JPS58146546A - Preparation of urethane compound - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a preparation raw material of isocyanates, without using a metallic chloride, in high selectivity and yield, by reacting a urea compound with CO and an organic hydroxyl compound in the presence of a specific catalyst system and an oxidizing agent. CONSTITUTION:A urethane compound of formula III is prepared by reacting a urea compound of formulaI(R<1>-R<4> are H, halogen, alkali, metallic atom, etc.) such as N,N'-diphenylurea, with CO and an organic hydroxyl compound of formula II (R is organic group) such as methanol, ethanol, etc. in the presence of an oxidizing agent comprising molecular oxygen. The reaction is carried out in the presence of a catalyst system composed of a component selected from platinum group metal and a compound containing platinum group element and a component selected from organic halides (e.g. organic bromide and organic iodide). The separation and recovery of the expensive platinum group compound and the organic halide can be carried out easily, and the process is economically advantageous.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing urethane compounds. Sara vca
Or is it a urea compound in the presence of an acid supplement? -Urethane compounds y! by oxidative carzanylation with carbon oxides and organic hydroxyl compounds! - Concerning a method of manufacturing.

Urethane compounds are important compounds used in carbamate yarns, etc., and recently there has been a demand for a method for producing urethane.

Methods for producing such urethane compounds using carbon silicates include aromatic nitro compounds, aromatic nitroso compounds, aromatic azoxy compounds, aromatic azoxy compounds, aromatic azoxy compounds, etc. A method in which urethane is reductively heated in the absence of a t' agent and a method in which aromatic amino acids and compound 11 are combined with wonton are known.

Furthermore, N, N-diaryl FK element? A method of applying urethane as a beak has also been proposed (%Kaisei 55-120552)
Publication No.). In this method, is Group II noble metal or its compound used as the main catalyst? Metals that can carry out the V-Tx reaction in the reaction system are used as cocatalysts, such as Hanawa Ihi copper, "enriched iron,""enrichediron,""enhancediron,""enrichediron,""enrichedvanadium," and "oxygen/4-nadium." However, these metal groups ([7] are highly erosive to metal materials such as reaction vessels, piping, and pulp, and therefore There is a problem in the construction that metal materials of high quality must be used.

Furthermore, in order to separate and recover the dissolved substances such as aromatic urethane, which is a product of these compounds, there is a drawback that it requires complicated operations and a large amount of cost. Ta.

In order to overcome these drawbacks, the researchers have developed Taretafu 11 compound by converting the dust compound into urethane using an acidic method. Regarding the method for producing Q, the reaction can proceed catalytically without using the chloride of the element that performs the Lewis acid V-Tx reaction, which is the main cause of these drawbacks. A completely new catalyst system was discovered, and based on this knowledge, the present invention was completed.

That is, in the present invention, in producing urethane compound V by reacting Kw true compound silicate dicarbonate and organic hysyloxylic compound with a compound in the presence of an oxidizing agent, 1) a compound selected from platinum group metals and platinum group element-containing compounds; and M) at least one selected from organic halides. ! It provides a method for creating 'all'.

The thick special agent of the present invention contains at least one compound selected from compounds containing platinum group metals and platinum group redundant elements, and at least one compound selected from organic halides. By using this catalytic system, urethane dilated products can be obtained with good selectivity and high yield from urea 11 compound.

Scary JI! In fact, this is a really surprising thing that was completely unknown until now, and is it mentioned above? Prior art (Unexamined Japanese Patent Publication No. 55-1
20552), which was completely unexpected. , 7 In other words, in the prior art, a white-group compound is used as the main catalyst, and a catalytic thread is used as a co-catalyst for the cyclization of elements that can carry out the Px reaction in the reaction system. , 1!Shi?11 A typical tactile thread is a combination of palladium monide and oxy-iron.In such a system, 21 palladium participates in the reaction. As the reaction progresses, 41 yuan is added to +1.0.
11 became palladium, and this was written by the 61st oxidized iron. Furthermore, it is thought that this divalent iron is converted into urethane compound V by the so-called one-car reaction type catalytic cycle, in which the divalent iron is converted into IN+ acid by the reaction and returns to the monovalent iron. .

As described above, it has been shown that in the prior art method, the chloride of an element that has a redox action is essential as a reoxidizing agent for the main catalyst in the reaction thread.As for the element that has such a function, rfi a -V An element capable of undergoing a redox reaction selected from elements of the a group and 71) to b group, specifically:
Copper, zinc, water needle, thallium, soot, titanium, arsenic, antimony, bismuth, vanadium, chromium, molybdenum,
Among them, only copper, vanadium, manganese, molybdenum, tungsten, antimony, and iron are mentioned in the examples. .

On the other hand, the uninvented method is
*V Are these compounds used at all? Contains no ingredients.

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.

It is unclear how such organic halides act in the reaction of the invention, but when combined with a compound containing a platinum group element, the acidity of the urea compound (It is clear that it plays an important role as a catalytic component in the t' reaction.

In other words, the urethanization reaction of this reaction will not proceed at all if an organic halide alone is used, and the urethanization reaction will hardly proceed under the conditions of this reaction even if only a platinum group metal or a compound containing a platinum group element is used. Even if it progresses, it will only require a small amount of urethane and compound. In particular, when only platinum group elements in the metallic state are used, hardly any urethane compounds are obtained. For example, palladium is one of the effective medium components for this reaction, but this reaction hardly progresses only with palladium black, which is a zero-valent metal palladium, but organic), For example, when organic iodide Y is added, a wonton compound can be obtained catalytically.

As described above, in the uninvented method, a solid platinum group compound in the gold lI4 state can also be used as one of the catalyst components. This shows that the separation and recovery of the 9+6 valent platinum group metals from the reaction system can be carried out by a simple method such as passing through the mouth, which is industrially advantageous.

Furthermore, unlike the heavy metals used in the prior art, organic halides can be separated,
Another major feature of the invention is that it is easy to recover and does not mix into the product as a contaminant.

The platinum group metals and platinum group element vt minerals used in the method of the present invention contain as a component at least one selected from platinum group elements such as palladium, rhodium, platinum, ruthenium, iridium, and osmium. If so, there is no particular restriction on these elements, and these elements may be cylindrical or may be components that form P compound V. graphite,
Supports such as silica, alumina, silica-alumina, silica-titania, titania, zirconia, barium sulfate, calcium carbonate, asbestos, bentonite, diatomaceous earth, polymers, ionic diatomaceous resins, zeolites, molecular sheep, magnesium silicate, magnesia, etc. It may also be carried by

Examples of platinum group elements in the gold state include metals such as palladium, rhodium, platinum, ruthenium, iridium, and osmium, these metal islands, and catalyst components containing these metal ions V are supported on the above-mentioned phase, and then hydrogen or metals reduced with formaldehyde, alloys or intermetallic compounds containing these metals, etc. are used. In addition, the alloy or gold alloy may be made of these platinum group metals, or may be made of other elements such as selenium,
tellurium, sulfur, antimony, bismuth, porcelain, bride, gold,
Curved lead, tin, vanadium, iron, cobalt, nickel, boron, lead, thallium, chromium, molybdenum, tungsten, etc.? It may include.

10,000, Ibi compounds containing platinum group elements include, for example, inorganic salts such as halides, sulfates, nitrates, phosphate groups, and borates; organic acid salts such as acetates, oxalates, and formates; Cyanides; hydroxy acids; oxides; sulfides: metal salts containing anions such as nitro groups, cyano groups, halogens, oxalate ions, and ammonia, amines,
Complex compounds of metals such as phosphines, complexes containing carbon oxide chelate ligands; organic configuration 17. Examples include organometallic compounds having a child or an organic group.

Among these catalyst components, those containing palladium or rhodium or both are particularly preferred; examples of such components include, for example, Pd black; pa-c, pa-
A1403, P(1-8102, Pd-TiO2, Pd
-ZrO2, Pd-BaSO4, P(l 0aCO3,
Supported palladium catalysts of pa-asbestos, Pd-zeolite, Pd-molecular sheep; P(1-P
b, P(1-Be, Pd-Te, Pa-
Hq, Pd-Tl, Pd-P, P(1
-C! u SPd-Ag, Pd-Fe, Pd-C
o, alloys or intermetallic compounds such as Pd-Ni, Pd-Rh; and alloys or intermetallic compounds thereof (t' compounds also supported on the above-mentioned carrier; paal2, pd
Br2, Pd engineering 2, P(1(No3)2, P(180,
Inorganic compounds such as Pd(OOOCHJ2, organic acids such as palladium oxalate; Pd(ON)2; pa
o; pass M2 (PdX4), +J2 (Pd
Palladium acid groups (M represents an alkali metal, ammonium ion, nitro group, cyano group, X is a halide bj.);
2. Ammine complexes of palladium such as (Pd(en)2)
)2, Pa012(PR<')2, Pd(C!0)
(PR3)3, Pd(PPh3), , paal(R)(
pph, , )2, Pd((1!2H4)(PPh3
)2, complexes such as Pd(03H5)+ (1' compounds or organometallic compounds (R represents M group Y); Pd
Complex compounds coordinated with chelate ligands such as (acac)2:□; Rh black; supported rhodium catalysts similar to Pd; Rh alloys or intermetallic compounds similar to Pd, and supported on these carriers Rh013 and hydrate, RhB
r3 and hydrate, Rh-3 and hydrate, Rh2 (804
) 3 & Inorganic compounds such as hydrated I @ 5Rh2 (OCOC
H3), ; Rh2O3, RhO2; M3(RhX
6) and hydrates (M and X have the same meanings as above); (
Rh(NH3)s )X3, (Rh(en)3)X37
z Which rhodium ammine complexes; Rh4(co)l
Rhodium carbonyl clusters such as z, Rh6(co)x6; (Rhcl(00)2)2, Rhc 13
(PR3)3, Rh(31(PPhs)3, RhX
((30) L2 (X has the same meaning as above, L is a ligand consisting of an organic phosphorus compound and an organic hydrogen compound), RhH(co)(pph, )3, and other complex compounds Or organic 11 compounds can be mentioned.

In the button of the present invention, only one type of these platinum group metals or compounds containing platinum group elements may be used, or two or more types may be used in combination, and there are no particular restrictions on the amount used. However, it is usually desirable that the component containing the platinum group element is in a range of 0.0001 to 50 mol based on the electrophoretic compound.

The organic halide used in the method of the present invention is an organic 11 compound represented by the general formula (1). Here, H is an m-valent organic group or a halide selected from the above-mentioned groups, F, C1, Br, and I, and m means a number of 1 or more.

In formula (1), when m is 2 or more, X may be a halogen species different from the secondary bulb.

In addition, in formula (1), halogen X in S is a hetero I other than carbon.
It may be bonded to 9 atoms, for example, nitrogen, phosphorus, oxygen, sulfur, selenium, etc.

As described above, in the method of the present invention, any conventional organic compound that forms a halide can be used. (Himono, aromatic aliphatic), location and substance,
71! A ring-type halloween and objects should be 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, sulfoxy groups, sulfone groups, carvnyl groups, ester groups, amyl groups, etc. or may carry an unsaturated group.

Examples of such organic halides include methyl halide, ethyl halide, hiprovir halogen (each isomer), decyl halide (ff isomer), amyl halide (each isomer), and halogen salt. Hexyl (each isomer), hioctyl halide (each isomer), perfluorohexyl halide (each isomer), perfluorohexyl halide (f-1h form), amyl halide, allyl halobinide, Halodanated methylene, haloform, tetrahalodenemethane, halogenated alkylidene, dihalogenated ethane (each isomer), trihalogenated ethane (each isomer), tetrahalodenedithethane,
Aliphatic mono- and polyhalonated compounds such as dihalogenated butane (each isomer), dihalogenated hexane (each isomer), dihaloethylene (each isomer): halogenbenzene,
Dihalogenbenzene (each isomer), trihalodanebenzene (each isomer), f) Dihalogenbenzene (each isomer)
, hexahalogen benzene, halodanaphthalene, dihalogen naphthalene (each isomer), halogen pyridine (multi-isomer), halogen toluene (%141 isomer, Hao
ly" y x Aromatic mono- and polyhalides such as tilbenzene (each isomer), phenyliodine dichloride V, iodosobenzene, iodoxypenvin; alicyclics such as halogenated cyclohexane, halogenated cyclodethane, etc. halogenated compounds such as benzyl, halogenated phenethyl; halogenated furan, halogenated tetrahydrofuran, halogenated thiophene, halogenated imidatol, halogenated Polycyclic halides such as halogenated piperidine; acid halides such as acetyl halogenide and penkameidoyl halide; N-halogensuccinimide P, N-halogenalkylamine, N-halogenide N-halogen substances such as N-acetamyl and N-halokenebenzamyl are preferably used.

Among such organic halides, organic bromides and organic iodides are preferred, and organic iodides are particularly preferred.

Regarding the amount of organic halide used in the invention,
Although there is no particular limit, J width is usually 0.001 to 10.
It is preferable to use it in the range of 000 times mole.

The urea compound used as a raw material in the present invention is a compound having at least one urea bond Y1 in the molecule as shown by the formula %. Here, the two lines connected to N represent bonds between the chamber atom and other atoms or groups. Such atoms or groups include hydrogen, halogen, alkali metal atoms, hyaloxyl groups, amino groups, aliphatic groups, alicyclic groups, araliphatic groups, cyclic groups, aromatic groups, etc. .

Also, these nitrogens themselves may be elements constituting a ring, or is the urea bond itself a ring? It may be something that is part of the configuration.

Such urea compounds may be unsubstituted urea, monosubstituted urea, di-substituted urea, trisubstituted urea, tetrasubstituted urea, or the like.

Examples of monosubstituted ureas include aliphatic substitutes such as methyl urea, ethyl urea, propyl urea, butyl urea, and hexyl urea; alicyclic ureas such as cycloderovir, cyclobutyl, and cyclohexyl urea; t-substituted ureas; aromatic aliphatic monosubstituted elements such as benzyl urea and I-7enethylurea; polycyclic monosubstituted ureas such as furanyl axillary and thiophenyl urea; phenyl urea, tolylurea, Aromatic monosubstituted ureas such as naphthylurea are used. Examples of the disubstituted urea include N,N-dimethylurea, N,N-diethylurea, N,N-dipropylurea, N,N-diptylurea, N,N-dihexylurea,
Aliphatic N,N-substituted urea terms such as N-techniques N-71 chilluria X, N-ethyl-N-ethyl atom; N,N-dicyclopropylurea, N.

Alicyclic N,N-disubstituted ureas such as N-dicyclobutylurea, NiN-dicyclohexylurea; N-cyclopropyl-N-methylurea, N-cyclohexyl-N-ethylurea; N,N-dibenzyl base Aromatic 1111 Fatty group N,N-diW-substituted ureas; N,N-diethylurea, N,N-dithiophenylwg
, N-7 ranyl-υ-methylurea and other heterocyclic N,N-
Shi-substitute swimming noodles; N, N-diphenyl urine, N, N-ditrile original, N, N-dinaphthyl urine X, N-phenyl-N
-Methyl urea, N-phenyl-N-methylurea, N
Aromatic N,N-dimethylureas such as -naphthyl-N-bensylurea, N-phenyl-N-cyclohexylurea; N,N'-dimethylurea, N,N'-diethylurea, N, N'-dipropylurea, N, N'-
Sibutylurea 3, N, N'-dihexylurea, N-ethyl-simethylurea, N-ethyl-N'-butylurea, N
-Aliphatic N such as -hexyl-N'-methylurea.

N'-cyf4e exchange ureas; N, N'-dicyclopropylurea, N, N'-dicyclobutyl urea, N
, N'-dicyclohexyl group 8, alicyclic groups such as N-cyclopropyl-N'-methylurea, N-cyclohexyl-N'-ethyl atom, etc.,
Aroaliphatic N,N'-disubstituted ureas such as N'-dibenzylurea X, N-benzyl-N'-methylurea; N,
Chronocyclic N,N'-di(K) derivatives;
, N'-diphenylurea, N, N'-ditolyl, N, N'-dinaphthyl 11 elements, N-phenyl-N
N-phenyl-N'-f methylurea, N-phenyl-N'N'-disubstituted ureas, and cyclic forms such as piperidyl urea and pyrrolidinyl urea! 4 elements
Compounds such as armpits are used. Examples of tri-replacement forms include trimene, triethyl urea, tripropyl urea, triethyl urea, trihexyl urea, N, N
--, F methyl-N'-ethyl urea, N, N-diethyl-N'-butyl urea, N-methyl-, N-ethyl-N'
-Aliphatic trisubstituted ureas such as ethyl urea; tricyclopropylurea, tricyclohexyl urea, N,N'-dicyclohexyl-'-methylwrea, N-cyclohexyl-
N-ethyl-N'-phthyl M, N.

,・n′□″・N-diethyl-“-7Alicyclic tridirect ureas such as clodecyl urea; trifuranylurea, trithiophenyl urea,
Heterocyclic urea terms such as u, N'-difuranyl-N-methylurea; N-cyclohexylurea, N, N-') If sil--phenylurea, N-phenyl-14-ethyl-N'-benzyl atom and other aromatic compounds 1jt#ureaφ; N-ethylpiperidylurea, N- Urea 1, which is an N-substituted cyclic nitrogen compound such as methylpyrrolidinyl urea, is used.

Examples of tetra-substituted ureas include dermoaliphatic tetratransferred ureas such as tetramethylurea, tetraethylurea, tetrapropylurea, tetrahexylurea, diethyldimethylurea, and ethyltrimethylurea; tetracyclozorobylurea;
Type 1 alicyclic tetras such as tetracyclohexyl urea, difurohexyl diethyl urea, and cyclobutyltrimethyl urea; aromatic aliphatic tetras such as tetrabenzyl urea, tribenzyl methyl urea, dibenzyl diethyl urea, and benzylt IJ methyl urea Substituted urea term: Heterocyclic tetra-substituted ureas such as tetrafuranylurea, tetrathiophenylurea, furanilt IJ methylurea; tetraphenylurea, tetratolylurea, tetranaphthylurea, methyltriphenylurea, diethyldiphenylurea, dicyclohexyldiphenyl Aromatic tetra-substituted ureas such as +7ethylurea (urea, naphthyl), etc. are used. Further, examples of cyclic urea compounds having a urea bond as a ring element include 2-imida-toron, 2-ibadaderin, biotin, hydantoin, N,N'-hexamethylene urea, parabanic acid, Benraiba Daderin and the like are used.

Furthermore, a compound having two 9+ original sums Y in the molecule,
For example, polyureas of polyamines such as N, ``-dimethylcarbamoylhexamethylenediamine, )l,N'-diphenylcarbamoylphenylenediamine, or polymeric bases having structural units represented by the following formula may also be used. In the substituted ureas, hydrogen of 11141 or more of the substituent is substituted with another substituent, such as a lower 8' group, an amino group, a carboxyl group, an ester group, an alkoxy group, a cyano group, or a cyano group. , a nitro group, a valethane group, a sulfoxide group, a sulfone group, a carbonyl group, an ami-P group, an aromatic group, an araliphatic group, or the like.

In order to obtain a urethane compound as a raw material for producing isocyanates, K is preferably an N,N'-disubstituted urea, and aromatic urethane compounds are particularly easily produced by using N,N'-diarylureas. .

One or more of these urea compounds may be used.

The organic hydroxyl compounds used in the present invention are -valent or polyhydric alcohols or -valent or polyhydric phenols. Examples of such alcohols include straight-chain alcohols having 1 to 20 carbon atoms. Alternatively, branched monovalent or polyvalent alkanols and alkenols, -valent or polyvalent cycloalkanols, cycloalkenols, aralkyl alcohols, and the like can be mentioned. Furthermore, these alcohols may contain other inert groups, such as halogen atoms, cyano groups, alkoxy groups, sulfoxy groups, sulfone groups, carbonyl groups, ester groups, amyl groups, etc.

Specific examples of such alcohols include methanol,
Ethanol, zolopanol (each isomer), butanol (
(each isomer), pentanol (each isomer), hexanol (each isomer), hexanol (each isomer), octatool (each isomer), nonyl alcohol (each a column), -f
"Syl alcohol (each isomer), undecyl alcohol (each isomer), lauryl alcohol (each isomer), tridecyl alcohol (each isomer), tetradecyl alcohol (each isomer), pentadecyl alcohol (each isomer) body)
Aliphatic alcohols such as cyclohexanol, cycloheptatool, etc.; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl Alkylene glycol monoethers such as ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether; ethylene glycol, teropylene glycol, diethylene glycol, diethylene glycol, glycerin,
Polyhydric alcohols such as hexanetriol and trimethylolpropane; aralkyl alcohols such as benzyl alcohol and the like are used.

Examples of mataphenols include phenol, various alkylphenols, various alkoxyphenols, various halodanated phenols, dihydroxybenzene, 4,4
'-dihydroxy-diphenylmethane, bisphenoroome, hypoxynaphthalene, etc. are used.

As the oxidizing agent used in the present invention, any conventional oxidizing agent may be used, but preferred are molecular oxidizing agents, organic nitro compounds, and especially mixtures thereof. Particularly preferred are molecular aerosols.

This molecular oxygen is pure oxygen or something containing oxygen Y, and may be air, or is there a literary name for air or pure oxygen? It may be diluted by adding other non-inhibiting gases, such as inert gases such as nitrogen, argon, helium, and carbon gas. In some cases, hydrogen, carbon oxide, hydrocarbons, chlorinated hydrocarbons, etc. may be included in the sedge.

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 (each isomer), and bis-nitrocyclohexyl)-methane; examples of aliphatic nitro compounds include nitromethane, nitroethane, Nitropropane (each isomer), nitrobutane (each isomer), nitropentane (each isomer), nitrohexane (each isomer), nitrodecane (each isomer), 1,2-dinitroethane, dinitropropane (container) column), dinitrobutane (each isomer),
Dinitropentane (each isomer), dinitrohexane (each isomer), dinitrodecane (each isomer), phenylnitromethane, bis-nitromethyl)-cyclohexane, bis-nitromethyl)-benzene, etc. are aromatic nitro compounds. For example, nitrobenzene, dinitrobenzene (each isomer), nitrotoluene (each isomer), dinitrotoluene (each isomer), nitrogiridine (each isomer)
, dinitropyridine (each isomer), nitronaphthalene (
(each isomer), dinitronaphthalene (each isomer), etc.

Furthermore, in these nitro compounds, at least one hydrogen has another substituent, such as a halogen atom, an amino group,
Cyano group, alkyl group, alicyclic group, aromatic group, aralkyl group, alkoxy group, sulfoxy group, sulfone group,
It may be substituted with a carbonyl group, an ester group, an amyl group, or the like.

In the present invention, the oxidizing agent is molecular l! ! In the case of two cables, the reaction proceeds according to the following general reaction formula.

(+: R1, R', R3, R' hydrogen, OIf
y, alkali, 4 gold atoms, hydroxyl group, amino group,
R represents an atom or group selected from an aliphatic group, an alicyclic group, an araliphatic group, a heterocyclic group, and an aromatic group, and R represents an organic group. ) Molecular oxygen may be less or more than our dragon, but
Mixtures of oxygen/carbon oxide or oxygen/organohydroxyl combinations should be used outside explosive limits.

In addition, when using an organic nitro compound as a silicate detergent,
The organic nitro compound itself also participates in the reaction and becomes urethane, so if the structure of the organic group is different from the substituent of the urea compound, a urethane compound corresponding to each structure will be obtained, and if the structures of both are the same, they will be the same. Needless to say, a urethane compound can be obtained.

In this case, the urethanization reaction proceeds according to the reaction formula shown in the arrow.

(Here, R1, R2, R3, R4, and R have the same meanings as above, and R5 represents the organic residue of the organic nitro-11 compound.) When only the organic nitro compound is used as a χ acid detergent, the urea compound and The serving ratio of the organic nitro compound is preferably 1 mole of nitro group per 2 moles of urea group.
Of course, it may be carried out at a location far from this stoichiometric ratio. - The equivalent ratio of urea group to nitro group is 1.1:1 to 4:1, good! C< is 1.5
: 1 to 2.5 : 1.

Of course, when molecular oxygen or other oxidizing agents are used simultaneously, the amount of the organic nitro compound may be less than the stoichiometric amount.

In the method of the present invention, it is preferable to use an excessive amount of the organic hydroxylated compound as the reaction solvent, but if necessary, a solvent that does not adversely affect the reaction can also be used. Such solvents include, for example, aromatic raw carbon hydroxide gradients such as benzene, toluene, xylene, and mesitylene; nitrites such as acetonitrile and pen-nitrile; sulfones such as sulfolane, methylsulfolane, and dimethylsulfolane; r Rochran, 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; -1N-
List amide compounds such as methylpyrrolidone and hexamethylphosphoramide P.

In the method of the present invention, other additives may be added to the reaction thread as necessary to carry out the reaction more efficiently.

Examples of such additives include zeolites, element-containing compounds and hydrohalide acid salts, onium halide compounds, 6th class amines, and hydrohalic acids, boric acid, gamma lumic acid, carbonic acid, and silicic acid. Alkali metal salts and alkaline earth metal salts of monoacids such as acids and organic acids are suitable.

In the method of the present invention, the reaction is generally carried out at a temperature range of 80 to 300C, preferably 120 to 220C. The reaction pressure is 5 to 500 kg/CIrL2, preferably 2
0~300 kll/cI! ? The reaction time varies depending on the reaction system, catalyst system, and other reaction conditions, but is usually from several minutes to several hours.

In addition, the reaction of the present invention can be carried out batchwise, or can be carried out continuously using the reaction components. A continuous method may also be used in which the reaction solution is continuously withdrawn while being supplied.

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

Example 1 N in a stirred autoclave with an internal volume of 143*J.

N'-Schiff x = A/ [element 20 m mol, ethanol 4Q red, palladium black υ, 5 atom, iodoform 0.5 m mob in the system replaced with K-Ihi carbon, - acid Ibi carbon k 80 kg/cML
", then 6 kg 7 am of oxygen" Y press-in, total pressure 86
The reaction mixture was incubated at 160°C for 1 hour with stirring, and the reaction mixture was passed through the mouth and analyzed by liquid analysis. As a result, the reaction rate of N,N'-diphenylurea was 85.
%, the yield of ethyl N-phenylcarbamate was 80%, and the selectivity was 94qb.

Implementation World 12-11 Instead of iodoform in Example 1, Keyanano 4 Kikai~
- The reaction was carried out in exactly the same manner as in Example 1, except that a lodenide compound was used. The results are shown in Table 1.

(Remaining colors below) Table 1 ([:, 0nN- is succinimyl group Iゎ-f] Comparative example 1 Halodane 1 was not used at all, and only palladium black was used. As a result of carrying out a similar reaction, N,
The reaction rate of N'-diphenylurea was 10%, and ethyl N-phenylcarbamate was produced with a yield of only 3%.
There were only 1.

Practical example 12 N, -dicyclohexyl urea 40 m mol, methanol 50 ml 1. Palladium black 0.5 rrv ato
m % methylene iodide 11.5 m mol ? As a result, the reaction rate of N,IJ'-dicyclohexylurea was 82, the yield of methyl N-cyclohexylcarbamate was 754, and the selectivity was 92. Example 16 The same reaction as in Example 1 was carried out using 4 Q m mol of N, N'-dibenzylurea, 4 Qmt of ethanol, 1 m of palladium black, 1 m of palladium black, 1 m of tetraio r methane, and 1 r++ruolv. As a result, the reaction rate of N, d-dibenzylurea was 130%, the yield of ethyl N-benzylcarbamate was 72%, and the selectivity was 90%.

Example 14 Reaction 2 was carried out in exactly the same manner as in Example 12, except that 3 Qrn mol of tetramethylurea was used instead of N,N'-dicyclohexylurea in Example 12.
The reaction rate of tetramethyl urea was 76%, the yield of N,N-nomethyl chloride/methyl acid was 654, and the selectivity was 89.

Examples 15 to 26 The same reaction as in Example 1 was carried out except that four platinum group metals or platinum group elements were used instead of palladium black in Example 1 (except for using an arsenic compound).

The results are shown in Table 2.

(Left space below) Table 2 In addition, in these examples, platinum group-v14 or platinum group (arsenide is Ll as a metal element, 5 my aton
u' is used, and the relevant expression is the weight of the supported catalyst component, 1Ilr.
I'm in charge of this.

(Pa-Te)10 was co-supported on activated carbon at a molar ratio of enriched palladium and tellurium dioxide Y of 10:6.
It was hydrogen-reduced at 50°C.

Example 24 The reaction was carried out in exactly the same manner as in column 1, except that urea 20 m mob was used instead of N,N'-diphenylurea in Example 1. The yield of ethyl was 80% and the selectivity was 91%.

Example 25 N in a stirring type autoclave with an internal volume of 2001,
N'-diphenylurea 50 mmol, nitrobenzene y15 mmol, methanol 5QmA, enriched palladium 1 mmol, methylene iodide 2! After adding IImol'lf and substituting Y-carbon in the system,
20 kg/cm" was press-fitted. Stir it for 1 d.
After reacting with O-C for 6 hours, 1g of reaction, ? The reaction rates of the analyzed polyester, N, N'-diphenylurea and nitrobenzene were 40% and 4B, respectively, and methyl N-phenylcarbamate was produced in an i4m mob.

Patent applicant: Asahi Ihi Sei Kogyo Co., Ltd.

Claims (1)

[Scope of Claims] I) Producing a urethane compound V by reacting a urea compound with carbon silicate and an organic hydroxyl compound in the presence of a #-forming agent, I) Platinum group ♀ and platinum group element? A urethane compound characterized by the use of a catalyst system consisting of at least one kind selected from the compounds mentioned above, and at least one kind selected from the organic halides. How to manufacture. 2 Claims in which the acid 1 agent is at least 414 residual from molecular oxygen and organic nitro(?) compound, 1λ1
How to describe the name. :1 The method according to claim 2, in which the metal element is molecular oxygen; 4, the method according to claim 2, in which the compound that excites the white metal group metal @S and the platinum group element, is a rhodium compound; The method described in Section g6. 5. Claims 41, 1llil to 444, wherein the organic halide is Misobromide and organic iodide.
How to write aloud. 6. The method according to claim 5, wherein the organic halide is an organic iodine ζ compound. 7. The method according to claims @11 to 6, wherein the urea compound is N,N'-diarylurea. 8. The method according to claim 7, wherein the gN,N'-diarylurea is N,N'-diphenylurea.