JPS60149552A - Preparation of urethane - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as agricultural chemicals, etc. in high yield and purity, by reacting a primary or secondary amine with CO and an organic hydroxyl compound in the presence of a specific catalyst while removing all or part of water formed by the reaction to the outside of the system. CONSTITUTION:A primary amine, e.g. NH3 or methylamine, or a secondary amine is reacted with CO and an organic hydroxyl compound, e.g. methanol, ethanol or propanol, in the presence of a catalyst system consisting of at least one selected from a compound containing a platinum group metal and element and at least one halogen compound, particularly containing preferably I as a halogen species, to afford a urethane. In the process, the reaction is carried out while removing all or part of water formed by the reaction to the outside of the system.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing urethane, and more particularly, to oxidative carzenylation by reacting a primary amine or a secondary amine with carbon monoxide and an organic hydroxyl compound in the presence of an oxidizing agent. The present invention relates to a method for producing urethane by.

Urethanes are important compounds used in carpameide pesticides and the like, and recently there has been a demand for an inexpensive method for producing them as a raw material for producing incyanates without using phosgene.

Conventionally, two main methods have been proposed as methods for producing urethane compounds using -carbon oxide. That is, one method is to reductively urethanize a nitro compound in the presence of an alcohol. For example, in the case of nitropencene, the reaction is represented by the following formula.

(R represents a radical.) However, in this reaction, 3 moles of -t1 supporting carbon are required per 1 mole of nitrobenzene, and 2 moles of carbon monoxide of this becomes worthless carbon dioxide. -The disadvantage is that only % of the amount of carbon oxide used is effectively utilized, and furthermore, in order to carry out this reaction continuously,-
A large amount of carbon dioxide must be separated from the mixed gas of carbon oxide and carbon dioxide, which is also a disadvantage in industrial practice.

Another method is to oxidatively urethanize a natural amine compound by reacting it with carbon monoxide and an alcohol in the presence of an oxidizing agent such as oxygen or an organic nitro compound. When aniline is oxidatively converted into urethane, the reaction is expressed by the following equation.

This method utilizes carbon monoxide more effectively than the above-mentioned method, and can be said to be a more preferable method.
In the method using the catalyst system described in Japanese Pat. The selectivity of urethane is 70-80 even when the reactivity of amine is 70-80.
The problem was that it was extremely low. Another problem was that as the amine reaction rate increased, the selectivity of urethane based on carbon monoxide further decreased.

Therefore, the present inventors have conducted intensive research to find a catalyst system that can produce urethane with high yield and high selectivity in a method of oxidatively converting flood-class amines or secondary amines into urethanes. We discovered 4!1 effective catalyst systems and proposed them earlier. These catalyst systems consist of at least one at 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 compound is a % effective cocatalyst. By using these catalyst systems, it was possible to greatly increase the yield and selectivity of urethane based on amine and carbon oxide compared to the prior art, but it was possible to increase the amine conversion rate to over 90%. It was found that as the catalyst temperature was increased, the selectivity of urethane on a -carbon oxide basis decreased slightly.As a result of intensive research to improve this point, the use of these catalyst systems was found. By combining this 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 yarn, not only the selectivity of urethane based on carbon oxide can be further improved, but also the reaction It was discovered that the speed and amine-based yield and selectivity could also be improved, and the present invention was completed based on these findings.

That is, the present invention provides an oxidizing agent, and (a) at least one selected from platinum group metals and compounds containing platinum group elements, and (b) at least one halogen compound in the presence of a catalyst system. In the method of producing urethane by reacting a primary amine or a secondary amine with carbon monoxide and an organic hydroxyl compound, all or part of the water produced by the reaction must be removed from the reaction system. An object of the present invention is to provide a method for producing urethane, which is characterized by reacting the urethane.

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 urethane using at least one selected from basic substances and/or chelating agents 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 the removal method using a carrier agent such as a reaction gas containing carbon oxide or a low-boiling point organic substance, the method of mixing with a part of the organic hydroxyl compound, and the method of combining these methods. Regarding the reaction method used, either a batch method or a flow method may be used for the liquid phase, but it is preferable to use a flow method for the gas component containing -carbon oxide.

Regarding the platinum group elements and compounds containing platinum group elements used in the method of the present invention, the components include noradium,
There is no particular restriction as long as it contains at least one element selected from platinum group elements such as rhodium, platinum, ruthenium, iridium, and δ-mium.These essential elements may be in a metallic state or form a compound. It may be a component that In addition, these catalyst components include, for example, activated carbon, graphite, silica, alumina, silica-alumina, silica-
They may be supported on carriers such as titania, titania, ziwonia, nocerium sulfate, calcium carbonate, asbestos, pentona, diatomaceous earth, polymers, ion exchange resins, zeolites, molecular seesaw, magnesium silicate, magnesia, etc. ,stomach.

Examples of platinum group elements in the metallic state include gold stripes such as palladium, rhodium, platinum, ruthenium, iridium, and osmium, metal blacks of these metals, and catalyst components containing these metal ions on the above-mentioned carrier, and then hydrogen or formaldehyde, and alloys or intermetallic compounds containing these metals are used. Also, alloys or intermetallic compounds are between these platinum group metals.

or other elements such as selenium,
tellurium, sulfur, antimony, bismuth, copper, silver, gold,
It may contain zinc, tin, metal, iron, metal, nickel, mercury, 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, l+I'+ acid salts, phosphates, and borates, and organic salts such as acetates, oxal salts, and formates. Acid salts, cyanides, hydroxides, oxides,
Metal salts containing anions such as sulfides, nitro groups, cyanide groups, halogens, and oxalate ions, and groups and complexes containing ammonia, amines, phosphines, -carbon oxides, chelate ligands, etc. Examples include metal complex compounds, organometallic compounds having M-organic ligands, or organic groups.

Among these catalyst components, those containing palladium, rhodium, or both are particularly preferable, such as Pa black; Pd (), P d A
l 203 , P d S r 02 , Pd i,
'+02, PdZrO2, Pd-BaSO4
, pdOaUO3, Pd-asbestos, Pd-heptaolite, Pd-molecular sieve, etc. Supported palladium catalyst Qi Pd-Pb, Pd-8e, Pd-Te
.

I'd-Hg, Pd-TIXPd-P, Pd-Ou
XPd-AgXPPd-0uXPd-A, Pd-Ni
, alloys or intermetallic compounds such as Pd-Rh, and these alloys or intermetallic compounds supported on the above-mentioned carriers, Pd (J'21PdBr2, PdI
2. Inorganic salts such as Pd (NO3)2, PdSO4, Pd (OCOCH3), organic acid salts such as radium oxalate, Pd(ON), PdO,
Pd8, M2 (PdX4), M, (PdX6) = ±4 represents halogen), (Pd (NH3)4
) X2, (Pd(en)z)X2 (X has the same meaning as above, en
represents ethylenedia□, stationmin), Pd(3t2(PhON)2.Pa
04(Pa3)z.

Pd (Co) (Pa3)3. Pd (PPh3)
4. Pd(M(It) (PI)h3)2゜Pd(υ
2H4) (PPh3)2, pa (03H5)2
complex compounds or organometallic compounds such as (R represents a 4 ash group), complex compounds coordinated with chelate ligands such as Pd(acac)2, supported rhodium catalysts similar to Rb black and Pd. Class, R, h alloy similar to Pd or gold M 1141
Compounds and those supported on carriers, Rh01z
and hydrates, RhBr3 and hydrates, ⇠hI3 and hydrates, Rh2(SO2)i and inorganic salts such as hydrates, ⇠h2(OCOCH3)4゜Rh2O3, RhO2+ M
3(n,"Xa) and hydrates (M, X have the same meanings as above), (Rb(NH3)5]X3, (R
h(en)s)Xa.

Ammine complexes of rhodium such as 1'Lb4((jO
)1□.

Rhodium cardinyl clusters such as ⇠h1I(Co)16, (R1+0A(Co)2)2, LehOt
3 (Pll, 3J3. RhUt (PPb3) 3゜几h
Complex compounds such as There are many 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 platinum group elements may be used.
4 or more may be used as a mixture, and there are no particular restrictions on its usage, but usually the platinum group element-containing component is 0.0001 to 50% of the primary amine or secondary amine.
It is preferable that the mole % of the paste is about 1 mol %.

The halogen compounds used in the present invention may be organic or inorganic halogen-poor compounds that do not contain platinum group elements, such as gold (ζ halides, halogenated onion compounds). - Sim compounds, compounds capable of producing onium halide compounds in the reaction system, halogen oxoacids or salts thereof, complex compounds containing halogens, organic halides, etc. are preferably used.

Examples of metal halides include alkali metals, alkaline earth metals, copper, and silver. jli! , lead, cadmium, mercury, aluminum, gallium, thallium, germanium, tL antimony, bismuth, titanium,
Halides such as zirconium, vanadium, niobium, tantalum, tellurium, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, and rare earth metals are used. Sometimes preferred are alkali metal and alkaline earth halides.

As alkali metal and alkaline earth metal halides, 1. f! 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, supra-iodide, magnesium iodide, calcium iodide, J, li- such as strontium iodide and norium iodide
Compounds of metals and single orogens, double salts such as sodium magnesium chloride, potassium magnesium chloride, potassium potassium chloride, potassium magnesium bromide,
Polyhalides such as potassium bromine fluoride, potassium iodine chloride, rubidium iodine chloride, cesium iodine chloride, cesium iodine chloride bromide, rubidium iodine chloride bromide, potassium iodine bromide, suprasium iodine bromide, rubidium iodine bromide And so on.

Onium halide compounds are compounds containing elements with lone pairs of electrons, in which protons or other cationic/ionic reagents are bonded to these lone pairs, and the elements with lone pairs of electrons are bonded to a co-southern bond valence. It becomes a positive ion by adding ``1'' to ``v'', and 41 halogen anions are added as a counter ion.

Such onium compounds include ammonium compounds ((R'R''R3R4N■)X,e), phosphonium compounds ((R'R2113R4P■]X■), arsonium compounds ((BtB2BsB4AsO)XO),
Stibonium compound ((RIR2R3R4Sb■)Xe
), oxonium compound ((n, tEL2a3o0 )
xe ), sulfonium compound ((RIIiL2R3
S■]X○), oxysulfonium compound ((+1ir
i3S (0))XO), selenonium compound ((B
IB2几3Se■)XC'), telluronium compound ((
BIFL2几3Te■〕X■), stibonium compound (
[R1几2R38n■)Xe), iodonium compound (
(R"rL"I■]X○) and the like. Here B
l.

几2, Bl, and R4 represent hydrogen or a group selected from an aliphatic group, an aromatic group, an alicyclic group, an araliphatic group, and a heterocyclic group, and each may be the same, or In some cases, it may be a constituent element of a ring containing an element that supports a lone pair of electrons. Also, X is F, C1.

Insert a halogen selected from Br and I. Of course, it may also be a compound containing two or more such onium groups in its molecule, or it may also be a polymer containing such onium groups in its main chain or side chain.

Such anion is an onium compound in which 710 ken) - rogonated onium compounds include amines or nitrogen-containing compounds, phosphine compounds, arsine compounds, stibine compounds, amines or nitrogen-containing compounds corresponding to nologonide or specific norogenides, It can be easily obtained by reaction with oxy compounds, sulfide compounds, sulfoxide compounds, selenium compounds, telluride compounds, etc. These compounds may be produced outside the reaction system, or they may be produced within the reaction system. These may also be generated. Of course, b may be produced by another method, or may be produced in the reaction system by another method.

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 norogenated phosphonium compounds. Ammonium compounds can be easily obtained by reacting a corresponding nitrogen-containing compound with hydrogen hydrogen, or by reacting a nitrogen-containing compound with an alkyl halogenide or an aryl halide. Examples of nitrogen-containing compounds include ammonia, amines such as primary amines, secondary amines, and tertiary amines, hydroxylamines, hydrazines, hydrazines, amines, oximes, and imides. Esters, amides and various
There are complex compounds.

Preferred 7-hydrogenide salts of nitrogen-containing compounds include:
Ammonium chloride, ammonium bromide, ammonium iodide type +4 types of ammonia, salts of aromatic amines such as diphenylamine, triphenylamine, methylamine, ethylamine, hexylamine, octylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, Salts of aliphatic amines such as dibutylamine, tripropylamine, methylethylamine, dimethylethylamine, diptylmethylamine, tributylamine, ethylene, diamine, hexamethylene diamine,
Salts of alicyclic amines such as cyclozolopylamine, cyclohexylamine, and N-methylcyclohexylamine; salts of aromatic aliphatic amines such as benzylamine, N-methylbenzylamine, N,N-diethylsone, noramine, and dibenzylamine. , piperidine, piperazine, morpholine, pyridine, quinoline, hegisamethylenetetramine,
Salts of nitrogen-containing monocyclic compounds such as ogizazole, thiazole, imidazole, triazole, benzotriazole, and noazabicycloundecene, and salts of amides such as dimethylacetamide and N-methylpyrrolidone are used.

Dropped quaternary ammonium rye 1? In particular, aliphatic quaternary ammonium rides such as halogenated tetramethylammonium, halogenated tetraethylammonium, halogenated tetrabutylammonium, halogenated trimethylethylammonium 1, halogenated diethyldibutelammonium, Alicyclic quaternary ammonium halides such as halogenated N,N,N-trimethylcyclohexylammonium, aromatic aliphatic quaternary ammonium halides such as halogenated tetrabenzylammonium, halogenated trimethylbennolammonium, halogenated N , N, N-), +) methylphenylammonium, aromatic quaternary ammonium halides such as halogenated N, N, N-triethylphenylammonium, halogenated N-methylpyridinium, halogenated N
-Ethylquinolinium, N-halogenide, N-dimethylpiperidinium, N-halide.

Heterocyclic quaternary ammonium halides such as N'-dimethyl imidazolinium 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.

1 also 2 Here, R' + R'' + R3+ X has the above meaning, and 几5 represents a divalent * machine group.

Examples of the halogenated phosphonium compounds include symmetrical tetraalkylphosphonium compounds such as halogenated tetramethylphosphonium, non-logonated tetraethylphosphonium, nor-rogenated tetrabutylphosphonium, non-rogenated enaltrimethylphosphonium, and halogenated enaltrimethylphosphonium. asymmetrical tetraalkylphosphonium compounds such as diethyl) Asymmetric tetraalkylphosphonium compounds such as α-naphthyl)triphenylphosphonium, alkylaryl mixed phosphonium compounds such as methyltriphenylphosphonium halides, phenyltrimethylphosphonium halides, and tetrabenzylphosphonium compounds such as methyltriphenylphosphonium halides; Alkylphosphonium compounds and the like are preferably used.

Examples of the halogenated arsonium compounds include symmetrical tetraalkyl arsonium compounds such as tetramethylarsonium halide, tetraethylarsonium halogenide, methyltriethylarsonium halogenide, and methyltriethylarsonium halogenide. Asymmetric tetraalkyl arsonium compounds such as dimethyldiethyl arsonium, symmetrical tetraaryl arsonium compounds such as norogenated tetraphenyl arsonium, halogenated methyltriphenyl arsonium, halogenated ethyl triphenyl arunium, halogenated Alkylaryl mixed arsonium compounds such as phenyltrimethylalunium are preferably used.

Examples of halogenated sulfonium compounds include symmetrical or asymmetrical alkylsulfonium compounds such as halogenated trimethylsulfonium, non-logonated triethylsulfonium, and non-logonated methyldiethylsulfonium, and arylsulfonium compounds such as halogenated triphenylsulfonium. Compounds, halogenated dimethylphenylsulfonium, halogenated methyldiphenylsulfonium compounds, etc., no-halogenated bicyclo-(2,2,1)-hebutane-1-
1P containing a ring halogenated sulfonium group such as sulfonium or thiopyrylium halide in the main chain or side chain
Summers are also preferably used, and examples of such polymers include those having the following main structural units.

2 (In the formula, 几1.B!, 几3.X have the above-mentioned relaxing taste)
Halogen oxoacids and their salts have an oxidation number of positive 1 or 3.
, 5.7 halogen oxygen acids and their salts, specifically hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromate acid, perbromate acid. , hypoiodic acid, iodic acid, iodic acid, orthoperiodic acid, metaperiodic acid, and their enemy salts. The cations of the salts may be of any type, such as ammonium ions and various types of gold, but alkali metal ions and alkaline earth metal ions are particularly preferred.

Such salts include, for example, sodium hypochlorite,
Potassium hypochlorite, calcium hypochlorite, hypochlorite) Hypochlorites such as cerium, chlorites such as sodium chlorite, lithium chlorate, sodium chlorate, potassium chlorate, chlorine Rubidium acid, cesium chlorate, magnesium chlorate, calcium chlorate, norium chlorate, aluminum perchlorate, calcium perchlorate, norium perchlorate, zinc perchlorate, cadmium perchlorate, perchlorate Perchlorates such as acid mercury, cerium perchlorate, lead perchlorate, and ammonium perchlorate; hypobromites such as sodium hypobromite and potassium hypobromite; and submersible salts such as sodium bromite. Bromates, lithium bromate, sodium bromate, potassium bromate, rubidium bromate, cesium bromate, magnesium bromate, calcium bromate, strontium bromate, barium bromate, silver bromate, zinc bromate, bromate Bromates such as cadmium, mercury bromate, aluminum bromate, lanthanum bromate, samarium bromate, lead bromate, ammonium bromate, perbromate 4 such as potassium perbromate, Ql sodium hypoiodite, Hypoiodites such as potassium hypoiodite, rubidium hypoiodite, cesium hypoiodite, calcium hypoiodite, norium hypoiodite, lithium iodate, sodium iodate, potassium iodate , potassium hydrogen iodate, rubidium iodate, cesium iodate, magnesium iodate, calcium iodate, strontium iodate, iodate A
IJium, silver iodate, gold iodate, zinc iodate, cadmium iodate, mercury iodate, aluminum iodate, iodate, indium, lanthanum iodate, cerium iodate, zoroseo iodate, gym, neodymium iodate, Iodates such as gadolinium iodate, lead iodate, ammonium iodate, n1 periodic lithium,
Sodium metaperiodate, trisodium orthoperiodate dihydrogen, disodium trihydrogen orthoperiodate, potassium metaperiodate, dipotassium trihydrogen orthoperiodate, tripotassium dihydrogen mesoperiodate, periodate Rubidium, cesium periodate, Noranium periodate, silver metaperiodate, iron periodate, silver orthoperiodate, silver trihydrogen orthoperiodate, zinc periodate, cadmium periodate , periodate salts such as lead periodate and ammonium periodate are 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 aluminum dichlorobromate, tetramethylammonium tetrabromoiodate, etc. Halogenation of potassium hexayo-tellurate, tetraethylammonium tetraiodomercurate, potassium tetraiodobismuth, sodium tetrabromocuprate, cesium tetrabromoferrate, norium hexaiodostannate, potassium tetraiodolearate, potassium hexabromotellurate, etc. Metallic acid salts, tetrabromo(diethylsuccinate)tin, octate(N,N-dimethylformamide)lanthanum triage 1', hexakis(
Tribromide, hexamine chromium tribromide, iodobentaamine chromium tribromide, tris(pyridine) chromium tripromide, tris(
Complexes having a ligand such as pyridine) molybdenum tribromide, hexaammine cobalt tribromide, and bis(2,2'-bipyridine) copper George are used.

In addition, organic halides have the general formula % formula %) (in the formula, R6 is an m-valent organic group, X is), rogene, m is 1
means an integer greater than or equal to ), and when m is 2 or more, X is 2
It may be a different halogen glaze than the glaze.

Further, the halogen X may be bonded to a heteroatom other than carbon, such as carbon, phosphorus, oxygen, -sulfur, selenium, or the like.

Examples of such organic halides include methyl halide, ethyl halide, propyl halide (
(Each isomer), Butyl halide (Each isomer), Amyl halide (Each isomer), Hexyl halide (Each isomer), Octyl halide (Each isomer), Perfluorohexyl halide (Each isomer) ), perfluorohebutyl halide (each isomer), hynyl halide, allyl halide, methylene halide, haloform, tetrahalogenmethane, alkylidene halide, dihalogenated ethane (each isomer), trihalogenated ethane ( Aliphatic mono- and polyhalides such as tetrahalogenated ethane, dihalogenated butane (each isomer), dihalogenated hexane (each isomer), dihaloethylene (each isomer); halogenbenzene, dihalogenbenzene (each isomer), trihalogenbenzene (each isomer), tetrahalogenbenzene (each isomer), hexahalogenbenzene, halogennaphthalene, dihalogennaphthalene (each isomer), halogenpyridine (each isomer), halogentoluene (each isomer), halogen ethylbenzene (each isomer), aromatic mono- and polyno-loginated compounds such as phenyl iodo dichloride, iodosobenzene, iodoxybenzene, alicyclic halogen such as halogenated cyclohexane, halogenated cyclobutane, etc. Aroaliphatic compounds such as halogenated benzyl, halogenated phenolic acid, etc.; halogenated furan, halogenated tetrahydrofuran, halogenated thiophene, halogenated imidazole, halogenated piperidine, etc. heterocyclic compounds, acid halides such as halogenated acetyl, and halogenated benzoyl, N-halogenconophosphoric acid 1mide, N-halogenalkylamine, N-halogenated benzoyl, etc.
7 Cetamide, N- such as N-tamerogen benzamide P, etc.
Halides and the like are preferably used.

Furthermore, these organic groups such as 7'L can be used with various substituents, such as nitro groups, lower alkyl groups, cyano groups, alkoxy groups, aryloxy groups, aromatic groups, sulfoxide groups, sulfone groups, carzenyl groups, and ester groups. , amine P group, etc., or may have an unsaturated group.

In addition, as halogen compounds, hydrogen halides such as hydrogen chloride, hydrogen bromide, hydrogen iodide, and hydrochloric acid,
Alternatively, the molecules themselves such as chlorine, bromine, and iodine can also be used.

Such halogen compounds may be used alone or in combination of two or more.

Further, when the amine or alcohol as a reaction raw material or other components of the catalyst contain I.logen, the addition of a 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 io
, ooo times the molar range.

The salt and basic substance used as an additional promoter in the present invention may be either inorganic or organic. Examples of such basic substances include lithium, sodium,
Alkali metals such as potassium, alkaline earth metals such as magnesium, calcium, and norium, lithium oxide, lithium peroxide, sodium oxide, sodium peroxide, sodium superoxide, potassium oxide, potassium peroxide,
Dipotassium trioxide, potassium superoxide, rubidium oxide,
, rubidium peroxide, dirubidium trioxide, rubidium superoxide, rubidium ozonide, cesium oxide, cesium peroxide, dicesium trioxide, cesium superoxide, cesium ozonide, and other alkali metal oxides, perylum oxide, oxidation Alkaline earth metal oxides such as magnesium, calcium oxide, calcium peroxide 1, strontium oxide, strontium peroxide, norium oxide, norium peroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, Alkali metal and alkaline earth metal hydroxides such as rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, nocerium hydroxide, sodium carbonate, sodium hydrogen carbonate, carbonic acid Salts of strong bases and weak acids such as potassium, potassium hydrogen carbonate, cerium carbonate, sodium silicate, magnesium silicate, potassium aluminate, calcium aluminate, sodium borate, potassium borate, and 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, thallium oxide, lanthanum oxide,
Oxides and hydroxides of rare earth elements such as cerium oxide and cerium hydroxide, lithium hydride, sodium hydride,
Hydrides such as sodium borohydride, calcium hydride, lithium aluminum hydride, sodium sulfide, sodium hydrogen sulfide, potassium sulfide, calcium sulfide, alkali metal or alkaline earth metal sulfides and hydrogen sulfides, water Quaternary ammonium hydroxide compounds such as tetraethylammonium oxide and tetrapropylammonium hydroxide, methyltriphenylphosphonium hydroxide,
Quaternary phosphonium hydroxide compounds such as tetramethylphosphonium hydroxide, tertiary sulfonium hydroxide compounds such as triethylsulfonium hydroxide, triphenylsulfonium hydroxide, sodium acetate, potassium benzoate,
Strong I such as rubidium oxalate, nomylium propionate, etc.
Salts of JK groups and weak organic acids, alkali metal and alkaline earth metal alcoholades such as sodium methylate, sodium ethylate, and calcium ethylate; alkali metals and alkaline metals such as sodium phenolate, potassium phenolate, and magnesium phenolate; Alkaline earth metal phenolates, alkali metal and alkaline earth metal amides such as lithium amide, sodium amide, calcium amide, lithium dimethylamide, trimethylamine, triethylamine, tri-butylamine,
Triphenylamine, diethylmethylamine, N, N-
Diethylaniline, N-methylpiperidine, N,N'-
Diethylpiperazine, N-methylmorpholine, triethylenediamine, hexamethylenebutramine, N, N, N
", N'-tetramethylethylenediamine, dicyclohexylethylamine, 1,2,2,6.6-pentamethylpiperidine, pyridine, quinoline, phenanthroline, inpol, N-methylimidazole, 1,8-diazabicyclo- (s, 4.0)-undecene-7(DB
U), tertiary amines such as 1,5-diazabicyclo-(4,3,0)-nonene-5 (DBN), cyclic nitrogen-containing compounds (but not having an N-H group), crown ether, aza crown ether, chia crown ether,
Crown compounds such as azacrown, and these crown compounds and lead bodies such as alkali metal and alkaline earth metal 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 chemically bonded.

Chelating reagents that can be used as additional cocatalysts in the present invention include a
-Dioximes, bipyridines and terpyridines such as 2,2'-bipyridine, 2,2'-biquinoline, and terpyridine, q-phenanthroline, 4,7-diphenyl-
q-7 enanthroline, 2.9--, It methyl-q-
q-phenanthroline such as phenanthroline, 2,9-dimethyl-4,7-diphenyl-q-phenanthroline, 4,7-dihydroxy q-7-phenthroline, 8-hydroxyquinoline, 5 .7-cyclo-8-hydroxyquinoline, 5,7-di'! Examples include 8-hydroxyquinolines such as rom-8-hydroxyquinoline, 5,7-diiodo-8-hydroxyquinoline, and 2-methyl-8-hydroxyquinoline, and quinoline carboxylic acids such as quinaldic acid and quinoline-8-carzenic acid. It will be done.

These basic substances or chelating reagents that can be used as additional promoters may be used alone or in combination of two or more. The amount used is also not particularly limited, but it is usually in the range of 0.01 to 1000 times the mole of the halogen compound, and usually 0.01 to 1000 times the amount of the metal element in the component containing the platinum group element. 01
It is preferably used in a molar range of 10,000 to 10,000 times.

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 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. Furthermore, in the secondary amine, the nitrogen atom itself may be an element constituting a ring, such as in pyrrole, piperidine, piperazine, morpholine, and the like.

Examples of such primary amines include ammonia, methylamine, ethylamine, propylamine (each isomer), butylamine (each isomer), pentylamine (
Aliphatic primary monoamines such as hexylamine (each isomer), P-decylamine (each isomer), ethylenediamine, diaminopropane (each isomer), diaminobutane (each isomer), diaminopentane (Each isomer)
, aliphatic primary diamines such as diaminohexane (each isomer) and diaminodecane (each isomer), 1゜2.3-)
Liaminoprono ξone, triaminohexane (each isomer)
, triaminononane (each isomer), aliphatic primary triamines such as triaminocyclono (each isomer), cyclozorobylamine, cycloditylamine, cyclopentylamine, cyclohexylamine, diaminocyclobutane,
Alicyclic primary mono- and polyamines such as diaminocyclohexane (each isomer), triaminocyclohexane (each isomer), benzylamine, di(aminomethyl)benzene (each isomer), aminomethylpyri, Gin (each isomer)
, di(aminomethyl)pyridine (each isomer), aminomethylnaphthalene (each isomer), -)(aminomethyl)naphthalene (each isomer), etc., aromatic aliphatic primary mono- and polyamines, aminofuran ( Heterocyclic primary amines such as aminotetrahydrofuran (all isomers), aminothiophene (all isomers), aminovirol (all isomers), and aminopyrrolidine (all isomers) are preferably used. It will be done.

In addition, examples of aromatic primary amines include aniline,
Diaminobenzene (each isomer), triaminobenzene (
(Each isomer), Tetraaminobenzene (Each isomer), Aminotoluene (Each isomer), Diaminotoluene (Each isomer), Aminopyridine (Each isomer), Diaminobiri, Zine (Each isomer), Triaminopyridine (each isomer), aminonaphthalene (each isomer), diaminonaphthalene (each isomer), triaminonaphthalene (each isomer), tetraaminonaphthalene (each isomer) and represented by the following general formula (TL) Monoamines, diamines of diphenyl compounds,
Each isomer of triamine and tetraamine is opened.

(In the formula, A is a simple chemical bond or -o-1-8-18
02-1(jo-1-(jONH-1-000-1-0
Represents a divalent group selected from (R7-R8)- and -N (R7)-. Also R7. R@ is H, an aliphatic group, or an alicyclic group. ) Furthermore, in these aromatic primary amines, at least one hydrogen on the aromatic ring is substituted with another substituent,
For example, substituted with halogen atom, nitro group, cyan group, alkyl group, alicyclic group, aromatic group, aralkyl group, alkoxy group, sulfoxide group, sulfone group, carbonyl group, ester group, amide group, etc. It's okay.

Particularly preferred among these aromatic amine compounds are aniline, 2,4- and 2,6-diaminotoluene,
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, dibenzylamine, diethylamine, ethylmethylamine, ethylzolopylamine, butylmethylamine, and ethylhexylamine. secondary amines, alicyclic secondary amines such as dicyclopropylamine, dicyclohexylamine, methylcyclohexylamine, N-
Methylaniline, N-ethylaniline, N-methyltoluidine (each isomer), diphenylamine, N,N'-diphenylmethanediamine, N,N'-dimethylphenylenecyaquin (each isomer), N-methylnaphthylamine (
each isomer), aromatic secondary amines such as dinaphthylamine (each isomer), aromatic aliphatic secondary amines such as dibenzylamine, ethylbenzylamine, diethylamine,
Heterocyclic acid secondary amines such as diethylamine and dithiophenylamine, pyrrolidine, virol, 3-pyrrolidone1. Cyclic secondary amines such as indole, carnoζazole, piperidine, piperazine, β-piperidone, γ-piperidone, imidazole, pyrazole, triazole, penzimitazole, morpholine, and 1,3-oxazine are preferably used. .

Furthermore, in these 2°4 primary amines and secondary amines, one or more hydrogen atoms of the organic group bonded to nitrogen may be substituted with other substituents, such as lower aliphatic groups, amine groups, cardixyl groups, and ester groups. , an alkoxy group, a cyan group, a halogen, a nitro group, a urethane group, a sulfoxide group, a sulfone group, a carzenyl group, an amide group, an aromatic group, an araliphatic group, or the like. Furthermore, these primary amines and secondary amines -C1
It may have an unsaturated bond.

It may also be a hydrazine type compound in which the above-mentioned amine group is directly bonded to an organic group having a 4-element atom through N-N.

Also, compounds having an amine group and hydroxylation in the molecule, such as ethanolamine, propatoolamine, 0-
Aminobenzyl alcohol and the like can also be used in the method of the invention, and in such cases cyclic urethanes can be produced.

One or more of these primary amines and secondary amines may be used.

The organic hydroxyl compound used in the method of the present invention is a -valent or polyvalent alcohol, or a -valent or polyvalent phenol, and examples of such alcohol include linear or branched alcohols having 1 to 20 carbon atoms. Examples include branched monovalent or polyhydric alkanols and alkenols, -valent or polyhydric cycloalkanols, cycloalkanols, and aralkyl alcohols. Furthermore, these alcohols may contain other substituents, such as halogen atoms, cyano groups, alkoxy groups, sulfoxide groups, sulfone groups, carzenyl groups, ester groups, and amide groups.

Specific examples of such alcohols include methanol,
Ethanol, propatool (each isomer), butanol (
each isomer), pentanol (each isomer), hexanol (each isomer), hexanol (each isomer), octatool (each isomer), nonyl alcohol (each isomer), decyl alcohol (each isomer) , undecyl alcohol (each isomer), lauryl alcohol (each isomer), tridecyl alcohol (each isomer), tetradecyl alcohol (
each isomer), aliphatic alcohols such as pentadecyl alcohol (each isomer), cycloalkanols such as cyclohexanol and cycloheptatool, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether , triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, phlopylene glycol monomethyl ether, zoropylene glycol monoethyl ether, nato alkylene glycol monoethers, ethylene glycol, zoropylene glycol, diethylene glycol, diethylene glycol , polyhydric alcohols such as glycerin, hexanetriol, and trimethylolpropane, and aralkyl alcohols such as benzyl alcohol.

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.

The oxidizing agent used in the present invention may be any conventional oxidizing agent, but preferred is molecular oxygen, an organic nitro compound, or a mixture thereof, and particularly preferred is molecular oxygen. This molecular oxygen is pure oxygen or a substance containing oxygen, and may be air, or air or pure oxygen may be mixed with other gases that do not inhibit the reaction, such as nitrogen, alkane, 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 halotanated 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), and bis-(trocyclohexyl)-methane; examples of aliphatic nitro compounds include, for example. Nitromethane, nitroethane, nitropronoson (each isomer), nitrobutane (each isomer),
Nitropentane (each A-isomer), nitrohexane (each isomer), nitrodecane (each isomer), 1,2-dinitroethane, dinitropropane (each isomer), dinitrobutane (each isomer), dinitrohentane (each isomer), dinitrohexane (each isomer), dinitrodecane (each isomer)
, phenylnitromethane, bis-(nitromethyl)-cyclohexane, bis-nitromethyl)-benzene, etc. Examples of aromatic nitro compounds include nitrobenzene, dinitrobenzene (each JI form), nitrotoluene (
each isomer), dinitrotoluene (each isomer), nitropyridine (each isomer), dinitropyridine (each isomer),
Nitronaphthalene/(each isomer), dinitronaphthalene(
Each isomer) and each isomer of the mononitro compound and dinitro compound of the -) phenyl compound represented by the above general formula (II).

Furthermore, in these nitro compounds, at least one hydrogen has 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 sulfo(Z')' group, a sulfone group, a carbonyl group, an ester group, an amyl group, or the like.

When molecular oxygen is used as the oxidizing agent in the method of the present invention, for example, the urethanization reaction of a primary amine proceeds according to the following general reaction formula.

R'(NH,). +0.5n ・02+n −(JO+
n -ROM---R' (NHOooB) + n
・1120 (here, R' and R represent organic groups, and n represents the number of amino groups in one molecule of the amino compound) Molecular oxygen may be less than the equivalent, or at most 1, but the oxygen/ -Acid I1 Carbon or mixtures of oxygen/organic hydroxyl compounds should be used outside the explosive limits.

Furthermore, when an organic nitro compound is used as a saponifying agent, the organic nitro compound itself also participates in the reaction and becomes urethane, so if its structure is different from that of the amino compound used, a different type of urethane compound can be obtained depending on the structure. It goes without saying that if both have the same structure, the same urethane compound can be obtained.

In this case, the urethanization reaction, for example the reaction of a primary amine, proceeds according to the following reaction formula.

2 几'(N)i2) +R"(NO2) + 3n ・
00+ 3n-ROH→2R' (NHOOOR)n+
R"(NHOOOR)n+ 2 n -H2O(R'
, R, and n have the same meanings as above, and 几"represents a residue other than the nitro group of the organic nitro compound.) When only the organic nitro compound is used as an oxidizing agent, primary amine or secondary amine and organic The quantitative ratio of the nitro compound is amine group 2
It is preferred to have 1 mole of nitro groups per mole, although it is of course possible to work away from this stoichiometric ratio, but in general the equivalent ratio of amino groups to nitro groups is between 1.1:t and 4:1, preferably 1
．． A range of 5:t to 2.5:1 is advantageously employed.

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

In the method of the present invention, it is preferable to use an excess of the organic hydroxyl compound as the reaction solvent, but if necessary, a solvent that does not adversely affect the reaction can also be used. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, nitriles such as acetonitrile and benzonitrile, sulfones such as sulfolane, methylsulfolane and dimethylsulfolane, tetrahydrofuran, 1. 4-dioxane,
Ethers such as 1,2-dimethoxyethane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and ethyl benzoate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, hexa Amino-P such as methylphosphorami-r
Examples include the following.

Furthermore, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, chlorotoluene, chlornaphthalene, and bromnaphthalene, which are types 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, ordiesters, 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 Kp/cm", preferably 2
The reaction time varies depending on the reaction system, catalyst system, and other reaction conditions, but is usually from 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 In a 500-liter autoclave, put 200 mmol of sweetfish, 120 ml of ethanol, and 3 mmol of sodium iodide.

2W% Pdi supported on powdered 8401 fcPd/5
After adding iOz8f and replacing the inner thread with gold-carbon oxide, the mixture was heated to 160 to 170°C while stirring. After reaching the predetermined temperature, a gas mixture consisting of 75% carbon oxide and 25% air was heated at 6 ONt/hr under a pressure of 80 h/cm''.

The reaction was carried out under stirring while introducing at a flow rate.

This reactor is equipped with a partial condenser at the top of the autoclave, and condensable gas components can be partially or completely condensed as necessary and circulated to the reactor. It is also possible to remove the entire amount of the condensed liquid component from the reaction system without doing so. 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.

At 2:00, the total amount of water produced by the reaction was removed along with a portion of the ethanol outside the reaction thread, 50% was removed, and the water was left in the reaction system in full view without removing all heat. The reaction results after the song were as shown in Table 1.

In this reaction, an amount corresponding to the amount of ethanol to be distilled was continuously injected into the reactor, and the liquid amount f:it was kept constant.

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

Examples 2 to 10 Table 2 shows the results of reactions conducted in the same manner as in Example 1, except for using various halogen compounds, basic substances, or chelating reagents shown in Table 2. In these examples, the water produced in the reaction along with a portion of the ethanol is 1
00% removed. An amount corresponding to the amount of ethanol to be distilled was continuously supplied to the reactor, and the liquid amount #1 was kept constant. Further, selectivity A and B represent the same meaning as above.

Example 11 Hexamethylene diamine 50 mmot, n-propatool 150 mmot, sodium iodide 3 mmotXPd black 1
- Using 5119 atom, the reaction was carried out in the same manner as in Example 1 while distilling the entire amount of water produced by the reaction out of the system together with a portion of 0-propatool. Further, an amount of n-propanol corresponding to the amount distilled out of the system was continuously supplied to the reactor.

The reaction formation after 1.5 hours was as follows. The reaction rate of hexamethylene diamine is 99%, and the yield of 1,6-di(n-propyl)hexamethylene dicarnomate is 96%.
%, the selectivity based on amine was 97%, and the selectivity based on carbon oxide was 93%.

When a similar reaction was carried out without removing water, the reaction rate of hexamethylene diamine was 949, and the yield of 1,6-di(n-propyl)hexamethylene dicare, 6mate was 90. , the selectivity of amine group j was 96%, but the reaction rate based on -carbon oxide was 8856.

Example 12 Di(n-hexyl)amine 100 m m0ts, tetraethylammonium iodide 3 mmol, Pd black 1
qatom and 120 d of ethanol were placed in an autoclave similar to that used in Example 1, and after replacing the inside of the system with carbon monoxide, the temperature was raised to 160 to 170°C, and then 15 vol% of carbon monoxide and 5 votX% of oxygen were added. Nitrogen 80vot
6% under a pressure of 100Ky/cm"
The reaction was carried out under stirring by four people at Mjtit at ONt/hr while distilling the produced water together with a part of the ethanol. Ethanol was continuously supplied to the reactor in an amount corresponding to the distilled amount. After 2 hours, the reaction rate of di(n-hexyl)amine was 96%, the yield of ethyl N,N-di(n-hexyl)carnomate was 91%, and the selectivity based on amine was 95%. The selectivity of the modified carbon standard was 93%.

Example 13 100 mmots of aniline = 50 mm of trobenzene
o4 ethanol 150 rril, K'ir palladium 10 mri+oL, potassium iodide 15? imo
t was placed in an autoclave similar to that used in Example 1, and after replacing the inside of the system with carbon monoxide, it was heated to 160 to 170°C. After reaching the predetermined temperature, -150 carbon oxide
The water was introduced at a flow rate of 5ONt/hr under a pressure of "Ky/cm".Produced water was removed along with a portion of the ethanol,
The reaction was carried out under stirring for 5 hours while continuously supplying as much ethanol as distilled to the reactor. As a result, the reaction rate of aniline and nitrobenzene was 329% and 34%, and ethyl N-phenylcalcimate was 45 mmol of C was produced. -Selectivity of carbon oxide to urethanization reaction is 90
%Met. A similar reaction was carried out without distilling off water, and 38 mmot of ethyl N-phenylcarbamate was produced, and the selectivity of -carbon oxide to the urethanization reaction was 75%.

Examples 14 to 19 The reaction was carried out in the same manner as in Example 1 except that various platinum group catalysts shown in Table 3 were used in place of Pd/8iOz in Example 1 while excluding the water produced by 100X. The results are shown in Table 3. Note that the selectivity A of ethyl N-phenylcalcimate is based on aniline, and the selectivity B is based on carbon monoxide. Further, in the platinum group catalyst, 2η2tom is used as the gold maple element, and the % light indicates the weight % of the metal supported on the carrier.

Table 3 Example 20 Anion/ion exchange resin (Amberlyst A
-26°OH form) was treated with hydroiodic acid to exchange the hyroxyl group with an iodine anion and then dried under reduced pressure at 100°C. This iodine-containing anion exchange resin 31, aniline 100 mmot, ethanol 11
The reaction was carried out in the same manner as in Example 1 except that 0 m/, palladium black 111 qatom was used, while water was distilled off together with a part of the ethanol.As a result, the reaction rate of aniline was 100%, and the reaction rate of N-phenyl The yield of ethyl calcimate was 99mm, and the selectivity based on aniline was 995mm.
The selectivity based on the -carbon oxide standard was 93%.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Scope of Claims] 1. A catalyst system comprising an oxidizing agent; (a) at least one selected from platinum group metals and compounds containing platinum group elements; and (b) at least one halogen compound. In a method for producing urethane by reacting a primary amine or a secondary amine with carbon monoxide and an organic hydroxyl compound in the presence of Method 2 for producing urethane characterized by reaction while removing Water produced by reaction is removed by reactive distillation method,
A patent claim in which the reaction gas contained in the silicate carbonized carbon is removed from the reaction yarn by any one of the following methods: removing it as a carrier, distilling it off together with a part of the organic hydroxyl compound, or a combination of these methods. Method according to claim 1 and Method 4 according to claim 1 or 2, in which at least one selected from basic substances and chelating reagents is used as an additional co-catalyst; Method 5 according to any one of claims 1 to 3, wherein is molecular oxygen, an organic nitro compound, or both; Claim @1, wherein the oxidizing agent is molecular oxygen.
6. Method 6 according to any one of claims 1 to 3, wherein the platinum group metal and the compound containing the platinum group element are palladium, solidium, solidium compounds, and rhodium compounds. 7. The method according to any one of claims 1 to 6, wherein the halogen compound is a metal halide & The metal halide is an alkali metal halide or an alkaline earth The method 9 according to claim 7, which is a metal-like metal halide, and claim 1, wherein the halogen compound is an onium halide compound or a compound capable of producing these in a reaction system. Method 10 according to any one of Items to iA6, wherein the halogenated onium compound is a halogenated ammonium compound, a halogenated phosphonium compound, a halogenated arsonium compound, or a halogenated sulponium compound. Method 11: The halogenated onium compound is a polymer containing a no-halogenated onium group in the main chain or side chain. Method 12 according to claim 9 or 10, wherein the halogenated onium compound is a halogen oxoacid. or a salt thereof. Method 13 according to any one of claims 1 to 6, wherein the halogen compound is a complex compound containing a halogen. Method 14 according to any one of claims 1 to 6, wherein the halogen compound is an organic halide; Method 15 according to any one of claims 1 to 6, wherein the halide species is bromine and/or iodine. Range @ Method 1a according to any one of Items 1 to 14 Claim 1 wherein the halogen species is iodine
Process 17 according to any one of claims 1 to 14, wherein the amine is a primary amine.
Process 18 according to any one of claims 1 to 16, wherein the primary amine is an aromatic primary amine.