DE2443826A1 - - Google Patents

Description

2343826

PATENT ADVOCATE

DR, I. MAAS

8 MUNICH 40

SCHi.EISSHElMERSTR.29?

TEL. 3592201/205

CASE: PF-50-01-1365B (Case B)

ATLANTIC FvICHFIELD COMPANY, Los Angeles, CAI. / USA

"Process for the production of urethanes"

The invention relates to a method for producing urethanes.

The invention relates in particular to a process for the production of urethanes (carbamic acid esters) and for the simultaneous Production of amines, in particular a process for the production of urethanes by reacting a one Hydroxyl group-containing compound with carbon monoxide and a nitrogen-containing compound under increased Temperature and pressure conditions in the presence of a catalyst

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tors and a base and / or water.

Up to now, urethanes have been at least partially produced industrially by reacting an isocyanate with a compound containing a hydroxyl group under elevated temperature conditions. Because of the cost of the isocyanate starting compounds and the resulting toxicity problems, it has become necessary to develop new processes for the industrial production of urethanes.

In US Pat. Nos. 3,338,956 and 3,448,140, urethanes were proposed to be prepared by reacting an organic compound containing at least one hydroxyl group with carbon monoxide and a nitrogenous compound at superatmospheric pressure and elevated temperature conditions in the presence of compounds of Cr, Ho, Vi ", Mn , Fe, Co, Ni, Ru, Rh, Os and Ir as catalysts.Although cheap nitrogen-containing compounds are used as starting materials in the processes known from these patents, various factors including the low product yields that can be achieved have the long reaction times required and the high pressures required mean that these processes have not proven to be economically viable for the industrial production of urethanes of high purity.One of the problems with which these known processes are afflicted is the fact that many of the proposed catalysts are expensive and difficult to separate from the desired urethane products. If a catalyst cannot be separated off for reuse, the catalyst losses generally have the consequence that the process is unsuitable for an industrial scale. Furthermore, the unseparated catalysts result in metallic contamination of the urethane products.

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It is therefore an object of the invention to provide an improved process for the production of urethanes.

Another object of the invention is a process for the production of urethanes with high purity, in the case of urethanes improved yields and better reproducibility result by reacting a hydroxyl group-containing one Compound with carbon monoxide and a nitrogenous compound in the presence of a catalyst, a base and / or water at relatively low temperature and pressure.

Another object of the invention relates to a method for achieving high urethane yields by reacting one Hydroxyl group-containing compound with carbon monoxide and a nitrogen-containing compound by use of selenium, sulfur or compounds derived therefrom as catalysts.

Another object of the invention relates to a process for the production of urethanes and for the simultaneous Production of amines that can be carried out on an industrial scale and economically.

Another object of the invention is to provide a method for making urethanes which is not accompanied by the toxicity problems mentioned.

These and other objects and embodiments of the invention emerge from the following description of the invention Method according to which an organic compound containing at least one hydroxyl group with Carbon monoxide and a nitrogenous compound at elevated temperature and pressure in the presence of a Containing sulfur, selenium, a sulfur compound, a selenium compound or a mixture of these compounds

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Catalyst is implemented. The method according to the invention for the production of urethanes is normally in the presence carried out a base and can also proceed in the presence of a solvent. It was further found that the presence of Viasser either instead of or in addition to the base, can lead to an improvement in the yield of the desired urethane products.

A hydroxyl group suitable for the process according to the invention containing compounds include monohydric or polyhydric alcohols, the primary, secondary or tertiary Contain hydroxyl groups as well as monohydric or polyhydric phenols. Mixtures of these compounds can also be used can be used. The alcohols can be aliphatic or aromatic and can be in addition to the hydroxyl groups have other substituents, which, however - as will be explained below - preferably in the case of the ones used Process conditions should not react with carbon monoxide.

In general, the compounds containing hydroxyl groups correspond to one of the general terms given below Formulas

R (OH) _n and R '(OH) _n

in which η is a number with a value of 1 or greater, preferably with a fourth from 1 to 3, R is an optionally substituted aliphatic, cycloaliphatic or araliphatic group which preferably contains 1 to 20 carbon atoms and R ^! an aromatic group containing one or more, preferably not more than three benzene rings, which can be condensed or bonded through single bonds directly or via bridging groups which, for example, oxygen,

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■ nitrogen or sulfur atoms or sulfoxide, sulfon, Be amine, amide or carbonyl groups or alkylene groups can, whose carbon chain e.g. by oxygen or Sulfur atoms, sulfoxide, sulfone or carbonyl groups interrupted can be, such as methylene, oxymethylene, - dimethylene sulfone or dimethyl enke tone groups.

The group R can be an alkyl, cycloalkyl, alkylene, cycloalkylene or aralkyl group, its main carbon chain if desired by, for example, oxygen, nitrogen or sulfur atoms, sulfoxide, sulfone, amine, Amide, carbonyl or carboxylic acid ester groups can be interrupted. The main chain can be used as a substituent, for example Contain alkyl, alkoxy, aryl or aryloxy groups, which normally have fewer than 10 carbon atoms. Particularly suitable compounds of the general formula

are monohydric alcohols such as methyl, ethyl, n- and sec-propylr-., n-, iso- and tert-butyl, amyl, hexyl, lauryl, Cetyl, benzyl, chlorobenzyl and methoxybenzyl alcohols as also diols, such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, triols such as glycerin, trimethylolpropane, hexanetriol, tetrols such as pentareythritol and Ethers of such polyols with the proviso that at least one non-etherified OH group is present. The ethereal one A group of such ether alcohols normally contains up to 10 carbon atoms and preferably represents represents an alkyl, cycloalkyl or aralkyl group which may be substituted, such as a haloalkyl group. Especially suitable compounds of the general formula

R (OH) _n

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are low molecular weight alkenols. Preferred connections of this type are methanol, ethanol, n-propanol, isopropanol, Butanol, sec-butanol, isobutanol, ethylene glycol, glycerine and triraethylol propane.

The phenolic compounds of the general formula

R '(OH) _n

can contain substituents in the benzene rings, for example alkyl groups and alkoxy groups with up to 10 carbon atoms and Kalogeiiatoine. Suitable monohydric and polyhydric phenols include phenol, chlorophenol, methylphenol, ethylphenol, butylphenol and alkylphenols, pyrocatechol, resorcinol / hydroquinone, 4,4'-dihydro: cydiphenylmethane, naphthols, chloronaphthols, methylnaphthol, chlorine naphthol, butylnaphthol, butylnaphthol, and octylnaphthol , Methylanthranol, ethylanthranol, butylanthranol and octylanthranol, phenanthrols, chlorophenanthrols, methylphenanthrol, ethylphenanthrol, but ^ / lphsnanthrol and octylphenanthrol, pyrogallol, phloroglucinol _} hydroxyhydroquinone and the ethers contain at least one non-OH-hydroxyl ether group. The etherifying group of such ether normally contains up to 10 carbon atoms, and preferably represents an alkyl ^ cycloalkyl or aralkyl group which may be substituted, such as a Z ₈ HaIogenalkylgruppe ,, Of the above-mentioned aromatic compounds phenol ^ _f octylphenol chlorophenols 4,4'-Dihydroxydiphenylmethane _s Naphthols »Anthranols and phenanthrols preferred, while phenol is the most preferred compound«

Suitable nitrogen-containing compounds are those compounds which have at least one non-cyclic group, in which a nitrogen atom directly to a single carbon atom and via a double bond to oxygen

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or another nitrogen atom is bonded. Such connections include organic nitro, nitroso, azo and azoxy compounds, which generally contain up to 24 carbon atoms contain, one, the organic nitro compounds and the nitroaromatic ones are generally preferred and tertiary nitroaliphatic compounds are the most preferred compounds.

According to the invention suitable nitro compounds include cononitro compounds, such as nitrobenzene, alkyl and alkoxynitrobenzenes, whose alkyl group contains up to 10 carbon atoms, Aryl and aryloxynitrobenzenes, which are phenyl, tolyl, xylyl, naphthyl, chlorophenyl, chlorotolyl, Contain chloroxylyl or chloraphthyl groups, Chlomitrobenzenes, dinitro compounds such as dinitrobenzene, e.g. o-, m- and p-dinitrobenzene, alkyl- and alkoxydinitrobenzenes, whose alkyl groups contain up to 10 carbon atoms, Aryl- and aryloxydinitrobenzenes which contain one of the above-mentioned groups as an aryl group, chlorodinitrobenzenes, Tr! Nitro compounds, such as trinitrobenzene, alkyl and alkoxytrinitrobenzenes, Aryl and aryloxytrinitrobenzenes which contain the above-mentioned groups as substituents and Chlorotrinitrobenzenes as well as similarly substituted mono- and polynitro derivatives of naphthalene, diphenyl-, diphenylmethane, Anthracene and phenanthrene compounds. Substituted or unsubstituted aliphatic nitro compounds, such as nitromethane, nitroethane, nitropropane, nitrobutane, 2,2-dimethylnitrobutane, nitrocyclopentane, nitrocyclohexane, Nitrocyclobutane, 3-methylnitrobutane, nitrooctadecane, 3-nitropropen-1, phenylnitromethane, p-bromophenylnitromethane, p-Nitrophenylnitromethane, p-Methoxyphenylnitromethane, Dinitroethane, dinitropropane, dinitrobutane, dinitrohexane, dinitrodecane, dinitrocyclohexane, dinitromethylcyclohexane and di- (nitrocyclohexyl) methane are used, of which however the primary, secondary and cycloaliphatic Compounds are less preferred because they result in a product

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lead mixture in which the urethane is part of the secondary constituent can. From this group of nitro compounds are the aromatic nitro compounds, such as nitrobenzene, nitrotoluene, Dinitrobenzene, dinitrotoluene, trinitrobenzene, 4,4'-dinitrodiphenylmethane, p-nitroanisole, p-nitrophenetol, o-nitrophenetol, 2,4-dinitroanisole, 2,4-dinitrophenetol, 3,5-dinitrobenzyl acetate, 1-chlorine, 4-dimethoxy-5-nitrobenzene, 1,4 ~ Din; ethoxy-2-nitrobenzene, p-nitrophenylnitromethane and the tertiary aliphatic nitro compounds such as 2-methyl-2-nitropropane and 1-methyl-1-nitrocyclohexane are preferred. The aromatic nitro compounds, i.e. the 2,4-, 2,5- and 2,6-dinitrotoluenes, are particularly preferred, m- and p-Dinitrobenzenes and 4,4'-Dinitrodiphenylmethane.

Examples of suitable nitroso compounds are aromatic Nitroso compounds such as nitrosobenzene, nitrosotoluene, Dinitrosobenzene, dinitros.0toluene and aliphatic nitroso compounds, such as nitrosobutane, nitrosocyclohexane and dinitro somethyl cyclohexane.

He findsur.gs according to suitable azo compounds correspond to the following general formula

R ₁ - N a N -

in which R ₁ and Rp, which can be identical or different, represent substituted or unsubstituted alkyl or aryl groups, as already indicated above with regard to the suitable nitro compounds. Azobenzene, nitroazobenzene, chlorazobenzene and alkyl or aryl substituted azobenzenes are particularly preferred

Azoxy compounds suitable according to the invention correspond to the following general formula

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R ₃ -HN

in the R ,. and R ,, which may be the same or different can, substituted or unsubstituted alkyl or aryl groups, v / ie they have already been mentioned above with regard to the. description suitable nitro compounds are indicated. Particularly preferred compounds are azoxybenzene, Nitroazoxybenzene, chlorazoxybenzene and alkyl and aryl substituted azoxybenzenes.

The invention also includes the use of any Mixture of "nitro compounds, nitroso compounds, azo or azoxy compounds with any mixture of Hydroxy compounds, as well as the use of compounds that have both functions, i.e. the use of Hydroxynitro compounds, Hydroxynitrοso compounds, Hydroxyazo compounds and hydroxyazoxy compounds, such as 2-hydroxynitroethane, 2-hydroxynitrosoethane, nitrophenols, Nitronaphthols, nitrosophenols, nitrosonaphthols, hydroxyazobenzenes and hydroxyazoxybenzenes. Mixtures can also be used these nitrogen-containing compounds are used. .

It has been found that the process according to the invention leads to the highest yields when using nitro compounds begins. Accordingly, it is preferred to use nitro compounds in place of the nitroso, azo or azoxy compounds.

The catalysts suitable for the process according to the invention include sulfur, selenium, sulfur compounds, selenium compounds and mixtures of these products. It was found, that the other representatives of the metals of group VIa

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of the periodic table, like tellurium metal, are not nearly as effective as the catalysts used according to the invention, is also evident from the examples.

The selenium metal, particularly in powder form, has been found to be at least as good or better than most Selenium compounds works. Nevertheless, good yields were obtained with compounds such as selenium dioxide, selenium dioxide and mixtures of these oxides, selenium oxychloride and titanium diselenide and selenium disulfide achieved. Sodium selenite, zinc selenite, zinc selenide, volfram selenide, selenium sulfide, Selenic acid, dimethyl selenide, diethyl selenide, diethyl diselenide, diphenyl selenide and carbonyl selenide are used will. Polyselenides such as diethyl polyselenide and dibutyl polyselenide can also be used. The achievable However, conversions and yields are not equivalent for all selenium compounds.

-o ^v

Apart from the somewhat better behavior of the selenium metal, especially when it is in powder form, compared to the selenium compounds mentioned above, the yields with selenium are somewhat better than with the sulfur catalysts. The oil catalysts contain sulfur as such, various inorganic sulfur compounds, such as hydrogen sulfide, carbonyl sulfide, carbon disulfide, Sodium sulfide, potassium sulfide, sulfur dichloride and organic Sulfur compounds, such as polysulfides and mercaptans and thioethers, which contain up to 20 carbon atoms, i.e. diethyl polysulphide, dioctyl polysulphide, Methyl mercaptan, ethyl mercaptan, cetyl mercaptan and the like can be used.

The catalyst material given above can be used as such or on an inert support material on which the catalyst is dispersed to increase the effective surface,

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can be used separately. As carrier materials for this purpose are aluminum oxide, silicon dioxide, carbon, barium sulfate, potassium carbonate, asbestos, bentonite clay, Diatomaceous earth, Fuller's earth, organic ion exchange resins and similar materials are suitable. A particular example of a catalyst having a support material is an ion exchange resin that contains selenium as the cation and a sulfonic acid or carboxylic acid function as the anion Resin contains, like a selenium-containing sulfonated macroporous styrene / divinylbenzene resin. It can also use selenium or sulfur-containing molecular sieves as well as complexes of selenium or sulfur with a ligand are used will.

A base and / or water must also be present in the reaction mixture. It has been found that both organic bases and metal salts of carboxylic acids are suitable. Organic bases suitable for the reaction include amines, such as triethylamine, pyridine, quinoline, N, N-dimethylaniline, diethylamine, tert-butylamine, 1,4-diazo-bicyclo- [2.2.2] octane, polyethylene polyamines, such as Ν, Ν , Ν ¹ , N'-tetraraethylethylenediamine, tetramethylenediamine, ethylenediamine and the like. Thus, aliphatic, aliphatic-aromatic and aromatic heterocyclic amines can be used in the reaction mixture. In addition, the amines can make up part of a polymer, as is the case with polyvinylpyridine. Compounds normally considered to be weak bases, such as the metal salts of carboxylic acids, sulfonic acids, and phosphoric acid, are the preferred bases; Examples of such compounds and salts of other weak acids are lithium acetate, sodium acetate, potassium acetate, palladium acetate, ruthenic acetate, the lithium salt of p-toluenesulfonic acid, the lithium salt of methylsulfonic acid, acid lithium phosphate, the lithium salt of boric acid, calcium acetate, sodium formate,

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Lithium formate and antimony triacetate. The acid salts can added in preformed form or prepared in the reaction mixture by adding the appropriate amounts dor adding the corresponding base and the corresponding acid. With regard to the type of acid used or the corresponding metal oxide or hydroxide used "exist no restrictions. Thus, aliphatic, cycloaliphatic and aromatic acids, such as propionic acid, Octanoic acid, cyclohexanecarboxylic acid, benzoic acid, oxalic acid, Malonic acid and the like can be used. However, the oxides and hydroxides are transition metal compounds more expensive than the alkali metal and alkaline earth metal hydroxides.

In view of the prior art finding that water must be completely excluded if If maximum yields are to be achieved, the beneficial effect of water in the reaction of the invention Procedure be surprising. It has been found that, for example, the use of sodium acetate containing water of crystallization results in a higher conversion of a nitrogenous compound than the use of anhydrous sodium acetate. In contrast to this finding, the prior art requires strictly anhydrous reactants. Although relatively high yields have been achieved using water without the use of a base, it is normally it is desirable to use both a base and water.

Although the process of the invention is typically and effectively carried out in the absence of a solvent however, a solvent can be used. Aromatic solvents such as benzene, Toluene, xylene, nitrile solvents such as acetonitrile and Benzonitrile, amide solvents such as N, N-dimethylformamide and Ν, Ν-dimethylacetamide, aliphatic, alicyclic or aro-

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matic sulfoxide and sulfone solvents, such as dimethyl sulfoxide, aliphatic halogenated hydrocarbons, such as 1,1,2-trichloro-i, 2,2-trifluoroethane, halogenated aromatic Hydrocarbons such as monochlorobenzene, dichlorobenzene and trichlorobenzene, ketones, esters and ether solvents such as Tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like can be used. The ether connections can e.g., aliphatic, aromatic or heterocyclic and can be used as monoethers or polyethers or as a combination such compounds are present. When the at least one hydroxyl group-containing organic compound in the applied Reaction conditions represents a liquid, this compound can be used as a solvent in certain cases serve, which is generally preferred.

At higher temperatures and pressures, the process according to the invention can advantageously be carried out in an inert diluent be performed. The preferred inert diluents are those materials in which the non-gaseous reactants are soluble, including some of the solvents mentioned above. Suitable inert diluents are aliphatic or aromatic hydrocarbons, such as n-pentane or toluene and ethers, Ketones and esters.

The invention is preferably carried out in such a way that the hydroxyl-containing compound carbon monoxide and converting the nitrogen-containing organic compound in at least molar amounts. However, it is preferred to use the hydroxyl-containing compound or the nitrogen-containing compound in a molar excess.

The molar ratio of the nitrogen-containing compound to the Catalyst can range over a wide range, for example from 5: 1 to 2000: 1, but a more preferred range the molar ratio of the nitrogen-containing compound

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to the catalyst ranges from 10: 1 to 1000: 1. It It is understood that the "moles" of the catalyst refer to the element selenium or sulfur and not to the element used Compounds when the catalyst is a compound refer to. The situation is similar with the nitrogen-containing one Compound where the active nitrogen-containing compound, e.g., the nitro group, is referred to so that when the nitrogen-containing compound is a dinitro compound such as dinitrotoluene, the half the molar amount, i.e. the equivalent ratio used will.

Similarly, with the amount of base used, the ratio of the nitrogen-containing compound (based on the equivalent nitrogen-containing group in the nitrogen-containing compound) to the base ranges from 50: 1 to 1:10. Although it is carried out in the absence of water and the reaction can only be carried out in the presence of an organic base, it is preferred, if water is used, to use this in a certain amount, based on the amount of the catalyst. Thus, the molar ratio of water to catalyst, ie, Se or S, can range from about 0.5: 1 to 1000: 1 or more, with a range of 1: 1 to 200: 1 being preferred. It has also been found that at reaction ^{temperatures above 175 °} C. when using water, a base can be dispensed with, although at temperatures below 175 ^° C. a base is used to achieve a good yield of the desired products and is generally preferred is to use the base together with smaller amounts of water. This water can be formed in situ, for example if a base such as potassium hydroxide and an acid such as acetic acid are used in equimolar amounts, potassium acetate and water being formed in equimolar amounts as weakly basic compounds. In general it is preferred

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to use an organic base such as pyridine or triethylamine as an additional amount of the required base.

It has also been found that, although the urethanes are generally the predominant reaction product of the invention Represent process, certain by-products are obtained. The main by-products are amines, which contribute to certain reaction conditions can be obtained as the predominant product. Reaction conditions that have an increased Promote amine formation, include the use of a sulfur catalyst and / or larger amounts of water. It seems, that the sulfur catalysts favor amine formation somewhat more than the selenium catalysts and that in certain cases In some cases, slightly larger amounts of water also promote the formation of amines.

However, the main aim of the invention is the production of urethanes, since amine production in general, compared is not economically favorable with the technically applied alternative processes. Even so, the following are some examples are given according to which nitrobenzene to aniline and dinitrotoluene to the corresponding mononitromonoamine compounds being transformed.

The order in which the reactants mixed is not critical and can be varied depending on the devices used. A simple process consists in the nitrogen-containing compound, the organic compound containing at least one hydroxyl group, the catalyst, the base and / or water to introduce into the reaction vessel, the appropriate amount - carbon monoxide and then heat the mixture to achieve the desired reaction. For the reaction there will be a suitable pressure vessel, such as an autoclave, which is preferably equipped with a heating device and a stirring device, such as a Stirrer or a shaking mechanism is used.

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Generally it is in the free space of the reaction vessel The amount of carbon monoxide contained is sufficient to achieve the desired To give pressure and to provide the reactant for the process. To the extent to which the reaction as additional carbon monoxide progresses, either intermittently or continuously, are introduced into the reaction vessel. Although larger or larger if desired Small amounts of carbon monoxide can be used, is generally the total amount added during the reaction of carbon monoxide about 3 to about 50 moles, preferably about 8 to about 15 moles of carbon monoxide per non-cyclic Group in which the nitrogen atom of the nitrogen-containing organic compound is attached directly to a single carbon atom and is bonded to an oxygen atom or another nitrogen atom via a double bond. The highest levels of carbon monoxide are generally required in a process in which carbon monoxide is continuously added however, by suitable recycling of the gas streams containing carbon monoxide, the total carbon monoxide consumption can be reduced significantly.

The reaction temperature is preferably maintained generally in a range of about 60 to about 250 ⁰ C in a range of about 100 to about 200 ⁰ C. A suitable reaction rate can be achieved within these temperature ranges while avoiding undesired side reactions. It will be understood, however, that any elevated temperatures lower than the temperatures at which the starting materials or products decompose can be used. The reaction is carried out, as stated above, at superatmospheric pressures, which are normally between about 10 and 500 atmospheres, although higher or lower reaction pressures can be used if other reaction conditions

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conditions adjusted accordingly. A 100 atmospheres applied, wherein the reaction is carried out within this pressure range suitably at a temperature below about 200 ⁰ C, but preferably only moderate Kohlenmonoxyddrücke in the range of about 10 up etv. Accordingly, the process of the present invention can advantageously be carried out at lower temperatures and pressures compared to the temperature and pressure conditions required in use of other catalytic metals heretofore proposed for converting hydroxy compounds and nitrogenous compounds to urethane products.

Although the process according to the invention is generally carried out batchwise, the reaction can, if desired, be carried out semicontinuously or even continuously. Ion exchange catalysts, for example, are particularly suitable for continuous process management. the Response time depends on the type of response component, the temperature, the pressure and the type of used Catalyst and the device used. Usually the response time is less than 180 minutes, the effectiveness of the catalysts used according to the invention allowing the reaction to proceed completely within a period of time between about 10 minutes and about 75 minutes.

After the reaction is complete, the The temperature of the reaction mixture is brought to room temperature and the pressure vessel is vented. The reaction product is then filtered in the usual way, Distilling or using other suitable separation methods to separate the urethane from the unreacted starting material, the solvent, the by-products, the catalyst, etc. to separate.

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The urethane products obtained by the process of the invention contain one or more urethane groups and can be monomeric or polymeric. Thus, the procedure for the production of monourethanes from mononitro compounds, nitroso compounds, azo compounds or

Azoxy compounds and monohydroxy compounds and for Manufacture of polyurethanes from polynitro compounds or polynitroso-, nitro- or nitroso-substituted Azo or azoxy compounds and nonofunctional hydroxy compounds adapted • '. • / earth. The urethane products obtained, in particular those urethanes which contain no more than three urethane groups per molecule can be used in suitable thermally or catalytically into the corresponding Isocyanates are converted.

Vie has already been specified, can according to the inventive Process anines are also produced, for example monoamines being formed from the mononitro compounds will. As already stated, the monourethanes are generally the predominant product, with . However, as can be seen from the examples, it is possible to form the amines in equal or predominant amounts. In the case of dinitro compounds, for example, the honoamine mononitro compounds are obtained as amine products, i.e. only one of the nitro groups is reduced to the amino group.

In addition, polyurethanes can be obtained by reacting polynitro-, polynitroso- or nitro-substituted azo or azoxy compounds with polyols and carbon monoxide. _{Thus, linear polyurethanes 9,} which are used, for example, as fibers or elastomers, can be made directly from diols, dinitro compounds and carbon monoxide or from hydroxynitrile compounds and carbon monoxide

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can be obtained while one is from mixtures of Di- or polynitro compounds., Diols or polyols and Carbon monoxide crosslinked polyurethanes obtained as flexible or rigid plastic materials are suitable.

The following examples are intended to further explain the invention, but without restricting them. The reactions given in these examples were carried out in stainless steel shaking autoclaves (No. 316 stainless steel). It will be understood, however, that cheaper stainless steels may and may not be employed corresponding reaction vessels, v; ie lined with glass Vessels, used v / can be grounded. The conversions and yields given in the examples are by gas chromatography and determined by liquid chromatography.

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example 1

10 nl of nitrobenzene and 15 ml of methanol were introduced into a 110 ml autoclave and at an initial carbon monoxide pressure of 183 atm. (2600 psig) held. The autoclave also contained 1.6 g of selenium metal and 1.6 ml of pyridine. After 45 minutes at a reactor temperature of 200-225 ⁰ C, the conversion of nitrobenzene was $ 8% and the yield of the obtained urethane product (methyl-N-phenylcarbamate) 88%.

When the procedure was repeated but using a reaction time of 3 hours, decomposition occurred with the maximum urethane product yield being only 53 % .

example

Ten milliliters of nitrobenzene and 15 milliliters of methanol were placed in a 110 milliliter autoclave and maintained at an initial carbon monoxide pressure of 190 atmospheres (2700 psig) at a temperature between 200 and about 225 ° C. 1.6 g of selenium metal and 1 g of triethylamine were also present in the autoclave. After 45 minutes the nitrobenzene conversion was 72% and the urethane product yield Ik% "

example

10 ml iJitrobenzol and 15 ml of methanol were introduced into a 110 ml autoclave and kept at a carbon monoxide initial pressure of 183 atm (2600 psig) in the presence of 0.5 g of selenium metal and 1 g sodium acetate trihydrate at a temperature of 200-225 ⁰ C. After 45 minutes the nitrobenzene conversion was 94% and the urethane product yield was 68 %.

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Repeated to the method of Example 3 at a reaction temperature of 18O ⁰ C and treated to the Roaktionsteilnehmer under the same conditions v / hile 90 minutes, the nitrobenzene conversion dropped to only 23%, while the Urethanproduktausbeute was 68%.

Example -4

10 al of nitrobenzene and 15 ml of methanol were introduced into a 110 ml autoclave and psig (2600) maintained in the presence of 1.5 g of selenium metal and 1.6 mL of pyridine at a carbon monoxide initial pressure of 183 atm at a temperature of 170 ⁰ C. After 60 minutes the nitrobenzene conversion was 22% v / while the urethane product yield was 50 % .

Similar conversions are obtained when using nitrocyclohexane and ethylene glycol reacts with carbon monoxide under the conditions given in this example.

example

10 ml of nitrobenzene and 15 ml of ethanol were placed in a 110 ml autoclave and in the presence of 0.5 g of seleraneta.il and 1.6 ml of pyridine at an initial carbon monoxide pressure of 183 atmospheres (2600 psig) at a reaction temperature of 200 to 225 ⁰ C implemented. After 60 minutes the nitrobenzene conversion was 10% and the urethane product yield was 52 %.

Similar conversions are obtained when dinitrosotoluene and resorcinol are used under the conditions given in Example 5 Reacts with carbon monoxide.

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example

10 ml nitrobenzene and 10 ml methanol were placed in a 110 ml autoclave and reacted in the presence of 2.2 g selenium dioxide and 1.6 ml pyridine at an initial carbon monoxide pressure of 193 atm (2750 psig) at 200-225 ° C. After 180 minutes the nitrobenzene conversion was 53 % and the urethane product yield was 63 %.

Example 7

10 ml of nitrobenzene and 15 ml of methanol were introduced into a 110 ml autoclave and in the presence of 3.3 g of selenium oxychloride and 1.6 ml of pyridine at a carbon monoxide initial pressure of 190 atm (27OO psig) at a temperature of 200-225 ⁰ C. implemented. After 60 minutes the nitrobenzene conversion was 100% and the urethane product yield was 42 %.

Example _ _8

10 ml of nitrobenzene and 65 ml of methanol with carbon monoxide in a 110 ml rocking autoclave at a temperature of 200 ⁰ C and at a carbon monoxide initial pressure of 21.1 atm (300 psig) reacted "In the autoclave were further 1 g selenium metal as a catalyst and 1.5 ml pyridine present. After a reaction time of 180 minutes, the nitrobenzene conversion was 52% and the urethane product yield was 76 %.

example

5 ml of nitrobenzene and 65 ml of methanol were in a 110 ml Introduced into the autoclave and with an initial carbon dioxide

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pressure of 21.1 atü (300 psig) at a temperature of 200 ⁰ C implemented. 0.5 g of metal selenium and 1.5 ml of pyridine were also used in the reaction. After 150 minutes the nitrobenzene conversion was 30 % and the urethane product yield was 67 %.

Example 10

5 ml Nitröbenzol and 65 ml of methanol were introduced into a 110 ml SchUttelautoklaven and reacted at a carbon monoxide initial pressure of 21.1 atm (300 psig) at 200 ⁰ C. The reaction vessel also contained 0.5 g of selenium metal and 1.6 ml of pyridine along with 1 g of sodium acetate trihydrate. After 75 minutes, the nitrobenzene conversion was 59 % and the urethane product yield was 50 %.

When the procedure of Example 10 was repeated with an initial carbon monoxide pressure of 35.2 atmospheres (500 psig), the nitrobenzene conversion was 80% and the urethane product yield was 67 % after 60 minutes *

Example 11

2.5 ml of nitrobenzene and 65 ml of methanol were placed in a 110 ml shaking autoclave and reacted at an initial carbon monoxide pressure of 35.2 atmospheres (500 psig) at 200 ° C. Also in the reaction vessel were 0.25 g of selenium metal and 1 g. Sodium Acetate Trihydrate Present After a "10 minute reaction time" resulted in a nitrobenzene conversion of 95% and a urethane product yield of 78 %.

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Example 12

5 ml of nitrobenzene and 30 ml of methanol were introduced into a 110 ml Schuttelautoklaven and reacted at a carbon monoxide initial pressure of 56.2 atm (800 psig) at a temperature of 200 ⁰ C. In addition, 0.5 g of selenium metal, 35 ml of tetrahydrofuran and 1 g of sodium acetate trihydrate were present in the autoclave. After a reaction time of 10 minutes, the nitrobenzene conversion was 64 % while the urethane product yield was 74 % .

Did you repeat that. Reaction of Example 12 was given at 170 ⁰ C, then a nitrobenzene conversion of 72% gave a Urethanproduktausbeute while after 60 minutes of 70%.

Example 13

5 ml of nitrobenzene, 30 ml of methanol and 35 ml of tetrahydrofuran were introduced into a 110 ml rocking autoclave and (800 psig) is reacted with a carbon monoxide initial pressure of 56.2 ATU at a temperature of 200 ⁰ C. In addition, 0.5 g of selenium metal and 2 g of sodium acetate trihydrate were present in the autoclave. After 10 minutes, a nitrobenzene conversion of 70% and a urethane product yield of 53 % was achieved.

Yfiederholte the reaction of Example 13 with the Unterschiedy that a reaction temperature of 17O ⁰ C was observed instead of 200 ⁰ C, then a nitrobenzene conversion of 100% and showed a Urethanproduktausbeute were obtained from

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Example 14

5 ml of nitrobenzene and 30 ml of methanol in a 110 ml rocking autoclave -were introduced, the (800 psig) at a carbon monoxide initial pressure of 56.2 atm, and was operated at a temperature of 17O ⁰ C. In addition, 35 ml of tetrahydrofuran, 0.008 mol of lithium acetate monohydrate and 0.5 g of selenium metal were present in the autoclave. After a reaction time "of 10 minutes, a nitrobenzene conversion of 94% and showed a Urethanproduktausbeute were obtained from 68% _r

In the repetition of Example 14, while maintaining a reaction temperature of 10O ⁰ C was found after 60 minutes, a Nitrobenzolumv / andlung of 100% _t during a Urethanproduktausbeute of 83% could be achieved.

Repeated to Example 14 again, but at an operating temperature of 15O ⁰ C instead of 170 ⁰ C as resulted after 60 minutes, a Nitrobenzolumv / andlung of 87% and a urethane yield of 85%. /

Finally led to the Example 14 at a reaction temperature of 13O ⁰ C instead of 170 ⁰ C, then was reached after 140 minutes, a nitrobenzene conversion of 89% and a Urethanproduktausbeute of 71%.

Example 15

5 ml of nitrobenzene and 30 ml of methanol were introduced into a 110 ml shaking autoclave together with 35 ml of tetrahydrofuran, 0.1 g of titanium disulfide and 0.008 mol of lithium acetate monohydrate. The autoclave was operated at a carbon monoxide initial pressure of 56.2 atm (800 psig) at a temperature of 150 ⁰ C. After 60 minutes the nitrobenzene conversion was 96% and the urethane product yield was 88 %. . '■

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If Example 15 was repeated without adding lithium acetate monohydrate, the nitrobenzene conversion was 0 %,

Example 16

0.29 g of lithium hydroxide, 0.72 g of acetic acid, 10 ml of nitrobenzene, 15 ml of methanol, 15 ml of dioxane and 0.5 g of selenium disulfide were placed in a 110 ml autoclave. The autoclave was maintained at a pressure of 183 Kohlennionoxyd initial atm (2600 psig) for 45 Hinuten at a temperature of 200 ⁰ C. After 45 minutes the nitrobenzene conversion was 100% and the urethane yield was 96 %.

Example 17

Ii ι.-ι ι ——i m i iiiiiiiii i..1 ' \

A 300 ml autoclave was charged with 0.29 g lithium hydroxide, 0.72 g acetic acid, 0.5 g sulfur, 5 ml nitrobenzene, 30 ml methanol and 35 ml tetrahydrofuran and operated for 75 minutes at an initial carbon monoxide pressure of 56 , 2 atm (800 psig) at a temperature of 17O ⁰ C. After this reaction time, the nitrobenzene conversion a Urethanproduktausbeute (methyl-N-phenyl carbamate) was 100% while scoring of 75%.

B__g is ρ ie j. J8_

10 ml of nitrobenzene, 65 ml of methanol, 1 g of sulfur, 1.6 ml of pyridine and 1 g of sodium acetate trihydrate were placed in a 300 μl autoclave, which was operated at an initial carbon monoxide pressure of 183 atm. (2600 psig) for 45 minutes at a temperature of 200 ⁰ C was maintained "The resulting nitrobenzene conversion was 83% while a Urethanproduktausbeute of 38% resulted. ·

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If the procedure of Example 18 was repeated with the difference that 2 g of sulfur were used instead of 1 g of sulfur, the result was a nitrobenzene conversion of 94% with a urethane product yield of 33 % »

Example 19

A 300 ml autoclave was charged with 10 ml of nitrobenzene, 65 ml of methanol, 0.5 g of sulfur and 1 g sodium acetate trihydrate and operated at a carbon monoxide initial pressure of 183 atm (2600 psig) at a temperature of 200 ⁰ C. After 45 minutes the nitrobenzene conversion was 46% and the urethane product yield was 32 %.

Example 20

# 10 ml of nitrobenzene, 15 ml of methanol, 15 ml of dioxane, 0.29 g of lithium hydroxide, 0.72 g of acetic acid, 0.10 g of selenium metal and 0.30 g of sulfur were placed in a 110 ml autoclave which was operated at an initial pressure of carbon monoxide was heated from 183 atm (2600 psig) during 45 minutes at a temperature of 200 ⁰ C. At the end of the reaction time, the nitrobenzene conversion was 75.2% and the urethane product yield was 82.5 %.

Example 21

0.29 g of lithium hydroxide, 0.72 g of acetic acid, 0.25 g of sulfur, 0.25 g of selenium metal, 10 ml of nitrobenzene, 15 ml of methanol and 15 ml of dioxane were introduced into a 110 ml autoclave which was operated at an initial carbon monoxide pressure of was maintained 183 atm (2600 psig) for 45 minutes at a temperature of 200 ⁰ C. A nitrobenzene conversion of 98% and a urethane product yield of 88.4 % were determined by gas chromatography.

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Example 22

0.29 g lithium hydroxide, 0.72 g acetic acid, 0.5 g selenium metal, 5 ml nitrobenzene and 65 ml methanol were placed in a 300 ml autoclave which was operated at an initial carbon monoxide pressure of 56.2 atmospheres (800 psig) for 60 minutes Minutes at a temperature of 150 ⁰ C was operated. The resulting nitrobenzene conversion was 100% while the urothane product yield was 81.2 % .

Example 23

The following approaches were carried out in a 300 ml autoclave, The autoclave was charged with the following materials in addition to base and / or water:

10 ml Nitrobenzene, 30th ml Methanol, 35 ml 1,4-dioxane and O, 5 g Selenium metal.

The reactions were carried out at an initial carbon monoxide pressure of 183 atm (2600 psig) for 30 minutes at a temperature of 20O ⁰ C. The following table shows the amounts of base and / or water used in the reaction and the nitrobenzene conversion:

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base

1 g sodium acetate trihydrate 1 g sodium acetate (melted)

1 g sodium acetate (melted) and 0.2 g water

0.48 g sodium hydroxide and 0.72 g acetic acid

1 g of anhydrous potassium acetate

1 g of anhydrous potassium acetate and 0.2 g of water

no base and no water

0.2 g of water

Nitrobenzene conversion (90

100 8

100

91 50

100

9 64

example

24

A 300 ml autoclave was filled with 0.29 g lithium hydroxide, 0.72 g Acetic acid, 0.50 g selenium metal, 10.7 nitrosobenzene, 30 ml Methanol and 35 ml of dioxane are charged and at an initial pressure of carbon monoxide of 183 atmospheres (2600 psig) for 30 minutes

200 ⁰ C held.

The analysis carried out at the end of the reaction showed a conversion of 100 % and a product yield of 70 %,

example

25th

0.29 g lithium hydroxide, 0.72 g acetic acid, 0.5 g selenium metal, 19.8 g azoxybenzene, 30 ml methanol and 35 ml dioxane were placed in a 300 ml autoclave and heated at an initial carbon monoxide pressure of 183 atm (2600 psig ) Implemented at 200 ⁰ C for 30 minutes.

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At the end of the reaction time analysis showed a conversion of 86 % and a yield of 69 % *

A number of approaches have been carried out with 2,4-dinitrotdluene, to show that after the inventive Process receives the corresponding diurethanes. The following examples illustrate the use of 2,4-DinitrOtoluene show were chosen from a large number of approaches in which the conditions or reactants have been varied widely, so that occasionally undesirably low yields or large amounts are undesirable By-products. The approaches described in the following examples gave high conversions and yields in terms of the aimed products. All batches were made in a 300 ml stainless steel shaking autoclave Steel (# 316) at an initial carbon monoxide pressure of 56.2 atmospheres (800 psig).

Example 26

A reaction mixture of 10.9 g (0.06 mol) 2,4-dinitro- ■ toluene, 65 ml (1.11 mol) ethyl alcohol, 0.56 g (0.01 mol) potassium hydroxide, 0.60 g (0 0.01 mol) of acetic acid and 0.5 g of selenium metal powder (0.006 mol) were placed in the reaction vessel, which was then pressurized with carbon monoxide. At a reaction temperature of 170 ⁰ C a 100% lge conversion of the dinitrotoluene was obtained after 15 minutes and found to have a Diurethanausbeute of 72%. An operation performed in a similar manner for 60 minutes at 150 ⁰ C gave a second batch of 100% and a Dinitrotoluolumwandlung Diurethanausbeute of 72%.

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Example 27

A mixture of 10.9 g (0.06 mol) of 2,4-dinitrotoluene, 35 ml (0.6 mol) of ethyl alcohol, 30 nl (0.21 mol) of triethylamine and 0.5 g (0.006 mol) of selenine metal powder was in The reaction vessel was placed and pressurized to 56.2 atmospheres (800 psig) with carbon monoxide. After reacting for 60 minutes at a temperature of 150 ° C, the conversion of dinitrotoluene was 100%, the yield of diurethane was 73 %, and the yield of monourethane was 3 %, indicating that a nitro group was not completely converted. Overall product yield 76 %.

Example 28

A mixture of 10.9 g (0.06 mol) 2,4-dinitrotoluene, 35 ml (0.6 mol) ethyl alcohol, 30 ml (0.37 mol) pyridine, 0.56 g (0.01 mol) potassium hydroxide , 0.60 g (0.01 mole) acetic acid and 0.05 g (0.0006 mole) selenium metal powder were added to the reaction vessel which was pressurized to 56.2 atmospheres (800 psig) with carbon monoxide. At a temperature of 160 ° C., 100 % conversion of the dinitrotoluene resulted over 60 minutes, 1% of the two nitroaminotoluene isomers, 19% nitromonourethane and 71 % diurethane being obtained as products. The total yield of urethanes or the selectivity to the urethanes was 90 %. In a similar approach, 0.072 g (0.006 mol) of selenium dioxide were used in place of the selenium metal powder as catalyst, the reaction was carried out for 50 minutes at 150 ⁰ C, with a 100% conversion of dinitrotoluene, a product yield of 3% nitroaminotoluene, 34 Yielded% monourethanes and 56 % diurethanes.

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Example 29

A mixture of 10.9 g (0.06 mol) 2,4-dinitrotoluene, 65 ml (1.11 mol) ethyl alcohol, 1.12 g (0.02 mol) potassium hydroxide, 1.2 g (0.02 mol) ) Acetic acid and 0.05 g (0.0006 mol) selenium metal powder were introduced into the reaction vessel, which was then brought to a pressure of 56.2 atü (800 ρsig) with carbon monoxide. The reaction -was carried out for 20 minutes at 150 ⁰ C to give a Dinitrotoluolumwandlung of 100% resulted. A product yield of 70% by weight of the monourethane and 19% by weight of the diurethane was achieved, which means an overall selectivity for urethanes of 89 % . In a similar approach, in which 1.68 g (0.03 mol) of potassium hydroxide and 1.80 g (0.03 mol) of acetic acid were used and the remaining reactants remained the same, a reaction time of 50 minutes at 150 was obtained ⁰ C a 100% dinitrotoluene conversion and a product yield of 3% nitroaminotoluene, 50 % monourethanes and 44 % diurethanes, which means a urethane selectivity of 94 % .

Example 30

A mixture of 10.9 g (0.06 mol) 2,, 4-dinitrotoluene, 35 ml (0.6 mol) ethyl alcohol, 15 ml (0.19 mol) pyridine _{9 and} 15 ml (0.11 mol) triethylamine 0.05 g (0.0006 mole) selenium metal powder was added to the reaction vessel, which was then pressurized to 56 _$ 2 atm (800 psig) with carbon monoxide. At a reaction temperature of ⁰ O 16Q and a reaction time of 60 minutes yielded a Dinitrotoluolumwandlung of 100% and a product yield of 8% ^ 68% Nitroaminotoluolen monourethanes and diurethanes I5%, which corresponds to a Gesamturethanausbeute of 78%. When adding 0.01 g of water to the same reaction mixture and carrying out the reaction for 40 minutes at 16O ⁰ C, obtained

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a 98 % dinitrotoluene conversion and a product yield of 14% nitroaminotoluenes, 75 % monourethanes and 18 % diurethanes, which means a total urethane yield of 93 % .

Example 31

To illustrate a continuous urethane synthesis, a pilot plant was constructed in which the liquid reactants were pumped along with a stoichiometric excess of carbon monoxide into a stirrer-operated reactor operated at 70.3 atmospheres (100 psig). The liquid mixture was in a typical run of 10 wt -.% Technical dinitrotoluene (80% of 2,4-dinitrotoluene and 20% of 2,6-dinitrotoluene), 87 wt .- ^ technical ethanol (denatured ethanol containing 2% benzene) 1% by weight acetic acid, 1% by weight potassium hydroxide and 1% by weight selenium dioxide as a soluble catalyst.

From the results obtained under various conditions results, it was determined that the optimum operating conditions of this system include a reaction temperature of 177 ° C (35O ⁰ F), a reaction time of half an hour and a pressure of 70.3 atm (100 psig). Under these conditions, a dinitrotoluene conversion of 100 * $ was achieved with selectivities with respect to the diurethanes of 90 to 95 % . At temperatures below 177 ⁰ C (35O ⁰ F), for example at 163 ° C (325 ° F) the conversion as a function of changes to the residence time, so that a reduction in the residence time of 1 hour to 1/2 hour and 1/4 hour at 163 ° C (325 ⁰ F) or the conversion of 100 to 90, 76% reduced. Furthermore arise when one (350 F ⁰⁾ is operating below 177 ⁰ C for 1/2 hour, lower and higher Diurethanausbeuten Monourethanausbeuten. If you work at temperatures above 177 ⁰ C (350 ⁰ F) and with residence times of more than 1/2 hour, lower yields are generally

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ten achieved on diurethanes in poorer quality. Under the optimal conditions, the conversion of dinitrotoluene is rapid even at low catalyst concentrations, with conversions of 90 % being achieved, for example, with only 0.07 wt.% Selenium catalyst in the feed.

These continuous approaches show the excellent technical applicability of the method according to the invention.

The following examples represent the manufacture of Amines. These examples are merely illustrative of a large number of approaches in which amines as one of the products were formed. These approaches used the same devices and procedures as them above with regard to the rudimentary examples are given.

Beis piel 32

A 300 ml stainless steel shaking autoclave (No. 316) was charged with 12.0 g (0 ^ 098 mol) nitrobenzene, 79 g (2.46 mol) methanol, 2.0 g (O ₉ 062 mol) sulfur (powder) , 1.0 g (0.0073 mole) sodium acetate trihydrate and 1.6 g (0.02 mole) pyridine were charged. The autoclave was initially pressurized to 56 ^ 2 atmospheres (800 psig) with carbon monoxide and the reaction mixture was during Reacted for 2 hours at 220 ° C

Compartment cooling to room temperature and venting gave "see that 77? ~ 4 mol% of the nitrobenzene was converted and aniline with a yield of 56 _{g of} 6 mol "% urethane and Aiit a yield of S ₉ 5 mol% formed

/ no ^ iO / 1

ty U e 9 I £. I I

-35- 2343826

At ρ ie 1 33

In the same 300 ml autoclave were added 10 ml (0.098 mol) of nitrobenzene, 100 ml of methyl alcohol, 1 g of sodium acetate and 1 g of powdered sulfur. The reaction vessel was placed (500 psig) with carbon monoxide to a pressure of 35.2 atm, and the reaction was carried out for 10 minutes at 220 ⁰ C. In this way, when nitrobenzolua was converted to 35.5 mol%, aniline was obtained in a yield (selectivity) of 30.4 mol% and urethane was obtained in a yield of 39.3 / 4.

Example 34

A mixture of 10.9 g of 2,4-dinitrotoluene, 100 ml of ethyl alcohol, 1.28 g of potassium acetate monohydrate, and 0.5 g of tail powder was placed in the 300 inl reactor which was pressurized with carbon monoxide to 35.2 atg (500 psig ) was brought. The reaction was carried out for 1 hour at 200 ° C., a conversion of 2,4-dinitro · * toluene of 44.8 mol% being achieved. The percentage selectivity, based on converted dinitrotoluene, was 40.2% for the two monourethane isomers in which one nitro group was not converted, 41% for the nitroaminotoluene isomers and less than 1.5 % for the diuretharie.

Example 35

A reaction mixture of 10.9 g of 2,4-dinitrotoluene, 35 ml of ethyl alcohol, 30 ml of pyridine, 1 g of water and 0.012 g of selenium metal powder was charged into the reactor, which was then pressurized with carbon monoxide to a pressure of 56.2 atmospheres (800 psig) was brought. The reaction was for 90 minutes at 15O ⁰ C.

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carried out with a dinitrotoluene conversion of 83 % was achieved. The result was a yield of mononitrourethanes, which contained a trace of diurethanes, of 14 % and a yield of nitroaminotoluenes of 78 %. A second batch was carried out under the same conditions as indicated above, with the difference that 0.4 g V / ater and 0.015 g selenium powder were used. A dinitrotoluene conversion of 90 % was achieved, the monourethane with a trace of diurethane being formed in a yield of 55 % and the nitroaminotoluene being formed in a yield of 45 % .

From the above it can be seen that the inventive Process is able to achieve the desired advantages. The process according to the invention can be technical for the manufacture of urethane products and amine by-products with high yields at relatively low operating temperatures and pressures and using relatively short periods of time Response times are applied.

A09812 / 1206

Claims (1)

-37-. 2343826 PATENT CLAIMS: Method of making urethanes, thereby
characterized in that an organic compound containing at least one hydroxyl group with carbon monoxide and a nitrogen-containing organic compound at elevated temperature and pressure in the presence of a catalyst,
such as selenium, sulfur, a selenium compound, a sulfur compound or a mixture of these products and at least one base and / or water. 2. The method according to claim 1, characterized in that that ethanol is used as the organic compound containing at least one hydroxyl group. 3 »Process according to claim 1, characterized in that the nitrogen-containing organic compound
Nitrobenzene used. 4. The method according to claim 1, characterized in, that one uses selenium metal as a catalyst. 5. The method according to claim 1, characterized in that that sulfur is used as a catalyst. 6. The method according to claim 1, characterized in that the catalyst used is a mixture of selenium and
Sulfur used «· 409812/1206 -38- 2343826 7. The method according to claim 1, characterized in that the nitrogen-containing organic compound is an aromatic Nitro compound, a tertiary aliphatic nitro compound, a tertiary cycloaliphatic nitro compound, a nitroso compound or an azp compound is used. 8. The method according to claim 7, characterized in that there is used as the nitrogen-containing organic compound an aromatic nitro compound is used. 9. The method according to claim 8 _t, characterized in that a dinitrotoluene is used as the aromatic nitro compound. 10. A process for the preparation of urethanes, characterized in that an organic compound containing at least one hydroxyl group with carbon monoxide and a nitrogen-containing compound ^ which has at least one non-cyclishe group, in which a nitrogen atom directly on a one of its carbon atom and · via a double bond is located on an oxygen atom or a nitrogen atom bonded XST _2, wherein überatomosphärischeii pressure and elevated Temperaturj lower than the temperature at which decomposition ^ occurs in the presence of an effective amount of a catalyst _s as selenium sulfur, a selenium compound, a sulfur compound or a Mixture of these products and at least one base and / or water reacted 11a method according to claim 1 NC _p ;, characterized in that the method under a carbon monoxide Einhalttmg "initial pressure between about 10 and about 100 atmospheres performed 2/1206 -39- 2343826 12. The method according to claim 10, characterized in that the temperature is kept below about 20O ⁰ C. 13. The method according to claim 10, characterized in that that both a base and water are present during the reaction. 14. A process for the production of urethanes and for the simultaneous production of amines, characterized in that an organic compound containing at least one hydroxyl group with carbon monoxide and a nitrogen-containing organic compound at a temperature between about 100 and about 200 ⁰ C and a pressure between about 10 and about 100 atmospheres in the presence of a catalyst such as selenium, sulfur, a selenium compound, a sulfur compound or a mixture of these products and at least one base and / or water, the catalyst being present in an amount corresponding to a molar ratio of the nitrogen-containing organic compound corresponds to the catalyst from 10: 1 to 1000: 1. 15. A process for the production of urethanes, characterized in that one carbon monoxide with one, at least a hydroxyl group-containing compound such as an aliphatic or aromatic alcohol or a phenol and at least one aromatic nitro compound in the presence of a catalytically effective amount of a selenium or Reacts sulfur-containing catalyst and at least one base and / or water. 16. A method for making urethanes, thereby characterized in that one carbon monoxide with at least one low molecular weight aliphatic alcohol and a dinitrotoluene in the presence of a selenium or sulfur-containing catalyst system and at least one base and / or water implements. 409812/1206 23A3826 17 »l / experienced according to claim 16, characterized in that the dinitrotoluene 2 _? 4-dinitrotoluene, 2y6-dinitrotoluene or a mixture of these compounds is used. Process according to claim 16, characterized in that the dinitrotoluene is 2 _i> 4-dinitrotoluene _! , 2,6-dinitrotoluene or a mixture of these products, uses seles metal and a base as the catalyst system » 409812/1206