SK330889A3 - Method for producing alkyl-n-arylcarbamates and/or dialkyl-n-aryldicarbamates - Google Patents

Abstract

A method is commenced by an aromatic nitro-compounds conversion or conversion of dinitro-compounds with aliphatic, cycloaliphatic or arylaliphatic alcohols having 1 - 10 carbons in a molecule, with carbon monoxide, with oxygen additives, and other gases at a temperature 70 - 240 degrees Celsius and pressure ranging from 0.1 to 30 Mpa during a catalytic activity of sulphur and selenium and the compounds thereof being present in an amount of 0.1 - 15 percent by weight with respect to the aromatic compounds. A promoter based on vanadic oxide, optionally on ferro oxides, is another component. An oxide, hydroxide or alcoholate of an alk. metal or earth in an amount ranging from 0.1 to 15 by weight, with respect to the aromatic nitro-compounds, is a cocatalyst. The most preferable are alcoholates of the alk. metals with alcohols having 1 - 5 carbons in a molecule.

Description

Technical field

The present invention relates to a process for the preparation of alkyl N-arylcarbamates and dialkyl N-aryl dicarbamates and their derivatives by a non-phosphorous route, using technically readily available raw materials and catalyst system components.

BACKGROUND OF THE INVENTION

Known / Jan Ju B., Nefedov BK: Sintezy na osnove oksida ugleroda, p. 130. "Khimija" Moscow (1987); Lapidus A.Ľ. and others: Izv. AN USSR ser. Chim. 1981, 133; NSR Pat. No. 1,901,202 / catalytic carbonylation of aromatic nitro compounds with carbon monoxide in an alcohol environment to alkyl N-arylcarbamates under the catalytic action of palladium compounds and the interaction of lewissic acids. Thus, nitrobenzene is carbonylated in high yield to ethyl N-phenylcarbamate in ethanol under the action of the PdCl ₂ -pyridine-FeCl ₃ catalyst system and a carbon monoxide pressure of 2-12 MPa at a temperature of 180-220 ° C. Similarly, on a heterogeneous catalyst (5% Pd / C and 5% Pd / Al ₂ O ₃ ) activated with ferric chloride by reductive carbonylation of 2,4-dinitrotoluene in ethanol, diethyl 2,4-toluylenedicarbamate is formed / Application No. Pat. NSR 2,603,574; CA 85, 123, 648 (1976); Manov-Juvensky, Nefedov BK: Uspechi Khim. 51, 889 (1981)]. However, the disadvantage is the sensitivity to the admixture of catalytic poisons in carbon monoxide and other raw materials and the need for precious metals and their compounds.

Selenium catalysts partially solve this problem. Thus, in the presence of selenium with the addition of aniline, triethylenediamine, diphenylurea, acetic acid, potassium or sodium acetate, nitrobenzene and 2,4-dinitrotoluene in ethanol at 170 ° C and carbon monoxide pressure of 7 MPa, they convert to ethyl N-phenylcarbamate and diethyl. High Yield -2,4-toluenedicarbamate / U.S. Pat. NSR 2,603,574 (1976); US Pat. 3,895,054; Japanese Pat. 79-115, 342 (1979); 92, 58472 (1980) and 57 (82) -17157 (1982), C.A. 98 128 131 (1983); European Pat. 193,982 (1986)]. However, the disadvantage is the considerable toxicity of selenium and its compounds, as well as too many components of the catalyst system. The process for the production of alkyl N-arylcarbamates by the conversion of aromatic compounds with aliphatic, cycloaliphatic or araliphatic alcohols and carbon monoxide in the presence of sulfur and / or compounds thereof, aromatic amino compounds or urea compounds, tertiary acid amines and / or alkali salts in addition to the oxidizing environment formed by oxidizing agents or metal oxides of the 1st, 2nd, 5th to 8th group of the periodic system of elements, then ammonia or amines (German Pat. No. 2,343,826; U.S. Pat. No. DE 2,838,754 A). According to other works / Bardzilovskij V. Ja. And others: Zur. he said, chim. 57, 360 (1984); Radoškin V. A. and others: ibid., P. In turn, the inhibitory effect of vanadium pentoxide on the carbonylation of nitrobenzene in methanol at 180 ° C and a carbon monoxide pressure of 22 MPa in the presence of a sulfur-containing catalyst together with sodium acetate trihydrate was found to inhibit carbonylation for 2 h. A mixture of vanadium pentoxide and iron oxide as well as iron oxide itself had a retarding effect. Of the sulfur compounds, thiourea and polysulfides / Radoskin B.A. and others: Žur. Ex. chim. 1987. 1426; Kolmakov A. I. and others: Ž. Obšč. chim. 58, 228 (1988)]. The production of alkylarylurethanes according to the author's certificate CS 269 691 represents a significant technical progress. However, the disadvantage is the too high need for an alkali carboxylic acid salt which is applied in an amount of 5 to 10% by weight. to a carbonylated aromatic nitro compound.

SUMMARY OF THE INVENTION

In accordance with the present invention, a process for the preparation of alkyl N-arylcarbamates and / or dialkyl S

N-aryl dicarbamates having an alkyl number of 1 to 10 by conversion of aromatic nitro compounds and / or dinitro compounds with aliphatic, cycloaliphatic or allylaliphatic alcohols;

OW / number of carbons in a molecule of 1 to 10 and with carbon monoxide at a temperature of 70 to 240 ° C and a pressure of 0.1 to 30 MPa, with a catalytic effect of sulfur and / or selenium and / or their compounds in an amount of 0.1 to 15%. %, based on the aromatic nitro compound or compounds, 0.1 to 15 wt. % of catalyst, 0.1 to 14 wt. % vanadium pentoxide or a mixture of vanadium pentoxide and iron oxide as a promoter and 0.03 to 7 wt. oxygen and / or peroxide, such that the cocatalyst is at least one oxide and / or hydroxide of the alkali metal and earth oxides and / or at least one alcoholate of the alkali metal and earth alcoholates having an alkyl number of 1 to 5.

The advantage of the process of the invention is a reductive carbonylation of higher speed due to the increased activity of the co-catalyst based on alkoxides and alkali metal hydroxides and earth metal compared to the alkali salts of carboxylic acids, C 2 to C _6, and thus much less use of co-catalyst as well as sulfur, or. compounds thereof. Another advantage is the possibility to carry out the process at a lower temperature and pressure and a higher selectivity of the reductive carbonylation of aromatic nitro compounds to alkyl-N-arylurethanes or alkyl-N-arylcarbamates, respectively.

Not only pure but even unrefined carbon monoxide, which may contain inert gases, but also hydrogen sulphide, carbonyl sulphide and oxygen addition may be used for the reductive carbonylation of the present invention. In addition, the use of high purity carbon monoxide generally requires the addition of oxygen to at least a reductive carbonylation environment.

Alkali metal oxides or hydroxides and soils are important cocatalysts, with alkali metal oxides and hydroxides being more effective, but especially alkali metal alcohols with aliphatic alcohols & carbon numbers 1 to 5 are more effective (but more difficult to execute) alcoholates of monovalent aliphatic alcohols. They may also be combined with C 1 -C 6 alkali metal salts of carboxylic acids.

Suitable aromatic compounds suitable for the reductive carbonylation of the present invention are: nitrobenzene and its halogen derivatives, nitrotoluenes and their halogen derivatives, dinitrotoluenes, nitroxylenes, trimethylnitrobenzenes, nitronaphthalene, dinitronaphthalenes, nitroanthracene and nitrobiphenylene.

The process can also be used for the reductive carbonylation of much more complex organic compounds containing a nitro or nitro group in the molecule, provided their thermal stability is at least at a temperature of at least 100 ° C.

Among the alcohols, these are mainly lower aliphatic and cycloaliphatic alcohols because the rate of reductive carbonylation decreases sharply as the length of the alkyl alcohol increases. More preferably, straight chain alcohols are less preferred, secondary are less suitable, and tertiary alcohols are the slowest to react. Most preferred are methanol, anhydrous ethanol, n-propanol, n-butanol, 2-propanol, isobutanol, n-pentanol, n-octanol, decanol and 2-ethylhexanol. Less suitable but useful are cycloaliphatic and arylaliphatic alcohols such as cyclohexanol, benzyl alcohol and the like. The alkyls of the present invention include cycloalkyls and arylalkyls.

The process according to the invention can be carried out continuously, semi-continuously and continuously.

Further data on carrying out the process of the invention as well as other advantages are apparent from the examples.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

100 g of nitrobenzene, 123 to 200 g of methanol, are weighed into a stainless steel rotary autoclave with an electrical resistance winding of 1 dm ³ , the amount of methanol being dependent on the amount of methanolic sodium methanolate cocatalyst added at a concentration of 10% by weight. the experiment was applied in total of 200 g of methanol. In addition, 10 g of elemental sulfur powder, 1.2 g of vanadium pentoxide and various amounts of forensic methoxide (about 10% by weight of sodium methoxide and horse) are added.

5.1% by weight) or sodium acetate and in one case solid powdered sodium hydroxide and in one case a mixture of potassium hydroxide and calcium oxide, respectively. potassium hydroxide and magnesium hydroxide. After the autoclave is closed and the air is purged with oxygen, carbon monoxide containing 0.5 vol. of hydrogen, 0.5 vol. of oxygen and 1.34% v / v of nitrogen to a pressure of 14 MPa and the rotation and heating of the autoclave is started until the desired reaction temperature of 150 ° C is reached. This temperature is maintained for 4 h at constant rotation. In 10 min. The pressure and temperature of the autoclave are recorded at intervals and maintained at 150 ± 2 ° C. After 4 h, the rotation of the autoclave is stopped, the contents are cooled, the unconverted carbon monoxide is drained, and the autoclave is weighed and analyzed.

The results obtained as well as other reaction conditions are shown in Table 1. Table 1

Added catalyst system component conversion nitrobenzene (%) selectivity (%) on the: kind of amount (% w / w) / (nitro benzene) kind of amount (% w / w) (nitrobenzene) methyl-N- fenylkar- carbamate aniline CHjCOONa 10 - - 99.5 74.3 15.5 CH ₃ COONa 5 - - 34.0 74.5 15.1 CH ₃ COONa 5.0 CH ₃ ONa 3.85 100 74.7 15.9 CH ₃ COONa 7.3 CH ₃ ONa 1.9 100 77.6 12.8 CH ₃ COONa 0.0 CH ₃ ONa 7.7 100 78.9 19.8 CHaCOONa 0.0 CH ₃ ONa 4.4 98.9 75.5 21.2 CHjCOONa 0.0 CH ₃ ONa 1.0 100 86.4 6.8 CH ₃ COONa 0.0 CH ₃ ONa 0.7 100 84.6 10.7 CH ₃ COONa 0.0 CH ₃ ONa 0.5 76.3 85.3 9.1 CH ₃ COONa 0.0 CH ₃ 0Na 0.1 29.4 75.3 8.2 - - CH ₃ OK 0.7 100 85.1 10.6 - - NaOH 1.5 99.9 82.3 14.7 CaO 1.0 NaOH 0.5 97.3 86.7 9.1 Mg (OH) ₂ 1.5 Koh 0.5 97.9 86.9 8.9

From the results in Tab. 1, the effect of sodium methoxide is much (by more than an order of magnitude) higher than that of sodium acetate as components of the nitrobenzene reductive carbonylation catalytic system. The missing amount in selectivity to methyl-N-phenylcarbamate and aniline to 100% is mainly methyl formate.

Potassium methoxide also has a high efficiency.

Example 2

The procedure is analogous to Example 1, except that instead of 200 g of methanol, the above aliphatic and arylaliphatic alcohols are used and instead of sodium methoxide other alkali metal and earth alcoholates are used. The type and quantity of these components as well as the results obtained are included in Table 2.

Table 2

alcohol Added catalyst system component conversion nitrobenzyl ethoxybenzene (%) Selectivity to alkyl-N-phenylcarbamate (%) kind of amount (% wt / nitrobenzene) kind of amount (% wt / nitrobenzene) methanol 200 CHjONa (CH _{3) 3} ConA 0.1 0.8 98 methyl-N-phenylcarbamate (91) n-pentanol 300 CH ₃ CH ₂ CH ₂ CH ₂ ONa (CH ₃ ) ₂ CHHO 0.5 0.5 97 pentyl-N-phenylcarbamate (92) n-Octanol 300 (CH ₃ CH ₂ O) ₂ Ca (CH 2 COK 0.4 0.8 96 N-octyl-fe- nylkarbamát (93) decanol 400 (CH _{3) 2} CHOK 1.5 86 denvl-N-fe- nvlkarbamát (94) nonylphenol 400 (CH ₃ CH ₂ O) ₂ Ca and CH ₃ (CH ₂ ) ₃ CH ₂ ONa 1.1 1.0 93 N-phenyl-N-phenylcarbamate (83) hexanol 300 CH ₃ (CH ₂ ) ₃ CH ₂ ON and Mg (OH) ₂ 0.5 0.3 89 hexyl-N-fe- nylkarbamát (92) cyclohexanone nol 300 CH ₃ ONa (CH 2 CHONa KOH 0.5 0.5 0.1 84 cyclohexyl-N-phenylcarbamate (88) cyclohexyl ethanol 300 CH ₃ CH ₂ ONa (CH ₃ ) ₂ CHOK NaOH 0.5 0.4 0.1 92 cyclohexylethyl N-fanyl carbamate (89) cyclohexyl ethanol 300 NaOH KOH 0.3 0.5 54 cyclohexyl- ethyl N- phenylcarbamate (88) ethanol 200 NaOH KOH LiOH 0.3 0.5 0.1 100 Ethyl N-phenylcarbamate (82)

Example 3

The procedure is analogous to Example 1, except that, instead of 100 g of nitrobenzene, 90 g of 1-nitro-naphthalene and 1.5 g of sodium methoxide (without sodium acetate) are weighed. Nitronaphthalene conversion reached 91% and selectivity to methyl N-naphthylcarbamate 89.3%.

Example 4

The procedure is analogous to Example 1, except that the feed to the autoclave is 68 g of 2,4-dinitrotoluene, 200 g of methanol, 10 g of sulfur powder, 2.5 g of sodium methanolate as cocatalyst and 1.8 g of vanadium pentoxide. The conversion of 2,4-dinitrotoluene reaches 98.4% and the selectivity to dimethyl 2,4-toluenedicarbamate (tolylene-2,4-dimethylcarbamate, dimethyltolylene-2,4-dicarbamate).

Example 5

The procedure is analogous to Example 3 except that 300 g of n-butanol are weighed in place of 200 g of methanol and the test time is 8 h.

The conversion of 1-nitronaphthalene is 90.5% and the selectivity to butyl N-naphthylcarbamate 89.9%. In another experiment otherwise similar, but instead of 200 g of methanol used 300 g of n-decanol, the conversion of 1-nitronaphthalene reached 97% and the selectivity to octyl-N-naphthylcarbamate was 92%.

Example 6

The procedure is analogous to Example 5, except that 1-nitronaphthalene is weighed with 100 g of chlorometrobenzene and 400 g of n-octanol is weighed with 300 g of n-butanol.

The conversion of 4-chlorometrobenzene is 69.2% and the selectivity to octyl-N- (4-chlorophenyl) carbamate 90.3%.

Ί

Example 7

The procedure is analogous to Example 1 except that 300 g of benzyl alcohol and 2.0 g of sodium methoxide are weighed in place of 200 g of methanol and the reaction time is 6 h. Nitrobenzene conversion reached 64.7% and selectivity to benzyl N-phenylcarbamate reached 88.9% and aniline 5.9%.

Under otherwise identical conditions, but using instead of 10 g of sulfur powder, only 0.5 g of hydrogen sulfide and 0.6 g of carbonyl sulfide, the nitrobenzene conversion reaches 87.3% and the selectivity to benzyl N-phenylcarbamate 90.5%.

Example 8

The procedure is analogous to Example 1 except that the reaction temperature is 170 ± 3 ° C and the feed to the autoclave is 100 g nitrobenzene, 200 g methanol, 1.3 g selenium powder and 1.0 g selenium dioxide, 1.1 g vanadium pentoxide and 2.5 g of sodium methanolate. Nitrobenzene conversion reached 89.3%, methyl N-phenylcarbamate selectivity reached 88.1% and aniline 6.3%. The remainder to 100% is methyl formate.

Under otherwise similar conditions and using instead of 2.5 g sodium methanolate 2.5 sodium butanolate the nitrobenzene conversion reaches 97% and the selectivity to methyl-N-phenylcarbamate reaches 93.1%.

Example 9

The procedure of Example 1 is followed, with 100 g of nitrobenzene, 200 g of methanol, 5 g of sulfur, 10 g of sodium acetate, 1.2 g of vanadium pentoxide being used for the first experiment.

For the second experiment, instead of 10 g sodium acetate, 1.5 g sodium methoxide was used. In the first experiment, nitrobenzene conversion was 42.5% and in the second, 98.8%. The selectivity to methyl-N-phenylcarbamate in the first experiment was 81.3%, in the second experiment 87.4% and to aniline 16.7%, respectively. 10.5%.

Example 10

The procedure is analogous to Example 1 except that 50 g of 2,4-dinitrotoluene is used instead of 100 g of nitrobenzene and only 1 g of carbonyl sulphide is used instead of 10 g of sulfur powder and the reaction time is 6 h.

The 2,4-dinitrotoluene conversion is 96-100% and the selectivity to dimethyl 2,4-toluylenedicarbamate is 88-92%.

Under otherwise the same conditions, but using only 30 g of 2,4-dinitrotoluene and 30 g of nitrobenzene instead of 50 g 2,4-dinitrotoluene, dinitrotoluene conversion reaches 98.7%, nitrobenzene% and selectivity to dimethyl 2,4-toluylenedicarbamate 89, 3% and methyl N-phenylcarbamate 94.8%. Example 11

The procedure is analogous to Example 10, except that 200 g of cyclohexanol are applied instead of 200 g of methanol, which, with 2,4-dinitrotoluene and carbon monoxide at 94% dinitrotoluene conversion, gives a selectivity of 65.2 dicyclohexyl-2,4-toluylenedicarbamate.

Using a mixture of nitrobenzene with 2,4-dinitrotoluene and 300 g of cyclohexanol with a conversion of nitrobenzene of 93.7% and 2,4-dinitrotoluene, the selectivity to cyclohexyl-N-phenylcarbamate is 91.3% and to dicyclohexyl-2,4-toluylenedicarbamate 59, 2%.

Industrial usability

The process according to the invention is applicable in the chemical industry, in particular in the production of organic intermediates.

Claims (1)

Process for preparing alkyl N-arylcarbamates and / or dialkyl N-aryldicarbamates with alkyls of 1 to 10, conversion of aromatic nitro compounds and / or dinitro compounds with aliphatic, cycloaliphatic or arylaliphatic alcohols having a carbon number of 1 to 10 and with an oxide at a temperature of 70 to 240 ° C and a pressure of 0.1 to 30 MPa, with the catalytic effect of sulfur and / or selenium and / or their compounds in an amount of 0.1 to 15 wt. %, based on the aromatic nitro compound or compounds, 0.1 to 15 wt. % cocatalyst, 0.1 to 14 wt. % vanadium pentoxide or a mixture of vanadium pentoxide and iron oxide as a promoter and 0.03 to 7 wt. oxygen and / or peroxide, characterized in that the catalyst is at least one oxide and / or hydroxide of the alkali metal oxides and / or at least one alcoholate of the alkali metal and earth alcoholates with an alkyl & carbon number