CZ9202006A3 - Process for preparing aryl urea and/or n,n' diaryl urea - Google Patents

Description

(57) A process for producing an aryl urea of the formula ArNHCONH 2 or Ν, Ν-diarylureas of the formula ArNHCONHAr in which Ar and Ar 'are the same or different and represent phenyl. alkyl- to dialkylphenyl with alkyl having 1 to 12 carbons, naphthyl, alkyl- to dialkylnaphthyl. It is carried out at 60 to 220 ^° C and a pressure of 0.2 to 30 MPa, so that ArNO2 after ^{A is} treated with carbon monoxide and ammonia or ArNH2 at a molar ratio of NH2: Ar'NO2 = 1 to 10: 1 with the addition of essential sulfur or S-compounds of mol.

t by weight of 34-80 g mol ^-1 and an aprotic or cycloaliphatic tertiary amines and / alebozlúčeniny di- to pentavalent vanadium .. s in an amount of 0.01 to 5% hmot./ArNO2.

The unconverted feedstock and catalyst system components are recirculated.

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A process for the preparation of aryl urea and / or NI of N-Si-SiP

Technical field

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The invention relates to a process for the preparation of aryl urea and / or N, N'-diaryl urea from starting nitroaromatics, carbon monoxide and ammonia or aromatic amines with the catalytic effect of technically available components of the catalyst system.

BACKGROUND OF THE INVENTION

US earlier known CBeilsteins Handbuch der orgamsener Chemie II, 12, p. 3252. Sprinqer-Verlag, Berlin (1956); Mitter W.

T. et al: Khimitskaya Soviet

2793 (1956);

Gosud. teach.

Krátkája izdateí. preparation

J. Am. Chem. Soc. 78, enciklopedija, p. 1165th

enciklopediya, Moscow (1961) 3

N, N-di-phenyl urea by heating aniline with urea at a temperature of about 170 ° C with Posgen to aniline as well as reducing nitrobenzene in the presence of iron pentacarbonyl. Also by oxidation with hydrogen peroxide as well as heating with sodium phenolate at about 200 ° C thiocarbanilide Phenyl isocyanate

Csilov E.A. et al. : Zur. obšč. chim. 18, 1060 (1948) 3, as well as by decomposing the adduct of phenyl isocyanate with sodium hydrosulfite CPetersen S .: Ann. 562,205 (1949) 3. However, these processes are complex, many by-products are eliminated, low yields are achieved and waste disposal is difficult.

Higher selectivity is obtained with carbonylation of aniline at a temperature of about 200 ° C and the presence of nickel or (1953) 3 as well as a carbon monoxide pressure of about 20 MPa at

W. et al. : Ann. 582 '. and aniline catalyzed by either propylene EPino P.

cobalt CReppe by carbonylation of octocarbonyl of double cobalt in the presence

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

(1952) 3 or acetylene EPino P. et al .: Ital. 31, 646 (1951) 3 at 150-250 ° C and

However, carbonylation of aniline is possible

et al., Chem. Ind. 34 Am. Chem. Soc - 74, 249 < Gazz. Chim. Ital. 81. pressure 20 to 50 MPa

Avg. 1975, 25/50, 140:

nitrobenzene and aniline are also catalyzed by mercury salts CTsuji J., Iwamoto N .: Jap. pat. 4096; 71, 12792 (1969) 3. Analogously, diPenyl urea derivatives similar to the tosgenation of aniline derivatives CKutepow D. F. et al .: Ž. obšč. chim. 30, 24S4 (1960) 1, as well as from aniline and carbonyl sulfide CHagelloch G.: Chem. Ber. 85, 258 (1958) 1, and in particular carbon dioxide CV. Brit. pat. 622955 (1949) 1 at elevated temperature and pressure. However, procedures are also complex and not very selective. However, N, N'-diphenyl urea can be prepared directly from nitrobenzene and carbon monoxide in the presence of an admixture of hydrogen or water at elevated temperature and pressure under the catalytic action of palladium and lewis acid compounds, with a selectivity of 70 to 88. CMacho, V. , Hudec J.Polievka M., FiladelPyova M.: Chem. A0 162837 (19751. Another method, yielding 77.7 N, N'-di-phenyl urea from a catalytic effect of palladium, rhodium and iridium chlorides, in addition also ferric chloride, and possibly octo-carbonyl of double cobalt at a temperature of 190 ° C and a pressure of 20 MPa CYamahara T. et al., Jap., Pat. 7, 234, 341 (1973); CA 78, 43167 (1973).

N- (3,4-Dichloro-phenyl) -N'-p-chloro-phenyl urea a

N- (p-chloro-phenyl) -N (p-tolylurea) CE European Pat. 225673 (1988). Also of interest here is the synthesis of N, N'-diPenylurea from nitrobenzene, carbonylsulfide, carbon monoxide and water with a selectivity of 65% and 35%. for aniline:

PhNO 2 + 6 CO + H ₃ 0 -> (PhNH) ₌ CO + 5 CO _e

CHARPER J, J .: J. Chem. Eng. Data 2, 21 (1976) 3. However, it requires a high carbonyl sulfide content. Ureas, which are interesting as intermediates for both pharmaceuticals and pesticides, are also investigated from the point of synthesis of amines and carbon dioxide CLurtak S., Lederer

P .: Chem. sheets 84, 673 by carbonylation of amines with oxide ((1990) 1, not only by reductive carbon monoxide but also by oxidative carbonylation of amines, in addition in the presence of oxygen:

RNH ₂

RNHa

WHAT

WHAT

1/2 0 ₂

-> (RNH) ₂ CO + H ₌

-> (RNH) ₂ + H ₂ 0 »frf86» aacs »vn«

CYosida T. et al. Tetrabedron Lett. 27, 3037 (1986); Reiter J.

et al., heterocycle. Chem. 6, 1751 (1988). However, the processes require the corresponding arylamines, whose preparation usually from the corresponding nitroaromatics is technically difficult.

The essence of the invention

According to the invention, a process for the production of aryl urea and / or N, N-diaryl urea of the formula ArNHCONHa and / or

ArNHCONHAr wherein Ar and Ar are as aiebo different, represents propenyl, alkyl dialkylPenyl to the alkyl carbon number of 1 to 12, naPtyl, alkyl and dialky1naPty1, at 60 to 220 ^* C and a pressure of 0.2 to 30 MPa uskutočrtuje by treating the aromatic nitro compound ArNO? with a gas containing carbon monoxide and ammonia and / or the aromatic amine Ar 1 NH ₂ at a molar ratio of ammonia and / or aromatic amine: aromatic nitro compound = 1 to 10: 1 with the aid of eleraentic 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 apical tertiary amine and / or an aprotic cyclic tertiary tertiary amine in an amount of 0.5 to 20 wt. and / or divalent to pentavalent vanadium compounds in an amount of 0.01-5% by weight, calculated on the aromatic nitro compound or nitro compounds, wherein the products and unconverted raw materials and the components of the catalytic system aromatic feedstocks are separated.

An advantage of the process of the present invention is an efficient catalyst system that consists of technically and raw material readily available components. Furthermore, the use of gases containing carbon monoxide can be utilized technically, without demanding pretreatment and purification. That is, the insensitivity of the catalytic system to the usual catalytic poisons. Last but not least, the process makes it possible to produce the necessary aryl ureas and N, N'-diaryl ureas with its Plexibility starting materials and catalyst system components, with high to complete conversion and selectivity.

The components of the catalyst system are aprotic tertiary aliphatic amines having a number of carbons in the alkyl range of 1 to 8 such as vanadium, vanadium, sodium, but trimethylamine, triethylamine, tripropylamine, triisopropylamine, tri-n-butylamine, triisobutylamine and the like. In case a protic target would be used. an amine such as methanolamine, although this would act as a component of the catalytic system, but moreover would competitively react with at least one hydroxyl group of the triethanolamine with the carbonylation product of the aromatic nitro compound, most likely with the intermediate nitrene.

cycloaliphatic tertiary amines; N-dialkyl cyclohexylamine, pyridine and its alkyl derivatives, N-alkylpyridines with alkyls of 1 to 4 carbons.

Among the divalent to pentavalent vanadium compounds, in particular, vanadium hydroxide, vanadium sulphate, vanadium oxychloride, vanadium sulfide, ammonium methanadate, potassium or metavanadate are among the most suitable ammonium metavanadate. The solvents usable in the reaction medium should be aprotic so that they do not compete competitively with carbonyl. These include dialkyl ethers, tetrahydrofuran, dioxane, aliphatic and aromatic hydrocarbons, dialkyl glycol ethers and the like.

An important component of the catalytic system is the sulfur, respectively. sulfur compounds having a molar mass of 34 to 80 gmol ^-x . Carbonyl sulphide and hydrogen sulphide are most effective, usually 17% by weight, calculated on the aromatic nitro compounds. The applied carbon monoxide need not be refined from the admixtures of sulfur and sulfur compounds. Conversely, the presence of carbonyl sulfide or hydrogen sulfide saves the need for deliberate addition to the carbonylation environment.

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

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

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

OHBBHWBISSSS ^ K '·' - ⁷ ? '.5

DETAILED DESCRIPTION OF THE INVENTION

Example 1

DOI to 1 and the costs of 'a rotary stainless steel is navaíi 50 After sealing the autoclave Eetee 1 carbon monoxide to a pressure of 14 bar the autoclave contents: a continuous rotáíf: for this to within ± 2 ^and C the autoclave was cooled, the product you are NN -difeny1 urea The conversion of nitrobenzene reaches selectivity to diPenyimurea 94

Example 2

The procedure is similar to the addition of 0 in the reaction medium. The conversion of nitrobenzene achieves selectivity to the N, NiPenyimo (ISO oor./min) autoclave from g of nitrobenzene, 150 g of aniline and hydrogen sulfide. Then it is led at room temperature. It is then heated to 150 ° C and held for 4 h. Then it is weighed, weighed, analyzed. Isolates 234-237 ^e C and 1Pormamia Foams. 22 ± 5 7. aniline S ± 3.

and on Foams1Pormamide 4 7 ..

in Example 1, only added to ammonium metavandate.

c 5 aniline 20 nu 95 7. a Foams 1 Pormamide

Example 3

Proceed as in the example

1, only 0.1 g of ammonium metavanadate NH4O5 and 5 triethylamine are added to the reaction medium. Conversion of nitrobenzene reaches 96 ± 4 7, aniline ± 4 7, and selectivity to N, N'-di-phenyl urea reaches 94 7 and to Foams 1 Pormamide 5 7.

Example 4

50 g of nitrobenzene, 150 aniline and triethylamines are weighed into the autoclave specified in Example 1. After the autoclave is closed, the carbon monoxide is brought to a pressure of 14 MPa. Thereafter, the autoclave is heated to a temperature of 150 ± with constant rotation and maintained at this temperature for 4 h. Nitrobenzene conversion reaches 24 7, aniline 10 7.

Foams 1Pormamide and pa selectivity

7 ..

on the

Example 5

The procedure is similar to that of Example 2 except that 2 g of hydrogen sulfide is added instead of 1 g. Thus, the catalytic system, respectively. a precursor in a basic medium form a NH _'S IN - H ₃ P. The conversion of nitrobenzene aosahuje 68 7 aniline and 18.2 X: the selectivity to diphenyl urea and 94 oosanuje 7 and Fen y 1 Formamide 3 X.

example

The procedure is similar to that of Example 4, except that 4 g of triisobut / lamin are added to increase the alkalinity of the environment.

, aniline 30 ± 27;

enyl Formamide 5 7. but at rsahraden 4 g conversion of nitrooenzene

Conversion of nitrobenzene reaches 99 ± 1 selectivity to diophenyl urea 94X and to otherwise similar conditions, triisobutyl amine 0.5 g sodium methoxide reaches 27 7. and aniline 7 X, with selectivity to diPhenyl urea 93 X and Pheny1Formamide 3 ·, 3 X.

Example 7

The procedure is similar to that of Example 5 except that 2 g of 3-methylpyridine and 2 g of N-dimethylcyclohexylamine are added to increase the alkalinity of the medium. Nitrobenzene conversion reaches 96 ± 4 X, aniline 30 and 3 X: selectivity to diphenylurea is 95 7. and

Phenyl Formamide 3.5X.

Example 8

The procedure is similar to that in Example 3 except that 0.1 g of vanadium pentoxide is used instead of 0.1 g of ammonium metavanadate. The conversion of nitrobenzene is 97%, the aniline 26%; the selectivity to N, N'-diphenylurea is 93.2 X and to the phenylformamide 3.9 X.

Example 9

The procedure is similar to ammonium metavanadate as in Example 3 except that vanadium sulphide is added instead of 0.1 g. Nitrobenzene conversion also reaches 98%, aniline 30.2%; the selectivity to N, N'-di-phenyimurea is 95% and to the phenyl 1 formamide 4X.

* 7

Example 10

Procedure 5a similar to NPUVOs, use 0.04 g of potassium tub bath, 0.01 g of vanadium hydroxide bath. Conversion of nitrobenzene selectivity to α-Foams and urea * Example 3, only instead of 0.1 g of diuretic acid, 0.02 g of gypsum metavanadate and 0.05 g of oxychloride are complete. aniline 32 ’/. and

Example 11

In a rotary autoclave of stainless steel, ointment 0.5 dra ³ , characterized in the example of nitrobenzene, 50 g dioxane, 5 g autoclave 30 g dry ammonia and containing impurities 1.4 7 vol. lead, 0.1 7 vol. sulfones of sulfide, r

0,3 7. vol. oxygen and 1.2 7 vol. dpsíka. With constant rotation

1, weigh out 50 g of sulfur powder and, after closing, the monolithic oxide to a pressure of 10 MPa.

pte 90 ° C for 4 h. Conversion; selectivity to N, N'-biphenylcarbonylation is carried out at a nitrobenzene temperature of 69 ± 47.

urea 89 7. and aniline 9 7 ..

Example i2

The procedure is similar to Example 11 except that it is added to the reaction medium as a component of the catalyst system

0.05 g of ammonium metavanadate and nitrobenzene conversion reaches phenyl urea of 90%.

the reaction temperature is 150 ± 2 ° C.

99.5 7. and selectivity in Example 12, using only the g of the catalyst system

Example 13

The procedure is similar to that in elemental sulfur being as a composer

Weigh 0,7 g hydrogen sulphide and weigh 50 g instead of 30 g ammonia. conversion is complete; selectivity to urea bitches 67 7. and aniline 11 7.

Example 14

Progress of nitrobenzene is achieved 97 ± 3 toluidine 9 7.

is similar to carbonylated 50

7. and selectivity v

g in Example 13, only instead of 50 g of 4-nitrotoiuene. Its conversion to 4-methylphenyl urea 69 7. and to

Example 15

Proceed similar to nitrobenzene with carbonylated conversion of about 93 ± phenyla urea 86 7.

as in Example 1-3, instead of 50 g of 50 q of 1-nitro-3-isooctyl benzene. his

7. and selectivity to 3-iso-phenyldioxane

Example 16

The procedure is similar to that of Example 11 except that tetrahydrofuran is also used instead of 5 g of aprotic solvent, 2 g of carbonyl sulphide with 0.5 g of dimethyidisulphide and in addition lutidine and 0.01 g of vanadium oxide are used instead of 5 g of sulfur.

The conversion of nitrooenzene reaches 89.7%; isolated phenylmcurea extract with heat *

143 ^e C is 73

Aprotic Dissolve and Unconverted:

both nitrobenzene and ammonia are used in the next experiment.

Example 17

The procedure is similar to that in Example 16, except that 50 g of dimethyl glycol ether is used instead of ου g of tetrahydrofuran and 0.01 g of vanadium sulphide and 0.044 g of vanadium oxide are used instead of υ, υΐ q of vanadium oxide. Nitrobenzene co-conversion reaches 93 7. and isolated phenyl urea yield 79

Example 18

The procedure is similar to that of Example 17 except that 50 g of 1,3-trimethyl-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 dimethylphenyl urea yield is 82%.

Example 19

The procedure is similar to that of Example 18 except that 50 g of 1-isooctyl-4-nitrobenzene is used instead of 50 g of dimethylnitrobenzene. Its co-conversion reaches 91 7, and the selectivity to 1-isooctylphenyl 1 urea 83 7. and 1-isooctyl-4-aminobenzene 7.5 7.

IN

UířViiíi · Prikisa uO

An autoclave of a volume of 0.5 OM ^3, cnarakterizovaného in Example 1. Weigh 50 niírobenzenu d, 150 g of aniline and components. The carbon monoxide is heated to room temperature at 14 MPa at room temperature. Mto 2S constantly. ·; The vacuum is rotated and this coffee is heated to a temperature of ± 2 = 2 2 and maintained during pressure.

Speed comparison of carbones!

The carbonylation of nitrobenzene, depending on the catalyst composition of 150 ° C and at this time, with a 4 ha decrease in the refrigeration experiments of the litical system, is shown in Table 1 and

The legend to FIG. 1 shows tab. 1, wherein the curve numbers are identical to the experiment numbers.

Tabu! Ka

Number Čokusu Catalyst system junction (i n * rpm / nitronenien NH4VD3 H2S CH3OM2 Kor n ber - loyal tro yen £ Z3 --- selectivity to Penyl- to Penylioc roraatide ίϊΐ íl] 1 ςι 4 5 0.2 2 10 0.0 0.2 2 0.0 1.0 0.2 4 0.0 0.0 0.2 2 10.0 0.0 0.0 2 10.0 0.0 19.5 26, 6 68.2 99 99 83 1,9 39 1,0 90,2 3,2 92.1 4,3 91.9 3.3

Industrial use of the process

Thus, honey is also attractive to urea diarrhea suitable for production; and chemical production with various arylsinsyl ureas and diarylureas as a pharmaceutical industry and especially with aryl substituents and which by other processes can only be technically produced by multi-step syntheses and processes.

Claims (2)

Patent claims A process for the preparation of aryl urea and / or N, N'-diaryl urea of the general formula ArNHCQNH = and / or ArNHCONHAr 'in which Ar and Ar' are the same or different and represent -Phenyl, alkyl- to dialkylPenyl with alkyls of 1 to 12. Naphthyl, alkyl to di-naphthyl 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 aromatic aroin Ar'NB p at the molar ratio ammonia and / or aromatic amine: aromatic nitro compound = 1 to 10: 1 with a multiplication of elemental n. = amine and / or aoroticeno amine in amounts of 0.3 to 20). Sulfur and / or sulfur compounds having a gmol ^-1 in an amount of 0.1 to aliphatic tertiary cycloaliphatic tertiary moles. “I! wt. and / or divalent to pentavalent vanadium compounds in an amount of 0.01 to 5% by weight, based on the aromatic nitro compound or aromatic nitro compounds, the products and unconverted starting materials and the components of the catalyst system components being separated. The process according to claim 1, characterized in that the aprotic tertiary aliphatic amines are trialkylamines having an alkyl number of 1 to 8, preferably triethylamine. The process according to claim 1 or 2, wherein the aprotic cycloaliphatic tertiary amine is N-alkylcycloamine, N-dialkylcyclohexylamine, pyridine, methylpyridines, dimethylpyridines, N-alkylpyridine, preferably N-dimethycyclohexylamine. The process according to claims 1 to 3, characterized in that at least one divalent to pentavalent vanadium compound. is selected from vanadium hydroxide, vanadium oxide, vanadium oxychloride, vanadium sulphide, vanadium sulphide, vanadium oxide and ammonium metavanadate. The process according to claims 1 to 4, characterized in that the carbonylation is carried out in the presence of an organic aprotic solvent, preferably dioxane.