SK200692A3 - Method of production of arylurea and/or n,n'-diarylurea - Google Patents

Description

Phenol sodium

Phenylisocyanate at a temperature of about

A. et al.

Žur. obšč. chim.

18, 1060 (1948) 3, as well as by decomposition of the adduct

Phenylisocyanate sodium hydrosulphite with sodium water CPetersen S

Ann. 562, 205 (1949)]. However, these processes are complex, many by-products are eliminated, yields are achieved and waste disposal is difficult

Higher selectivity is achieved with aniline carbonylation at an ambient temperature of 200 ° C and a carbon monoxide pressure of about 20 MPa in the presence of nickel or cobalt EReppe

W. et (1953) 1, as well as aniline carbonylated catalyzed by octocarbonyl di-cobalt in the presence of propylene buc [Pino P.

et al. Chem. Ind. Am. Chem. Soc • 74, Gä ľľ ľ. Chim. Ital. pressure 20 to 50

MPa

34, 511 (1952) 3, styrene CNatta G. et al .: J.

2496 (1952) 3 or acetylene CPino P. et al. :

81, 646 (1951) 3 at 150-250 ° C and

However, carbonylation of aniline can also be xatalyzed by the mercury salts of CTsuji J., Iwamoto N .: Jap. pat. 4096; 71, 12792 (1969). Analogously, d-i-phenyl urea derivatives are similarly formed as well as by phosgenation of aniline derivatives Cutepow D.F. et al .: 1st Obst. chim. 30, 2484 (1960) 1, as well as from aniline and carbonyl sulfide L. Hagelloch G .: Chem. Ber. 83. 258 (1958) 1, and in particular CO. Brit. pat. <522955 (1949) 1 at elevated temperature and pressure. However, procedures are also complex and not very selective. However, N, N'-di-phenyl urea can be prepared directly from nitrobenzene and carbon monoxide in the presence of hydrogen or water admixtures at elevated temperature and pressure under the catalytic action of the palladium and lewis acid compounds, with selectivities of 70-88%. CMacho, V., Hudec

J., Polievka M., Philadelphia M.: Chem. Avg. 25/50,140 (1975);

MS. AD 162837 (19751. Another method, yielding 77.7 N, N from nitrobenzene and aniline under the catalytic action of palladium, rhodium and iridium chlorides, in addition also of ferric chloride and possibly also of octocarbonyl of double cobalt at a temperature of 190 ° C and a pressure of more than 20 MPa. diphenylureas CYamahara T. et al .: Japanese Pat., 7, 234, 341 (1973); CA 78, 43167 (1973) 1.

N- (3,4-Dichloro-phenyl) -N'-β-C-chloro-phenyl urea and

N- (p-chlorophenyl) -N (p-tolylurea) CE European Pat. 225673 (1988). Of interest in this respect is also the synthesis of N, N'-di-urea ureas from nitrobenzene, carbonylsulfide, carbon monoxide and water with selectivity of 65 7 and 35 7 to aniline:

PhNO ₂ + 6 CO + H ₂ O ^: > (PhNH) ₂ CO + 5 CO ₂ [Harper JJ: J. Chem. Eng. Data 2, 21 (1976) 1. However, it requires a high carbonyl sulfide content. In addition, ureas which are of interest as intermediates for both drugs and pesticides are also investigated for synthesis from amines and carbon dioxide CLurtak S., Lederer P .: Chem. sheets 84, 673 (1990) 1, not only by reductive carbonylation of amines with carbon monoxide, but also by oxidative carbonylation of amines, in addition in the presence of oxygen:

RNH ₂ + CO + 1/2 0 ₂ > (RNH) ₂ C0-> (RNH) ₂ + · h ₂ + h ₂ orosida T. et al .: Tetrahedron Lett. 27, 3037 (1986); Feiter J. et al. : Heterocycle. Chem. 6, 1751 (1988). However, the processes require the corresponding arylamines, which are usually technically difficult to prepare from the corresponding nitroaromatics.

SUMMARY OF THE INVENTION

According to the present invention, a process for producing aryl urea and / or

N, N -diarylureas.

ArNHC0NH of formula _2, and / or

ArNHCONHAr ‘in which Ar and Ar 'are the same or different and the image is

Phenyl, alkyl to dialkylene of phenyl 1 with alkyls of 1 to 10 carbon atoms

12, naphthyl alkyl of 1 k. y 1 to f t y 1 at 60 <= »r

220 [deg.] C. and a pressure of 0.2 to 0.2

The MPa is carried out by treating the aromatic nitro compound ArNQ with a gas containing carbon monoxide and ammonia and / or the aromatic amine Ar 'NH ₃ at a molar ratio of ammonia and / or aromatic amine: aromatic nitro compound = až to 10: 1 with the interaction of elemental sulfur and / or sulfur compounds having a molar mass of 34 to 80 gmol ^-1 in an amount of 0.1 to 10% by weight, and an aprotic aliphatic tertiary amine and / or an aprotic cycloaliphatic tertiary amine in an amount of 0.5 to 20% by weight. and / or compounds of two to five years of vanadium in an amount of 0.01 to 5% by weight, calculated on the aromatic or aromatic compounds, wherein the products and the unconverted starting materials and the components of the catalyst system are separated.

An advantage of the process according to the invention is an efficient catalytic system consisting of technically and raw materials readily available components. Furthermore, the possibility of using carbon monoxide-containing gases technically, without the need for pretreatment and refining. Thus, the insensitivity of the catalyst system to conventional catalytic poisons. Last but not least, the process makes it possible to produce the necessary aryl ureas and N, N * -diaryl ureas by the flexibility of the starting materials and components of the catalyst system, with high to complete conversion and selectivity.

The components of the catalytic system are aprotic tertiary aliphatic amines having a carbon number of 1 to 8 such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tri-n-butylamine, triisobutylamine and the like. Should a protic target be used. an amine, such as three ethanolamine, would act as a component of the catalyst system, but moreover would competitively react with at least one hydroxyl group of triethanolamine with an intermediate carbonylation of the aromatic nitro compound, most likely with intermediate nitrene.

Zero-tertiary tertiary amines are particularly suitable

Alkyl -alkyl-, respectively. N-dialkyl cyclohexylamines, pyridine and its alkyl derivatives, N-alkylpyridines with alkyls having a carbon number of 1 to 4.

Among the divalent to pentavalent vanadium compounds, in particular, vanadium hydroxide, vanadium sulphate, vanadium oxide, vanadium oxychloride, vanadium sulphate, vanadium oxide, ammonium metanadate, potassium or sodium methanadate are preferred, but ammonium methate is most preferred. The solvents usable in the reaction medium should be aprotic so that they do not compete competitively with carbonylation. These include other ethers, tetrahydro-furan, dioxane, aliphatic and aromatic hydrocarbons, dialkyl glycol ethers and the like.

An important component of the catalytic system is sulfur, resp.

sulfur compounds having a molar mass of 34 to gmol ^-1 .

More particularly, carbonyl sulfide and hydrogen sulphide are usually sufficient

7th

%, calculated on aromatic nitro compounds. The applied carbon monoxide need not be refined from the admixtures of sulfur and sulfur compounds.

Conversely, the presence of carbonyl sulphide or hydrogen sulfide saves their need for deliberate addition to the carbonylation environment.

Unconverted reactants as well as components of the catalytic system should be recirculated.

The process of the invention may be carried out continuously, semi-continuously or 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

50 liters of nitrobenzene, 150 g of aniline are weighed into a half-liter rotary (180 rpm) stainless steel and one more hydrogen sulphide is closed to close the autoclave. It is then brought to a pressure of 14

MF'a at room temperature. Nato se

QContinuous rotation of the autoclave is heated to 150 ° C at this accuracy of ± 0 ° C for 4 h. Then the autoclave is cooled and the product is removed, weighed, analyzed. The N, N-di-phenyl urea is isolated

t. t.

234 to C and phen / l form.

nitrobenzene conversion reaches

7. The aniline has a selectivity to diphenylurea 94 and to beny 1 form m d d 4 7.

Example 2

The procedure is analogous to Example 1 except that 0.1 g is added to the reaction medium

Nitrobenzene conversion reaches 60 ± ammonium metavandate.

7. aniline 20 ± 47 7 N, N-α-phenyl urea -activity

7. and phenyl form m 32 32.

Example 1

The procedure of Example 1, but in addition, the reaction medium was added 0.1 g of ammonium metavanadate Ichnja _ΝΗ Λ ₃ and 00 5 q triethylamine. The conversion of nitrobenzene reaches 96 ± 4 7, aniline ± 4 7, and the selectivity to N, N'-diphenylurea reaches 94 7 and to phenylenediamine 5 7.

Example 4

50 g of nitrobenzene, 150 q of aniline and 5 Q of triethylamine are weighed into the autoclave specified in Example 1. After the autoclave is closed, the carbon monoxide is brought to a pressure of 14 MF'a. The autoclave is then heated to 150 ± 2 ° C with constant rotation and held for 4 h. The conversion of nitrobenzene reaches 24 7, aniline 10 7, and sectivity to diphenyl urea 89 7 and to biphenyl formamide 8 7.

- á

Example 5

The procedure is analogous to Example 2 except that 2 g of hydrogen sulfide is added instead of 1 g. Thus, the catalytic system, respectively. the Drekurzor in a basic medium consisting of NH 'VO ₃ - _H2S Nitrobenzene conversion reached 68 7, 18.2, and an aniline 7 .; the selectivity to the aryl phenyl urea reaches 94 7 and to the phenyl 1-formamide 3 7.

Example 6

The procedure is analogous to Example 5, except that 4 g of triisobut 1 amine are added to increase the alkalinity of the environment. Nitrobenzene conversion is 99 ± 17.7, aniline 30 ± 27; selectivity for di-pheny1 urea 94 7. and for pheny1 Kormami d 5 71.

However, under otherwise similar conditions, but substituting 0.5 g of sodium methoxide for 4 g of tris-1-amine, the conversion of nitrobenzene reaches 27 7 and aniline 7 7, with selectivity to urea diphenylene 93 7 and 1formamide 3,3 7 ..

Example 7

The procedure is analogous to Example 5 except that 2 g of 3-methylpyridine and 2 g of N-dimethylcyclohexylamine are added to increase the alkalinity of the medium. The nitrobenzene conversion is 96 ± 4%, the aniline is 30 ± 3,7; the selectivity to the d-i-phenyl urea is 95 7. a

Pen y 1 f or m id 3.5 7 ..

Example 8

The procedure is analogous to Example 3 except that 0.1 g of vanadium pentoxide is used instead of 0.1 g of ammonium metavanadate. Nitrobenzene conversion reaches 97%, aniline 26%; selectivity to N, N'-diphenylurea is 93.2% and to phenylformamide 3.9.7.

Example 9

The procedure is analogous to Example 3, except that vanadium sulfide is added instead of 0.1 g of ammonium methanate. Nitrobenzene conversion also reaches 98%, aniline 30.2%; selectivity to

The N, N-di-urea bitches reach 95% and for the phenylformamide 4 7.

Example 10

The procedure is as in Example 3 was used instead of L, 1 g NH _{3, and} V0 is used 0.04 g of vanadium pentoxide, 0.02 g of potassium metavanadate, 0.01 g of caustic hexanoate and 0.05 g of vanadium oxychloride Icnet. Nitrobenzene conversion is complete. aniline 32 7. and selectivity to di Peny 1 urea 95.2 7.

Example 11

Weigh 50 g of nitrobenzene, 50 g of dioxane, 5 g of powdered sulfur and, after closing the autoclave, 30 g of dry ammonia and carbon monoxide to a pressure of 10 MPa, into a rotary stainless steel autoclave of 0.5 dm ³ , as described in Example 1. admixture 1,4 7. vol. hydrogen, 0.1 7 vol. 1sulPidu carbones,

0,3 7. vol. Oxygen and 1,2 carbonylation carried out when the trobenzene reaches 68 temperature of 90 ° C for 4 h. conversion

7 .; selectivity to N, N'-d iPenylurea 89

7. and aniline

7th

Example 12

The procedure is similar to that of Example 11, except that in addition, the reaction medium is added as a component of the catalyst system.

0.05 g of ammonium metavanadate and the reaction temperature is 150 ± ° C

Nitrobenzene conversion reaches

99.5

7. and selectivity to

Foams 1 urine 90 90.

Example 13

The procedure is analogous to Example 12, except that elemental sulfur is used as a component of the catalyst system

Weigh 0,7 g hydrogen sulphide and weigh 50 g instead of 30 g ammonia. Conversion is complete; selectivity to Peny 1 urea 87 7. and aniline 11 7.

Example 14 is similar to carbonylation 50

7. and selectivity

Progress of nitrobenzene is achieved 97 + 3 t o i d i n 9 7.

in Example 13, only instead of 50 g of 4-nitrotoluene. Its conversion to 4-methyl Peny 1 urea 89 7 and to

Example 1

I

The procedure is similar to nitrobenzene and carbonylated g of 1-nitro-3-isooctylbenzene is carbonylated. his

7. and selectivity to 3-isooctylPenyl urea

7th

Example 16

The procedure is analogous to Example 11, except that 50 g of tetrahydrofuran is used instead of 50 g of dioxane as aprotic solvent, 2 g of carbonyl-1-sulfide is used instead of 5 g of sulfur.

The lutide of tin achieves dimethyldisulphide in addition to 30 g of ammonia and 3 g of vanadium. Conversion of nitrobenzene and 0.01 g of oxide

7 .; yield of isolated melting point phenyl urea

The aprotic solvent and the unconverted nitrobenzene and ammonia are used in the next experiment.

143 “C is 73

7th

Example 17

The procedure is analogous to Example 16, except for 50 g and &gt;.

tetrahydroPuran is used 50 g of dimethyl glycol ether and 0.01 g of vanadium oxide is used instead of 0.01 g of vanadium sulphide and 0.044 g of vanadium oxide. Nitrobenzene conversion reaches 93% and isolated Penylurea yield 79%.

Example 18

The procedure is analogous to Example 17 except that 50 g of 1,3-dimethyl-5-nitrobenzene is used instead of 50 g of nitrobenzene and the temperature instead of 90 ° C is 120 ° C. The conversion of 1,3-dimethyl-5-nitrobenzene is 98% and the yield of the foam is 1 foam.

Example 19

The procedure is analogous to Example 18 except that 50 g of 1-isooctyl-4-nitrobenzene is used instead of 50 g of dimethylnitrobenzene.

Its conversion reaches 91 7. and selectivity to 1-isooctyl 1 Penylurea 83 7. and 1-isooctyl -4-aminobenzene 7.5 7.

Frí k 1 ad

In a <7 autoclave of 0.5 dm &^lt; ^{1 &gt};, characterized by the charge of ign itrobenzene, 150 g of aluminum and the system.

The carbon monoxide is then pressurized at room temperature in the example of the room component

Bar. Then, the car is heated to 150 ° C at room temperature.

maintained at 4 ° C for 4 h and the pressure drop is recorded.

Carbonylation rates of experiments 1 to carbonylation were compared

11 of the system is shown in Table 1 and FIG. First

Fig. 1 shows tab. 1, wherein the curve numbers are identical to the experiment numbers.

Legendu k

Table 1

The attempt number Composition of catalytic system (X haot./nitrobenzene) Nitrobenzene conversion iX1 selectivity to phenylalanine [11 to phenylforaaaid II1 NH ₄ VO ₃ HjS (C >H ₉ ) ₃ N CHjONa 1 0.2 2 10 0.0 19.5 88 1.9 2 0.2 2 0.0 1.0 26.6 89 1.0 3 0.2 4 0.0 0.0 68.2 90.2 3.2 4 0.2 2 10,0 0.0 99 92.1 4.3 5 0.0 2 10,0 0.0 99 91.9 3.3 --------------!

Industrial applicability of the process

The process is suitable for the production of aryl ureas and diaryl ureas as intermediates in the chemical and pharmaceutical industries, and is particularly attractive for the production of aryl ureas with substituents on aryl and diaryl ureas with various aryl, which by other processes can only be technically produced by multi-step syntheses and processes.

7 ^{b <} Idoc

Claims (3)

Patent claims A process for the production of aryl urea and / or N, N'-diaryl urea, of the general formula ArNHCONH ₂ and / or ArNHCQNHAr ', in which Ar and Ar' are the same or different and represent phenyl, alkyl- to dialkylphenyl with alkali counts of 1 to 12, naphthyl, alkyl to dialkynaphthyl, at a temperature of 60 to 220 ° C; and. A pressure of 0.2 to 30 MPa, characterized in that the aromatic nitro compound ArNO ₂ is treated with a gas containing carbon monoxide and ammonia and / or an aromatic amine Ar 1 NH ₌ at a molar ratio ammonia and / or aromatic amine: aromatic nitro compound 1 to 10 and the interaction of elemental sulfur and / or sulfur compound having a molar mass of 34 to 80 gmol ^-1 in an amount of 0.1 to 10 10 7. materials. and aorotic and tertiary tertiary amine and / or tertiary amine and / or tertiary cycloaliphatic tertiary amine 0, o to 20 7th %, and / or divalent to pentavalent vanadium compounds in an amount of 0.01-5% by weight, calculated on the aromatic nitro compound or aromatic nitro compounds, the products of the unconverted starting material and the components of the catalytic system being separated Production method according to claim 1, characterized in that the aprotic tertiary aliphatic amines are trialkylamines having an alkyl number of 1 to 5 carbon atoms. 8, preferably triethylamine. The process of claim 1 wherein the aprotic cycloaliphatic tertiary amine is N-alkylcycloamine, N-dialkylcyclohexylamine, pyridine, methylpyridines, dimethylpyridines, N-alkylpyridine, preferably N-dimethylcyclohexylamine. The process according to claims 1 to 3, wherein the at least one divalent to pentavalent vanadium compound is selected from vanadium hydroxide, vanadium oxide, vanadium oxychloride, vanadium sulfide, vanadium sulfide, vanadium oxide and ammonium metavanadate. Method according to one of Claims 1 to 4, characterized in that the carbonylation is carried out in the presence of an organic aprotic solvent, preferably dioxane.