JPS58144359A - Preparation of urethane compound - Google Patents

Abstract

PURPOSE:To prepare the titled compound in high yield, by reacting a urea compound with carbon monoxide and an organic hydroxyl compound in the presence of an oxidizing agent using a catalyst system composed of a platinum group metal and an onium compound having halogen as the anion. CONSTITUTION:A urethane compound is prepared by reacting a urea compound (e.g. N,N-dimethylurea; excluding aromatic urea compounds) 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, etc.) using a catalyst system composed of (A) at least one substance selected from platinum group metal and a compound containing platinum group element (e.g. PdCl2) and (B) at least one substance selected from an onium compounds wherein the anion is halogen (e.g. iodine), e.g. ammonium compounds, phosphonium compounds, of formula (R<1>-R<4> are H, aliphatic group, etc.; X is halogen), etc.

Description

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

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

Urethanes are important compounds used in carbamate pesticides, etc., but conventionally they have been produced by reacting corresponding incyanates with alcohols or by reacting corresponding amines with chloroformic acid esters. Ta. However, in any of these methods, in order to produce incyanates or chloroformates used as raw materials, K has drawbacks such as the need to use phosgene, which is highly toxic and highly corrosive.

On the other hand, a method has also been proposed in which primary amines, carbon monoxide, and alcohols are oxidatively converted into urethanes using a metal group catalyst without using phosgene. (4!f Kaisho 55
140551) Furthermore, a method of oxidatively converting ureas into urethanes has also been proposed. (Unexamined Japanese Patent Publication No. 55-120
However, in all of these methods, as a cocatalyst, copper chloride, iron chloride, iron oxychloride, vanadium chloride, vanadium oxychloride, etc., are Lewis acids, and the chlorination of an element that can undergo a redox reaction in reaction F. These dissolved chlorides are highly corrosive to metal traps such as reaction vessels, piping, and valves, so expensive metal materials must be used. There is a problem with the equipment. Furthermore, since these dissolved chlorides are separated and recovered from the urethane product, K has the drawback of requiring complicated operations and a large amount of cost.

In order to overcome these drawbacks, the present inventors have conducted intensive research on a method for producing urethane compounds by oxidatively converting urea compounds (excluding aromatic urea compounds) into urethanes. Lord of! ! The catalytic trap reaction can proceed without using Lewis acids or chlorides of elements that cause redox reactions. A completely new catalyst system was discovered, and the present invention was completed based on this discovery.

In other words, 1 the present invention provides a method for producing a urethane compound by reacting a urea compound (excluding aromatic urea compounds) with carbon oxide and an organic hydroxyl compound in the presence of an oxidizing agent. At least one compound selected from compounds containing a group metal and a platinum group element; The present invention provides a method for producing urethane, characterized in that it uses a catalyst system comprising seeds.

A major feature of the present invention is that at least 1 s of K, selected from platinum group metals and compounds containing platinum group elements, is used.
and at least one kind selected from onium compounds whose anions are halogens.Using this catalyst system results in good selectivity and high selectivity from urea compounds. A urethane compound is obtained in high yield.

This is a truly surprising fact that was completely unknown until now, and is based on the prior art (Japanese Unexamined Patent Application Publication No. 55-197).
120552), which was completely unexpected. That is, in this prior art, a catalyst system in which a platinum group compound is used as a main catalyst and a chloride of an element that can undergo a redox reaction in one reaction system is used as a co-catalyst, for example, a chloride system as seen in the Tora example is a typical example. A catalyst system that combines palladium and iron oxychloride is used.

In such a system, divalent palladium participates in the reaction, and as the reaction progresses, it is reduced to zero-valent palladium, which is reoxidized by trivalent iron oxychloride to divalent palladium. At the same time as returning, trivalent iron is reduced to divalent iron, and this divalent iron is further oxidized by an oxidizing agent to form trivalent iron Kp, Ru, through the so-called Wallaker reaction type catalytic cycle. It is thought that the main product, urethane, is provided.

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

An example of an element with such a function is Ma in the periodic table.
- Elements that can undergo redox reactions selected from Va group and Ib-11b group elements, specifically copper, zinc, mercury, thallium, tin, teta/, arsenic, antimono, bismuth , vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, etc., among which only copper, vanadium, manganese, molybdenum, tungsten, antimony and iron are mentioned in the examples. Moreover, these examples are only for urethanization reactions of aromatic urea compounds, and there are no examples of reactions for aliphatic or alicyclic urea compounds.

In contrast, the method of the present invention uses onium compounds whose anions are halogens or compounds that can be produced in a reaction system, and these compounds do not contain any metal components or Under normal reaction conditions, the cation moiety cannot undergo a redox reaction.

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.

Although it is unclear how such onium compounds in which the anion is a chloride anion act in the reaction of the present invention, in the case of combination with a platinum group metal or a compound containing a platinum group element, K It is clear that it plays an important role as a catalyst component in the oxidative urethanization reaction of urea compounds.

In other words, the urethanization reaction of this reaction does not proceed at all if only a metal oniumide whose anion is 7-rogen is used, and even if only a platinum group metal or a compound containing a platinum group element is used, the conditions of this reaction are So, the urethanization reaction hardly progresses?

Or, even if it progresses, it will only give a small amount of urethane compound, especially if only platinum group elements in the metallic state are used.
Almost no urethane compounds are obtained. For example, palladium is one of the effective catalyst components for this reaction,
This reaction hardly progresses when only palladium black, which is zero-valent metal palladium, is used alone. However, when an onium compound whose trapping anion is a halogen, such as tetramethylammonium iodide, is added, a urethane compound 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 it can be recovered, which is industrially advantageous.

Another major feature of the present invention is that it uses onium compounds whose anions are halogens, and since most of these compounds are water-soluble, they can be easily separated and recovered from the product. Therefore, unlike the conventionally used heavy metal chlorides, they do not mix into products as contaminants.

The platinum group metal and platinum group element-containing compound used in the method of the present invention may contain at least one component selected from platinum group elements such as palladium, rhodium, platinum, ruthenium, iridium, and osmium. There are no particular limitations, and these elements may be in a metallic state or may be components forming a compound.

In addition, these catalyst components are activated carbon, graphite, and silica.

Supported on carriers such as alumina, silica-alumina, silica-titania, titania, zirconia, barium sulfate, calcium carbonate, asbestos, bentonite, diatomaceous earth, polymers, ion exchange resins, zeolites, molecular sheep, magnesium silicate, magnesia, etc. It may be something.

Examples of platinum group elements in the metallic state include palladium, rhodium, platinum, ruthenium, iridium, and osmium. Formaldehyde-reduced materials and alloys or intermetallic compounds containing these metals are used. The alloy or intermetallic compound may be one of these platinum group metals, or it may contain other elements such as selenium,
Tellurium, sulfur, antimony, bismuth.

It may contain copper, silver, gold, zinc, tin, /<nadium, iron, konorut, nickel, mercury, thallium, chromium, molybdenum, tungsten, and the like.

On the other hand, compounds containing platinum group elements include, for example, inorganic salts such as halides, sulfates, nitrates, phosphates, and borates; organic acid salts such as acetates, oxalates, and formates; and fan compounds. ; Hydroxides; Oxides; Sulfides; Metallic acid salts containing arions such as nitro groups, cyano groups, halogens, oxalate ions, and ammonia, amines, phosphines, carbon oxide chelate ligands, etc. metal complex compounds such as salts or complexes containing; organometallic compounds having organic ligands or organic groups; and the like.

Among these catalyst components, those containing palladium or rhodium or both are particularly useful, such as black: Pd-C, Pd-A.
ll0@, Pd-8i0. ,
Pd-T10. , Pd-ZrO@.

Pd-Ba804, Pd-CaC0g, Pd-
Supported palladium catalysts such as 7sbest, Pd-zeolite, Pd-molecular sieve: Pd-Pb
, Pd-8e, Pd-Te.

Pd-Hg, Pd-TI, Pd-P,
Pd-Cu, Pd-Ag, Pd-Fe
, Pd-Co, Pd-Ni, Pd-Rh
alloys such as metals, intermetallic compounds; and alloys or intermetallic compounds supported on the above-mentioned carriers; P
dC1,.

PdBr, , PdI, , Pd (No,),
, Inorganic salts such as P4804: Pd (OCOCH
, ), , Palladium oxalate Table Which organic acid salts: P
d (CN), : PdO; Pd8 : M, (
:PdX, :l.

M, palladate salts (M
is an alkali metal, am/monium ion, and four nido groups.

It represents a cyano group, and X represents a halogen. ):(Pd
(!GIRI4) Xl, CP (1(em),)
Ammine complexes of palladium with Xl (X has the same meaning as above).

The axis represents ethylene cyanide Z); Pace (Ph
CN).

PdC4(PRs)1, Pd(CO)(PH1)
s, Pd(PPhs)a.

PdC4(R) (PPhs)* −Pd ((4Ha
) (PPhs)*, complex compounds or organometallic compounds such as Pd (CsHi)m (R represents an organic group)
: Complex compounds coordinated with chelate ligands such as Pd(acac) ; RhCLH and hydrate, R
hBr- and hydrate, RhI and hydrate.

Inorganic salts such as SOi and hydrates: Rh,
(OCOCH,)4: Rh, 0□, Work 0. ;M@(
XI) and hydrates (M and X have the same meanings as above)
: (ph(r'1ns)s)Xs-(Rh (en
)s J Xs and other ammine complexes of rhodium;
Rhodium carbonyl clusters such as ms: (R
hCt(Co)1)1, RhCLH(PR-,.

RhCt(PPh, ), RhX(Co)L,
(X has the same meaning as above, L is a ligand consisting of an organic phosphorus compound and an organic arsenic compound), RhH
Examples include complex compounds such as (CO) (PPhs)s and organometallic compounds.

In the present invention, only one of these platinum group metals or compounds containing platinum group elements may be used.

In addition, two or more kinds may be used as a mixture, and there is no particular restriction on the amount used, but it is usually desirable that the amount of the component containing the platinum group element is in the range of o, ooot to 50 mole based on the urea compound. .

It is also used in the present invention. An onium compound whose anion is a halogen is a compound containing an element with a lone pair of electrons, in which a proton or other cationic reagent binds to these lone pairs, and the element with a lone pair of electrons forms a covalent bond. It has a cation with an increased valence of 1, and has an l.rogen anion as a counter ion.

Such onium compounds include ammonium 17A
Compound, hox honi? compound ((R”R”R”
R'Pe)Xe) ammonium compound ((R"R"
R''R'As8)Xo), stibonium compound ((
R'R"R"R'8b") R”R”R”8e(0)Xo), sev
/ Nify A Compound ((R”R”R”8e°)X
o),? #05? Compound A ((R"lL"R@Te")
Xo), stibonium compound ((R"R"R'8-
)Xo), Yokudonicum compound ((R'R"I')X
o) Nato Power I Ke6 Rel. ko j r R', R”
.

Bl and B4 represent a group selected from a hydrogen-containing aliphatic group, an aromatic group, an aliphatic group, and an araliphatic group, and each may be the same, or in some cases, a lone electron group. It may also be a component of a product containing elements having pairs, and X is F, CL, Br in the above convention.

■Represents a halogen selected from.

Such halogenated dime compounds are ammonia, amines, phosphine compounds, arsine compounds, stibine compounds, oxy compounds, sulfide compounds, sulfoxide compounds, selenide compounds corresponding to /% hydrogen halides or organic halides. , a telluride compound, etc.), and these may be produced outside the reaction system or may be produced within one reaction system. Of course, it may be produced by other methods, or may be produced within the reaction system by other methods.

Among these, halogenated ammonium compounds, halogenated phosphonium compounds, non-halogenated alnonium compounds and halogenated sulfonium compounds are preferred, and halogenated ammonium compounds and halogenated phosphonium compounds are preferred in terms of percentage.

The halogenated ammonium compound usually refers to a 7-hydrogen halide salt and a quaternary ammonium I-ride of a nitrogen-containing compound having a group represented by the general formula (1). Here, three or four lines connected to N represent bonds between the nitrogen atom and other atoms or groups, and X is the same as above.
) represents F, CI, Br, I.

In formula (1), examples of atoms or groups bonded to nitrogen include hydrogen, alkali metal atoms, tetraxyl groups, aliphatic groups, aliphatic groups, aromatic groups, araliphatic groups, and heterocyclic groups. There is. Further, in formula (1), nitrogen may itself be an element constituting a term, such as piperidine, pyridine, or quinoline.

Furthermore, two or more groups represented by formula (1) may be present in the molecule.

Such ammonium halide compounds.

It can be easily obtained by reaction of a corresponding nitrogen-containing compound with a hydrogen halide, reaction of a nitrogen-containing compound with an alkyl halide or an aryl halide, or the like.

Examples of nitrogen-containing compounds that can form salts or quaternary ammonium halides with hydrogen halides, alkyl halides, or aryl halides include ammonia; amines such as primary amines, secondary amines, and tertiary amines; ; hydroxylamines; hydrazines; hydrazones; amino acids; oximes, 4-imidoesters; amides, and various nitrogen-containing heterocyclic compounds.

Preferred hydrogen halide salts of nitrogen-containing compounds include salts of ammonia such as ammonium chloride, ammonium bromide, and ammonium trichloride; salts of aromatic amines such as diphenylamine and triphenylamine; methylamine, ethylamine, propylamine, Butylamine, hexylamine, octylamine, dimethylamine, trimethylamine/J diethylamine, triethylamine, dipropylamine, tripropylamine, dibutylamine, tripropylamine, methylethylamine, dimethylethylamine, diethylmethylamine, ethylbutylamine,
Salts of aliphatic amines such as dibutylmethylamine/, tributylamine/, trihexylamine 7% edele/diamine, hexamethylenediamine; alicyclic amines such as cyclopropylamine, cyclohexylamine% N-methylcyclohexylamine; Salts of; benzylamine, N-
Salts of aromatic aliphatic amines such as methylbenzylamine, N,N-diethylbe/zylamine/, dibenzylamine; piperidine, piperazine, morpholine.

Pyridine, quinoli/, hexamethylenetetrami/, oxazole, thiazole, imidazole, triazole,
Salts of nitrogen-containing heterocyclic compounds such as N/citriazole and diazabidiclow/decene; dimethylacetamide, N
-Amide salts such as methyl birolide/etc. are used.

In addition, quaternary ammonium halides include tetramethylammonium chloride,!・Aliphatic quaternary ammoniums such as Tet2ethyla/monium halide, Tetrapropyla/monium halide, Tetrabutylammonium halide, Trimethylethylammonium halide, Trimethylbutylammonium halide, Diethyldibutyla/monium halide, etc. 7 ~ Rides;
aliphatic quaternary ammonium 7-rides such as dimethylcyclohexylammonium; aromatic aliphatic quaternary ammonium such as norologenated tetrabearzylammonium, nororogenated trimethylpe/silua/monium;
Monicum halides; halogenated N, N, N-)limethylphenylammonium/Slogenated N.

Aromatic 4 such as N,N-)ethylphenylammonium
class ammonium halides; N-methylpyridinium halide, N-ethylpyridinium halide, N-methylquinolinium halide.

Halogenated N-ethylquinolinium, Halogenated N, N
Heterocyclic quaternary ammonium halides such as -dimethylpiperidinium, halogenated N, and N/-dimethylimidazolinium are preferably used.

Examples of halogenated phosphonium compounds include:

Symmetrical tetraalkylphosphonium compounds such as halogenated tetraethylphosphonium, halogenated tetraethylphosphonium, halogenated tetrapropylphosphonium, halogenated tetrabutylphosphonium, halogenated tetrahexylphosphonium, etc.: halogenated ethyltrimethylphosphonium, halogenated diethyldimethylphosphonium Asymmetric tetraalkylphosphonium compounds such as halogenated tetraphenylphosphonium, halogenated tetra(p-)lyl)phosphonium; symmetrical tetraarylphosphonium compounds such as halogenated (α-su7)
Asymmetric tetraarylphosphonium compounds such as methyl)triphenylphosphonium: 7% 0 Saponified methyltriphenylphosphonium.

Ethyltriphenylphosphonium halide, halog/
Preferably used are furkylaryl mixed water sphoenium compounds such as phenyltrimethylphosphonicum halides, and tetraaralkylphosphonium compounds such as tetrabenzylphosphonium halides.

Examples of halogenated alumnium compounds include symmetrical tetraalkylalnonium compounds such as tetramethylarsonium halide and tetraethylarsonium halide; asymmetrical tetraalkylalnonium compounds such as methyltriethylalnonium halide and dimethyldiethylarsonium halide. Symmetrical tetraarylarsonium compounds of the halogenated tetraphenylalnonium group; methyltriphenylalunium halide, ethyltriphenylalunium halokenide,
Alkylaryl mixed alnonium compounds such as halogenated phenyltrimethylarsonium are preferably used.

Examples of halogenated sulfonium compounds include ti? ,
halogenated) 9 Symmetrical or asymmetrical alkylsulfonium compounds such as methylsulfonium halide, triethylsulfonium halide, and methyldiethylsulfonicum halide; Arylsulfonic compound f such as triphenylsulfonium halide; dimethylphenyl halide Preferred are alkylarylsulfonium compounds such as sulfonium and halogenated methyldiphenylsulfonium; t-shaped sulfonicum compounds such as halogenated bicyclo-(2,2,1')-hebuta-7-1-sulfonium and halogenated thiopyrylium oxide; used.

These 7-rogenated onium compounds can be used alone or in combination of two or more. Of course, one molecule may contain two or more onium halide groups with the same meaning.

Also, among these more onium halide compounds, hap
Those containing bromine, Fl, or s are preferably used, and those containing iodine are particularly preferred.

The amount of the halogenated onicum compound used in the present invention is not particularly limited, but it is usually o, oei to 16,000 with respect to the amount of the metal element in the component containing the platinum group element used. It is preferable to use it in twice the molar range.

The urea compounds used as raw materials of the present invention exclude aromatic urea compounds in which an aromatic group is directly bonded to 9 atoms, and have urea bonds as shown in the following formula % in one molecule. A compound containing at least one Here, two consecutive NK lines represent a bond between a nitrogen atom and another atom or #i group. Such atoms or groups include hydrogen, halogen, alkali metal atoms, hydroxyl groups, amine groups, aliphatic groups, alicyclic groups, araliphatic groups, and heterocyclic groups. Further, these nine elements may themselves be elements constituting 3]l, or the urea bond itself may be a part constituting the ring.

Such urea compounds may be unsubstituted urea, monosubstituted urea, disubstituted urea, trisubstituted urea, or tetrasubstituted urea. Examples of monosubstituted ureas include aliphatic monosubstituted ureas such as methylurea, ethylurea, tetravirurea, butylurea, and hexylurea; cyclopropylurea and cyclobutylurea.

Alicyclic monosubstituted ureas such as cyclohexyl urea; aromatic aliphatic monosubstituted ureas such as be/dylurea and β-7enel urea; heterocyclic monosubstituted ureas such as furanylurea and thiophenyl urea are used. . Examples of disubstituted ureas include N,N dimethylurea, N,N-diethylurea,
N, N-dipropylurea, N, N-dibdelurea, N,
N-dihexafluorurea% N-ethyl-N-methylurea, N
Fatty complex N,N-disubstituted ureas such as -ethyl-N-butylurea: N,N-dicyclopropylurea, N,N-dicyclobutylurea, N,N-synchexylurea, N
-Cyclopropyl-N-1f urea I Alicyclic N,N-disubstituted ureas such as N-cyclohexyl-N-ethylurea: N,N-dibenzyl [substituted, N-benzyl-N-methylurea, etc.] Aroaliphatic N,N-disubstituted ureas: N,N-
Heterocyclic N,N-disubstituted ureas such as diethylurea, N,N-dithiophenylurea, N-7 ranyl-N-methylurea: N,N'-dimethylurea, N,N'-diethylurea, N , N'-dipropylurea, N,N'-diptylurea, N,N'-diethylurea, N-ethyl-N'-methylurea, N-ethyl-N'-butylurea, N-hexyl-N'- Aliphatic N,N'-disubstituted ureas such as ethyl urea; N,N'-dicyclopropylurea, N,N'-synchrobutyl urea, N,N'-dicyclohexyl urea,
Alicyclic N such as N-cyclopropyl-N'-methylurea IN-cyclohexyl-N'-etherurea.

N'-disubstituted ureas: NaN'-dibenzylurea l, N
-Aroaliphatic N,N' such as benzyl-N'-methylurea
-Disubstituted ureas; N, N'-diethylurea, N, N'-
Heterocyclic N,N'-disequilibrium ureas such as dithiophenyl urea; ureas of cyclic nitrogen compounds such as piperidyl urea and pyrrolidinyl urea are used. Examples of tri-substituted ureas include trimethylurea, triethylurea, tripropylurea, tributylurea, trihexylurea, N, N
-dimethyl-N'-ethylurea, N,N-diethyl-N
Aliphatic trisubstituted ureas such as '-butylurea, N-methyl-N-ethyl-N'-butylurea; tricyclopropylurea, tricyclohexylurea I N,N'-dicyclohexyl-N'-methylurea l N-cyclohexyl-N-
Ethyl-N'-butyl urea, N,N-diethyl-N'-
Alicyclic trisubstituted ureas such as cyclobutyl urea Heterocyclic trisubstituted ureas such as nitri7ranyl urea, trithiophenyl urea, N,N'-di7ranyl-N-methylurea: N-
Ureas such as cyclic nitrogen compounds such as ethylpiperidylurea and N-methylpyrrolidinylurea are used. Examples of tetra-substituted ureas include aliphatic tetra-substituted ureas such as tetramethyl urea, tetraethyl urea, tetrarubuvir urea, tetrahexyl urea, diethyl dimethyl urea, and ethyl trimethyl urea; tetracyclopropylurea, nato-di-fufurea, and Schifte-tetra-substituted urea; Alicyclic tetra-substituted ureas such as butyl trimethyl urea; aromatic aliphatic tetra-substituted ureas such as tetrapenzyl urea, tribenzyl methyl urea, dibenzyl diethyl urea, and benzyl trimethyl urea; tetra-7ranyl urea;
Heterocyclic tetra-substituted ureas such as tetrathiophenyl urea and 7-tnyrutrimethyl urea are used. Cyclic urea and 1 to 2-imidasilone, 2-imidazolitone, biotin, hydantoin, parabanic acid, etc. are used.

Furthermore, in these substituted ureas, one or more hydrogen atoms in the substituent may be substituted with other substituents, such as a lower aliphatic group, an amino group, a carboxyl group, an ester group, an alkoxy group, a cyano group,
/%Dgen, nitro group, urethane group, sulfoxide group,
It may be substituted with a sulfone group, a carbonyl group, an amide group, an aromatic group, an araliphatic group, or the like.

One or more of these urea compounds may be used above.

The organic human xyl compounds used in the present invention include industrial value or polyvalent alcohols, or monovalent or polyvalent heptenols, and such carbonyl groups include, for example, linear or Branched monohydric or polyhydric alkanols and alkenols Monohydric or polyhydric cycloalkanols, cycloalkanols, aralkyl alcohols, and the like can be used. Furthermore, these alcohols are inert and have cypress groups such as halogen atoms, cyano groups, alkoxy groups,
It may contain a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, etc.

Specific examples of such alcohols include methanol,
Ethanol, propatool (each A41), butanol (
(each isomer), pentanol (each isomer), hexanol (each isomer), heptatool (each isomer), octatool (each isomer), nonyl 7k:7-l (each isomer)
, Tesyl alcohol (each isomer), Undecyl alcohol (each isomer), Lauryl alcohol (each isomer), Tridecyl alcohol (each Ju column), Tetrazosyl alcohol (-L body), etc. Aliphatic alcohols ; Cycloalkanols such as cyclohexanol and cycloheptatool; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , alkylene glycol monoethers such as fvxk' rangel glycol monoethyl ethernato; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, cyfropylene glycol, glycerin, hexanetriol, trimethylolpurpane; benzyl alcohol These include nato aralkyl alcohols. □ Examples of phenols include phenol, various alkylphenols, various alkoxyphenols, various halogenated phenols, dihydroxybenzene, 4.4'
-dihydroxy-diphenylmethane, bisphenol-
A1 hydroxynaphthalene and the like are used.

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

This molecular oxygen is pure oxygen or a substance containing oxygen, which may be air, or air or pure oxygen may be mixed with other gases that do not inhibit the reaction, such as nitrogen, argon, helium, carbon dioxide, or other inert gases. In addition, it may be diluted. In some cases, it may also contain gases such as hydrogen, carbon oxide, hydrocarbons, and halogenated hydrocarbons.

Further, the organic nitro compound may be any of alicyclic, aliphatic, and aromatic nitro compounds. Examples of alicyclic nitro compounds include nitrocyclobutane, nitrocyclopentane, nitrocyclohexane, dinitrocyclohexane (each isomer), bis-cyclohexyl)-methane, and examples of aliphatic nitro compounds include 2=)0methane. , nitroethane, nitropropane (each isomer), nitrobutane (each isomer), nido p-bebutane (each isomer), nitrohexane (each isomer), nido tetradeca/ (each isomer), 1.2- Dinitroethane, dinitropropane (each isomer), Dinitrobentane (each isomer), dinitrohexane (each isomer).

Dinitrodecane (each isomer), phenylnitromethane,
Examples of aromatic nitro compounds include nitroethane/, dinitrobenzene (each isomer), nitrotoluene (each isomer), and dinitrotoluene (each isomer). ).

Nitropyridine (each isomer), dinitropyridine/(each isomer), nitronaphthalene/(each isomer).

Examples include di=)os7sauce/(each isomer).

Furthermore, in these nitro compounds, at least one hydrogen is substituted with another substituent such as a halogen atom, an amino group,
It may be substituted with a cyano group, an alkyl group, an alicyclic group, an aromatic group, an aralkyl group, an alkoxy group, a sulfoxide group, a sulfo/group, a carbonyl group, an ester group, an amide group, or the like.

In the present invention, when the oxidizing agent is molecular oxygen.

The reaction proceeds according to the following general reaction formula.

(In this ζ, R1, R1, 1%1, R4 are selected from hydrogen, halogen, alkali gold lli atom, hydroxyl group, amino group, aliphatic group, alicyclic group, araliphatic group, heterocyclic group) (R represents an organic group.) Molecular oxygen may be less than or more than the equivalent amount, but
Oxygen/carbon oxide or oxygen/organic hydroxyl compound mixtures should be used outside the explosive limits.

In addition, when an organic nitro compound is used as an oxidizing agent, the organic nitro compound itself also participates in the reaction and becomes diurethane, so if the structure of the organic group is different from the substituent of the urea compound,
It goes without saying that urethane compounds corresponding to each structure can be obtained, and if both structures are the same, the same urethane compound can be obtained.

In this case, the urethanization reaction proceeds, for example, according to the following reaction formula.

+2H,0 (where Bl, Bl, Bl, R4 and R
has the same meaning as above, and R represents an organic residue of an organic nitro compound. ) When using only an organic nitro compound as an oxidizing agent, it is preferable that the quantitative ratio of the urea compound and the organic nitro compound is 1 mole of dinitro group per 2 moles of urea group, but of course this stoichiometric ratio It may be carried out at a remote location. Generally, the equivalent ratio of urea group to nitro group is 1
．． 1:1'&Ishi 4:1. The ratio is preferably 1.5:1 to 2.5:1.

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

In the method of the present invention, it is preferable to use an excessive amount of organic hydroxyl compound as the reaction solvent, but it is also possible to use a solvent that does not adversely affect the reaction depending on the PK. Examples of such solvents include aromatic hydrocarbons such as L'd, benzene, toluene, xylene/, mesitylene; chlorbe/ze/, dichlorobenzene, trichlorbe/
Zey, Fluop-benzene, Chlortoluene, Chlornaphthalene/.

7. Rogenated aromatic hydrocarbons such as promnaphtali y
; Chlorhexane, chlorocyclohexane, trichlorotrifluoroethane/, methylene chloride.

Halogenated aliphatic hydrocarbons or halogenated aliphatic hydrocarbons such as carbon tetrachloride; nitriles such as acetonitrile/I/, he7, and/nitrile; sulfones such as sulfolane, methylsulfolane, and dimethylsulfolane;
Tetotsuhydrofuray, 1,4-dioxa 7.1J-
Ethers such as dimethoxyethane; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and ethyl benzoate; N,N-dimethylformamide, N,N-dimethylacecyamide, N-methylpyrolide/hexamethylphosphor Examples include amides such as Ruamide.

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

Suitable examples of such additives include, for example, tertiary amines, alkali metal salts and alkaline earth metal salts of acids such as boric acid, aluminum/acid, carbonic acid, silicic acid, and organic acids. be.

In the method of the present invention, one reaction is usually carried out at 80 to 300°C.

Preferably a1! It is carried out in a temperature range of O-ate°C.

Moreover, the reaction pressure is S to 500 h/d, preferably! ! 0~
The reaction time varies depending on the reaction system, catalyst system, and other reaction conditions, but is usually from several minutes to several hours.

Moreover, the reaction of the present invention can also be carried out batchwise.

A continuous system may also be used in which the reaction solution is continuously withdrawn while the reaction components are continuously supplied.

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

Example 1 Stirring type autoclave KN, N' with internal volume 14G
- After adding 20 mm0 L of dicyclohexyl urea, 40 mm of ethanol, 0.5 η3 tom of palladium black, and 2 m mot of tetramethylammonium iodide and replacing the inside of the system with carbon monoxide, the amount of -carbon oxide was 864/j, and then 6 k/j of oxygen. After pressurizing eIi and reacting at 160°C for 1 hour with stirring, the reaction mixture was filtered to obtain a pale yellow solution. As a result of analyzing this solution, N, N'
The reaction rate of -dicyclohexyl urea was 96%, the yield of ethyl N-cyclohexylcarbamate was 94%, and the selectivity was 98%.

Examples 2 to 16 Various I-Roge/onium compounds were used in place of dimethylammonium iodide in % of implementation! Table 1 shows the results of the same reaction as in Example 1 except that mmot was used.

Table 1 Comparative Example 1 The same reaction as in Example 1 was carried out using only palladium black without using any onium halogenide compound.
, the reaction rate of N'-dicyclohexylurea is ss, and N-
Ethyl cyclohexylcarbamate was produced in a yield of only 291.

Example 1.

d1. except that urea '81 mmot was used instead of N,N'-dicyclohexylurea in Example IK. wait<
As a result of carrying out the same reaction as in Example 1, the reaction rate of urea was 8.
The yield of ethyl carbamate was 8,441 and the selectivity was 95.

Example 18 The same reaction as in Example 1 was carried out, except that in place of N,N'-dicyclohexylurea in Example IK, and tetramethylurea gQ mrnol was used in 9. As a result of carrying out the same reaction as in Example 1, the reaction of tetramethylurea The yield of ethyl N,N-dimethylcarbamate was 65% and the selectivity was 90%.
Met.

Example II The same reaction as in Example 1 was carried out except that KN,N'-di(n-butyl)urea 20 mm6t was used instead of N,N'-dicyclohexylurea in Example IK. , the reaction rate of N,N'-di(n-butyl)urea is 9
41, the yield of N-n-butylcarbami/ethyl acid is 8
After 8 hours, the selection rate was 94%.

Example 2G N was added to a stirred autoclave with an internal volume of 200 m.
N'-di(β-7znetyl)urea 20mlnot,
Z Tanol Sod, activated carbon K Rh/C1 carrying 5w'J of rhodium? After adding 3 mmg of tetramethylammonium iodide and replacing the inside of the system with carbon monoxide, 80 Kf/j of -carbon oxide and then 6 Kp/- of oxygen were introduced under pressure. After reacting at 160°C for 1 hour while stirring, the reaction mixture was filtered and the filtrate was analyzed.

The reaction rate of N,N'-di(β-phenethyl)urea is 92%.
.

The yield of ethyl N-(β-7enethyl)carbamate is 8
The selectivity was 92% for 5 samples.

Comparative Example 2 Example 2 without using tetramethylammonium iodide
The same reaction as in 0 was carried out, but the reaction rate of %N, N'-di(β-phenethyl)urea was 9g6, and N-(β-7enethyl)
The yield of ethyl carbamate was 21 or less.

Example 21 N, N' in a stirring autoclave with an internal volume of 200
-di(1-hexyl)urea 36 mmots 2) 0 benzene 15 mm0L, methanol 50-1 palladium chloride 0.5! After adding 3 mmot of tetrabutylammonium trichloride and replacing the inside of the system with carbon monoxide.

- Carbon oxide 141)4/- was press-injected. As a result of analyzing the 0 reaction solution reacted at iso℃ for 5 hours from Ka1&Mazena, the reaction rates of N,N'-di(n-hexyl)urea and nitrobenzene were 349G and 38G, respectively, and N-n
- 13 mm0L and 3rnmo of methyl octylcarbamate and methyl N-phenylcarbamate, respectively
L was being generated.

! l! Examples 22 to 29 Table 2 shows the results of similar reactions in Example I using a platinum group metal or a compound containing a platinum group element in place of palladium black.

In the Examples of Table 2, the platinum group metal or platinum group compound was used as a metal element at 0.5η atom k.

The indication indicates the weight percent of supported catalyst component.

(Pd-Te)/C was obtained by co-supporting activated carbon-trapped palladium chloride and tellurium dioxide at a molar ratio of 10:3.

Hydrogen reduction at 350°C yields fc.

Claims (1)

[Claims] 1. In producing a urethane compound by reacting a urea compound (excluding aromatic urea compounds) with carbon oxide and an organic hydroxyl compound in the presence of an oxidizing agent, (!l) At least one selected from platinum group metals and compounds containing platinum group elements, and (b) selected from onium compounds whose anions are halogens and compounds that can produce these in a reaction system. Method 2 for producing a urethane compound characterized by using a catalyst system comprising at least one type of oxidizing agent λ The method according to claim 1, wherein the oxidizing agent is molecular oxygen, an organic nitro compound, or both. is molecular oxygen; Claims 1 to 3, wherein the platinum group metal and the compound containing the platinum group element are palladium, rhodium, a palladium compound, and a rhodium compound. The method described in Claims 1 to 4, wherein the onium compound is an ammonium compound, a phosphonicum compound, an arunium compound, or a sulfonium compound & Claim 1, wherein the halogen species is Tatsumoto to the method described in Section 5.