JPS60163853A - Preparation of urea - Google Patents

Abstract

PURPOSE:To obtain a urea in high yield in high selectivity, by reacting a primary amine or a secondary amine with carbon monoxide in the presence of molecular oxygen and a specific catalyst while removing formed water. CONSTITUTION:A primary amine or a secondary amine is reacted with carbon monoxide in the presence of molecular oxygen and a catalyst consisting of one selected from a metal of platinum group and a compound (e.g., palladium, rhodium, palladium compound, or rhodium compound) containing the metal of platinum group, and a halogen molecule or a halogen compound (e.g., alkali metal halide, sodium iodide, or ammonium halide compond) at 80-300 deg.C. The reaction is carried out while water formed by the reaction is being removed by out of the reaction system by reaction distillation method, a method to use a gas for reaction, containing carbon monoxide, as a carrier gas, a method to distill it away together with part of organic solvent, etc., to give the desired substance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved process for producing ureas by reacting primary or secondary amines with carbon monoxide in the presence of molecular oxygen.

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 (Chem, Ab-+ Vol. 57, 84
13, 1962), cobalt carbonyl (Can
, J. Chem, vol. 40, p. 1718,
1962), silver acetate (J, Org, Chern,
, vol. 37, p. 2670, 1972) mercury acetate (Chem, Ab, vol. 7'1, 31813c,
1973), but as a method using nonmetallic compounds, sulfur (J, Org, Chem, 2
6, p. 3309, 1961), selenium (J,
Amer, Chem, Soc, vol. 93, 6
344 pages, published in 1971).

However, methods using metal compounds other than platinum group metals have the disadvantage that the yield and selectivity of the ureas produced are not so high. Furthermore, methods using sulfur or selenium generally have excellent yields and selectivities and can be said to be preferable methods, but separation and recovery of catalyst components is difficult and requires complicated operations and large costs.

On the other hand, a method using platinum group metals (Sho Kosho 53-4112
Publication No. 3 and J, Org, Chem, 40
Volume, 2819 pages.

(1975) have also been proposed, but 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. Moreover, the yield is about 60% at most.

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 for producing ureas that has fewer of the above-mentioned drawbacks, yet has a high yield and high yield. We discovered and proposed a catalyst system that can produce ureas with high selectivity.

These catalyst systems consist of at least one metal selected from platinum group metals and compounds containing platinum group elements, and at least one type of halogen compound, and the halogen compound includes bromine or iodine. It has also been found that the compounds are particularly effective cocatalysts.

By using these catalyst systems, the yield and selectivity of ureas based on amines and carbon oxides could be greatly improved compared to the prior art, but the conversion rate of amines could be improved by more than 90%. It was found that as the temperature was increased, the selectivity of ureas on a -carbon oxide basis decreased slightly.As a result of intensive research to improve this point, we found that using these catalyst systems, By combining the method with a method in which the reaction is carried out while removing all or part of the water produced by the reaction from the reaction system, not only the selectivity of ureas based on carbon oxide can be further improved, but also the reaction rate can be increased. It was also found that the yield and selectivity based on amines can be further improved, and the present invention was completed based on these findings.

That is, the present invention provides a catalyst comprising molecular oxygen and (b) at least one selected from platinum group metals and compounds containing platinum group elements, and (b) at least one halogen molecule or octahalogen compound. In a method for producing ureas by reacting a primary amine or a secondary amine with carbon monoxide in the presence of a reaction system, all or part of the water produced by the reaction is removed from the reaction system. An object of the present invention is to provide a method for producing ureas, which is characterized in that the reaction is carried out at the same time.

Furthermore, the present invention provides, in addition to the above catalyst system and reaction method,
The object of the present invention is to provide a method for producing ureas using at least one selected from basic substances and chelating reagents as an additional promoter.

The method of removing all or part of the water produced by the reaction from the reaction system, which is a feature of the present invention, may be any method as long as water can be substantially removed, but distillation is performed using a reactive distillation method. Particularly preferred are methods for removing organic solvents by using a carrier such as a reaction gas containing carbon oxide or a low-boiling organic substance, a method for distilling off the organic solvent together with a part of the organic solvent, and a method for combining these methods. Therefore, the reaction method may be either a batch method or a flow method for the liquid phase, but it is preferable to use a flow method for the gas component containing -carbon oxide.

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 include, for example, activated carbon, graphite, silica, alumina, silica-alumina, silica-titania, titania, zirconia, barium sulfate, calcium carbonate, asbestos, bentonite, diatomaceous earth, polymer, ion exchange resin, zeolite, It may be supported on a carrier such as molecular sheep, magnesium silicate, or magnesia.

Examples of platinum group elements in the metallic state include metals such as palladium, rhodium, platinum, ruthenium, iridium, and osmium, these metal blacks, and catalyst components containing these metal ions on the carrier as described above. Afterwards, those treated with hydrogen, hydrazine, or formaldehyde, and alloys or intermetallic compounds containing these metals are used. Further, the alloy or intermetallic compound may be one of these platinum group metals, or may be one of these platinum group metals, or may contain other elements such as selenium, tellurium, sulfur, antimony, bismuth, copper, silver, gold, zinc, tin, vanadium, It may contain iron, cobalt, nickel, mercury, lead, thallium, chromium, molybdenum, tungsten, etc.

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 cyanides. , hydroxides, oxides, sulfides, nitro groups, cyanide groups, halogens, metal salts containing anions such as oxalate ions, and ammonia, amines, phosphines, carbon oxides, chelate ligands Examples include metal complex compounds such as salts or complexes containing such compounds, and organometallic compounds having organic ligands or organic groups.

Among these catalyst components, those containing palladium or rhodium or both are particularly preferred, such as Pd black; Pd-C, Pd-Al□
Oa, Pd-8in□, Pd-TiO2, Pd-Zr0
．． , Pd-BaSO4, Pd-CaCO3, Pd-asbestos, Pd-zeolite, Pd-molecular sheep and other supported palladium catalysts; Pd-Pb, Pd
-8e,,Pd-Te.

Pd Hg SPd TI SPd P SPd Cu
SPdAg%Pd-Fe, Pd-Co,
Alloys or intermetallic compounds such as Pd-Ni and Pd-Rh, and these alloys or intermetallic compounds supported on the above-mentioned carriers;

PdBr2, Pd I2, Pd (NO3)2, Pd
Inorganic salts such as SO2 ↓Pd (0COCH3), ,
Organic acid salts such as palladium oxalate; Pd(CN)
2, Pd01PdS, M, (PdX, ), M2 (Pd
Palladate salts represented by
ammine complexes of palladium such as [Pd(en)2]Xg (X has the same meaning as above and en represents ethylenediamine);
, PdCt2(PRa)2, Pd(CO)(PRa
)a, Pd(PPh3),, PdCt(R)(pph
3) 2, Pd (C2H4) (PPha)2, Pd
Complex compounds such as (CaHs)2 or organometallic compounds (R
represents an organic group); complex compounds coordinated with chelate ligands such as Pd (acac)2; Rh black, Pd
Supported rhodium catalysts similar to Pd; Rh alloys or intermetallic compounds similar to Pd, and those supported on a carrier; R
hCl3 and 11 water boxes, RhBr3 and hydrates, Rh
Inorganic salts such as R112 and hydroxides, Rh2(So, )a and hydrates; R112(0COCHa)Rh,
03, RhO□, M3[RhX6] and hydrate (M,
has the same meaning as above), [IRh (NI(a)
Rh4 (CO)12, Rh, (C
O) Rhodium carbonyl clusters such as □6;
[RhC7(CO)2)g, :Rh cz3(PRa
)3, RhC2(PPhs)s, 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 (CO
) (PPh, )a and other complex compounds or organometallic compounds.

In the present invention, only one kind of these platinum group metals or compounds containing platinum group elements may be used, or two or more kinds thereof may be used as a mixture, and the amount used is particularly controlled; (Normally, the platinum group element-containing component is 0.0001 to 50% relative to the primary amine or secondary amine.)
Preferably, it is in the morchi range.

The halogen compound used in the present invention may be either organic or inorganic as long as it is a halogen-containing compound that does not contain platinum group elements, such as metal halides,
Onium halide compounds, compounds that can produce onium halide compounds in the reaction system, halogen oxoacids or salts thereof, complex compounds containing halogens, organic)
Rogenides 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, antimony, bismuth, titanium, zirconium,
Halides such as vanadium, niobium, tantalum, tellurium, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, and rare earth metals are used. Particularly preferred are alkali metal and alkaline earth metal halides.

Examples of alkali metal and alkaline earth metal halides include sodium fluoride, cesium fluoride, barium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, Barium chloride, lithium bromide, sodium bromide, rubidium bromide,
Cesium bromide, magnesium bromide, strontium bromide, barium bromide, lithium iodide, sodium iodide,
Potassium iodide, rubidium iodide, cesium iodide,
Compounds of a single metal and a single halogen such as magnesium iodide, calcium iodide, strontium iodide, and barium iodide; double salts such as magnesium sodium chloride, magnesium potassium chloride, calcium potassium chloride, and magnesium potassium bromide 4 Polyhalides such as potassium fluoride bromine, potassium iodine chloride, rubidium iodine chloride, cesium iodine chloride, cesium iodine chloride bromide, rubidium iodine chloride bromide, potassium iodine bromide, cesium iodine bromide, rubidium iodine bromide, etc. can be given.

Onium halide compounds are compounds containing elements with lone pairs of electrons, in which protons or other cationic reagents bind to these lone pairs, increasing the covalent valence of the element with lone pairs of electrons. m% ion, and has a chlorogen anion as a counter ion.

Such onium compounds include ammonium compounds ((R'R"R3R4N":) Xo), phosphonium compounds ((R"R"R"R'P■]Xθ), 7 p
v Soram compound ([:RIR2R3R'As”:
)Xe), stibonium compound ((R”R”R3R4S
b■]X6), oxonium compound ((R”R”R”0
(f3) Xo) 1,
= UA compound ((R'R"R"Se")Xe),
Telluronium compound ((R” R2R3Te■]Xθ)
, stannonium compound ([R”R2R3Sn■]Xe
), iodine; um compound ([R'R2I'') , represents a group selected from heterocyclic groups, each of which 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 is F,
Represents a halogen selected from CL, Br, and I. Of course, it may be a compound having two or more such onium groups in its molecule, or it may even be a polymer containing such an onium group in its main chain or side chain. Halogenated onium compounds, which are onium compounds in which is a halogen, include amines or nitrogen-containing compounds, phosphine compounds, arsine compounds, stibine compounds, oxy compounds, sulfide compounds, sulfoxide compounds, and 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 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 arsonium compounds, and halogenated sulfonium compounds, and particularly preferred are halogenated ammonium compounds and halogenated phosphonium compounds. Halogenated ammonium compounds can be easily obtained by reacting a corresponding nitrogen-containing compound with hydrogen halide, or by reacting a nitrogen-containing compound with an alkyl halide or an aryl halide. , Example 1; ammonia, primary amine, secondary amine,
Amines such as tertiary amines, hydroxylamines, hydrazones, hydrazones, amino acids, oximes,
These include 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. Salts of aliphatic amines such as amine, dimethylamine, trimethylamine, diethylamine, triethylamine, dibutylamine, tripropylamine, methylethylamine, dimethylethylamine/, dibutylmethylamine, tributylamine, ethylenediamine, hexamethylenediamine etc.; cyclopropyl Salts of alicyclic amines such as amines, cyclohexylamine, and N-methylcyclohexylamine; Salts of aromatic aliphatic amines such as benzylamine, N-methylbenzylamine, N,N-diethylbenzylamine, and dibenzylamine; Piperidine , piperazine, morpholine, pyridine, quinoline, hexamethylenediamine, oxazole, thiazole, imidazole, triazole,
Salts of nitrogen-containing heterocyclic compounds such as benzotriazole and diazabicycloundecene; dimethylacetamide;
Amide salts such as N-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 diethyldibutylammonium; Alicyclic quaternary ammonium halides such as N, N, N-)limethylcyclohexylammonium; Aroaliphatic quaternary ammonium halides such as halogenated tetrabenzylammonium and halogenated trimethylbenzylammonium;; Halogenated N
Aromatic quaternary ammonium halides such as halogenated N', N', N-)ethylphenylammonium; halogenated N-methylpyridinium, halogenated N-ethylphenylammonium; Heterocyclic quaternary ammonium halides such as norinium, N-halogenated, N-dimethylpiperidium, and N-halogenated N'-dimethylimidazolinium are preferably used.

Further, as the polymer containing a halogenated ammonium group in the main chain or side chain, for example, a polymer having the following main structural units is suitably used.

6Ra 2 Here, R1, R2, R3, and X have the above-mentioned childish taste, and R
8 represents a divalent organic group.

Examples of the halogenated phosphonium compounds include symmetrical tetraalkylphosphonium compounds such as halogenated tetramethylphosphonium, halo)lylated tetraethylphosphonium, and halogenated tetrabutylphosphonium compounds.
Asymmetrical tetraalkylphosphonium compounds such as halogenated ethyltrimethylphosphonium and halogenated diethyldimethylphosphonium 1. Symmetrical tetraarylphosphonium compounds such as halogenated tetraphenylphosphonium and halogenated tetra(p-)'J'phosphonium; halogen Asymmetric tetraarylphosphonium compounds such as (α-naphthyl)triphenylphosphonium; alkylaryl mixed phosphonium compounds such as halogenated methyltriphenylphosphonium and halogenated phenyltrimethylphosphonium; 5 Tetraalkylphosphonium such as halogenated tetrabenzylphosphonium Compounds and the like are preferably used.

Examples of the halogenated arsonium compounds include symmetrical tetraalkylarsonium compounds such as monohalogenated tetramethylaldinium and halogenated tetraethylarsonium; asymmetrical tetraalkylarsonium compounds such as halogenated methyltriethylalunium and halogenated dimethyldiethylarsonium; Alkyl arsonium compounds; symmetrical tetraaryl arsonium compounds such as halogenated tetraphenylarsonium; alkylaryl such as halogenated methyltriphenylarsonium, halogenated ethyltriphenylarsonium, and halogenated phenyltrimethylarsonium Mixed arsonium compounds and the like are preferably used.

In addition, examples of halogenated sulfonium compounds include Example i
C. Symmetrical or asymmetrical alkylsulfonium compounds such as trimethylsulfonium halide, triethylsulfonium halide, and methyldiethylsulfonium halide; Arylsulfonium compounds such as triphenylsulfonium halide; dimethylphenylsulfonium halide, methyldiphenyl halide Alkylarylsulfonium compounds such as sulfonium
Cyclic sulfonium compounds such as halogenated bicyclo-(2,2,1)-hebutane-1-sulfonium and halogenated thiopyrylium are preferably used.

Polymers containing a halogenated phosphonium group or a halogenated sulfonium group in the main chain or side chain are also preferably used, and such polymers include, for example, those having the following main constituent units. .

2 (wherein R1, R2, R3, and X have the above meanings)
Halogen oxoacids and their salts have an oxidation number of positive 1.3.
．． 5.7 halogen oxygen acids and their salts, specifically hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromic acid, perbromic acid, It refers to iodic acid, iodic acid, iodic acid, orthoperiodic acid, metaperiodic acid, and salts of these acids. The cations of the salts may be of any kind, such as ammonium ions and various metal ions, but alkali metal ions and alkaline earth metal ions are particularly preferred.

Such salts include, for example, sodium hypochlorite,
Hypochlorites such as potassium hypochlorite, calcium hypochlorite, barium hypochlorite; Chlorites such as sodium chlorite; Lithium chlorate, sodium chlorate, potassium chlorate, chloric acid Chlorates such as rubidium, cesium chlorate, magnesium chlorate, calcium chlorate, barium chlorate; aluminum perchlorate, calcium perchlorate, barium perchlorate, zinc perchlorate, cadmium perchlorate, perchlorate Zinc acid, cerium perchlorate,
Perchlorates such as lead perchlorate and ammonium perchlorate; Hypobromites such as IJum and potassium hypobromite; Bromites such as thorium bromite; Lithium bromate, sodium bromate, potassium bromate, rubidium bromate, cesium bromate, magnesium bromate, calcium bromate, strontium bromate, barium bromate, silver bromate, zinc bromate, cadmium bromate, bromine Bromates such as acid mercury, aluminum bromate, lanthanum bromate, zamarium bromate, lead bromate, ammonium bromate; perbromates such as potassium perbromate; sodium hypoiodite, hypoiodite overnight Potassium, rubidium hypoiodite, cesium hypoiodite,
Hypoiodates such as calcium hypoiodite and barium hypoiodite, stium iodate, sodium iodate, potassium iodate, potassium hydrogen iodate, rubidium iodate, cesium iodate, magnesium iodate, iodine calcium acid, strontium iodate,
Barium iodate, silver iodate, gold iodate, zinc iodate, cadmium iodate, mercury iodate, aluminum iodate, indium iodate, lanthanum iodate,
Iodates such as cerium iodate, proseodymium iodate, neodymium iodate, gadolinium iodate, lead iodate, ammonium iodate; lithium periodate, sodium metaperiodate, trisodium dihydrogen orthoperiodate, Disodium trihydrogen orthoperiodate, potassium metaperiodate, dipotassium trihydrogenorthoperiodate, tripotassium hydrogenperiodate, rubidium periodate, cesium periiodate, barium periodate, metaperiodate Periodates such as silver iodate, silver periodate, orthoperiodate, silver trihydrogen orthoperiodate, zinc periodate, cadmium periodate, lead periodate, ammonium periodate, etc. is used.

The halogen-containing complex compound may be either a cationic or anionic halogen-containing complex compound, such as polyhalogenated halogen acid salts such as ammonium dichlorobromate and tetramethylammonium tetrabromoiowoodylate. : Metal halides such as potassium hexaiodotellurate, tetraethylammonium tetraiodomercurate, potassium tetraiodobismuthate, sodium tetrabromocuprate, cesium tetrabromoferrate, barium hexaiodostannate, potassium tetraiodolearate, potassium hexabromotellurate, etc. Acid salts: tetrabromo(diethylsuccinate)tin, octate(N,N-dimethylformamide)lanthanum triyosite, hexakis(urea)
Chromium tripromide, hexaammine chromium tripromide, iodopentaamine chromium tripromide & lJs(pyridine) chromium tripromide, tris(pyridine)
Complexes having a ligand such as molybdenum triodide, hexaammine cobalt tripromide, bis(2,2'-bipyridine) copper josite, etc. are used.

In addition, organic halides are those represented by the general formula % formula % (wherein, R6 is an m-valent organic group, X is a halogen, and m is an integer of 1 or more), and m is 2 or more, X is 2
There may be more than one different halogen species.

Furthermore, the halogen X may be bonded to a heteroatom 1 other than carbon, such as nitrogen, phosphorus, oxygen, sulfur, or selenium.

Examples of such organic halides include methyl halide, ethyl halide, propyl halide (
(Each isomer), Butyl halide (Each isomer), Aluminum halide (Each isomer), Hexyl halide (Each isomer), Octyl halide (Each isomer), Perfluorohexy halide/ ' (each isomer), perfluorohebutyl halide (14-mer), hinyl halide,
- Allyl halide, methylene halide, haloform, tetrahalogenmethane, alkylidene halide, dihalogenated ethane (each isomer), tri-halogenated ethane (each isomer), tetrano-halogenated ethane, dihalogenated butane Aliphatic mono- and polyhalides such as (each isomer), di-halogenated hexane (each isomer), di-loethylene (each isomer); halogenbenzene, dihalogenbenzene [E].

Trihalogenbenzene (each isomer), tetrahalogenbenzene (each isomer), hexahalogenbenzene, halogennaphthalene, dihalogenated phthalene (each isomer), halogenpyridine (each isomer).

Aromatic mono- and polyhalides such as halogen toluene (%Ai form), halogen ethylbenzene (each isomer), phenyl iodo dichloride, iodosobenzene, iodosobenzene; Fatty compounds such as halogenated cyclohexane and halogenated cyclobutane o'j ylt[+5; Aroaliphatic halides such as halogenated benzyl and halogenated phenethyl; Heterocyclic halides such as halogenated furan, halogenated tetrahydrofuran, halogenated thiophene, halogenated imidazole, and halogenated piperidine; Acid halides such as halogenated acetyl and halogenated benzoyl; N-halogensuccinimide, N
-N-halides such as halogenalkylamine, N-halogenacetamide, and N-halogenbenzamide 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.

Further, as the halogen compound, hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen iodide, and hydrohalic acid, or halogen molecules themselves such as chlorine, bromine, and iodine can also be used.

Such halogen compounds are lf! Ii may be used alone, or two or more types may be used in combination.

Further, when the amine as one reaction raw material or other components of the catalyst contain a halogen, the addition of the halogen compound can be omitted.

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

The amount of the halogen compound used in the present invention is not particularly limited, but is usually 0.001 to 10
,000 times the molar range.

The basic substance used as an additional assistant in the present invention may be either inorganic or organic. Examples of such female 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 Vide, potassium peroxide, dipotassium trioxide, potassium superoxide, rubidium oxide, rubidium peroxide, dirubidium trioxide, rubidium superoxide, rubidium ozonide, cesium oxide.

Cesium peroxide, dicesium trioxide, cesium superoxide,
Oxides of alkali metals such as cesium ozonide; oxides of alkaline earth metals such as berylum oxide, magnesium oxide, calcium oxide, calcium peroxide, strontium oxide, strontium peroxide, barium oxide, barium peroxide; water Lithium oxide, sodium hydroxide,
potassium hydroxide, rubidium hydroxide, semiram hydroxide,
Alkali metal and alkaline earth metal hydroxides such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide; sodium carbonate, sodium hydrogen carbonate.

Salts of strong bases and weak acids such as potassium carbonate, potassium hydrogen carbonate, barium carbonate, sodium silicate, magnesium silicate, potassium aluminate, calcium aluminate, sodium borate, barium borate; carbides such as calcium carbide and cesium carbide hydroxides and oxides of aluminum group metals such as aluminum hydroxide, potassium hydroxide, indium hydroxide, thallium hydroxide, and thallium oxide; of rare earth elements such as lanthanum oxide, cerium oxide, and cerium hydroxide Oxides and hydroxides; 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; methyl hydroxide) IJ
Quaternary phosphonium hydroxide compounds such as phenylphosphonium and tetramethylphosphonium hydroxide; Tertiary sulfonium hydroxide compounds such as triethylsulfonium hydroxide and triphenylsulfonium hydroxide; sodium acetate, potassium benzoate, rubidium oxalate , salts of strong bases and weak organic acids such as barium propionate; alkali metal and alkaline earth metal alcoholades such as sodium methylate, sodium ethylate, calcium ethylate; sodium phenolate, potassium phenolate, magnesium phenolate Alkali metal and alkaline earth metal phenolates such as lat; alkaline metal and alkaline earth metal amides such as lithium amide, sodium amide, calcium amide, lithium dimethylamide; trimethylamine, triethylamine, tri-n-butylamine, triphenyl Amine, diethylmethyl7ty, N,N-diethylaniline, N-methylpiperidine, N,N'-diethylpiperazine, N-methylmorpholine, triethylenediamine, hexamethylenetetramine, N,N,N',N'-tetra Methylethylenediamine, dicyclohexylethylamine.

1.2.2,6.6-pentamethylpiperidine, pyridine.

Quinoline, phenanthroline, indole, N-methylimidazole, 1,8-diazabicyclo-(5,4
,0)-undecene-7 (DBU), 1,5-diazabicyclo-(4,3,0)-nonene-5(I)BN) and cyclic nitrogen-containing compounds (however, N- Crown compounds such as crown ether, aza crown ether, thia crown ether, aza crown, and complexes of these crown compounds with alkali metals and alkaline earth metal scrap ions 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 may be chemically bonded.

Further, as the chelating reagent used as an additional cocatalyst in the present invention, α-dioximes such as dimethylglyoxime, benzyldioxime% 1,2-cyclohexanedione dioxime; 2,2'-bipyridine, 2,2'
- Bipyridine and terpyridine such as piquinoline and terpyridine; q-phenanthroline, 4.7-diphenyl-q-phenanthroline% 2.9-dimethyl-q-
q-7 enanthrolines such as phenanthroline, 2,9-dimethyl-4,7-diphenyl-q-phenanthroline, and 4,7-cyhydroxy-q-phenanthroline;
8-hydroxyquinoline, 5,7-dichloro-8-hydroxyquinoline, 5,7-dipromo-8-hydroxyquinoline, 5,7-diiodo-8-hydroxyquinoline, 2-methyl-8-hydroxyquinoline, etc. Quinallic acid and quinolinecarboxylic acids such as quinaldic acid and quinallic acid/-8-carboxylic acid can be mentioned.

These basic substances or chelating reagents that can be used as additional promoters may be used alone or in combination of two or more. There is also no particular restriction on the amount used, but it is usually in the range of 0.01 to 1,000 times the mole of the halogen compound, or usually 0.01 to 1,000 times the amount of the metal element in the component containing the platinum group element. ．． O
It is preferably used in an amount of 1 to 1 o, o o o times by 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 represented by the following formula (%) in one molecule. Here, one or two lines connected to N represent a bond between a nitrogen atom and another atom or group, and such atoms or groups include hydrogen,
halogen, alkali metal, hydroxyl group, amino group,
Examples include aliphatic groups, alicyclic groups, aromatic groups, araliphatic groups, and heterocyclic groups. Further, in the secondary amine, the nitrogen atom itself may be an element constituting a ring, such as habiroll, piperidine, piperazine 71 morpholine, and the like.

Such primary amines include, for example, ammonia, methylamine, ethylamine, flobylamine (all isomers), butylamine (all isomers),
7 Mine (each isomer), hexylamine (each isomer)
, aliphatic primary monoamines such as dodecylamine (each isomer), ethylenediamine, diaminopropane (each isomer), diaminobutane (each isomer), diaminopentane (each isomer), diaminohexane (each isomer) ), aliphatic primary diamines such as diaminodecane (each isomer);
Aliphatic primary triamines such as 1,2,3-triaminopropane, triaminohon (each isomer), triaminononane (each isomer), triaminododecane (each isomer); cyclopropyl Alicyclic primary mono- and polyamines such as amine, cyclobutylamine, cyclopentylamine, cyclohexylamine, diaminocyclobutane, diaminocyclohexane (each isomer), triaminocyclohexane (each isomer); benzylamine/, di(amino methyl)ben('/(each isomer), aminomethylpyridine (each isomer), di(aminomethyl)pyridine (each isomer), aminemethylnaphthalene (each isomer), di(aminomethyl)naphthalene (each Aroaliphatic primary mono- and polyamines such as (isomers); Aminofuran (each isomer)
Heterocyclic primary amines such as , aminotetrahydrofuran (all isomers), aminothiophene (all isomers), aminopyrrole (all isomers), and aminopyrrolidine (all isomers) are preferably used.

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

(In the formula, A is a simple chemical bond or -〇-1-S-1-
SO□-1-CO-1-C0NH-1-COO-1-C
(R7) represents a divalent group selected from (R'') - and -N(R7)-.

Further, R7 and R11 are H1 aliphatic groups and alicyclic groups. ) Furthermore, in these aromatic primary amines, at least one hydrogen on the aromatic ring may be substituted with another substituent, such as a halogen atom, a nitro group, a cyan group, an alkyl group, an alicyclic group, or an aromatic group. , an aralkyl group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, an ester group, an amide group, or the like.

Particularly preferred among these aromatic amine compounds are aniline, 2,4- and 2,6-diadenotoluene,
These are chloraniline (each isomer), dichloroaniline (each isomer), 4,4'- and 2,4'-diaminodiphenylmethane, and 1,5-diaminonaphthalene.

Examples of secondary amines include aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, diethylamine, ethylmethylamine, ethylhexylamine, butylmethylamine, and ethylhexylamine. $4 Alicyclic secondary amines such as dicyclopropylamine, dicyclohexylamine, methylcyclohexylamine; N-methylaniline, N-ethylaniline, N-methyltoluidine (each isomer), diphenylamine, N, N' - Aromatic secondary amines such as diphenylmethanediamine, N,N'-dimethylphenylene difuran (each isomer), N-methylnaphthylamine (each isomer), dinaphthylamine (each isomer)j dibenzylamine , ethylbenzylamine, diethylamine, and other aromatic aliphatic secondary amines; difuranylamine, dinaphthylamine, and other heterocyclic secondary amines; pyrrolidine, pyrol, 3-pyrrolidone, indole, carbazole, piperidine, piperazine ,β
Cyclic tack secondary amines such as -piperidone, γ-piperidone, imidazole, pyrazole, triazole, benzimidazole, morpholine, and l,3-oxazine are preferably used.

However, in these primary amines and secondary amines, one or more hydrogens of the organic group bonded to nitrogen may be substituted with other substituents, such as lower aliphatic groups, amino groups, carboxyl groups, etc.
It may be substituted with an ester group, an alkoxy group, a cyano group, a halogen, a nitro group, a urethane group, a sulfoxide group, a sulfone group, a carbonyl group, an amide group, an aromatic group, an araliphatic group, or the like. Furthermore, these primary amines and secondary amines may have unsaturated bonds.

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

These primary amines or secondary amines can be used alone or in combination of two or more. When two or more are used, an asymmetric urea compound can also be obtained. When a polyvalent amine having more than 1 amino group 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.

For example, in the case of a primary monoamine, the ureation reaction of the present invention proceeds according to the following general formula: O2RNH,0CO+TO2 → RNHCONHR+H,0 (R represents an organic group) Molecular oxygen is equivalent It may be less or more, but should be used within a range such that the acid violet/carbon oxide or oxygen/amine mixture is outside the explosive limits.

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.

Such solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; nitriles such as acetonitrile and benzonitrile; sulfolanes such as sulfolane, methylsulfolane, and dimethylsulfolane; tetrahydrofuran, 1. 4-dioxane,
Ethers such as 1,2-dimethoxyethane; acetate/
Ketones such as , methyl ethyl ketone; Esters such as ethyl acetate and ethyl benzoate; Amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoramide, etc. Examples include tertiary amino acids such as triethylamine, tributylamine, pyridine, and quinoli.

Furthermore, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, chlorotoluene, chlornaphthalene, and bromnaphthalene, which are one type of organic halides used as cocatalysts of the present invention; Halogenated aliphatic hydrocarbons or halogenated alicyclic hydrocarbons such as chlorhexane, 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 and alkali metal salts and alkaline earth metal salts of acids such as boric acid, aluminic acid, carbonic acid, silicic acid, and organic acids.

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

The reaction pressure is in the range of 1 to so Ky/cdl, preferably 20 to 300 to 9/-, and the reaction time varies depending on the reaction system, catalyst system, and other reaction conditions, but is usually several minutes to several hours. .

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

Example 1 200 mmot of aniline in a 500-autoclave
.

Tetramethylurea 120m7! , sodium iodide 3m
P with 2Wq6 of Pd supported on mot, powdered sio,
After adding d/sto and sr and replacing the inside of the system with carbon monoxide, the system was heated to 160 to 170°C while stirring. After reaching a predetermined temperature, a mixed gas consisting of 75 g of carbon oxide and 25 g of air was heated at 60 Nt/hr under a pressure of 80 Kg/aA.
The reaction was carried out with stirring while introducing at a flow rate of .

This reactor has a partial condenser installed at the top of the autoclave, and condensable gas components can be partially or completely condensed as needed and circulated to the reactor. It is also possible to remove the entire amount of the condensed liquid component from the reaction system without circulating it. Further, in order to maintain the liquid amount in the reactor at a predetermined level, it is also possible to continuously inject liquid components into the reactor using a pump, as necessary.

There are two cases in which almost all of the water generated by the reaction was removed from the reaction system together with the reactive gas, one where it was removed by a small percentage, and one where the entire amount of water was left in the reaction system without removing all the heat. The reaction results after 1 hour were as shown in Table 1.

Table 1 Selectivity A and B represent the selectivity of ureas based on amine and carbon oxide, respectively.

Examples 2 to 10 Table 2 shows the results of reactions carried out in the same manner as in Example 1, except that various halogen compounds, basic substances, or chelating reagents shown in Table 2 were used. In these examples, the water produced in the reaction, along with the reactive gas, is approximately i
oo% removed. Further, selectivity A and B represent the same meaning as above.

Example 11 Di(n-butyl)amine 150 rnmot% Palladium black I Wq atom, sodium iodide 2 mm
The reaction was carried out in the same manner as in Example 1 except that 150 oz N benzene was used. Almost the entire amount of water produced by the reaction was removed along with a portion of the benzene, and approximately the same amount of benzene as the distilled amount was continuously supplied to the reactor.

The reaction results after 1 hour showed that the reaction rate of di(n-butyl)amine was 80%, the yield of N,N,N',N'-tetra(n-butyl)urea was 71%, and the reaction rate of di(n-butyl)amine was 71%. Standard selection rate is 9
At 4%, the selectivity based on -carbon oxide was 93%. A similar reaction was carried out without removing water, and the reaction rate of di(n-butyl)amine was 63%, and the yield of N,N,N',N'-tetra(n-butyl)urea was 52%. - The selectivity based on amine was 88%, and the selectivity based on carbon oxide was 80%.

Examples 12 to 17 Water produced in the same manner as in Example 1 except that a platinum group catalyst not shown in Table 3 is used instead of Pd/5in2 in Example 1. Table 3 shows the results of the reaction conducted with exclusion. Note that selectivity A and B have the same meaning as above.

The Ushida platinum group catalyst uses 2 W atom as the metal base beam, and the display does not indicate the weight J% of the metal supported on the carrier.

k! Table J3 Example 18 Anion exchange resin (Amberlyst A-
26, OH form) was treated with hydroiodic acid to exchange the hydroxyl group with an iodine anion and then dried at 100° C. under reduced pressure. This iodine-containing anion exchange resin 31, anisoy 100 mmotSN, N'-dimethylacetamide 120m, palladium black 2Mgat
The reaction was carried out for 1 hour while water was distilled off in the same manner as in Example 1 except that Om was used. The reaction rate of aniline was 100%, the yield of N',N'-diphenylurea was 99%, the selectivity based on aniline was 99q6, and the selectivity based on -carbon oxide was 94%.

Patent applicant Asahi Kasei Kocha Co., Ltd. 51-

Claims (1)

[Scope of Claims] 1 Molecular oxygen; (a) at least one selected from platinum group metals and compounds containing platinum group elements; and (b) at least one halogen molecule or halogen compound.
In a method for producing urea by reacting a primary amine or a secondary amine with carbon monoxide in the presence of a catalyst system consisting of Method 2 for producing ureas characterized by reacting while removing water from the outside. Water produced by the reaction can be removed using a reactive distillation method, a method in which a reaction gas containing carbon oxide is used as a carrier, and an organic solvent. Method 1 according to claim 1, in which a basic substance and a chelating reagent are removed from the reaction thread by either a method of distilling off together with a part or a method combining these methods. A method table according to claim 1 or 2 in which at least one selected from the above is used. A patent in which the platinum group metal and the compound containing the platinum group element are palladium, rhodium, a palladium compound, and a rhodium compound. Claim 1
2. Method i according to claim 1, 2, or 3. Method a according to claim 1, 2, 3, or 4. The halogen compound is a metal halide. is an alkali metal halogenide or an alkaline earth metal halide, the method 7 according to claim 5, wherein the halogen compound is an halogenated onium compound or a reaction system capable of producing these. The method according to claim 1, 2, 3 or 4, wherein the halogenated onium compound is a halogenated ammonium compound, a halogenated phosphonium compound, a halogenated arsonium compound or a halogenated sulfonium compound.Claim 7.t', wherein the halogenated onium compound is a polymer containing an onium group in its main chain or side chain. or the method 1α according to claim 8. The halogen compound is a halogen oxoacid or a salt thereof. The method IL according to claim 1, 2, 3, or 4, wherein the halogen compound is 12. The method according to claim 1, 2, 3 or 4, wherein the halogen compound is a complex compound containing a halogen. Claim 1, wherein the halogen compound is a modified halide; Items 2 and 3-1: Method 1λ according to claim 4, wherein the halogen species is bromine and/or iodine; Claim 14, wherein the halogen species is iodine; Claim 14, wherein the halogen species is iodine range 1
3. The method ir according to claim 1, wherein the amine is a primary amine.
16. The method according to claim 15, wherein the primary amine is an aromatic primary amine.