JPS58162567A - Preparation of urea compound - Google Patents

Abstract

PURPOSE:To prepare a urea compound in high yield and selectivity, by reacting a primary amine or secondary amine with carbon monoxide in the presence of molecular oxygen using a specific catalyst system. CONSTITUTION:The objective urea compound can be prepared by reacting a primary amine or secondary amine with carbon monoxide in the presence of molecular oxygen at 80-300 deg.C under 1-500kg/cm<2> pressure. The reaction is carried out in the presence of one or more catalysts selected from platinum group metals, compounds containing platinum group element (e.g. palladium, rhodium compound, etc.), halogen molecule, compounds containing halogen (e.g. metal halide, halogenated onium compound, etc.) and basic substances (e.g. alkali metal).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of Vc primary amines or secondary amines in the presence of molecular oxygen.
The present invention relates to a method using a specific catalyst system in the production of ureas by reacting a class amine with carbon monoxide.

Various methods for producing ureas from amines and carbon monoxide have been proposed. For example, methods using metal compounds other than platinum group metals include nickel iodide or cobalt iodide (Ohem, Ab, etc.).

57, p. 8413, 1962), cobalt carbonyl ((3an, J, Chem, vol. 40,
1718 pages, 1962), Vinegar #Silver (J, Org,
Ohem, vol. 37, p. 2670, 1972), acetic acid water fIi (Ohem, Ab, vol. 79, p. 2670, 1972),
31813c, 1973), and methods using nonmetallic compounds include sulfur (J, Org,
Ohem, vol. 26, p. 3309, 1961)
, Selenium (J, Amer, Ohem, SOc,,
Volume 93, page 6344, 1971, etc.) are known.

However, methods using metal compounds other than platinum group metals have the disadvantage that the yield and selectivity of the ureas produced are not very high. In addition, the method using sulfur or seleno is generally excellent in yield and selectivity and can be said to be a preferable method, but separation and recovery of catalyst components is difficult and requires complicated operations and a large amount of cost.

On the other hand, a method using platinum group metals (Japanese Patent Publication No. 53-4112
3 and J. Org, Ohem, vol. 40, p. 2819, 1975) have also been proposed,
All of these methods involve the reaction of an aromatic nitro compound, an amine, and carbon monoxide, and are methods for producing a urea compound having an aromatic group derived from an aromatic nitro compound, and the yield is at most 60%. It is about %.

Therefore, the present inventors have conducted intensive studies on a method for producing ureas from primary amines or secondary amines and carbon monoxide, and have found a method that does not have the above-mentioned drawbacks and allows the reaction to proceed catalytically. We discovered a catalyst system that could achieve this goal and filed an application earlier, but it became clear that halogen molecules or halogen-containing compounds play an important role as co-catalysts in this catalyst system. , discovered that the yield and selectivity of ureas can be further improved by adding a basic substance to this catalyst system, and that the selectivity of oxygen to the urea reaction is improved, and in order to complete the present invention. It was exhausting.

That is, the present invention provides a method for producing ureas by reacting a primary amine or a Fi secondary amine with carbon monoxide in the presence of molecular oxygen, which includes: (1) a platinum group metal and a compound containing a platinum group element; At least 41 types selected from among (1) At least one type selected from halogen molecules or compounds containing halogen; (c) At least one type selected from basic substances Q. An object of the present invention is to provide a method for producing ureas, which is characterized by using a catalyst system consisting of the following. ~The platinum group metals and platinum group element-containing compounds 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 is no limit to the percentage, and these elements may be in a metallic state or may be components forming a compound. In addition, these catalyst components include active rays, graphite, silica, alumina, silica-alumina, silica-titania, titania, zirconia, sulfuric acid, calcium carbonate, asbestos,
It may be supported on a carrier such as bentonite, diatomaceous earth, polymer, ion exchange resin, zeolite, molecular sieve, magnesium silicate, magnesia, or the like.

Examples of platinum group elements in the metallic state include metals such as radium, rhodium, platinum, ruthenium, iridium, and osmium, the heat of these metals, and catalyst components containing these metal ions on the carrier as described above, Those that have been reduced with hydrogen or formaldehyde, and alloys or intermetallic compounds containing these metals are used.Also, the alloys or intermetallic compounds may be those of these platinum group metals. , other elements such as selenium, tellurium, sulfur, antimony, bismuth, copper,
It may contain steel, gold, zinc, tin, vanadium, iron, cobalt, nickel, wood-like, lead, thallium, chromium, molybdenum, tungsten, and the like.

On the other hand, examples of compounds containing platinum group elements include inorganic salts such as halides, sulfates, nitrates, phosphates, and borates; organic acid salts such as acetates, oxalates, and formates; compounds; hydroxides; oxides; sulfides;
Metal salts containing anions such as nitro groups, cyanide groups, halogens, and oxalate ions, as well as ammonia and amines,
Metal complex compounds such as salts or complexes containing phosphines, carbon oxide chelate ligands, etc.; organometallic compounds having organic ligands or organic groups; and the like.

Among these catalyst components, those containing palladium or rhodium or both are particularly preferred, such as Pd black; Pd -0, Pd -
At, '03, Pd 5i02, Pd Ti (%,
Pd-ZrO□, Pd-Ba804, Pd 0a
003, Pd-asbestos, Pd-zeolite, Pd-
Compatible palladium catalysts such as molecular sheep iP
d-Pb1IPd-8e1Pd-Te.

Pd Hg, Pd TIS Pd-P,
Pd-0u% PdAg.

Pd-Fe, Pd-Co, Pd-Ni, Pd-
Alloys or intermetallic compounds such as Rh; and these alloys or intermetallic compounds supported on the above-mentioned carrier; Pdd/4, PdBr1, Pd x=, Pd
(NOs)*, inorganic salts such as pd804; Pd
(OOOOOHs)t, organic acid salts such as palladium oxalate; pd(as), ; pdo; pds;
Palladate salts represented by M, (pdx4), u2 (pdx6) (M represents an alkali metal, ammonium ion, nitro group, or cyano group, and X represents -.logen); CPdCNHs)a]Xs 1. (Pd(
Ammine complexes of palladium with en)z:)Xt (
X has the same meaning as above and represents ethylenediamine. ); pdcz, (phcN) snow, pacz
, (pR,), %pd(co)(PR3)s, Pd(
PPh3)1, Pd04(R)(PPhs)*, pd(
c TomiH4XPPh3)! Lead compounds or organometallic compounds such as pd-(c, hiki) (a represents an organic group); complex compounds coordinated with chelate ligands such as Pd(acac)1; Rb black ; Supported rhodium catalyst similar to Pd@; Rh alloy or intermetallic compounds similar to P+ and those supported on a carrier; nhct3 and hydrate, RhBr3 and hydrate, RhI and hydrate, Rht (804)3 and inorganic salts such as hydrates;
Rh2(OOOC!Hs)4 i ah=o3, Rh
01; Ms(RbXs:) and hydrate (M, X have the same meanings as above) i [Rh(NH3)s)X
rhodium carbonyl clusters such as rhodium ammine complexes Rh4(00)u, Rh1l(Co)16 such as (FLh(en)s)Xs;
o), ), RhCl3(PRIs)3, nhct(p
phs)s, RhX(00)L! (X #'i has the same meaning as above, L is a ligand consisting of an organic phosphorus compound and an organic arsenic compound.), RhH (Co) (PP
Complex compounds or organometallic compounds such as h3)3 can be used.

In 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 as a mixture, and there is no particular restriction on the amount used, but Usually, it is desirable that the component containing the platinum group element is in the range of Q, 0001 to 50 mol-0 relative to the primary amine or secondary amine.

In addition, the compound containing norogen used in the present invention is
The compound may be either organic or inorganic as long as it does not contain platinum group elements, such as metal halides,
onium compounds, compounds capable of producing onium compounds in the reaction system, oxic acid or salts thereof, complex compounds containing halogens,
Organic compounds and the like are preferably used.

Examples of metal halides include alkali metals,
alkaline earth metals, copper, silver, zinc, cadmium, mercury,
Aluminum, gallium, thallium, germanium, tin, lead, antiseptic, bismuth, titanium, zirconium, vanadium, niobium, tantalum, tellurium, chromium, molybdenum, tungsten, manganese, rhenium, iron, metal, nickel, rare earth metals ) and rogenides are used. Particularly preferred are alkali metal and alkaline earth metal 7-logides.

Examples of alkali metal and alkaline earth metal chlorides include sodium fluoride, cesium fluoride, barium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, Strontium chloride, lithium chloride, lithium bromide, sodium bromide, rubidium bromide, cesium bromide, magnesium bromide, strontium bromide, barium bromide, lithium iodide, sodium iodide, potassium iodide, iodide Compounds of rubidium, cesium iodide, magnesium iodide, calcium iodide, strontium iodide, iodide) (with single metals such as lium) and Rogge; sodium magnesium chloride, potassium magnesium chloride, chloride Double salts such as calcium potassium and magnesium potassium bromide; potassium bromine fluoride, potassium iodine chloride, rubidium iodine chloride, cesium iodine chloride, cesium iodine chloride bromide, rubidium iodine bromide, potassium iodine bromide, cesium iodine bromide , rubidium iodine bromide, borino ro such as rubidium bromide, and genides. 'An onium halide compound is a compound containing an element with lone pairs of electrons, in which protons or other cationic reagents are bound to these lone pairs, and the element that absorbs the lone pair of electrons has a covalent valence l. is increased to become a cation, and has a halogen anion as a counter ion.

Examples of such onium compounds include ammonium compounds ((R'R"R3R'N")Xo), phosphonium compounds ((R"R"R'R'P(9]X"), and arsonium compounds ((a 'FL2R3R'As'')Xo), stibonium compound ([R'FL2a'g'5b(f3
) Xo), oxinium compound ([R'a”a”o°
]X0), sulfonium compound ([R'a"a's°]
X0), oxysulfonium compound ([RIR″a”s
@(o)) Xo), selenonium compound ((R'R”
R"8ee) Xe), f / l / 0 nium compound ((a'a"a3Tee) I''] may be the same, or in some cases may be a constituent element of a ring containing an element having a lone pair of electrons.Also, X, C1, Br, I
Represents a halogen selected from Of course, it may be a compound having two or more such onium groups in its molecule, or it may be a polymer containing such onium groups in its main chain or side chain.

Halogenated onium compounds whose anion is a halogen are amines or nitrogen-containing compounds, phosphyl compounds, arsine compounds, stibine compounds, oxy compounds, and sulfide compounds corresponding to hydrogen halides or organic halides. , sulfoxide compounds, selenide compounds, telluride compounds, etc., and these may be produced outside the reaction system or may be produced within the reaction system. . Of course, it may be produced by other methods, or may be produced within the reaction system by other methods.

Preferred among these are halogenated ammonium compounds, halogenated phosphonium compounds, . . . halogenated alumnium compounds and halogenated sulfonium compounds, and particularly preferred are halogenated ammonium compounds and halogenated phosphonium compounds.・・Ammonium rogenide compounds are similar to the corresponding nitrogen-containing compounds.
It can be easily obtained by reaction with hydrogen halogenide, reaction of nitrogen-containing compound with alkyl halide, or aryl halide. Examples of such nitrogen-containing compounds include ammonia, primary amines, Amines such as secondary amines and tertiary amines; Hydroxylamines;
Examples include hydrazines; hydrazo/s; amino acids; oximes; 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 iodide; salts of aromatic amines such as diphenylamine and triphenylamine; methylamine, ethylamine, hexylamine, and octylamine. Amine, dimethylamine, trimethylamine, diethylamine, triethylamine, dibutylamine, tripropylamine, methylethylamine, dimethylethylamine, dibutylmethylamine, tributylamine, ethylenecyamine,
Salts of aliphatic amines such as hexamethylene diamine; salts of alicyclic amines such as cyclopropylamine, cyclohexylamine, N-methylcyclohexylamine; benzylamine, N-)thylhensylamine, N,N-diethylpencylamine, Salts of aromatic aliphatic amines such as dibenzylamine; nitrogen-containing heterocyclics such as piperidine, piperazine, morpholine, pyridine, quinoline, hexamethidi/tetramine, oxazole, thiazole, imidazole, triazole, benzotriazole, diazabicycloundecene, etc. Salts of compounds; dimethylacetamide, N-
Amide salts such as methylpyrrolidone are used.

Examples of quaternary ammonium halides include aliphatic quaternary ammonium halides such as halogenated tetramethylammonium, halogenated tetraethylammonium, halogenated tetrabutylammonium, halogenated trimethylethylammonium, and halogenated diethylsifthylammonium; Alicyclic quaternary ammonium halides such as , N, N -)limethylcyclohexyl a/monium; Aroaliphatic quaternary ammonium halides such as halogenated tetrabenzylammonium and halogenated trimethylpe/dylammonium; halogenated N, N, N
-T! J) fruphenylammonium, hao care N, N, N-)! Aromatic quaternary ammonium halides such as J ethylphenylammonium; halogenated N-methylpyridinium, halogenated N-ethylquinolinium, halogenated N,N-dimethylpiperidinium, halogenated N, heated methyl imidazo Heterocyclic quaternary ammonium halides such as linium are preferably used.

As the polymer containing a halogenated ammonium group in the main chain or side chain, for example, those having the following main structural units are preferably used.

-CH, -0H- 1 2 R', R'', i'L'', Xij are as described above, and represent a divalent organic group RsFi.

Examples of halogenated phosphonium compounds include symmetric tetraalkylphosphonium compounds such as halogenated tetramethylphosphonium, halogenated tetraethylphosphonium, and halogenated tetrabutylphosphonium; asymmetric types such as halogenated ethyltrimethylphosphonium and halogenated diethyldimethylphosphonium Tetraalkylphosphonium compounds; symmetrical tetraphenylphosphonium halides, tetra(p-)lyl)phosphonium halides; tetraarylphosphonium compounds; asymmetrical such as (α-naphthyl)triphenylphosphonium halides; Tetraarylphosphonium compounds; alkylaryl mixed phosphonium compounds such as halogenated methyltriphenylphosphonium and halogenated phenyltrimethylphosphonium; tetraaralkylphosphonium compounds such as halogenated tetrabenzylphosphonium and the like are preferably used.

Examples of the halogenated arsonium compounds include symmetrical tetraalkyl arsonium compounds such as halogenated tetramethylarsonium; um/% halogenated tetraethylarsonium; Jimechi.

Asymmetric tetraalkylarsonium compounds such as diethylalunium; symmetrical tetraarylarsonium compounds such as detraphenylalunium;
: Alkylaryl mixed arsonium compounds such as rum, halogenated ethyltriphenylalunium, and halogenated phenyltrimethylarsonium are preferably used.

In addition, examples of halogenated sulfonium compounds include *,
-3) Trimethylsulfonium halide, symmetrical or asymmetrical furkylsulfonium compounds such as triethylsulfonium halogenide and methyldiethylsulfonium halide; 7!7-rusulfonium compounds such as triphenylsulfonium halide i. Alkylarylsulfonium compounds such as dimethylphenylsulfonium and halogenated methyldiphenylsulfonium; halogenated bicyclo-(2,2,1)-hebuta7-
Sulfonium compounds such as 1-sulfonium and thiopyrylium halides are preferably used.

In addition, polymers containing a halogenated phosphonium group or a halogenated sulfonium group in the main chain or side chain are preferably used, and examples of such polymers include those having the following main structural units. .

) 1 (In the formula, R'sR2+[LstX4''; Oxygen acids and their salts, specifically hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromate acid, bromic acid, hypoiodic acid, It refers to iodic acid, iodic acid, orthoperiodic acid, metaperiodic acid, and salts of these acids.

The cations of salts may be of any kind, such as ammonium ions and various metal ions.
Particular preference is given to alkali metal ions and alkaline earth metal ions.

Examples of such salts include hypochlorites such as sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and barium hypochlorite; 1g salts such as sodium chlorite; Lithium chlorate, sodium chlorate, potassium chlorate, rubidium chlorate, cesium chlorate, magnesium chlorate, calcium chlorate, barium chlorate, aluminum chloride, calcium perchlorate,
Perchlorates such as barium perchlorate, zinc perchlorate, cadmium perchlorate, mercury perchlorate, cerium perchlorate, lead perchlorate, and ammonium perchlorate; sodium hypobromite, Hypobromites such as potassium bromite,
Bromite salts such as IJium; lithium bromate, bromate acid) IJium, potassium bromate, rubidium bromate, cesium bromate, magnesium bromate,
Calcium bromate, strontium bromate, barium bromate, bromate, zinc bromate, cadmium bromate, bromate wood tone, aluminum bromate, bromate rank/, samarium bromate, lead bromate, ammonium bromate, etc. Bromates - perbromates such as potassium perbromowood; sodium hypoiodite, potassium hypoiodite, rubidium hypoiodite, cesium hypoiodite, calcium hypoiodite, Hypoiodates such as barium iodate; lithium iodate, sodium iodate, potassium iodate, potassium hydrogen iodate, rubidium iodate,
Cesium iodate, magnesium iodate, calcium iodate, strontium iodate, barium iodate, silver iodate, gold iodate, zinc iodate, cadmium iodate, mercury iodate, aluminum iodate, iodate/ Iodates such as dium, lanthanum iodate, cerium iodate, proseodymium iodate, neodymium iodate, gadolinium iodate, lead iodate, ammonium iodate; lithium periodate, sodium metaperiodate, orthoperiodate Trisodium dihydrogen woodylate, disodium trihydrogen ortho-periodate, potassium metaperiodate, dipotassium trihydrogen ortho-periodate, tripotassium hydrogen periodate, rubidium periodate, periodate Cesium acid, periodate) barium wood, silver metaperiodate, silver menperiodrate, silver orthoperiodate, silver trihydrogen orthoperiodate, zinc periodate, cadmium periodate, Trace iodates such as lead iodate and ammonium periodpurate are used.

A complex compound containing a halogen may be one containing either a cationic or anionic halogen, such as ammonium dichlorobromate, tetramethylammonium tetrabromoiodate, etc.; Halogenated IsM salts such as potassium iodotellurate, tetraethylammonium tetraiodomercuryate, potassium tetraiodobismuthate, sodium tetrabromostelate, cesium tetrabromoferrate, barium hexasedostannate, potassium tetraiodolearate, potassium hexabromotellurate, etc. ;tetrabromo(diethylsuccinate)tin, octate(N.

N-dimethylformamide) lanthanum triiodite,
Hexakis (urea) chromium tripromide, hexaa/
Mi/chromium tripromide, iodopentaa/mi/chromium triiodite, tris(pyridine)chromium tripromide, tris(pyridine) molybdenum tripromide, hexaamminecobalt tripromide, bis(2,2'-
Complexes having a ligand such as bipyridine/) copper diiodite are used.

, and an organic halide is a general formula % formula %) (wherein, R' tf is an m-valent organic group, X is a halogen, m
#-i means an integer greater than or equal to 1. ), and if m is 2 or more, then x#-
It may be two or more halogen species.

Further, the halogen χ may be bonded to a heteroatom other than carbon, such as nitrogen, sulphur, oxygen, sulfur, or selenium.

Examples of such organic halides include methyl halide, ethyl halide, and propyl halide (
(6 isomers), butyl rogenide (each isomer),...
Rogge/amine chloride (each isomer), Rogge/hexyl chloride (
(Each isomer), Octyl halide (Each isomer), Perfluorohexyl halide (Each isomer), Perfluoroheptyl halide (Each isomer), Vinyl halide,
Allyl halide, methylene halide, haloform,
Tetrahalogen meta/, alkylidene halide, dihalogenated ethane (each isomer), trihalogenated ethane (
aliphatic monomers such as tetrahalogenated ethane, dihalogenated butane (each isomer), dino-Rogge/hexa/ (each isomer), dino-loethylene (each isomer), etc. Loge/chemicals; halogen benzene/, dihalogen pen 4. nia (each octamer), trihalogenase/(each isomer), tetrahalogenbenzene (each isomer), hexahalogenbenzene, halogentoluene, cyhalogennaphthalene/(each isomer), no-rogenpyridine (
Aromatic mono and borino halides such as halogen toluene (each isomer), halogen ethylbenzene (each isomer), phenyl iodo dichloride, iodosobenzene, iodoxybenzene; halogenated cyclohexane, halogenated Alicyclic compounds such as cyclobutane/
Chemical compounds; Aroaliphatic compounds such as benzyl chloride and 7-enethyl halide; halogenated furan,
No-logenated tetrahydrofuran, halogenated thiophene/, no10-genated imidazole, halogenated piperidine 7
Heterocyclic compounds, such as; acid compounds such as acetyl, benzoyl, etc.
N-rhodanides such as -haloke/succinimide and N-halogenalkylbenzamide are preferably 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, sulfoxide groups, sulfone groups, carbonyl groups, ester groups, amide groups, etc. or may have an unsaturated group.

Compounds containing halogens include hydrogen chloride, hydrogen bromide,
Hydrogen halides such as hydrogen iodide and hydrohalic acids can also be used, although in this case it is preferred that the basic substance is used on an equidistant plate rather than the hydrogen halide.

Compounds 1-1. containing such halogen may be used alone or in combination of two or more.

Furthermore, when the amine as a reaction raw material or the basic substance as another component of the catalyst contains halogen, it is not necessary to separately add a compound containing halogen.

Among the compounds containing halogen used in the method of the present invention,
Those in which the halogen species is bromine or bromine are preferred, and those containing bromine are particularly preferred.

The basic substance used in the present invention may be either inorganic or tangential. Examples of such basic substances include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as magnesium, calcium, and barium; lithium oxide, lithium peroxide, sodium oxide, sodium peroxide, and superoxide. Sodium, potassium oxide, potassium peroxide, dipotassium trioxide, potassium superoxide, rubidium oxide, rubidium peroxide, dirubidium trioxide, rubidium superoxide, rubidium ozonide, cesium oxide, cesium peroxide, cesium trioxide, super Oxides of alkali metals such as cesium oxide and cesium ozonide; oxides of alkaline earth metals such as beryllium oxide, magnesium oxide, calcium oxide, calcium peroxide, strontium oxide, stro/thium peroxide, barium oxide, and barium peroxide. Oxides; alkali metals and alkaline earths such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, etc. Hydroxides of similar metals; sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, barium carbonate, sodium silicate, magnesium silicate, potassium aluminate, calcium aluminate, sodium borate, barium borate, etc. Salts of strong bases and weak acids; calcium carbide,
Carbides such as cesium carbide; hydroxides and oxides of aluminum group metals such as aluminum hydroxide, gallium hydroxide, indium hydroxide, thallium hydroxide, and thallium oxide; lanthanum oxide, cerium oxide, cerium hydroxide, etc. Oxides and hydroxides of rare earth elements ↓ Lithium hydride,
Hydrides such as sodium hydride, sodium borohydride, calcium hydride, lithium aluminum hydride;
Sodium sulfide, sodium hydrogen sulfide, potassium sulfide,
Sulfides and hydrogen sulfides of alkali metals or alkaline earth metals such as calcium sulfide; quaternary ammonium hydroxide compounds such as tetraethylammonium hydroxide and tetrapropylammonium hydroxide; methyltriphenylphosphonium hydroxide, tetrahydroxide Quaternary phosphonium hydroxide compounds such as methylphosphonium; Tertiary sulfonium hydroxide compounds such as triethylsulfonium hydroxide and triphenylsulfonium hydroxide; Strong bases such as sodium acetate, potassium benzoate, rubidium oxalate, barium propionate, etc. and salts with weak organic acids; alkali metal and alkaline earth metal alcoholades such as sodium methylate, sodium ethylate, calcium ethylate;
Alkali metal and alkaline earth metal phenolates such as sodium phenolate, potassium phenolate, and magnesium phenolate; Alkali metal and alkaline earth metal amides such as lithium amide, sodium amide, calcium amide, and lithium dimethylamide; trimethylamine , triethylamine, tri-n-butycyamine, triphenylamine, diethylmethylamine, N
, N-diethylaniline, N-methylpiperidine, N,
N'-diethylpiperazine, N-methylmorpholine, triphenylamine, hexamethylenetetramine, N.

N, N', N'-tetramethylethylenecyamine, dicyclohexylethylamine, 1,2,2,6.
6-pentameglubiberidine, pyridine/, gynoline,
Phenanthroline, indole, N-methylimidazole, 1,8-diazabicyclo-(5,4,0)-undecene-7 (DBU), 1,5-diazabicyclo-(4,
Tertiary amines such as 3,0)-nonene-5 (DBN) and cyclic nitrogen-containing compounds (but those that do not have an N-H group);
Crown compounds such as crown ether, aza crown ether, thia crown ether, and aza crown, and complexes of these crown compounds with alkali metals, alkaline earth metal ions, and the like are used. Furthermore, there may be two or more of these groups exhibiting basicity in the molecule, or even if they form part of a polymer such as an anion exchange resin having a quaternary ammonium hydroxide group. good. Further, these basic substances or groups having basicity may be supported on a solid or chemically bonded.

These basic substances may be used alone or in combination of two or more Fi.

There are no particular restrictions on the amount of the halogen-containing compound and basic substance used in the present invention, but the amount of the halogen-containing compound is relative to the amount of the metal element in the platinum group element-containing component used as the halogen. Usually 0.001
It is preferable to use the basic substance in a molar range of ~10,000 times, and the basic substance is usually used in a molar amount of 0.01 to halogen.
It is preferable to use it in the range of ~t, ooo times the mole.

The primary amine or secondary amine used as a raw material in the present invention is a compound containing at least one amino group in one molecule as represented by the following formula %. Here, one or two aFi connected to N represents a bond between a nitrogen atom and another atom or group, and such atoms or groups include hydrogen, halogen, alkali metal, hydroxyl group, Examples include amino groups, aliphatic groups, alicyclic groups, aromatic groups, araliphatic groups, and heterocyclic groups. Furthermore, in the secondary amide 7, the nitrogen atom itself may be an element constituting a ring, such as in pyrrole, piperidine, piperazine, morpholif, and the like.

Examples of such primary amines include ammonia,
Aliphatic primary monoamines such as methylamine, ethylamine, propylamine (each isomer), butylamine (each isomer), pentylamine (each isomer), hexylamine (each isomer), dodecylamine (each isomer), etc. aliphatic primary substances such as ethylenediamine, diaminopropane (each isomer), diaminobutane (each isomer), diaminopenkune (each isomer), diaminohexane (each isomer), diaminodecane (each isomer), etc. Diamines; 1.2.3 = Aliphatic primary triamines such as triamino, propane, triaminohexane (each isomer), triaminononane (each isomer), triaminododecane (each isomer); cyclopropyl amine, cyclobutylamine, cyclopentylamine,
Alicyclic primary mono- and polyamines such as cyclohexylamine, diaminocyclobutane, diaminocyclohexane (each isomer), triaminocyclohexane (each isomer); benzylamine, di(aminomethyl)benzene (each isomer) ), aminomethylpyridine (each isomer), di(aminomethyl)viridi/(each isomer), aminomethylnaphthalene (each isomer), di(aminomethyl)naphthalene (
Aroaliphatic primary mono- and polyamines such as aminofuran (isomers), aminotetrahydrofuran (isomers), aminothiophene (isomers), aminovirol (isomers), aminopyrrolidine ( Heterocyclic primary amines such as each isomer) are preferably used.

In addition, examples of aromatic primary amines include aniline, diaminobenzene (each isomer), triaminobenzene (each J1 body), tetraaminobenzene (each isomer), aminotoluene (each isomer), and diaminotoluene. (Each isomer)
, aminopyridine (each isomer), diaminopyridine (each isomer), triaminopyridine (each isomer), aminonaphthalene (each isomer F), diaminonaphthalene (each isomer), triaminonaphthalene (each isomer) , tetraaminonaphthalene (each isomer), and monoamine, diamine, triamine, and tetraamine isomers of the diphenyl compound represented by the following general formula.

〇One (in the formula, A is a simple chemical bond, or -〇-1-s-1
-80! -1-co-1-0ONH-1-COO-1-
Select from c(a') (a Lee- and -NCR')-1lj
t also represents a valence group. Also R6. R7 is an H1 aliphatic group. ) In addition, in these aromatic 1@amino, at least one hydrogen atop the aromatic group may be substituted with another substituent, such as a halogen atom, a nitro group, a cyano group, an alkyl group, an alicyclic group, an aromatic group, or an aralkyl group. It may be substituted with a group such as a group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, a nistyl group, an amide group, etc.

Particularly preferred among these aromatic amine compounds are aniline, 2,4- and U:216-diaminotoluene, chloranili/(each isomer), dichloroaniline (each isomer), 4. 4'- and 2,4'-diaminodiphenyl meta-7,1,5-diaminonaphthalene.

In addition, examples of secondary amines include dimethylamine,
ethylamine, dipropylamine, dibutylamine,
Aliphatic secondary amines such as dibenzylamine, dinaphthylamine, ethylmethylamine, ethylpropylamine, butylmethylamine, and ethylhexylamine; alicyclic groups such as dicyclofurobylamine, dicyclohexylamine, and methylcyclohexylamine Secondary amines: N-methylaniline, N-ethylaniline, N-methyltoluidine (each isomer), diphenylamine, NHN'-diphenylmethanediamine, N,1-dimethylphenylenediamine (each isomer), N-methylnaphthylamine (each isomer), dinaphthylamine (each isomer); aromatic secondary amines such as dibenzylamine, ethylbenzylamine, cyclobutylamine; dinaphthylamine, dithiophenylamine, etc. Heterocyclic secondary amide 7; pyrrolidine, pyrrole, 3-pyrrolidone, indole, carbazole, hypericin, piperazine, β-
piperidone, r-piperidone, imidazole, pyrazole, triazole, benzimidazole, morpholine,
Cyclic secondary amines such as 1,3-oxasif are preferably used.

In addition, in these primary amines and secondary amines,
One or more hydrogens of the organic group bonded to nitrogen are other substituents,
For example, lower aliphatic groups, amine groups, carboxyl groups, ester groups, alkoxy groups, cyanogen groups, halogens, nitro groups, urethane groups, sulfoxide groups, sulfo/groups, carbonyl groups, amide groups, aromatic groups, araliphatic groups. It may be substituted with a group or the like. Furthermore, these primary amines and secondary amines 7 may have unsaturated bonds.

It may also be a hydrazine type compound in which the above-mentioned amino group is directly bonded to an organic group having a nitrogen atom through N--N.

These primary amines or secondary amines may be used alone or in combination of two or more. When 21 g or more is used, an asymmetric urea compound is obtained.

Furthermore, when a polyvalent amine having two or more amine groups in one molecule is used, polyureas can also be obtained.

The molecular oxygen used as an oxidizing agent in the present invention is pure oxygen or a substance containing oxygen, which may be air, or other gases that do not inhibit the reaction with air or pure oxygen, such as nitrogen, argon, helium, etc. , or diluted with an inert gas such as carbon dioxide. In some cases, it may also contain gases such as hydrogen, carbon oxide, hydrocarbons, and halogenated hydrocarbons.

In the ureation reaction of the present invention, for example, in the case of a primary monoamine,
The process proceeds according to the following general formula:

2RNHz+ CO+-HO鵞→RNHOONHR+ H,0 (R represents an organic group.") Molecular oxygen may be less or more than the equivalent amount, but the mixture of oxygen/-carbon oxide or oxygen/amine has the explosive limit It should be used within the range that is outside the scope.

Although the method of the present invention can be carried out without using a solvent, it is also preferable to carry out it in a suitable solvent.

Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; nitrites such as acetonitrile and benzonitrile; sulfones such as sulfolane, methylsulfola/, and dimethylsulfolane; tetrahydrofuran, 1.4 -dioxane,
1. Ethers such as 2-dimethoxyethane; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate and ethyl benzoate i N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, Amides such as tetramethylurea and hexamethylphosphoramide can be used.

Furthermore, H1 organic halides used as cocatalysts of the present invention include halogenated aromatic hydrogenated hydrogens such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, chlorotoluene, chlornaphthalene/bromnaphthalene; chlorhexane, Halogenated aliphatic hydrocarbons or halogenated alicyclic hydrocarbons such as chlorocyclohexane, trichlorotrifluoroethane, methylene chloride, and carbon tetrachloride are also used as solvents.

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

Suitable examples of such additives include zeolites, orthoesters, ketals, acetals, enol ethers, and trialkylorthoborates.

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

In addition, the reaction pressure is 1 to 500 kt/cm", preferably tL<U
The reaction time ranges from 20 to 300 ky/3", and the reaction time varies depending on the reaction system, catalyst system, and other reaction conditions.
Usually it takes several minutes to several hours.

Further, the reaction of the present invention can be carried out either batchwise or continuously in which the reaction solution is continuously drawn out while continuously supplying the reaction components.

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

Example 1 Aniline 40 trmol, tetramethylurea 401I/, in a stirred autoclave with an internal volume of 14011 tons,
Haradium black 0.51 valom, iodoform 0.
After adding 3 mrr + r + t and 1 mmoL of rubidium hydroxide, and replacing the inside of the system with carbon monoxide, -8
0kI/cWP1 Then 6 kql/cm" of oxygen was injected. After reacting at 160°C for 1 hour with stirring, the reaction mixture was analyzed and the reaction rate of aniline was 95.
%, the yield of N,N'-diphenylurea was 92%, and the selectivity was 97%.

Note that palladium was not detected in the solution.

In addition, the selectivity of the reacted oxygen to the urea conversion reaction was #i93. As a result of carrying out a similar reaction without using rubidium hydroxide, the reaction rate of aniso/ti was 56, the yield of N, gardiphenyl urea was 39, and the selectivity was 70%. Further, Examples 2 to 13 of Oxygen Urea Conversion Reaction The results of reactions carried out in exactly the same manner as in Example 1 using various halogens or halogen-containing compounds and basic substances are shown in the first page.

Basic substance #i1 mmot was used in these examples.

A 10% aqueous solution of tetrapropylammonium hydroxide/11 was used. DBU is 1,8-diazabicyclo-[5,
4,0〕-〕undesen-.

(Left below) Example 14 Anion/exchange resin (Amberlyst A-
The hydroxyl groups were exchanged with iodine anions by treatment of the 26°OH form) with hydroiodic acid and then dried at vacuum F at 100°C. This iodine-containing anion exchange resin l? , rubidium hydroxide 3 mmot%n-hexylamine 740 mmot1 tetramethylurea 401
111 palladium black 0.5+119 atom internal volume 1
40 Place in a stirring autoclave and remove the gold in the system.
After replacing with carbon oxide, -carbon oxide at 80 kf/c1
11t% oxygen was then injected at 6 kg/cm'' to bring the total pressure to 8.
After reacting at 120°C for 1 hour while stirring, the reaction mixture was filtered and the liquid was analyzed. As a result, the reaction rate of n-hexylamino was 9 s%, N, r/-
Ji.

(n-hexyl)urea yield Fi 91%, selectivity 96
It was qi.

Using palladium black and anion exchange resin separated by filtration as is, rubidium hydroxide 3 mmo
As a result of repeating the same reaction by adding 1, the reaction rate of n-hexylamine was 96%, the yield of N,N'-di(n-hexyl)urea was 91%, and the selectivity was 95%. However, the results were similar.

Furthermore, the selectivity of the reacted oxygen to the urea formation reaction was 90%. The selectivity of oxygen to the urea reaction when rubidium hydroxide was not used was 1175%.

Example 15 Cyclohexylamine 740 mmot, rhodium black 0.
The reaction was carried out in the same manner as in Example 1, except that 51119mtom, N,N-dimethylformamide 4011/, methyl iodide 1 mmot, )ethylamide 71 mmot was used, and the reaction rate of cyclohexylamino was 83 mmot. The yield of N,N'-dicyclohexylurea was 75%, and the selectivity was 90%.

Example 15 Same operation as Example 1 except that 40 mmol of di(n-butyl)amine, 0.5 μatom of palladium black, 2 mmol of tetramethylammonium iodide, 2 mmol of ethylamine, and 50 ml of benzene were used. As a result of the reaction, the reaction rate of di(n-butyl)amine was 55%, the yield Fi of N,N,N',N'-tetra(roptyl)urea was 44%, and the selectivity was 80-. .

Examples 16 to 21 and Comparative Examples Compounds containing various platinum group gold R″dl and platinum group elements (
Using 0,511yatom) and a halogen or a compound containing a halogen (l mmot) and a basic substance (1 mmoj) as metal atoms, aniline (4
Table 2 shows the results of a urea conversion reaction of 0 mmot) conducted in the same manner as in Example 1 and a comparative example.

In these Examples, C represents activated carbon, and C represents the weight of the supported catalyst component. Pd-Te
No. 10 is a product in which palladium chloride and tellurium dioxide were co-supported on activated carbon at a molar ratio of lθ to 3, and then hydrogen-reduced at 350°C.

(Hereafter, extra colors)

Claims (1)

[Claims] 1. A method for producing ureas by reacting a primary amine or a secondary amine with carbon monoxide in the presence of molecular oxygen, comprising (-) a platinum group metal and a platinum group element; (b) at least one selected from halogen molecules or compounds containing halogen; (c) at least one selected from basic substances; Method 2 for producing ureas, characterized by using a catalyst system consisting of: Method 1 according to claim 1, wherein the platinum group metal and the compound containing the platinum group element are palladium, rhodium, a palladium compound, or a rhodium compound. A patent claim in which the halogen-containing compound is a metal halide, an onium halide compound, a compound capable of producing an onium halide compound in a reaction system, a halogen oxoacid or a salt thereof, a complex compound containing a halogen, or an organic halide. Method 4 according to claims 1 and 2, wherein the halogen-containing compound is a metal halide. Method 5 according to claims 1 to 3, wherein the metal halide is an alkali metal halide or an alkaline earth. The method according to claim 4, in which the halogen-containing compound is a similar metal halide.Claims 1 to 3, in which the halogen-containing compound is an onium halide compound or a compound capable of producing these in a reaction system. 7. The method according to claim 6, wherein the halogenated onium compound is a halogenated ammonium compound, a halogenated phosphonium compound, a halogenated arsonium compound, or a halogenated sulfonium compound & The halogenated onium compound is halogenated The method 9 according to claim 6 or 7, which is a polymer containing an oniram group in the main chain or side chain; A method 10 according to claims 1 to 3, wherein the halogen-containing compound is a complex compound containing NO. (g) Method 1 according to claims 1 to 3, which is a halogenide? - Method 13 according to claims 1 to 11, in which the halogen species is bromine or iodine; Process 14 according to claim 12, in which the halogen species is iodine; Patent, in which the amine is a primary amine Method 1K according to claims 1 to 13. Method 1K according to claim 14, wherein the primary amine is an aromatic primary amine.