JPH0830038B2 - Manufacturing method of urethane and carbonate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a urethane and a carbonate ester by reacting an organic compound containing a primary amine, carbon monoxide, molecular oxygen and a hydroxyl group. . Urethanes are important compounds per se as carbamate-based pesticide raw materials, but since they can be easily converted into isocyanates by heat treatment, they have recently become inexpensive as intermediates for isocyanate production that do not use toxic phosgene. A manufacturing method is desired.

On the other hand, carbonic acid esters are compounds which are useful as a starting material for producing a polycarbonate and also as an esterifying agent, a solvent and the like.

(Prior Art) Conventionally, urethanes and carbonates have been produced by a phosgenation method of primary amines and alcohols, but in recent years, various methods have been proposed which do not use highly toxic phosgene.

Methods for producing urethane without using phosgene are roughly classified into a method using a nitro compound as a raw material and a method using a primary amine as a raw material.

A method using a nitro compound as a raw material is a nitro compound such as nitrobenzene, an organic compound having a hydroxyl group such as alcohol, and carbon monoxide in the presence of a platinum group compound such as palladium or rhodium or a catalyst containing selenium as a main component. This is a method for producing urethane by reduction by reacting, for example, JP-A-55-51048, JP-A-52-153936, and JP-B-45-24.
No. 137 and Japanese Patent Publication No. 52-43822. Further, JP-A-57-32250 and JP-A-57-32251 disclose that an aromatic nitro compound, an organic compound having a hydroxyl group and carbon monoxide are reacted in the presence of a catalyst containing palladium as a main component to react urethane and carbon dioxide. A method for the simultaneous production of esters is described. On the other hand, a method using a primary amine as a raw material uses oxygen or a nitro compound as an oxidizing agent, and a primary amine such as aniline, an organic compound containing a hydroxyl group, and carbon monoxide are added to palladium, rhodium, or ruthenium. Is a method of oxidatively producing urethane by reacting in the presence of a catalyst mainly composed of a platinum group compound such as JP-A-55-124750.
JP-A-55-120550, JP-A-55-120551 and JP-A-59-172451.

(Problems to be Solved by the Invention) In these methods using a nitro compound or a primary amine as a raw material, a catalyst mainly containing a platinum compound or selenium is used, but the main catalyst itself has a low urethane synthesis activity. As a co-catalyst, iron chloride, iron oxychloride, vanadium oxychloride, lithium hydroxide, halides, Lewis acids, etc., and catalysts have been developed in combination with pyridine, quinoline, etc. as ligands. However, while the use of these co-catalysts or ligands improves the urethane synthesis activity, the catalysts are multi-component and complicated, so that expensive white metal compounds can be efficiently recovered from the reaction product solution after the reaction. It has the drawback of being complicated to operate and expensive to reuse.

(Means for Solving the Problem) As a result of various investigations by the present inventors, a catalyst for producing urethane by a reaction with an organic compound containing a primary amine, carbon monoxide, molecular oxygen, and a hydroxyl group has been studied. ,
The present invention has been completed by finding that urethane and carbonic acid ester can be efficiently produced at the same time by carrying out the above reaction in the presence of a catalyst containing copper and halogen as effective components, which is different from the conventional catalyst system.

That is, the present invention uses a catalyst comprising at least one selected from copper and a compound containing copper, and at least one selected from halogens selected from iodine, chlorine, and bromine,
A method for producing a urethane and a carbonic acid ester, which comprises reacting an organic compound containing a primary amine, carbon monoxide, molecular oxygen, and a hydroxyl group.

The feature of the present invention is to use a novel catalyst system mainly composed of copper, which is completely different from the conventional catalyst system mainly composed of platinum group element or selenium. This is to obtain a high urethane synthesis activity in the carbonyl oxide reaction of amine. Since urethane and carbonic acid ester are obtained in the same catalyst system, in the method of the present invention, it is presumed that two reactions represented by the following general formula proceed simultaneously.

(However, R ₁ and R ₂ are an alkyl group or an aryl group,
n is an integer of 1 or more. The copper catalyst used in the method of the present invention only needs to contain copper as a component, and may be a component that forms metallic copper and a compound. The copper catalyst may be supported on a carrier such as activated carbon, graphite, silica or alumina.

Copper compounds that can be used as a catalyst include, for example, copper iodide,
In addition to inorganic compounds such as copper bromide, copper chloride, copper oxide, copper sulfate and copper nitrate, and organic acid copper such as copper acetate, oxalic acid and copper formate, ammonia, amines, phosphines, carbon monoxide, chelate Examples thereof include salts or complex compounds containing a ligand and the like. The amount of the copper catalyst used is 0.001 to 100 g atom, preferably 0.01 to 10 g atom, in terms of copper atom based on 1 mol of the amine group. When the amount of the catalyst is less than 0.001 g atom, the reaction rate is low, and when it is more than 100 g atom, there is no adverse effect but it is not economical, so the above range is practical.

The halogen used in the present invention is selected from iodine, bromine and chlorine, but one kind or a mixture of two or more kinds may be used, and iodine is particularly preferable.

The usage form of halogen may be a halogen molecule itself or an organic or inorganic compound containing halogen. Examples of the halides include metal halides such as alkali metals and alkaline earth metals, onium halide compounds such as ammonium salts and phosphonium salts, oxo acids or salts of halogens, organic halides such as methyl halides and ethyl halides. Is. The amount of halogen used is 0.01 to 100 times, and preferably 0.1 to 10 times, the equivalent of 1 g atom of copper in terms of halogen atoms.

The catalyst of the present invention contains copper and halogen as active ingredients, but other elements such as tellurium, sulfur, antimony, bismuth, zinc, tin, vanadium, iron, cobalt, nickel, manganese, thallium, chromium and molybdenum. , Tungsten, etc. can also be used together as appropriate.

As the primary amine as the raw material of the present invention, an aliphatic, aromatic, alicyclic or heterocyclic compound having at least one amino group in the molecule can be used.

Aromatic amines and heterocyclic amines include, for example, aniline, 1,2-diaminobenzene, 1,4-diaminobenzene,
Isomers of chloroaniline, 3.4-dichloroaniline, 4,
-Isopropylaniline, p-toluidine, chlorotoluidine, xylidine, alkoxyaniline, nitroaniline isomers, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminotoluene, 3,4-diaminotoluene, 3,5-diaminotoluene, 2-amino-4-nitrotoluene, 2-amino-3
-Nitrotoluene, 2-amino-5-nitrotoluene,
Aminophenols, diaminoxylene, aminonitroxylenes, aminonaphthalenes, aminoanthracenes, chloroaminobenzoic acids, aminobenzenesulfonic acids, 4,4-diaminodiphenylmethane, 2,2-diaminodiphenylmethane, 2,4-diaminodiphenylmethane ,
Examples include tris- (4-aminophenyl) -methane, aminopyridines, aminoquinolines, aminopyrroles, aminofurans, aminothiophenes, and 2-aminobenzothiazoles.

Alicyclic amines include, for example, aminocyclobutane, aminocyclopentane, cyclohexylamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4
-Diaminocyclohexane, bis- (aminocyclohexyl) -methanes.

Aliphatic amines include, for example, methylamine, ethylamine, 1-propylamine, 2-propylamine, 1-butylamine, 2-butylamine, isobutylamine, t.
-Butylamine, 1-pentylamine, 1-hexylamine, 1-heptylamine, 1-octylamine, 1-
Decylamine, 1-dodecylamine, ethylenediamine, diaminopropanes, diaminobutanes, diaminopentanes, diaminohexanes, diaminooctanes, diaminodecanes, benzylamine, bis- (aminomethyl) -cyclohexanes, bis- (amino Methyl) -benzenes.

Examples of the hydroxyl group-containing organic compound used in the present invention include alcohols and phenols having at least one OH group in the molecule.

Alcohols include, for example, methanol, ethanol, n
-Propanol, isopropanol, n-butanol,
These are t-butanol, n-pentanol, n-hexanol, cyclohexanol, benzyl alcohol, cycloethanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol and trimethylolpropane.

Phenols include, for example, phenol, naphthols,
These are anthranol, phenanthrole, and hydroxybenzofurans.

The amount of the organic compound containing a hydroxyl group used is 1 mol or more, preferably 5 mol, per 1 mol of the amino group.
It is more than a mole. The upper limit of the amount used is not particularly limited, but is practically 200 mol or less. If it is more than this, the space-time yield decreases, which is not preferable.

The method of the present invention does not particularly require a solvent, but it is also possible to use a solvent inert to the reaction. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, alicyclic hydrocarbons such as cyclohexane and tetralin, aromatic hydrocarbons such as benzene, toluene and xylene, nitriles such as acetonitrile and benzonitrile. , Sulfolane, sulfones such as dimethyl sulfoxide, tetrahydrofuran, ethers such as 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, ethyl acetate, esters such as ethyl benzoate, chlorobenzene, dichlorobenzene, chlorohexane, Examples thereof include halogenated hydrocarbons such as trichlorotrifluoroethane.

The molecular oxygen used in the present invention may be pure oxygen, air, or a gas obtained by diluting an inert gas such as argon, helium, nitrogen, carbon dioxide gas, or the like with any other gas that does not inhibit the reaction. On the other hand, as carbon monoxide, pure carbon monoxide gas, and the above-mentioned inert gas, and in some cases, mixed gas containing hydrogen, hydrocarbon gas and the like can also be used.

The reaction temperature of the present invention is 50 to 300 ° C., preferably 1
It is in the range of 00 to 250 ° C. If the reaction temperature is less than 50 ° C, the reaction rate is low, and if it exceeds 300 ° C, side reactions increase. The reaction pressure is 1 to 500 kg / cm ² , and practically 20 to 3
0 kg / cm ² is preferred. The reaction time depends on the catalyst system, catalyst amount,
Although it depends on the reaction conditions and the like, it is usually several minutes to several hours.

The present invention can be suitably implemented by a batch system or a continuous system.

(Effects of the Invention) The present invention is a method for producing urethane and carbonic acid ester from an organic compound containing a primary amine, carbon monoxide, molecular oxygen and a hydroxyl group, and uses phosgene having strong toxicity as in the current method. The advantage is that it is not handled and there is no by-product of hydrochloric acid.

Conventional catalyst systems are mainly composed of expensive platinum group elements such as palladium, rhodium and ruthenium or toxic selenium, and in order to improve the activity and stability of the catalyst, a co-catalyst containing different metal elements, coordination Since there is no choice but to use a large amount of additives, additives, etc., the catalyst composition tends to be multi-component and complicated.

On the other hand, in the method of the present invention, high activity can be obtained with an inexpensive copper-based catalyst system, and since the catalyst is a simple system and does not contain a different metal, the recovery and reuse of the catalyst can be carried out smoothly. There are advantages.

As described above, the method of the present invention is an industrially advantageous method because it can efficiently produce the corresponding urethane and carbonate ester from the organic compound containing a primary amine and a hydroxyl group.

(Example) Next, the method of the present invention will be described more specifically by way of examples.

Example 1 1 g (10.7 mmol) of aniline, 25 g (543 mmol) of ethanol and 0.48 g (2.52 mmol) of copper iodide were charged into an autoclave made of Hastelloy having an internal volume of 100 ml and sealed. This has a carbon monoxide partial pressure of 75 kg / cm ² G and an air partial pressure of
Fill each gas to 35 Kg / cm ² G, and set the reaction temperature to 158
The reaction was carried out at 0 ° C for 2 hours. After the reaction, the residual gas was purged while cooling the autoclave, and the reaction product liquid was analyzed by an internal standard method using a high performance liquid chromatograph and a gas chromatograph. As a result, the yield of urethane (ethyl N-phenylcarbamate) based on aniline was 92.3%.
And at the same time, 0.91 mmol of diethyl carbonate was produced.

Examples 2 to 5 Reactions were carried out in the same manner as in Example 1 except that the reaction temperature was changed to 175 ° C, 165 ° C, 145 ° C and 132 ° C. As a result, the urethane yield and diethyl carbonate yield based on aniline were as follows.

Example 6 A reaction was conducted in the same manner as in Example 1 except that 0.16 g (2.52 mmol) of metallic copper and 0.38 g (2.52 mmol) of sodium iodide were used as catalysts.

As a result, the standard urethane yield of aniline was 42.2%, and the yield of diethyl carbonate was 7.05 mmol.

Example 7 In the same manner as in Example 1, 1 g (8.61 mmol) of 1,6-hexamethylenediamine, 25 g (780 mmol) of methanol and 0.48 g (2.52 mmol) of copper iodide were charged, and carbon monoxide was added thereto. Pressure is 75Kg / cm ² G, Air partial pressure is 35
Each gas was filled so as to obtain Kg / cm ² G, and the reaction was performed at a temperature of 175 ° C. for 1 hour.

As a result, diurethane based on 1,6-hexamethylenediamine (dimethyl 1,6-hexamethylenecarbamate)
The yield was 66.6%, and dimethyl carbonate was 4.45 at the same time.
Mmol produced.

Example 8 1 g (7.34 mmol) of meta-xylenediamine as a raw material
Was carried out in the same manner as in Example 7, except that was used.
As a result, a diurethane [1,
The yield of dimethyl 3-phenylenebis (methylene) biscarbamate] was 66.8%, and the yield of dimethyl carbonate was 7.53.
Became millimolar.

Example 9 A reaction was conducted in the same manner as in Example 8 except that 0.25 g (2.52 mmol) of copper chloride was used as a catalyst. As a result, the diurethane yield based on meta-xylenediamine was 37.9%, and at the same time, 7.11 mmol of dimethyl carbonate was produced.

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Claims (1)

[Claims] 1. A primary amine using a catalyst system comprising at least one selected from copper and compounds containing copper and at least one selected from halogen selected from iodine, chlorine and bromine. A method for producing a urethane and a carbonic acid ester, which comprises reacting an organic compound containing carbon monoxide, molecular oxygen, and a hydroxyl group.