CS269691B1 - The process for producing alkylaryluretenes and / or? dialkylaryluretánov - Google Patents

Abstract

Method for producing alkylarylurethenes and/or dialkylarylurethenes by converting aromatic nitro compounds with C^ to C10 alcohols (mol. alcohol/nitro compound ratio ω = 2 to 13) and carbon monoxide at a temperature of 90 to 200 °C and a pressure of 3 to 30 MPa under the catalytic effect of sulfur or ethylene, as well as their compounds (H^S, COS) in an amount of 0.1 to 15 t of nitro compound, 0.1 to 15 wt. %. alkaline salts of weak acids (sodium or potassium salts of carboxylic acids C^ to Cg) and in the presence of a promoter (VgO^ or a mixture of VgO^ 8 ře2°3^ in an amount of 0.1 to 14 wt. % and an activator (02, H2°2t tert. butyl hydroperoxide, di-tert. butyl peroxide, cumene hydroperoxide, dicum yl peroxide) in an amount of 0.03 to 7 wt. %. The method is useful in the chemical industry for the production of organic intermediates (alkylarylurethanes, dialkylurethanes) isocyanates, diisocyanates, by a fog-free method, pesticides, etc.

Description

The present invention relates to a process for the preparation of urethanes, in particular alkylphenylurethanes, reepalkyl-N-phenylcarbamates and their derivatives, dialkyltoluenedicarbamates and their derivatives by the phosphorus-free route, using technically readily available starting materials and catalytic systems.

Known (British Pat. Nos. 1,087,896 and 1,092,157 and 1,246,217; German Pat. No. 1,901,202, European Pat. No. 0014,845 A1; Lapidus At et al., Vol. 1339) is the catalytic carbomylation of organic nitro compounds in the environment of alcohols to urethanes, resp. carbanates RN0 ₂ + 3C0 + R'OHRNHCOOR '+ 2 CO, with catalytic action mainly of palladium and rhodium at a temperature of 150 - 230 ° C and a carbon monoxide pressure of 5 to 40 MPa. Thus nitrobenzene is carbonylated in high yield to ethyl N-phenylcarbamate (ethylphenylurethane) in ethanol in the presence of the PdCl 2 -pyridine-FeCl 2 catalyst system under a carbon monoxide pressure of 2-12 MPa at 180-220 ° C. With increasing palladium chloride content the reaction rate increases, but without ferric chloride the reaction practically does not take place and palladium chloride is reduced to palladium black / Niazov, Nefedov et al .: Decl. AN USSR 258, 898 (1981); Jan Ju. B., Nefedov BK: Syntheses on the basis of oxido ugleroda, p. 130, Chemistry Moscow (1987) /. Similarly, on a heterogeneous catalyst (5% Pd / C and 5% Pd / AlgO 4) activated with ferric chloride, methyl-N-phenylcarbamate (50%) and diethyl-2 were synthesized by carbonylation of nitrobenzene in methanol and 2,4-dinitrotoluene in ethanol. , 4-toluylenedicarbamate (89%) / Manov-Juvenskij, Nefedov: Uspechi chim. 21 · 889 (1981); patent application NSR 2 603 574 (1976); CA 82, 123,648 (1976). However, the disadvantage is the need for precious metals and their compounds, as well as their sensitivity to the admixture of catalytic poisons in carbon monoxide and other raw materials.

Selenium catalysts show high activity and selectivity in the synthesis of urethanes (carbamates). Thus, in the presence of selenium with additions of aniline, triethylenediamine, diphenylurea, acetic acid, potassium or sodium acetate, nitrobenzene and 2,4-dinitrotoluene in ethanol at a temperature of 170 ° C and a carbon monoxide pressure of 7 MPa, they are converted to ethyl N-phenylcarbamate and High Yield Diethyl 2,4-Toluylene Dicarbonate (U.S. Pat. 3,895,054; pat. NSR Application 2,603,574 (1976); jappat. 79-115 342 (1979) C.A. ^ 2, 58 472 (1980); Japanese pat. 57 (82) -17 157 (1982); C.A. £ 8, 128 131 (1983); European Pat. 193,982 (1986). However, the disadvantage is the multicomponentity of the catalyst system, the considerable toxicity of selenium and its compounds, as well as from a technical point of view, their difficult recovery.

A partly similar disadvantage is the method of urethane production by conversion of aromatic compounds with aliphatic, cycloaliphatic or araliphatic alcohols and carbon monoxide in the presence of sulfur and / or selenium and / or their compounds, as well as aromatic amino compounds or urea compounds, tertiary amines and / or alcoholic eols. , in addition to the oxidizing medium formed by the oxidizing agents or metal oxides 1, 2, 5, to 8 of the Periodic Table of the Elements, then ammonia or amines / NSR Pat. 2,343,826; German patent application De 2 338 754 A ₁ ; USA pat. 3,895,054; Dutch Pat. 75 02 156; CA 84, 30723 ¢ 1976) /. Under the other work / Bardzilovskij V. Ja. and others: Zur. prikl. chim. 57, 360 (1984); Radoškin VA and others: Ibid., E. 600-602 /, a negative (inhibitory) effect of vanadium oxide on the carbonylation of nitrobenzene in methanol, at a temperature of 180 ° C and a carbon monoxide pressure of 22 MPa in the presence of a sulfur-containing catalyst together with sodium acetate trihydrate B was found so that carbonylation for 2 h did not start.

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The mixture of vanadium oxide b with iron oxide as well as the iron oxide itself also had a retarding effect. Pyridine additives not only did not retard carbonylation, but partially increased selectivity to phenylurethanes. Salts from sulfur compounds in the presence of amines used to catalyze nitrobenzene carbonyl and e have been shown to be suitable thiourea in combination with pyridine, as well as polyeulfines (Kolmakov A. I. et al., Z. Vol. Chim. 58, 228 (1988)).

These deficiencies are addressed by a process for the preparation of alkylarylurethanes and / or dialkylarylurethanes by the conversion of aromatic nitro compounds and / or dinitro compounds and aliphatic, cycloaliphatic or lytalic alcohols C1- to b carbon monoxide under the catalytic action of sulfur and / or selenium and / or seleniums and / or compounds thereof. in an amount of 0.1 to 15% by weight, calculated on the aromatic compound or compounds of 0.1 to 15% by weight, of the alkaline salts of weak acids, promoters and activators, carried out in such a way that the carbonylation is carried out at a temperature of 90 to 200 ° C and a pressure of 2%. to 30 MPa, the zero ratio of alcohol or mixture of alcohols / aromatic nitro compound or mixture of nitro compounds is from 2 to 15, the alkali salt forming sodium and / or potassium and at least one carboxylic acid C 1 to C 8. The promoter consists of vanadium oxide or a mixture of vanadium oxide and iron oxide in an amount of 0.1 to 14% by weight, and the activator oxygen and / or peroxide in an amount of 0.03 to 7% by weight. The urethanes thus produced are intermediate products, in particular the production of isocyanates and diisocyanates, pesticides, anticorrosive additives and the like.

The advantage of the production method according to the invention is the technical simplicity! of a three-component catalyst system, the use of the activating effect of oxygen * and / or peroxides, enabling its active effect to reduce the consumption of catalyst system components. Furthermore, a high carbonylation reaction rate and a high selectivity to alkyl-, reep. dialkylarylurethanes, even using crude carbon monoxide, which may contain, in addition to inert gases and hydrogen, hydrogen sulfide, carbonyl sulfide and oxygen. The other three components not only do not need to be removed from technical carbon monoxide! as is usual in other processes, on the contrary, their presence is useful. This is because the use of high-purity carbon monoxide qi additionally requires the addition of oxygen, sulfur or sulfur compounds. .

An important component of the catalyst system is saline and / or sulfur and / or their compounds, with selenium and its compounds being more effective but much more technically available and toxic. Among the sulfur compounds, the most suitable are carbonyl sulfide, hydrogen sulfide, carbon disulfide and thiols. Thiourea, disulfides and the like can also be used. In addition to the above, the highly effective element * sulfur * is an even more effective selenium.

From the alkali metal salts of weak acids, in addition to the sodium and potassium salts of the individual monocarboxylic acids C 1 to C 8, technically readily available mixtures of sodium salts of carboxylic acids C 6 to C 8 can be used, leaving a more known product in the oxidation process of cyclohexane to cyclohexanol and cyclohexanone. oxidation of alkanes and p. The term carboxylic acid is also to be understood as meaning hydroxy acids, keto acids and any impurities of dicarboxylic acids and other oxygenated organic compounds. However, non-hydrated boils are more suitable because water impurities reduce the selectivity to urethanes. The promoter is vanadium oxide or a mixture of vanadium oxide β with iron oxides, in particular iron oxide. If b * only works with small amounts of oxygen or peroxide in the reaction medium, higher amounts of vanadium oxide or its mixture with iron oxide are required, i.e. closer to the upper limit of 14% w / w of nitro compound, and if s * works with a high content of oxygen or peroxide. the required amounts are close to the lower limit of 0.1% by weight. '

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Oxygen is required in the reaction medium either in molecular form or in atomic or oligomers, in particular in the form of ozone. The upper limit of 7% w / w of the nitro compound is limited by the safety of the production method of the present invention. It is more convenient to add oxygen as a carbon monoxide additive, especially in the continuous operation of the process of the present invention.

Of the peroxides, hydrogen peroxide is particularly suitable, preferably in the form of an aqueous solution with a concentration of more than 30% by weight. Sodium peroxide and barium peroxide are less suitable but useful. Also suitable are organic hydroperoxides and peroxides with a half-life at 90 DEG C. of at least 1 hour, such as tert-butyl hydroperoxide, di-tert. butyl peroxide, cumene hydroperoxide, dicumyl peroxide and the like.

The carbon monoxide used for the preparation of the urethanes according to the invention has a purity of 50 to 99.5% by volume, a concentration lower than 50% by volume. it is also usable, but higher pressure is needed. Concentration higher than 99.5 * vol. is, of course, permissible, but requires special separation and refining equipment and, in addition, inefficient costs.

Particularly suitable impurities in carbon monoxide are: oxygen, hydrogen sulfide and carbonyl sulfide. Practically proportional to their amount, it is suitable to reduce the amounts of separately added sulfur and / or selenium and their compounds, as well as oxygen or peroxide to the reaction medium of the reductive carbonylation of organic nitro compounds to urethanes according to the invention. .

Suitable aromatic compounds for the reductive carbomylation according to the invention are aromatic nitro compounds, nitrobenzene, 4-nitrochlorobenzene, 3,4-dichloronitrobenzene, 1,3-dinitrobenzene, o-nitrotoluene, n-r * rotoluene, p-nitrotoluene, 2,4 -dinitrotoluén, 2,6 dinitrotoluene ~ _t ^ nitrbnaftalán ritroantracén, nitrobifenylén atá.

The alcohols are in particular aliphatic, cycloaliphatic and aryaliphatic alcohols with mol. by weight of 32 to 330, with primary and secondary alcohols being more suitable. The most suitable are methanol, ethanol, n-propanol, 2-propanol, butanols, amyl alcohols, 2-ethylhexanol, cyclohexanol, benzyl alcohol, hexalal alcohol and decanol, dodecanol. Alcohols in the present invention also include cycloalkyls and arylalkyls.

The process can be carried out continuously, semi-continuously and continuously. Other data on the realization of the epoch as well as other advantages are evident from the examples.

Example 1

Weigh 100 g of nitrobenzene, 200 g of methanol, 10 g of powdered sulfur, 10 g of anhydrous sodium acetate, 13.2 g of vanadium oxide and 4.2 g of morpholine into a 1 dupre stainless steel rotary autoclave with an electric steam evaporator. Then, after closing the autoclave, the air is removed by blowing with carbon monoxide and finally the carbon monoxide is brought to a pressure of 14 MPa / 25 ° C. Carbon monoxide as an impurity contains 0.03% by volume. oxygen; 2.20% vol. of hydrogen and 1.34% vol. nitrogen. Thus, a total of 0.04% by weight, of molecular oxygen, based on the weight of nitrobenzene, is present in the reaction medium. Then ea rotates the autoclave and heats up to 160 ° C. It is then maintained for 5 h, during which the pressure drops to 18.9 MPa to 14.9 MPa. However, the conversion of nitrobenzene is only 78.5%, the selectivity to methylphenylurethane (methyl N-phenylcarbamate) is 83.1% and to aniline is 8.4%.

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Example 2

The procedure is similar to Example 1, except that carbon monoxide is used instead of 0.03% by volume. oxygen contains 0.38% vol. oxygen and 1.59% vol. of hydrogen to give a reaction medium of 0.50-0.02% by weight, nitrobenzene molecular oxygen, and the experiment time instead of 5 h is 3 h. During this time, the conversion of nitrobenzenes reaches 100%, the selectivity to methylphenylurethane 92.0% and to aniline 8%.

Example 3

100 g of nitrobenzene, 200 g of methanol, 10 g of sulfur, 10 g of anhydrous sodium acetate and 1 g of vanadium oxide are weighed into a rotary stainless steel autoclave with a volume of 1 .mu.m specified in Example 1. Then the autoclave is closed without removing air, carbon monoxide is brought to a pressure of 19 MPa. Carbon monoxide as a primes contains 0.09% by volume of oxygen and 1.61% by volume. hydrogen. Thus 0.34% by weight of molecular oxygen, calculated on nitrobenzene, is introduced into the reaction medium. Then the rotation and heating of the autoclave up to a temperature of 140 ° C is started. The conversion of nitrobenzene is then 99.7%, the selectivity to methylphenylurethane 93.4% and to aniline 6.6% is kept to within 5 hours with an accuracy of -2 ° C.

Similar conversion of nitrobenzene and selectivity to methylphenylurethane is achieved using 10 g of anhydrous potassium acetate instead of 10 g of sodium acetate.

Example 4

8 g of 2,4-dinitrotoluene, 200 g of methanol, 10 g of powdered sulfur, 10 g of sodium acetate and 4 * 2 g of vanadium oxide are weighed into a 1 .mu.m rotary autoclave characterized in Example 1. After sealing, carbon monoxide is introduced into the autoclave with a yield of 0.09% by volume. oxygen to a pressure of 15 MPa / 25 ° C. So get into the reaction medium! and gets a total of 0.34% by weight, molecular oxygen / nitrobenzene. The reductive carbonylation takes place with constant stirring of the contents of the autoclave by rotation at a temperature of 160 - 2 for 4 hours. The conversion of 2,4-dinitrotoluene reaches 98.5% and the selectivity to the corresponding toluene -2,4-dicarbamate (dimethyl 2,4-toluenedicarbamate, tolylene-2,4-dimethylcarbamate, dimethyltolylene-2,4-dicarbamate) 76% »

Example 5

100 g of nitrobenzene, 200 g of methanol, 10 g of powdered sulfur, 10 g of anhydrous sodium acetate and 1.2 g of vanadium oxide are weighed into a 1 dm 2 stainless steel rotary autoclave. After closing the autoclave without removing air, carbon monoxide with an impurity content of 0.06% by volume is introduced. oxygen, 2.7% vol. of hydrogen and 1.35% vol. nitrogen, to a pressure of 14 MPa / 25 ° C. Thus, a total of 0.32% by weight of molecular oxygen / nitrobenzene is introduced into the reaction medium. Reducing, resp. reductive carbonylation is carried out at 150-2 ₀ C for 4 hours with a conversion of 86.7% of the nitrobenzene, the selectivity to 92.5 metylfenyluretán Ϊ aniline and 2.3%.

Example 6

100 g of nitrobenzene, 462 t of n-butanol, 10 g of powdered sulfur, 10 g of anhydrous sodium acetate and 1.2 g of vanadium oxide are weighed into a 1 dm 2 stainless steel reaction autoclave specified in Example 1. After closing the autoclave, carbon monoxide with admixtures of 0.06% by volume is introduced into the autoclave without removing the air. oxygen, 2.7% vol. of hydrogen and 1.35% vol. nitrogen, to a pressure of 14 MPa. 0.32% w / n-nitrobenzene molecular oxygen is thus introduced into the reaction medium. The carbonylation is carried out at a temperature of 150 - 2 ° C. During 4 h the conversion of nitrobenzene reaches 78%, the selectivity to butylphenylurethane (butyl-N-phenylurethane) 88% and aniline 11.7%.

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Example 7

The procedure is similar to Example 6, except that 462 g of n-butanol are used instead

462 g of sec * butyl alcohol. Nitrobenzene conversion reaches 50% and selectivity per sec.

butylphenylurethane 94%.

Example 8

100 g of nitrobenzene, 200 g of methanol, 10 g of powdered elemental sulfur, 10 g of anhydrous sodium acetate and 1.2 g of vanadium oxide are weighed into the autoclave specified in Example 1. The autoclave is then closed and 14 MPa of carbon monoxide with admixtures of 1.59% by volume are introduced into it without removing air. of hydrogen and 0.09% by volume. oxygen. A total of 0.33% w / n-nitrobenzene molecular oxygen thus enters the reaction medium. The reductive carbonylation is performed at 141 - 2 ° C for 5 h. The conversion of nitrobenzene reaches 99.7 selectivity to methylphenylurethane 93.4% and to aniline 6.6%,

Example 9

The procedure is similar to Example 8, except that after closing the autoclave, the air is removed from it with oxygen, which is then left in the autoclave at a pressure of 0.1 MPa and, in addition, carbon monoxide at a pressure of 0.06% by volume is brought to a pressure of 14 MPa. Oxygen ------ (* 2.7% hydrogen by volume and 1.35% nitrogen by volume). Thus, a total of 1.1-0.05% w / n-nitrobenzene molecular oxygen enters the reaction medium. The carbonylation is carried out at a temperature of 150 - 2 ° C for 5 h. The conversion of nitrobenzene reaches 99.8%, the selectivity to methylphenylurethane 92% and the aniline 8%.

Example 10

The procedure is as in Example 8, only instead of 10 g of anhydrous sodium acetate, using 10 g of a mixture of sodium salts of carboxylic acids and hydrokarboxylevých C ₄ to C. The conversion of nitrobenzene is 98.6%, the selectivity to methylphenylurethane 91.8% and to aniline 8.2%.

Example 11

Weigh 100 g of nitrobenzene, 200 g of methanol, 10 g of powdered sulfur, 10 g of anhydrous sodium acetate and other additives listed in Tab. 1. The autoclave is then closed and carbon monoxide with an admixture of 0.093% by volume is brought to a pressure of 14 MPa / 25 ° C without removing air. oxygen. Thus, a total of 0.33% by weight, of molecular oxygen, based on nitrobenzene, is introduced into the reaction medium. Then for 45 to 60 min. while the autoclave is constantly rotating, its contents are heated to 160 ° C and maintained for 4 to 5 hours. The results obtained, depending on the third and further additives to the carbonylation catalyst system (additives to sulfur and sodium acetate) are summarized in Table 1.

Example 12

Using a rotary autoclave made of stainless steel with a volume of 1 dm 2 specified in Example 1, the effect of temperature was examined. The initial temperature-dependent carbon monoxide pressure is 12.5 to 16.5 MPa. Carbon monoxide as an impurity contains 0.06% by volume. oxygen, 2.7% vol. of hydrogen and 1.35% vol. nitrogen.

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Air is removed from the autoclave by purging with oxygen. Thus, the total molecular oxygen content in the autoclave is 1.0 - 0.05% w / v / nitrobenzene. In addition to the above, the autoclave charge consists of 100 g of nitrobenzene, 200 g of methanol, 10 g of powdered sulfur, 10 g of anhydrous sodium acetate and 3.2 g of vanadium oxide.

Further data and achieved results are given in Table 2.

Table 2

Temperature ° C Initial pressure CO / 25 ° C MPa Own experiment time min. ' Nitrobenzene conversion% selectivity% on: methylphenylurethane aniline 80 and 2 16.5 240 21.0 100 0 120 - 2 14.5 300 52.1 89.8 8.1 130 t 2 14.0 300 98.9 91.8 8.1 140 t 2 15.0 300 99.7 93.7 6, ³ 160 and 2 14.0 300 98.9 85.3 8.9 190 12.5 230 95.3 77.8 19.9

Example 13

Using a 1 dm 3 rotary autoclave with a basic charge of 100 g of nitrobenzene, 200 g of methanol, 10 g of anhydrous sodium acetate, 7 g of aniline, 4.2 g of morpholine, 13.2 g of iron oxide and 1.2 g of vanadium oxide are examined influence of the amount of sulfur, at the initial pressure of carbon monoxide (impurities: 0.03% by _{volume of 0 2} , 2.20% by volume of H ₂ , 1.34% by volume of N ₂ ) 14 MPa / 25 ° C, at the carbonylation temperature 160 - 2 ° C. The autoclave is not purged with another gas before the introduction of carbon monoxide, i.e. air is not removed from it. Thus, the total amount of molecular oxygen present in the reaction medium is 0.22% w / n-nitrobenzene. The reaction time is 300 min. With 10 g of sulfur, 5 and 1 g of sulfur, a nitrobenzene conversion of 99.5, 95 and 14.7% is achieved; selectivity to methylphenylurethane = 93.2, 9Y and 93.1%; selectivity to aniline = 6.5, 5.8 and 5.5%.

Example 14.

Reducing, resp. Reductive carbonation of nitrobenzene with carbon monoxide in the presence of methanol and under the catalytic action of the system sulfur - sodium acetate - vanadium oxide is carried out in a rotary autoclave (42 rpm ^-1 ) made of stainless steel with a volume of 1 dm ³ . The effect of the initial pressure of carbon monoxide (admixture: 1.5% by volume H ₂ ; 0.03% by volume O ₂ ) on the conversion of nitrobenzene, the selectivity of methylphenylurethane and aniline formation, at 150-2 ° C for 5 h is investigated. The batch consists of: 100 g of nitrobenzene, 200 g of methanol, 10 g of powdered sulfur, 10 g of anhydrous sodium acetate, 1.2 g of vanadium oxide and carbon monoxide. The achieved results are summarized in tab. 3.

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Initial pressure C0 / 20 ° C MPa Total content 0 ₂ in the reaction medium% w / w / nitrobenzene Nitrobenzene conversion% Selectivity% on: methylphenylurethane anylin 3.5 0.224 46.1 90.1 9.3 7.6 0.235 67.3 94.1 3.7 13.2 0.25 73.4 92.1 6.6 14.0 0.253 99.1 90.9 7.9

Example 15

Carbonylation of nitrobenzene with carbon monoxide in the presence of various melts of methanol and the catalyst system sulfur - sodium acetate - vanadium oxide, to methylphenylurethane (methyl N-phenylcarbamate) is carried out at a temperature of 150 to 2 ° C and an initial pressure of carbon monoxide (mixed with 0.4% oxygen, 1.2% hydrogen and 0.84% nitrogen) 14 MPa / 25 ° C. The duration of each experiment is 4 h. The batch for each experiment consists of 100 g of nitrobenzene (0.81 mol), x g of methanol, 10 g of powdered sulfur, 10 g of sodium acetate and 1.2 g of vanadium oxide. The initial amount of oxygen in each experiment is from 0.98 to 1.7% by weight, oxygen / nitrobenzene. The results obtained, the effect of the amount of methanol, are summarized in Table 4.

Weighing of reactors ..... Molar ratio of methanol to nitrobenzene Nitrobenzene conversion% Selectivity% to: methyl- nitrobenzene methanol 8 mol 8 mol phenylurethane aniline 100. 0.81 26.5 0.83 1.02 25.1 83.6 11.2 100 0.81. 50.0 1.56 1.93 59.3 89.9 9.8 100 0.81 100 3.12 3.85 74.3 91.7 5.7 100 0.81 200 6.24 7.70 99.7 85.7 13.5 100 0.81 300 9.36 11.56 100 83.6 ll, ²

Example 16

80 g of 4-nitrochlorobenzene, 200 g of anhydrous ethanol, 10 g of carbon disulfide, 8 g of potassium propionate, 1.1 g of vanadium oxide and 1.3 g of iron oxide are weighed into the autoclave specified in Example 1. The initial pressure of carbon monoxide is 14 MPa / 25 ^c C. The oxygen content in the reaction medium is 1.6% by weight of 4-nitrochlorobenzene. The reductive carbonylation time is 5 hours. The conversion of 4-nitrochlorobenzene is 98.7%, the selectivity to ethyl N- (4-chlorophenyl) carbamate 91.3% and 4-chloroaniline 5.9%.

Example 17

The procedure is similar to Example 16, except that instead of 10 g of carbon disulfide, 0.5 g of powdered sulfur, 3.5 g of carbonyl sulfide and 5 g of carbonyl sulfide and 5 g of hydrogen sulfide are placed in an autoclave. The conversion of 4-nitrochlorobenzene is 99.3%, the selectivity to ethyl N- (4-chlorophenyl) carbamate 91.9% and 4-chloroaniline 5.8%.

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Example IB

The procedure is similar to Example 5, except that instead of 100 g of nitrobenzene, 90 g of 1-nitronaphthalene are weighed. The conversion of nitronaphthalene reaches 84% and the selectivity to methylnaphthyl acetate (methyl N-naphthyl to arbaate reaches 91.1%).

Example 19

The procedure is as in Example 9, except that instead of 100 g of nitrobenzene, 80 g of 1-nitronaphthalene are weighed and 300 g of n-butanol are weighed out instead of 200 g of methanol and the experiment time is 6 hours. The conversion of 1-nitronaphthalene is 89.1% and the selectivity to butylnaphthylurethane (butyl N-naphthylcarbamate) is 89.8%.

Example 20

The procedure is the same as in Example 19, except that instead of 300 g of n-butanol, 400 g of 2-ethylhexanol are weighed out. The conversion of nitronaphthalane is 57.3% and the selectivity to 2-ethylhexylnaphthylurethane is 89.7%.

Example 21

The procedure is similar to Example 20, except that 400 g of benzyl alcohol are weighed out instead of 400 g of 2-ethylhexanol. The conversion of nitronaphthalene reaches 58.1% and the selectivity to benzylnaphthylurethane reaches 91.2%.

Claims (5)

SUMMARY OF THE INVENTION A process for producing alkylarylurethanes and / or dialkylarylurethanes by converting aromatic nitro compounds and / or dinitro compounds with aliphatic cycloaliphatic or aryl aliphatic alcohols C 1-4 to oxalate under the catalytic effect of sulfur and / or eel and / or compounds thereof. % of from 0.1 to 15 wt. % fatty acids, based on the aromatic compound or compounds, 0.1 to 15 wt. fatty aliphatic salts of weak acids, promoters and activators, characterized in that the carbonylation is carried out at a temperature of 90 to 200 ° C and a pressure of 2 to 30 MPa, the molar ratio of alcohol or alcohol / aromatic nitro compound or nitro compound mixture is from 1 to 15, wherein the alkaline salt comprises a sodium and / or potassium salt of at least one carbonyl acid C 1 -C 8, a vanadium oxide promoter or a mixture of vanadium pentoxide with an iron oxide of 0.1 to 14 wt. fatty acid activator and oxygen and / or peroxide in an amount of 0.03 to 7% by weight. fatty. 2. Process according to claim 1, characterized in that the alkali salt forms anhydrous sodium carbonate of at least one carboxylic acid to C8, preferably a mixture of sodium salts of C8 to C8 carboxylic acids and hydrocarboxylic acids to C8, obtained from alkaline waters such as of a cyclohexanol acyclohexanone process by oxidation of cyclohexanone. 3. A process according to claim 1, wherein the oxygen is at least one atomic, molecular, and preferably ozone-admixed. 4. A process according to any one of claims 1 to 3, wherein the peroxide is a concentrated water soluble peroxide, preferably concentrated hydrogen peroxide and hydrogen peroxide and / or an oil soluble peroxide group of cumene hydroperoxide. butylhydro peroxide, dicamyl peroxide, di-tert. butylperoxide. 5. Process according to claim 1, characterized in that the uhoxin oxide has a purity of 50-59.5% by volume, with a yield of up to 100% being at least one gas fails from hydrogen, nitrogen, oxygen, carbon dioxide, methane, hydrogen sulfide. , ametiol carbonyl sulfide.