JPS58126854A - 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., Pd-C) and at least one selected from alkali metal halides (e.g., NaI) and alkaline earth metal halides (e.g., CaI2) are used as a catalytic system.

Description

[Detailed description of the invention] The present invention relates to a method for producing aromatic urethane.

More particularly, the present invention is directed to a method for producing an aromatic urethane by reacting an aromatic urea compound with carbon monoxide X and an organic hydroxyfur compound in the presence of an oxidizing agent to oxidatively carbonylate it.

Aromatic urethanes are one of the essential compounds used in carbamate-based 1klk, etc., and recently there has been a demand for an inexpensive method for producing them as raw materials for the production of aromatic incyanates that do not use phosgene.

As a method for producing such an aromatic urethane using monolithic carbon IA, aromatic nitro compounds, aromatic nitrone compounds, aromatic azo compounds, aromatic cinnabar azoxy compounds, etc. are reduced in the absence of an oxidizing agent 1. A method of urethanizing an aromatic amine compound oxidatively and a method of urethanizing an aromatic amine compound oxidatively are known.

Furthermore, a method of converting KN, N'-diaryl urea into urethane was also proposed.
Publication No. 2). In this method, a noble group metal or its compound is used as the main catalyst (-1 iron chloride, iron oxychloride, vanadium chloride, vanadium oxychloride, etc. as a co-catalyst) to perform a redox reaction in one reaction system. It is necessary to introduce chlorides containing metals into the reaction system. (For this reason, there is the problem of having to use expensive metal materials.Additionally, it is common knowledge that these metal chlorides are separated from the higher boiling point substances of the aromatic urethane product.)・YC has the drawback that it requires complicated operations and a large amount of cost.
child.

In order to overcome these drawbacks, the present inventors have made extensive research into a method for producing aromatic urethane compounds by oxidatively urethanizing aromatic urea compounds, and as a result, have discovered that the main cause of these drawbacks is Lewis a! We have discovered a completely new catalyst system that allows the +redonx reaction to proceed catalytically without using 5yc* chlorides, etc., and based on this knowledge, we have completed the present invention.

Namely, the present invention is directed to the presence of a cooling agent], the presence of a W platinum group metal and a compound containing a platinum group element in producing an aromatic urethane by reacting an aromatic urea compound with carbon monoxide and an organic hydroxyl compound. A few selected from among
seeds, and a small amount (both 1
The present invention provides a method for producing aromatic urethane, which is characterized by using a catalyst system consisting of ash.

As described above, the major feature of the present invention is that the present invention is characterized by the fact that the present invention is characterized by the fact that only a small amount of metals are selected from among platinum group metals and compounds containing platinum group elements, and alkali metal halides and alkaline earth metal halides. Sho (tomo 1f9)
By using a catalyst system in combination with 111i,
By using this catalyst system, aromatic urethane can be obtained from aromatic urea compounds with good selectivity and high yield.

This is a fact that was completely unknown until now and is a very serious matter).
5-120552), which was completely unexpected. In other words, in this prior art, a catalyst system in which a platinum group compound is used as a main catalyst, a redox reaction is carried out in the reaction thread, and chloride of the base material is used as a co-catalyst, for example, as shown in Example 944 as a typical example. For catalyst systems that combine radium chloride and iron oxychloride, such as
・Te(・ru. In these 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 become divalent palladium. At the same time as returning to valence palladium, 3
1 itb of iron is reduced to divalent iron, and further? It is thought that the main product, aromatic urethane, is produced through a so-called straw-reactive catalytic cycle in which the iron of 2N is reoxidized by the oxidizing agent and returned to iron of 311II. .

Thus, in the prior art process, it is ignored that the chloride of an element having a redox reaction is essential as a reoxidizing agent of the main catalyst in the five-reaction system.

Elements with such 8 functions are listed in l of the periodic table.
a ” 'J A substance that can undergo a redox reaction selected from the a group and 1b-Vlb group elements, specifically copper, zinc, mercury, thallium, tin, titanium, arsenic, Examples include anti-7, bismuth, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, etc. Among them, only copper, vanadium, manganese, molybdenum, tungsten, anti-7, and iron are examples. It is only stated in.

On the other hand, the method of the present invention uses 1 m and ua of the periodic table.
This method uses halides of alkali and alkaline earth metals, which are elements 11 and 1m, but group 11 and 1m elements X were thought to have no effect on redox reactions under normal reaction conditions, Beyond the above? ``T'BL jutsu i
In c., the use of these compounds is not contemplated at all. Therefore, the reaction of the present invention can be carried out in the above-mentioned manner. It is presumed that the reaction mechanism is completely different from that described in 'T technology.

It is not clear what mechanism the alkali metal halides and alkaline earth metal halides act in the reaction of the present invention, or compounds containing platinum group metals and platinum group 7cX. When combined with, it serves as a catalyst component for the oxidative urethanization reaction of the aromatic base compound,
It is clear that this is having a negative effect. In other words, when only alkali metal halides or alkaline earth metal halides are used, the unreacted aromatic urethanization reaction does not proceed at all, and platinum group compounds are Even when using only compounds containing
Under the conditions of this reaction), the aromatic urethane formation reaction does not move rapidly, or even if it is carried out, only a small amount of aromatic urethane is produced.Especially when only the platinum group element in the metallic state is used, Aromatic urethane is difficult to obtain. For example, palladium is one of the effective catalyst components for this reaction.
However, this reaction does not proceed substantially with only palladium black, which is zero-valent metal palladium. death,
Also, halides of alkali metals - halides of alkaline earth metals? 11) When cesium iodide or the like is added, aromatic urethane can be obtained almost quantitatively.

In this way, 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, which means that the expensive platinum group compound can be separated from the reaction system by a simple method such as filtration. , it has been shown that 1 yield can be obtained.

In addition, halides of alkali metals and halides of alkaline earth metals are easy to separate and recover, unlike the chlorides of heavy metals iI4, which are used in the prior art described above. One of the major features of the present invention is that it does not mix into substances as contaminants.

Compounds that ameliorate platinum group metals and H metals used in the method of the present invention include palladium, rhodium, platinum, ruthenium, iridium, osmium, and other platinum group elements. Sho l (tomo lllll)
'ff1i is %K 111J @ k@ (, these principals may be 4itII & Jojuku.

It may be a component that forms a compound. However, these catalyst components are active vertically, graphite, and 7 rica.

Alumina, silica-alumina, silica-chikunia.

Titania, zirconia, barium barium, visceral acid carunium, asbestos, bentonite, quince earth, holimar,
It can also be supported on carriers such as ion-containing aliphatic fat, theolite, molecular weight, magnesium silicate, and magnesium silicate.

Gold is an important platinum group element, and Shiorie supports metals such as palladium, rhodium, platinum, ruthenium, iridium, and osmium, these metal islands, and catalyst components containing these metal ions on the above-mentioned carrier. After that, there are those that are reduced with hydrogen or formaldehyde, and alloys containing these gold-14 (such as & or other 7[:j
For example, cererium, tellurium, sulfur, antimony, bismuth, copper, steel, gold, zinc, tin, vanadium, iron, cobalt, nickel, wood-like, button, thallium, chromium.

It may also contain molybdenum, tungsten, etc.

Compounds containing platinum group elements include halides, sulfates, nitrates, phosphates, and borates.
Which inorganic salts; prudent salts such as vinegar flt salts, oxalates, formates; cyanides; hydroxides; sulfates; Metal wire rings containing anions such as oxalate ions, and metal compounds such as salts or chelates containing ammonia, amines, phosphine chains, -oxidized longitudinal chelate ligands; Examples include organometallic compounds 4Ill having groups.

Among these, those containing palladium or erodium or both Y are particularly preferable, and examples of such materials include Pa seed; pa-C, Pa-
AlzO,, Pd-8i0. , Pa-Ti%, Pd
-Zr0. ,Pd-Ba5O,,Pd-CmC01,p
ii- Asbestos, Pd-zeolite, Pa-molecular sheep etc. supported Balasicum 1111i1;
pct-pb, Pd-8@, Pd-'r@, P
d-Hg, Pd-Tl, Pd-P, Pd-Cu, Pd-
Mg, Pd-F@.

Pd-Co, Pd-Nj, Pa-Rh TL
Which alloys or intermetallic compounds; and how these alloys or intermetallic compounds are supported on the above-mentioned carrier; pa
ct, , PaBr, , Pal, , Pa(NO,
), , Pd8o, and other inorganic salts; Pd(UC(J
CH, ), , 11g2 of available materials such as palladium
Hanataka 1: Pd(CN)R; PdO;
Pd8; Ml[PdX'4], MI
LPdX] Palladium #R salts (M represents an alkali metal, ammonium ion, nitro group, cyan group, X' represents a halogen);

Palladium amino acids such as jPd (ea) z)
In, PdC1,(PR”),,Pd(CO)(Pit
”)m, Pa(PPM mountain, PaL:1(Rsu()'Ph
,),.

Pd(C,ki,)(PPh-,,Pd(CsHs)t
TL any complex compound or organometallic compound (Ha is an alkyl or aryl group tR1); Pd(ae
Complex compounds coordinated with chelate ligands such as me%; R
b Black; Supported rhodium catalysts similar to Pd; Rh alloys or intermetallic compounds similar to Pd and those supported on supports; kbcl and hydrates, , RhBr and hydrates, ah, ( so4), and inorganic salts such as hydrates; Rh, (OCOCR,); Rb, θ1, hh
o, ;Ma [RbX) and hydrate (M, X' are the same mer t% -') as above);
″)'s -CRbC60)＠〕X'B TL ト(
1) O') Ram's Anmin Otaiken; Rh4(co
), 1, Rhodium carbonyl clusters such as Rh@(CO)ts; [RhC1(CO)m lt, Rh
C1m(PR”)s, RhC1(PPM, ), gh
X' (CO) L Tomi (xl has the same meaning as above, L&
Examples include aphrodisiac compounds or organometallic compounds such as RhH(CO)(PPbs)s, which is a ligand consisting of a phosphorus compound and an organic compound.

In the present invention, any number of compounds containing these platinum group metals or platinum metals may be used, and especially IIJ@ for mixed Li of 1 or 1 or more types may be used. However, it is desirable that the component rich in platinum and 7C is usually 0.0001 to 50 mol% of the urea and aromatic compounds.

In addition, the alkali metal halides and alkaline earth metals used in the uninvented method are combined with lithium, sodium, potassium, rubidium, cesium, and turanthium.

Helium, magnesium, calcium, strontium, barium, radium, and other chemical compounds, specifically fluoride, sodium fluoride, potassium fluoride, and rubidium fluoride.

Comparison of cesium, fluoride, and feces IJ
Liwam, magnesium fluoride, calcium fluoride, strontium fluoride, chlorium fluoride, radium fluoride, lithium chloride, sodium chloride.

Potassium chloride, rubidium chloride, cesium chloride.

Furanwum chloride, beryllium chloride, magnesium chloride, calcium chloride, strontylanochloride.

1 salt, Baliwam, radium chloride, lithium bromide, sodium bromide, rubidicum bromide, nested cesium.

Fruit 1 Sifuranium, beryllium bromide, magnenium bromide, strontium bromide, radium bromide, lithium iodide, sodium iodide.

Potassium iodide, rubidium iodide, cesium iodide,
Furanium iodide, beryllium iodide.

Compounds of single metals such as magnesium iodide, calcium iodide, strontium iodide, barium iodide, radium iodide, etc. and rogens; magnesium sodium chloride, magnesium potassium chloride, calcium potassium chloride, magnesium bromide Double salts with potassium:
Potassium bromine fluoride, potassium iodine chloride, rubidium iodine chloride.

Cesium iodine chloride, cesium iodine bromide chloride.

Rubidium bromide, iodine chloride, calicum iodine bromide.

Examples include polyhalides such as cesium iodine bromide, rubidium iodine bromide, etc. These alkali metal and alkaline earth metal halides III may be used alone (or in combination with two or more bridges). They may be used in combination.Among these halogenated IJs, those rich in bromine or iodine are preferred, and iodides are particularly preferred.

The amount of the alkaline earth metal and alkaline earth metal halide used in the present invention is 1%.
Q is preferably used in a mole range of 10,001 to 1,000 times the amount of gold principal in the component containing the platinum group principal used.

The aromatic urea compound used as a raw material in the present invention may be any type of urea as long as its hydrogen is substituted with one or more aromatic groups.

Particularly preferred are N,R-dicamerated aromatic urea compounds represented by the following general formula (1).

A
r and ni' may be different or the same. Furthermore, in these aromatic groups, at least one hydrogen on the aromatic group is substituted with another substituent, such as a halogen atom,
May be substituted with a nitro group, amino group, cyano group, alkyl group, nisan group, yJ group group, aralkyl group, alkoxy group, sulfoxide group, sulfone group, carbonyl group, ester group, amide group, etc. .

Examples of such aromatic urea compounds include N, N'
-diphenylurea, ~'-di(p-tolyl)urea, N,N'-di(o-tolyl)urea, he-N'-di(p-aminophenyl)urea, N,N'-di (0-aminophenyl)urea, he,N'-di(p-nitrophenyl) urea, N,N'-ci (o-nitrophenyl)urea, he,N'-di(3-amino-2-methyl phenyl)urea, N,N'-di(3-amino-4-methylphenyl)urea, N,N'~di(5-amine-2~
methylphenyl)urea, N,N'-di(3-nitro-4-methylphenyl)urea, heNl-di(5-nitro-2-methylphenyl)urea, he,N'-di(3-
nitro-2-methylphenyl)urea, 8-(3-amino-2-methylphenyl)-he'-(3-nitro-2-methylphenyl)urea, he(3-amino-4-methylphenyl)-N '-Mochi(3-nitro-4-methylphenyl)urin-(5-amino-2-methylphenyl)-8'-(5-nitro-2
-methylphenyl)mlN-(3-amino-2-methylphenyl)-he'-(5-7minor-2-methyl7enyl)urea, N-(3-amino-2-methylphenyl)-N
'-(3-amino-4-methylphenyl)urea, N-(
3-amino-4-methylphenyl)-to'=(5-amino-2methylphenyl)W books, N-(3-=draw 2-
methylphenyl) -h'-(s-amino-2-methylphenyl)urea, N-(3-nitro-2-methylphenyl)-N'-(5-nitro-2-methylphenyl/i & element, , N'-di(1-naphthyl)urea, he, he'-di(2-naphthyl)urea, he, N'-di(6-amino-1-naphthyl)urea, he, he'-di(4 -amino-1-naphthyl)urea, N'-di(6-nitro-
1-naphthyl) urea, he, he'-di (4-nitroamino-1-naphthyl) urea and θζ are preferable for bamboo having a structural unit represented by the formula.
-diphenylurea, he, he'-di (3-amino-2-
methylphenyl)urea, to,N'-di(3-amino-
4-methylphenyl) urea, N,N'-di(5-aminol-2-methylphenyl) urea and naphthyl group.

The organic hydroxyl compounds used in the invention are -hydric or polyhydric alcohols, and (.) are -hydric or polyhydric phenols. Examples of such alcohols include IR, Examples include monohydric or branched chain monohydric or polyhydric alkanols and alkenols, -hydric or polyhydric cycloalkanols, 7-chloroalkenols, and aralkyl alcohols.Furthermore, these alcohols may contain other inert substituents. , for example, a halogen (Jl-), a cyano group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, etc.
・.

Specific examples of such alcohols include methanol,
Ethanol, glopanol (111 bodies), butanol (
1, pentanol (each isomer%), heptatur (
valley! A note), heptatool (4!rJi4 companies), octatool (each isomer), Noni #7 A: l-# (
%149F), decyl alcohol (% isomer),
Undenru alcohol (% isomer), lauryl alcohol (each isomer), tridenrua"'" (%JiH
EIF), f) aliphatic alcohols such as yf decyl alcohol% isomer), beta/tadefur alcohol (each isomer); 7-chloroalkasols such as 7-clohexanol and cycloheptatool; ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol 7-methyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, etc. Alkylene/glycol monoethers; polyhydric alcohols such as ethylene glycol, flopylene glycol, diethylene glycol, cyfurobylene glycol, glycerin, hexanetriol, and trimethylolpropane; aralkyl alcohols such as benzyl alcohol and the like are used.

In addition, enols such as phenol, various alkylphenols, various alkoxyphenols, halogenated phenols, dihydroxybenzene, 4,4
'-dihydroxy-diphenylmethane, bisphenol-A, hydroquinaphthalene, etc. are used.

As the oxidizing agent used in the present invention, ordinary oxidizing agents can be used, but preferred are molecular oxygen, organic nitro compounds, and mixtures thereof.%
Preferred is molecular oxygen.

Molecule t1; oxygen is pure oxygen or something containing oxygen, and may be air, or air or Mli! The reaction mixture may be replaced with another gas that does not inhibit the reaction, for example, an inert gas such as phoneme, argon, helium, or carbon dioxide. Also, in some cases, hydrogen, -8
．． Contains gases such as R-hydrogen, halogenated carbonized wood (
・But...

In addition, organic nitro compounds may include hR&, both aliphatic and aromatic nitro compounds (・.Alicyclic nitro compounds include, for example, nitrone clobutane, nitrone clobutane, nitrocyclohexane, dinitrocyclohexane (each isomer 11F), bis-(trocyclohexyl)-methane, and fatty non-nitro compounds include nitrometh/, nitroethane, nitrochrono <7 (tanikoshi), nitrobutane (each isomer), nitro-(butane ( valley isomer), nitrohexane (each isomer)
, nitrodecane<q! rs isomer), 1,2-dinitroethane, dinitroethane (each isomer), dinitrobutane (
To Taniisha Salary Dinitropentane (each 與憔悴), Dinitrohexane (Tani isomer), Dinitrodecane (Tani 49 one)
, phenylnitromethane, bis(nitromethyl)-cyclohexane, bis(nitromethylnobenzene), and examples of nitro compounds include nitrobenzene,
dinitrobenzene (1145 bodies), nitrotoluene (6
71 companies), dinitrotoluene (each isomer), nitropyridine (each isomer), dinitropyridine (each isomer),
Dinitronaphthalene (% isomer) and the missing general formula (■I
Mononitration of diphenyl compound represented by -8C~
-, -CO-, -C(JNH-, -COO-, -C(
) t ri (represents a divalent group selected from ni 1 and -he () 1 li -. also u', ) t! is H1 fat Uj & group,
It is an alicyclic group. ) Also, i6 to these nitro compounds
(・, at least one hydrogen has another 11 substituents, such as ・halogen baby, amine group, cyano group, alkyl group, 1
11#l group group, aromatic group, sulfone group, carpol group,
T-substituted with ester group, amide group, etc. (・Moyoyo-・
.

Among these nitro compounds, Bamboo, nitrobenzene, nitrotoluene (/?!r
! I4 injection), nitroethane/(tani isomer), 2.4-
&() 2.6-dinitrotoluene, dichloronitrobenzene (each isomer, 4,4'- and 2,4'-dinitrodiphenylmethane, 1,5-dinitronaphthalene, etc. are preferred.

In the present invention, if the copper acid is a molecular enemy, the reaction will be the following one-sided reaction. Tjru.

ArfNHCCJINliAr' -t U, 5(J,
fCO+2)tUH-ArNHCuCJR 士Ar'1
NHC (JOR1H,U (here, ArjoyohiAr' represents an aromatic group, H represents an organic group) The molecular weight is less than the equivalent (or more is fine, but
Mixing tubes of carbon or organic hydroxyl compounds should be used outside the explosion field.

In addition, when an organic nitro compound is used as an oxidizing agent, the organic nitro compound itself participates in the reaction and becomes urethane.If the structure of the organic group is different from the aromatic group of the aromatic urea compound, the structure of each Needless to say, a polyurethane compound corresponding to the above can be obtained, and if the structures of the two are the same, a diluted aromatic polyurethane compound can be obtained.

For example, is the urethanization reaction carried out according to the following reaction formula? 'T.

2ArNHcONHAr'+lt'NO, 13CO+5
RUH-+ HC to 2Ar (JOR+2Ar'NHC
(X)h 10R'M] CUOR12H! U (Ar, Ar represents an aromatic group, R,)t' represents an organic group. ) When only organic nitro compounds are used as oxidizing agents, the ratio of aromatic urea compounds to organic nitro compounds is preferably 1 mole of nitro groups per 2 moles of urea groups. It may be carried out at a position different from the quantity-to-quantity ratio. Generally, the equivalent ratio of amino group to nitro group is x, l:1yz (.4:11, preferably 15:1 to 2.s:1). Ru.

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 uninvented method 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 organic hydroxyl compound 9IJ in a concentrated manner as a reaction solvent, but if necessary, a solvent inert to the reaction can also be used. Such solvents can be used as aromatic compounds such as benzene, toluene, xylene, and mesitylenate; halogens such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, chlorotoluene, chlornaphthalene, and fromnaphthalene Aromatic carbonized woody plants; chlorhexane, chlorocyclohexane, trichlorotrifluoroethane, methylene chloride, carbon tetrachloride, etc., logogenated aliphatic rehydrogenated hydrogen or] rogenated aliphatic hydrocarbons; acetonitrile , nitriles such as benzonitrile; sulfones such as sulfolane, methylsulfolane, dimethylsulfolane; tetrahydrofuray, 1.4-
Ethers such as dioxane and 1,2-dimethoxy7ethane; ketones such as acetone and methylsulfolane; esters such as ethyl acetate and ethyl benzene; N,N-dimethylformamide, N,N-dimethylacetamide,
Examples include amides such as h-methylpyrrolidone, tetramethylurea, and hexamethylphosphoramide.

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.

Examples of such additives include zeolates, salts of nitrogen-containing compounds and hydrogen halides, quaternary ammonium salts, and tertiary amines! ! 111, and alkali metal salts and alkaline earth metal salts of acids such as boric acid, aluminium, carbonic acid, silicic acid, and organic acids.

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□, preferably 20 to 30
The reaction time varies depending on the reaction system, catalyst system, and other reaction conditions, but is usually from several minutes to several hours.

Furthermore, the reaction of the present invention can be carried out in a one-minute manner, or the reaction solution can be continuously extracted while continuously supplying the reaction components.
It can also be carried out in a one-by-one manner.

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

Sou JIIi gal into a stirring autoclave with an internal volume of 140 Iu, h'-
Diphenyl axillary wood 20m mol, ethanol 40m
7.Put palladium black, ajvatom, and cesium iodide 5mn1OJ in the system and replace it with a vertical turret. The total pressure was 86·kl/d. 160 while stirring
After reacting for 1 hour, the reaction mixture was analyzed for taste, and the reaction rate of he, he'-diphenylurea was 1.
00%, the yield of hephenylcarbamine ethyl is 98
%, the selectivity was 98%.

So) IiN 2 ~ l 6 Woodcutter's alkali metal halide @ or alkaline earth metal halide 501 fT instead of cesium iodide,
For OJ (・The reaction was the same as in Example 1 except for &
* is shown in Table IK.

Table 1 Comparative Example 1 The same reaction as in Example 1 was carried out using only palladium black without using any alkali metal halide or alkaline earth metal halide. The reaction rate was 10%, and ethyl hephenylcarbamate was produced with a yield of only 3%.

Example 17 Contents N-
'-di(0-methylphenyl)urea 25 mmoA.

Ethanol 50y, Hh/Cl with 5 wt% rhodium supported on #i carbon), cesium iodide 6m mo
l;, and after replacing it with thread-like one-enemy carbon, add -carbon oxide to 80 at 11/at, then 1 m cumulative 5 kp/c.
m”k Press-fit L Ta.

After reacting at 160°C for 1 hour while allowing the mixture to rise, the reaction mixture was filtered and the filtrate was analyzed.
The reaction rate of 0-methylphenyl)urea is 95%, N-(0
-Yield of methylphenyl)carbamate ether is 88%
The selectivity was 93%.

Comparative Example 2 The same reaction as in Example 17 was carried out using cesium iodide and T(1,.), but the reaction rate of H'-di(0-methylphenyl)urea was 9%, The yield of 0-methylphenyl)carbamic acid ether was 2% or more.

Example 18 In Example 17, Kltu black 0.
4 to a tom and to, to'-diphenyl urine collection 25
The reaction was carried out in exactly the same manner as in Example 17 except that m mol was used. As a result, the reaction rate of N,N'-diphenylurea was 80%, the yield of ethyl hephenylcarbamate was 72%, and the selectivity was low. was 90%.

Comparative Example 3 The same reaction as in Example 18 was carried out using 9m of cene iodide, but the reaction rate of N,N'-diphenylurea was 8%.
The yield of h-phenylcarbamine ethyl was 2% or less.

Example 19 N was added to a stirring autoclave with an internal volume of 200a14.
N'-diphenylurea 30mmo/, nitropenzene 1
5mmo#, methanol 50%, palladium chloride 0.5
m rbQ confusion, after adding cesium iodide 5 m mob and replacing the heavy weight with a book to make it one enemy, - carbon oxide true intention 12
4/d press fit.

After reacting at 180°C for 4 hours without stirring, the reaction rates of electroconversion, r', l, I'q/-diphenylkimoto and nitrobenzene were 25% and 3, respectively.
At 0%, N-phenylcarbamine methyl is 14 m
Generate a mold (・1 piece.

Example 20\26 The reaction was carried out in exactly the same manner as in Example 1, except that various platinum group metals or compounds containing platinum Yasumoto 3IC were used in place of badge rum in Example 1.

The conclusion! lLt stripes shown in Table 2 (extra color below) Table 2 In these examples, 0.59 atom is used as the metal element for the platinum group metal or platinum group compound, and the % representation is 1° of the supported catalyst component. Indicates amount%.

(Pd-'I'e)/C is obtained by co-supporting palladium chloride and tellurium dioxide at a molar ratio of 1O:3 on an active substance, and then reducing the volume with water at 350°C.

! Yukei Applicant: Asahi Kasei Korikyu Shiki Company

Claims (1)

[Claims] Presence of 1i1-forming agent1. In producing an aromatic urethane by reacting an aromatic urea compound with a monodispersed ester and an organic hydroxyl compound, at least 111 left from A of the compound containing an IAJB gold group metal and a platinum group element, ( B
Method 2 for producing aromatic and urethane compounds using a catalyst system consisting of at least 11m different from alkali gold woven halides and alkaline earth metal halides. The method according to Claim 1, wherein the agent is a molecular Al element, an organic nitro compound, or its rectangular counterpart; 3. The method according to claim 1, in which the platinum group metal and the compound containing the platinum group element are half palladium, simple rhodium, palladium compounds, and rhodium compounds. The method 4 according to claim 1 Homata &
Method 5 according to item 1 or 92 or 3. Claim IP where the II-forming agent is molecular oxygen! l
The method described in paragraph 1 or 2 or 3 or 4