave with an internal volume of 140-
-20 mmol of phenyl urea, 40 mmol of ethanol, 0.5 ~ atom of para/lam, 5 mmoli of titramethyla/monium iodide, and replaced the system with carbon monoxide. acid 4
6 Press fit into K4/c1n21. While stirring16
After reacting at 0° C. for 1 hour + dJ, the reaction mixture was filtered to obtain pale yellow #liquid gold. As a result of total analysis of this solution, NνN'
The reaction rate of -diphenylurea was 100%, the yield of ethyl N-phenylcarbamate was 99%, and the selectivity was 99%.

When ethanol was removed from this M solution under reduced pressure, yellow crystals were precipitated. The crude crystals were recrystallized from N-phenylcarbamine ethylteh'), 1, which had a purity of 99%, and white crystals with a purity of 100% were obtained.

Examples 2 to 14 All reactions were carried out in the same manner as in Example 1, except that a salt of a nitrogen-containing compound and hydrogen halide or a quaternary ammonium halide (5 m mof f) was used instead of tetramethylammonium iodide. Ayu-mai-kin first table.

Margin below! Table 1 Comparative Example 1 As a result of carrying out the same reaction as in Example 1 using only palladium black without using a bottle of nitrogen compound and hydrogen chloride or a quaternary ammonium salt, NtN' At a reaction rate Fit of -diphenylurea of 05%, ethyl N-phenylcarbamate was produced with a yield of only 3%.

Example 15 NtN/
-di(0-methylphenyl)urea 25 mmo/.

Ethanol 50-1 activated carbon loaded with 5 W% rhodium, fc, Rh101 t, and 5111 mo/tetramethylammonium iodide were added, and after replacing the system with carbon monoxide, -carbon oxide was replaced with 80 Q/lx", Then, oxygen was injected at a rate of 6 hours/cm''. 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 NνN1-di(0-methylphenyl)urea was 94%, and that of ethyl N-(0-methylphenyl)carbamate was 94%. The yield was 88'A and the selectivity was 94%.

Comparative Example 2 Conducted without using tetrabutylammonium iodide? 1
The same reaction as l15 was carried out, but N + N'-di(0-
The reaction rate of methylphenyl)urea was 9%, and the yield of ethyl N-(O-methylphenyl)carbamate was less than 2%.
Met.

Implementation l11116 Ruthenium black instead of Ithlo, s m moj'
and NtN'-diphenylurea except for using 25 mmol? Kayakomai, NtN, which underwent the same reaction as 1115
The reaction rate of '-diphenylurea was 78%, the yield of N-7 enyl carbami 7#R ethyl was 71%, and the selectivity was 91%.
Met.

Comparison-j3 Performed without using tetramethylammonium iodide t1
The same reaction as '1J16 was carried out, but the NvN'-diphenylurea reaction rate was 8% and the yield of ethyl N-phenylcarbamate was 2% or less.

Table row 17 Internal volume 2007! Stir-fried Takeshi Autocrepe Nv
N'-diphenyl HA 30 m mats nitrobenzene 15 mm61. Methanol 50m% palladium chloride 0.5m rno/, tetrabutylammonium iodide 5m, mol were added, the system was replaced with gold-carbon oxide, and after that, 140 kg/lx of -[carbon] was injected. The mixture was reacted for 5 hours at tso''c.

The reaction solution was analyzed and the results showed that the reaction rates of NνN'-diphenylurea and nitrobenzene were 26% and 33%, respectively.
%, methyl N-phenylcarbamate is l 5 m
mo/ was generated.

Examples 18 to 24 Table 2 shows g* obtained by carrying out the same reaction as in Example 1 using various platinum group metals or compounds * referred to in platinum group element 1 instead of palladium black.

The following is a blank Table 2. In these examples, 0.5 qatom is used as the metal element for the platinum group metal or platinum group compound, and the % ratio indicates the ratio of the combined catalyst components. Pd-1'
e10 is obtained by co-supporting palladium chloride and gold tellurium dioxide on activated carbon at a molar ratio of lθ to 3, followed by fC and hydrogen reduction at 350°C.

4I: Stream side 25 In an autoclave with an internal volume of 140 mm, add NνN'-diphenylurea 2 OFF 1 moe, ethanol 40 mm, palladium black 0.5 W atorn, triethylamine 8
mmol.

Add propyl iodide 5 m mat t-m in the system
After lt chivalry with carbonized carbon, - fermented carbon'it too time/12
, then oxygen? The reaction mixture was filtered at 8'@t, and the filtrate was completely analyzed.The reaction rate of NtN'-diphenylurea was 19s%, and the reaction rate of NtN'-diphenylurea was 19s%. The yield of ethyl phenylcarbamate was 96% and the selectivity was 97%.

Example 26 Pyridine 5m mop instead of triethylamine.

Hydroiodic acid (57% solution, i
f) was used to perform anti-shrinking in the same manner as in Example 25. As a result of analyzing the reaction solution, the reaction rate of NνNZ-diphenylurea was 90%, the yield of ethyl N-phenylcarbamate was 85%, and Selection 4 was successful at 94%.

Patent applicant: Asahi Kashu Kogyo Co., Ltd.

Claims (1)

[Claims] A method for producing an aromatic urethane by reacting an aromatic urea compound with carbon monoxide and an organic hydroxyl compound in the presence of a 1g-forming agent, comprising: (a) a platinum group metal and a platinum group element At least one building selected from among the compounds, and (b
Using a catalyst thread consisting of a salt of a J-functional nitrogen compound and a hydrogen halide, a quaternary ammonium salt, or at least one selected from compounds capable of producing these in a reaction system. Method 2 for producing an aromatic urethane compound having a % characteristic. Method 3 of Kiei in Claim 1, in which the oxidizing agent is molecular oxygen or an organic nitro compound, or both. Platinum group metal and platinum group element-organized compound The method according to claim 1 or 2, wherein is palladium, rhodium, a palladium compound, or a rhodium compound. Method 5 according to claim 1, 2 or 3, in which the wood is iodine; 5, the method according to claim 1, 2 or 3, in which the oxidizing agent is molecular oxygen; or the method described in paragraph 4.