SK279487B6 - Method of alkyl-n-arylcarbamate and/or dialkyl-n-aryldicarbamate preparation - 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 production of alkyl N-arylcarbamates and dialkyl N-aryl dicarbamates and their derivatives by the phosgene-free route, using technically readily available raw materials and catalyst system components.

BACKGROUND OF THE INVENTION

Known / Jan Ju B., Nefedov B.K .: Sintezy na osnove oksida ugleroda, p. 130. "Khimija" Moscow (1987); Lapidus A.Ľ. and others: Izv. AN USSR ser. Chim. 1981,133; NSC Pat. No. 1,901,202 / catalytic carbonylation of aromatic nitro compounds with carbon monoxide in an alcoholic environment to alkyl-Narylcarbamates 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 effect of the PdCl2-pyridine FeCl3 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% PCI / Al 2 O 3) activated with ferric chloride by reductive carbonylation of 2,4-dinitrotoluene in ethanol, diethyl 2,4-toluylenedicarbamate / patent application no. NSR 2,603,574; 85, 123, 648 (1976); Manov-Juvenskij, Nefedov, B.K .: Uspechi Chim. 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 their compounds, aromatic amino compounds, urea compounds, tertiary 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. Ex. chim. 57, 360 (1984); Radoškin V.A. and others: ibid, p. In turn, the inhibitory effect of vanadium pentoxide on nitrobenzene carbonylation 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 within 2 h. A mixture of vanadium pentoxide and iron oxide as well as iron oxide itself also had a retarding effect. Of the sulfur compounds, thiourea and polysulfides have proved to be the most suitable. 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 wt. to a carbonylated aromatic nitro compound.

SUMMARY OF THE INVENTION

According to the present invention, a process for the preparation of alkyl N-arylcarbamates and / or dialkyl N-aryl dicarbamates having an alkyl number of 1 to 10 by converting aromatic nitro compounds and / or dinitro compounds with aliphatic, cycloallatic or arylaliphatic alcohols having 1 to 10 carbon atoms. 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% by weight, calculated on the aromatic nitro compound or compounds; %, 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, is carried out 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 according to the invention is the higher rate of reductive carbonylation caused mainly by the higher activity of the cocatalyst based on alcoholates or hydroxides of alkali metals and soils compared to the alkali salts of carboxylic acids C ₂ to C 8 and thus considerably lower consumption of cocatalyst. 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 also unrefined carbon monoxide, which may contain inert gases, but also hydrogen sulfide, carbonylsulfide and oxygen admixtures, can 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 or soils are important cocatalysts, with alkali metal oxides and hydroxides being more effective, but especially alkali metal alcoholates with aliphatic alcohols having a carbon number of 1-5. C5. They may also be combined with the alkali salts of C 1 -C 8 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.

SK 279487 Β6

Among the alcohols, these are mainly lower aliphatic and cycloaliphatic alcohols, as the rate of reductive carbonylation decreases sharply as the length of the alkyl alcohol increases. More preferably, straight chain alcohols are preferable, secondary are less suitable, and tertiary alcohols are the slowest to react. Most suitable include methanol, anhydrous ethanol, n-propanol, n-butanol, 2-propanol, isobutanol, n-pentanol, noctanol, decanol and 2-ethylhexanol. Less suitable but useful are cycloaliphatic and arylaliphatic alcohols such as cyclohexanol, benzyl alcohol and the like. Alkyls in this invention also 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 1-day electrical resistance winding, the amount of methanol being dependent on the amount of methanolic sodium methoxide solution added as a cocatalyst at a concentration of 10% by weight. a total of 200 g of methanol is applied. In addition, 10 g of elemental sulfur powder, 1.2 g of vanadium pentoxide and various amounts of sodium methanolate (with horse, sodium methanolate 10% by weight and horse. H2O = 5.1% by weight) or sodium acetate and in one case solid powdered powder are added. 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. It is maintained at this temperature under constant rotation for 4 h at 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

Pridwý koanpMMt katalytieiého ay «lé« · Conversion • ttr * beni4mi (¾) SalcktMt * (%) for: kind of naebtv · (% taBota.y MtnbeuxAU drob meobtvo (% hawttuy / charcoal · / rtyl-Nťeeyikarbaaáf • mu · CHjCOONi 10 - - 99.5 74.3 15.5 CHjCOONi 5 - - 34.0 74.5 15.1 CHjCOONa 5.0 CH, she 3.35 100 74.7 15.9 CH3COON1 7.3 CH, ON * 1.9 100 71.6 12.8 CH ₃ COONi 0.0 CH, she 7.7 100 78.9 19.8 CHjCOON · 0.0 CHjON * 4.4 98.9 75.5 21.2 CHjCOONi 0.0 CHjON * 1.0 1O0 86.4 6.8 CHjCOONi 0.0 CHjON * 0.7 1O0 84.6 10.7 CHjCOONa 0.0 CH3ON1 0.5 76.3 85.3 9.1 CHjCOONi 0.0 CHjON a 0.1 29.4 ?in.. 8.2 CHjOK 0.7 100 »81 10.6 NaOH 1.5 99.9 82.3 14.7 0 0 * 1.0 NaOH 0.5 97.3 86.7 9.1 MxŕOHh 1.3 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 lack of selectivity to methyl-N-phenylcarbamate and aniline up to 100% is mainly methylformate.

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

AlMboi R-Maiý koepMeat katalytfcMb · ipcte · Conversion of zombies PM MektMta • and aUcyVNfeeyl · ktfbaaaat (H) dragon toMtBj ttree * * OBz4a | dragon BMIatva (% ttBMa / akroOeaaaa) radmoi 200 CHONa (CHjhCCNa OJ oj 9a ox & l'N * feayttart · mátali a-pcntuol 300 CMiCHrCHzCHiONB (CH _S), CHOK OJ 0.5 97 peat (N-phenyl) at 192) n Okuda 300 (CH 3 CH 2 Cl 2 -Ca (CH 3 CO 2 0.4 o, t % ofayNN-fcrytaittakt ( «) decanol 400 (CHjJjCHOK 1.5 at Allyl-N fcnyUcutaaiái (U) ňonyiíeeol 400 (CHjCHjOJjC »OWCHjhCltyON» M L0 93 N-thyaminate (83) b ““ ¹ 300 CHXCHiijCKjON · MííOHJi 0.5 OJ 99 hexyl-N-phosphonic acid (92) cyUehcxa * nol 300 CH, ONa (CHihCHWa KOH OJ OJ OJ S4 cyidofcexyi-N-ľcnyfarba 'rt (88) cyldoheryl ethanol 300 CH, CH 2 Na tCH x H CHOK NaOH 0.5 0.4 0.1 92 nkMnyl · ajt-i + fayt tnhiBI <W) oyclobexyl-ethanol 300 NaOH KOH OJ UJ $ 4 TTN cUaol 200 NaOH KOH ĹKM 0.3 O.5 OH in 100

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 1-N-naphthyl 1-carbamate 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) reaches 74.9%.

Example 5

The procedure is analogous to Example 3 except that 300 g of n-butanol is 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 reaches 97% and the selectivity to octyl N-naphthylcarbamate is 92%.

Example 6

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

SK 279487 Β6

The conversion of 4-chloro-mitobenzene was 69.2% and the selectivity to octyl-N- (4-chlorophenyl) carbamate was 90.3%.

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 reached 87.3% and the selectivity to benzyl N-phenylcarbamate 90.5%.

Example 8

The procedure is similar to Example 1 except that the reaction temperature is 170 + 3 ° C and the autoclave charge 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 except that 100 g of nitrobenzene, 200 g of methanol, 5 g of sulfur, 10 g of sodium acetate, 1.2 g of vanadium pentoxide are 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 identical conditions, but using only 30 g 2,4-dinitrotoluene and 30 g nitrobenzene instead of 50 g 2,4-dinitrotoluene, dinitrotoluene conversion reaches 98.7%, nitrobenzene 99% 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 instead of 200 g of methanol, 300 g of cyclohexanol are applied 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)

A process for the preparation of alkyl N-arylcarbamates and / or dialkyl N-aryldicarbamates with alkyls of 1 to 10, conversion of aromatic nitro and / or dinitro compounds with aliphatic, cycloaliphatic or arylaliphatic alcohols having a carbon number of 1 to 10 and carbon monoxide 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 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 having an alkyl number of 1 to 5.