DE3133794A1 - Process for the preparation of n-aryl-n'-(mono-or disubstiuted)-urea derivatives - Google Patents

Description

D ?: Stir. · "· ^ _ ■■ - ^;

_r -. _r ^F / r / · ■ '· "■ ■ · ν'" - ·. PCT / HU81 / 03003

Ku .. ·.: ■ :: ■ · ■ '· ■■■■■ -'-' '5 /, 3133794

YERPAHREN FOR THE PRODUCTION OF N '- (MONO- OR DISUBSTI-TUIERFEN; N-ARYL HAENSTOPF DERIVATIVES

The invention relates to a new traversing · * "or the production of N'-mono- or dieubetituierten ϊ-Ajryl-harnetoff derivatives of the general Pormel (I) _t

R ¹

Aryl -NH-CO-N (I)

X ²

Aryl is an optionally substituted phenyl group is and

1 2

£ and R each for an optionally substituted alkyl, cycloalkyl, alkoxy or phenyl group stand or

12th

R and R together with the neighboring Sticketoffetoa

form a nitrogen-containing heterocyclic which contains a further heteroatom. can or

one of R and R can also stand for hydrogen,

1 2

with the proviso that when one of R and R represents an optionally substituted phenyl group, because others only have one hydrogen atom or one if necessary substituted alkyl or alkoxy group can"

33216-3699

The phenyl group represented by "aryl" may preferably have 1 or more halogen atom (s), nitro group (s), lower alkyl group (η), lower alkoxy group (s) , lower trihaloalkyl group (s), lower alkylthio group (s), as optional substituents ) or a phenoxy group © , which is optionally substituted by the groups listed in this paragraph.

12th

R and R can be used as an alkyl or alkoxy group

preferably 1 to ^ - contain carbon atoms, while

1 2

rend the cyoloalkyl groups represented by R and R preferably contain 5 to 8 carbon atoms. These groups can optionally have, for example, the following substituents : a hydroxyl group, carboxy group, alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl group, substituted Phe-

1 2

nyl group or heteroaryl group. Of the nitrogen-containing heterocyclic groups represented by RRN-

the morpholino group is preferred. The compounds of the general formula (I)

are biologically active or can be converted into biologically active substances.

Some representatives of these compounds of the general formula (I), in which aryl is defined as above, R is hydrogen or an optionally substituted alkyl or cycloalkyl group and R is an optionally substituted alkyl or cycloalkyl group, have a pesticidal, primarily herbicidal, action on (see e.g. R. Wegler: Chemie der

Pesticides, Springer Verlag, Berlin-Heidelberg-New York, 1970, pp 241-255), other compounds of general formula (I) as th _e N- (4-nitrophenyl) -N '- (3' -pyridylinethyl) -urst off (Pyrinuron), can be used as rodenticidal agents. Further representatives of these compounds of the general

1 ? nen formula (I) in which one of R and R is hydrogen and the other is an optionally substituted one Phenyl group is pharmaceutically active or can be used as an intermediate for the preparation of pharmaceutically active agents can be used.

Preferred representatives of these compounds of the general formula (I) are as follows:

N-phenyl-N *, N'-dimethyl urea (fenuron), a herbicidal Substance,

IT-Phenyl-li '- (2-methylcyolohexyl) urea (Siduron), a herbicidal substance,

W- (4-chlorophenyl) -N *, K'-dimethyl urea (Monuron), a herbicidal substance,

K- (3,4-Dichlorophenyl) -N'-methyl-N'-butyl-urea (Neburon), a herbicidal substance, U- (3 _ff 4_Dichlorophenyl) -N ^> , N'-dimethyl-urea (Diuron), a herbicidal substance,
$ _ (3_Trifluoromethylphenyl) -N ', N * -dimethy! -Urea

(Fluoromethuron), a herbicidal substance, »

Ii- (3-chloro-4 ~ trifluoromethylphonyl) -N ^t , N ^r -dimothyl-harnotof ^ a herbicidal substance,
N_ (3_Chloro-4-methylphenyl) -IT ', K'-dimothy! -Urea

(Chlortoluron), a herbicidal substance, H- (4 ~ Iaopropylphenyl) ~ N », N'-dimothyl urea (isoprothuron), a herbicidal substance, H- (3 »4-Diohlorophenyl) -carbamoyl-morpholine, a herbi-

ft

cidal substance,

N- (3-chloro-4-bromophenyl) -oarbamoyl-morpholine, a herbicidal substance,

N-O-chlorophenylJ-carbamoyl-morpholine, a herbicidal Substance,

H- (4 ~ chlorophenyl) -carbamoyl-morpholine, a herbicidal Substance,

N- (3-chloro-4 ~ methoxyphenyl) -N ', ^{N'-dimethyl-l} harnstofi

r.

(Metoxuron), a herbicidal substance,

<■

If- / 7 "4- (4-chlorophenoxy) -phenyl__7-li ', li'-dimethyl-urea (chloroxuron), a herbicidal substance, 3Sr_ (4-chlorophenyl) -N'-methyl-II'-niethoxy-urea (Monolinuron), a herbicidal substance, Ii- (4-bromophenyl) -ir'-ynethyl-N ^> -methoxy-urea (Metobromuron), a herbicidal substance, jj_ (3 _t 4_Dichlorophenyl) -N'-methyl-ff'- methoxy-urea (Linuron), a herbicidal substance,] j_ (3_Chloro-4-broraophenyl) -Ii * -niethyl-II'-methoxy-urea (Chlorbromuron), a herbicidal substance,

it

H- (3-pluoro-4-bromophenyl) ~ N *, N'-dimethyl urea, a herbicidal substance,

H- (3-Pluoro-4-ohlorophenyl) -N ', N ^f -dimethyl-harnetoff, a herbicidal substance,

^ - (J-Fluoro ^ -chlorophenylJ-N'-methyl-N'-methoxy-urea; a herbicidal substance

3r- (3-pluoro-4-0'odphenyl) -N '-methyl-N' -aethoxy-urea f, a herbicidal substance,

li -. (4-Chlorophetiyl) -Ii '- (3-methyl ~ 4-chlorophenyl) urea, a herbicidal substance,

F- (4 ~ Mtrophenyl) -] T- (3'-pyridy! Methyl) -urea (Pyrinurou), a herbicidal substance,

N- (4-chlorophenyl) -N * - (3 »4-dichlorophenyl) urea

t 1

(Triolooarban), a bacteriostatic agent, N- (4-Ifitrophenyl) -li '- (4-nitrophenyl) urea (Nicarbasin), a coccidiostat, and

ff- (4-chlorophenyl) -] y ^f - (3-trif luoromethyl-4-ohlorophenyl) - -urea (cloflucarban), an antiseptic «

The most widely used methods for the preparation of compounds of general formula (I) are based on the reaction of isocyanates and amino derivatives. According to one of these methods, isocyanates become the general Porznel Aryl-ITCO with amines of the general formula

1 2

UHR K reacted, while another method uses isocyanates of the general formula R -WCO and amines of the general formula Aryl-WHp ⁰ ^ - ⁸ reactants.

A general description of these reactions is given in Houben-Weyl's methods of organic chemistry (Georg Thieme Verlag, Stuttgart, 1952, Volume VIII, pages 154-156) contain «

The in the above methods ala starting material Isocyanates used are generally produced βο, that the corresponding amines are reacted with phosgene or that the corresponding carbamates or Urea derivatives are subjected to thermal decomposition (see Houben-Weyl: Methods of Organic Chemistry; Georg Thieme Verlag, Stuttgart, 1952, Volume VIII, pages 119-128).

It is well known that phosgene is harmful to health, which is why reactions in which If phosgene is used, certain safety measures should be observed. Another The disadvantage is that the reaction is accompanied by the formation of a large amount of hydrochloric acid, which is difficult to remove causing serious corrosion problems. The methods for the production of isocyanates by thermal decomposition are very expensive because they are very material-intensive and require a lot of energy. So is the production of isocyanates, which are used as starting materials in the synthesis of urea derivatives of the general formula (I) are used, cumbersome, too complicated and expensive, and the reaction cannot be carried out economically on an industrial basis. Another The disadvantage is that the isocyanates - because of their high reactivity - are unstable compounds and only one can be stored for a limited time, sometimes only for a few days. For example, take 4-nitro-phenyl-isocyanate water during storage and then condenses, where-

resulting from dimers, trimers and other oligomers nioht in the next step can be reacted with amines (see Houben-Weyl: Methods of organieohen Chemie, Georg Thieme Verlag, Stuttgart, 1952, Volume VIII, page 159).

It is also known that, for the preparation of urea derivatives, carbamates can be reacted with corresponding primary or secondary amines in the presence of tertiary amine catalysts (see, for example, J. Am. Chem. Soc. 2 £ »4458-4463 / 1954 /). ! Naoh the literature, however, are only phenyl carbamates and substituted Phenyl carbamates sufficiently reactive (Houben-Weyl Methods of Organic C _Q emie, Georg Ihieme Verlag, Stuttgart, 1952, Volume VIII, pages 161-162), and if lower Alkyloarbamate that much are easier to prepare than the phenyl or substituted phenyl esters in question, are used as starting material, the reaction brings a very low yield and requires an extremely long time or else no reaction occurs at all. Therefore, in large-scale processes, lower alkyl carbamates are used for the production of urea derivatives; they are first decomposed with heat, which requires a lot of energy, and then the isocyanates are reacted with amines.

It follows that with regard to the reaction time, the availability of starting materials and the safety of the processes none of the previously known methods for the production of urea derivatives

completely satisfactory i3t.

The aim of the invention is to find a new method for the preparation of urea derivatives of the general formula (I), the readily available starting substances requires finished products within a short period of time delivers with high yield and is not harmful to health Substances used.

The invention is based on the knowledge that lower alkyl carbamates can be converted directly, ie without first converting them into isocyanates, into corresponding urea derivatives in a short time and with high yield if they are converted with corresponding amines in the presence of higher tertiary alkylamine catalysts instead of those previously used lower tertiary amines (mostly triethylamine or pyridine) are implemented. It has also been observed that when phenyl or substituted phenyl carbamates are used as the starting material in the above reaction and the lower tertiary amine catalyst is replaced by a higher tertiary alkylamine, the necessary end products are obtained in higher yield. In these latter cases the yield sometimes doubles or more; For example, N- (4-cyanophenyl) ~ N ^f ~ (3-pyridylmethyl) urea can be obtained with a yield of 85 to 90 % , instead of 43 % _f if the procedure according to Example 2 of Hungarian Patent No. 168 295 is followed

Accordingly, the invention relates to a

new process for the preparation of urea derivatives of the general formula (I),

R ¹ aryl - SH - 00 - H (I)

\ ²

12 where aryl, E and R are defined as above , by the

implementation of a carbamata of the general formula (II) R ¹ R ² N - CO - X (II)

with an amine of the general formula (III),

Aryl - NH ₂ (III)

or of a carbamate of the general formula (IV) Aryl - NH - CO - X '(IV)

with an amine of the general formula (V)

R ¹ R ² NH (V)

1 2

wherein R, R and aryl are as determined above and X represents a lower alkoxy, phenoxy or substituted phenoxy group, in the presence of a tertiary Amine catalyst. According to the invention, a tertiary acylamine, which has a total of at least 6 carbon atoms and at least one alkyl chain with aind.ea.tans Contains 4 carbon atoms, or a mixture alone tertiary alkylamines used as a catalyst.

As is evident from the above definition, euoh ^di (C-,., "Ikylj-butylamines can be used as tertiary alkyl araiEikatalyeatorea. The reaction is always preferred in the presence of tertiary amines, in which the highest alkyl chain at least 8, in particular at least 12, Has carbon atoms.

The other two alkyl groups bonded to the nitrogen atom can be lower alkyl groups, such as methyl or ethyl groups. Based on our own experience, the catalytic effect of the tertiary allylamines generally changes parallel to the number of carbon atoms in the highest alkyl chain, i.e. the greater the number of carbon atoms in the highest chain, the shorter the reaction time and the higher the yield of the desired urea derivatives. Of the tertiary alkylamine catalysts, the following compounds are particularly preferred: triootylamine, HN-dimethyl-n-octylamine, N, H- -dimethyl-n-dodecylamine, ir.Ji-dimethyl-n-hexadecylamine and the corresponding ir _t N-diethyl or N-methyl-N-ethyl compounds. These substances are commercially available on loan.

As already mentioned above, mixtures of higher tertiary alkylamines can also be used as catalysts in the process according to the invention. On the basis of economic considerations, single mixtures of technical quality are preferred in large-scale processes, since these mixtures are much cheaper than the pure tertiary amines without their catalytic activity being significantly reduced. Of the mixtures of higher tertiary alkyl amines are _Z .B. the products of the company Hoechst AG with the trademark "Genamin" and those of the company Akzo with the trademark "Armeena" are mentioned.

The term "lower alkoxy group" used in Connection with the substituent X is used, relates

calibrate to CL, alkoxy groups such as methoxy, ethoxy, etc. The designation used in connection with Group X. "Substituted phenoxy" refers to the phenoxy groups with one or more under the reaction conditions inert substituents such as halogen atoms or Alkyl, alkoxy, trihaloalkyl and / or nitro groups. Particularly Preferred representatives of the gubatituents bonded to the pheaoxy group are electronically bonded groups (e.g. halogen atoms, nitro groups), since the phenoxycarbainates with electron-withdrawing substituents on the aromatic ring under the conditions according to the invention in particular are reactive.

According to the invention, the lower alkyl carbamates, which were previously considered unsuitable for the direct industrial production of urea derivatives, can be converted directly into the corresponding urea derivatives within a few hours with a yield of 80% and more. If phenoxy or substituted phenoxycarbamates are used as starting materials, the end product can be obtained with almost quantitative yield in a similar reaction.

The starting materials (i.e. the carbamates and the primary or secondary amines) are preferred in practically equimolar Mengai used, although one of the Reactates can also be used in excess. The higher tertiary alkylamine catalyst becomes the chamber in an amount of 0.05 to 2 hol, preferably 0.5 bia 1.2 IJoI, based on 1 mole of the lower ^^ ren molar amount

-AH-

present starting material it, added. If a mix If a catalyst from higher tertiary amines is used, this ratio relates to the total amount of the tertiary amines.

The reaction is generally in an inert Solvents such as benzene, toluene or xylene, preferably carried out with the reaction mixture boiling. The excess of a higher tertiary alkylamine can also serve as a solvent, or sometimes the The reaction can also take place without a solvent or diluent.

The urea derivatives of the general formula (I) are generally weak in the reaction medium soluble and separate as pests when the mixture is cooled · In such cases the end products Duroh filtering or spinning can be separated. The mother liquor obtained, the solvents, higher tertiary Alkylamine catalyst, small amounts unreacted Containing starting material and dissolved end product can be used again as a reaction medium for further reaction steps be used. This can affect the specific need for reactants and catalyst. be lowered. In such cases it is preferred to use the starting materials in equimolar proportions to avoid the accumulation avoiding any of the reactions in the mix. To the recirculation of the mother liquor generally increases the yield, since there are no further steps after the first step Losses result from dissolving the end product.

- AS

It is also preferred to allow the mixture to be distilled while boiling thereby Water traces and alcohol produced during the reaction removed. In this case, it is not necessary, naaaer-free Auagangaaubatanzen and dry solvents too use"

The end products that aich when cooling from the Reaction mixture does not separate, can with known Methods such as evaporation, case-by-case, with non-solvent Means, etc. are separated from the room. In particular Areas of application * so if the urea derivatives Used in agriculture e.g. ala pesticides will aollen, iat ea not always necessary to get them from to separate the Refktionagemiaoh, as this mixture, erfoiderlkhaj.-. if, after adding the necessary additives, directly for the production of agrochemical compositions (such as spray. "" solutions, impregnated grains or granules, etc.) can be used · For the same purpose can the mother liquors obtained after the separation of the solid end products, which a certain amount of not

dissolved urea derivatives can be used. Depending on the final application, the separated crude urea derivatives as such or according to cleaning for use.

The process according to the invention can equally be used to produce symmetrical and asymmetrical substituted urea derivatives are used.

The inventive method is with the help the following non-limiting examples

thoroughly illustrated. Dnboi oolite are mentioned, that ee is the primary goal of the byopics that expands To show the application of the new procedure, eo that it was not sought in all reactions to achieve the optimal result. As an example: the number of recirculation indicated in the examples of the mother liquors does not represent the maximum possible value. Experience has shown that the mother liquors can at least be recirculated ten times.

The layer chromatographic analyzes mentioned in the examples were carried out on Merok Kieselgel 60 IVjc * - plates. The melting points are uncorrected values.
example 1

Production of N- (4-Nitrophenyl) -IT - (; 3-pyriäylmethyl) - -uratoff '

4.22 g (0.02 mol) of ethyl N- (4-nitrophenyl) carbamate, 1.80 g (0.0167 mol) of 3-aminomethylpyridine and 3.18 g (0.0173 mol) of tributylamine Dissolved in 25 ml of dry toluene and the mixture is heated to boiling for 5 hours. The separated product is filtered off, washed twice with 10 ml of acetone each time and dried. .4,33 S (85 »1 #) N- (4-nitrophenyl) -N * - (3-pyridylmethyl) - -urea are obtained; Melting point: 222-224 ⁰ C (the authentic sample melts at 223-225 C).

The above reaction is repeated with the difference that 1.72 g (0.0175 mol) of triethylamine as a catalyst can be used. The end product is just beginning

about 4 hours of simmering to separate. The mixture is boiled for 36 hours, then the separated product is filtered off and washed twice with 10 ml of acetone each time. 3.3 g (64.9 %) of N- (4-nitrophenyl) -! * '- (3-pyridyllaethyl) urea are obtained; Melting point: 222-224 ⁰ C. Example 2

Preparation of H- (4-Wltrophenyl) -I] "^> - (3-pyridylmethyl) - -urea

196.13 g (1 mol) methyl-N- (4-nitrophenyl) -car-

for _r

bamate, 108.14 g (1 mol) 3-aminomethyl-pyridine and 106.7 g (0.5 mol) Ν, Ν-dimethyl-n-dodecylamine are dissolved in 3 liters of xylene Any traces of water present are removed from the Gemisoh together with the alcohol formed in the Dean-Stark trap. Within 15-20 minutes of the start of boiling, the end product begins to separate from the Gemisoh. The mixture is heated to boiling for 4 hours, then the suspension is filtered at about 100-110. The filter cake is washed twice with 100 ml each of hot xylene and a small amount of acetone and then dried in vacuo. 218.6 g (80.3 %) of N- (4- nitrophenyl) -N '- (3-pyridylmethyl) urea are obtained; Melting point: 221-223 ⁰ C. Example 3 Production of ff- (4-ffitrophenyl) -ff '- (3-pyridylmethyl) -

-urea

The procedure is as described in Example 2, with the difference that 0.5 mol of N, N-dimethyl-n-he; cadecylamine can be used as a catalyst. 240.67 g

- Af-

(88.4 %) N- (4-nitrophenyl) -N '- (3-pyridy! Methyl) -urea are obtained; Melting point: 222-224 ⁰ C. Example 4 Preparation of N- (

-urea

A mixture of 5 to 88 g (0.03 mol) of methyl-N- (4-nitrophenyl) -carbemate., 2.70 g (0.025 mol) of 3-aminomethyl- pyridine, 9.6 ml of Genamin CS 302D ( a mixture of Ν, ΪΓ- -Dimethyl-G ^^^ Q olkylaminen, product from Hoeohst AG) and 50 ml of xylene are placed in a flask equipped with a 20 cm Vigreux column and a Dean-Stark trap and the mixture is heated to boiling for 2 hours. During this time 6 ml of a mixture of water, methanol and xylene accumulate in the trap. The mixture is filtered hot, the crystalline end product is washed twice with 5 ml of hot xylene each time and then with a little acetone and dried. 6.0 g (88.2 %) of N- (4-nitrophenyl) -Ii * - (3-pyridylmethyl) -urea

obtain; Melting point: 223-225 ⁰ G.

Example 5 Production of N- (4 ~ nitrophenyl) -R * - (3-pyridylmethyl) -

-urea

11.77 g (0.06 mol) methyl-N- (4-nitrophenyl) -

carbamate, 5.4 g (0.05 mol) 3-aminomethyl-pyridine, 18.7 g (0.065 mol) Genamin SH 302 D (a mixture of N, IT-dimethyl- -C -.,: -.Ο alkylamines, manufactured by Hoechst AG) and 200 ml of toluene are in the example 4

given device, and the mixture is heated to boiling for 4 hours. During this time 15 ml of a mixture of water, methanol and toluene accumulate in the trap. The separated fuel is filtered off, washed twice with 10 ml of hot toluene each time, the piltrate is then combined with the washing solution, and the geroisoh obtained is used as a reaction medium in the above reaction. The mother liquor is recirculated ten times. The results of the individual cycles are summarized in Table 1.
Table 1

number
of
Cycle Weight, End product
g melting point, C. Ana loot, % 1 10.85 221-223 79.72 2 12.95 223-225 95.15 3 11.95 222-224 87.80 -.- ■ - ■ _ 4th 10.65 221-223 78.25; 5 11.00 222-224 80.82 6th 11.82 224-225 86.84 "■ '" ·' 7th 12.65 224-226 92.94 8th 10.50 223-225 77.14 9 11.00 222-224 80.82 10 13.28 224-226 97.57

Average 11.66

85.70

Example 6 Production of N, N * -biaH-Nitror> henyl) -harnetoff

9.81 g (50 mmol) methyl N- (4-nitrophenyl) carbamate, 6.9 e (50 mmol) 4-nitroaniline, 140 ml xylene

and 11.8 g (about 50 mmol) Genamin CS 302 D (a mixture of N, N ~ (IÜmetiayl) C ₁₀ _ _{18 f} elkylaininen product of the company Hoeohet AG) are added to a flask equipped with a Rüokflußkühler , and then the mixture is heated to boiling. The yellow crystals of the end product appear in the 3rd minute of the boiling process, and the amount of crystalline precipitate increases rapidly.After 0.5 hours of boiling, the thick, orange-colored crystal suspension is filtered while hot in vacuum, the filter cake is filled twice with 20 ml of hot xylene and then washed with acetone, finally the product is dried in vacuo12.78 g (85 _t 2 %) N, N'-bis (4-nitrophenyl) urea are

t. .

keep. The product proves to be uniform when it is examined by SohiohtChromatographie using a mixture of η-hexane and acetone as solvent in the ratio 3: 1. The ohromatographic appearance of the product is identical to that of the authentic sample.
Example 7 Preparation of N.N'-bisC ^ nitrophenyl) urea

The procedure is as in Example 6, with the difference that the flask has a distillation column is connected, the mixture is kept under leiohtem boiling and constantly methanol from the mixture Will get removed. After 2 hours of reaction, the end product is filtered off, 50 mmol of methyl-N- (4-nitrophenyl) -

I /

-oarbamate and 50 mmol of 4-nitroaniline are added to the filtrate and the reaction is repeated. The results of the four consecutive cycles are summarized in Table 2.
Table 2

number
of
Cycle E η
Weight, d'product
g yield, % Chromatographic
Appearance 1 13.36 89.1 uniformly 2 14.30 95.3 uniformly 3 13.58 90.5 uniformly 4th 14.75 98.3 uniformly

Annotation:

On the basis of the melting point, the quality of the end product cannot be adequately characterized as the compound begins to sublime immediately after melting.
Example 8 Preparation of N - ^ - chlorophenyD-carbamoyl-morpholine

A mixture of 9.28 g (50 mmol) methyl-N- - (4-chlorophenyD-carbamate, 4.36 g (50 mmol) morpholine,

100 ml of xylene and 10.6 g (50 mmol) of N _f N-methyl-tetradecylamine are carefully heated under boiling for 6 hours. Methanol is continuously removed from the mixture by distillation. The heating is then turned off and the mixture is allowed to cool and stand overnight. The separated crystals are filtered off and dried. 9.1 g (75.6 %) N- (4-oilorophenyl) -

carbamoyl morpholine are obtained; Melting point: 196-200 ⁰ C (the authentisohe sample melts at 196-200 ⁰ C) Example 9

Production of N- (4-chlorophenyl) -N ^> - (3 _t 4 ~ dichlorophen.Yl) - -urea

A mixture of 4.61 g (25 mmol) of methyl IT- (4-chlorophenyl) carbamate, 4.07 g (25 mmol) of 3,4-iLohloraniline, 100 ml of toluene and 4.7 g (25 mmol) 1T, N-dimethyl- dodecylamine is reacted for 20 hours as described in Example 8, and then the mixture is allowed to cool. 4.60 g (58.4 %) of N- (4-chlorophenyl) -N '- (3,4- -dichlorophenyl) -urea are separated from the mixture as all crystalline substances.
Example 10

Preparation of N- (3t4? -Dichlorphenyl) -carbamoYl-roorpholine A mixture of 5.50 g (25 mmol) methyl-N- (3,4- -dichlorphenyl) -carbamate, 2.18 g (25 mmol) morpholine, 100 ml of xylene and 4.7 g (25 mmol) of 2i, N-dimethyl-dodeoylamine are reacted as described in Example 8 for 12 hours. The crystalline substance which separates on cooling is filtered off, 25 mmol of methyl N- (3,4-dichlorophenyl) carbamate and 25 mmol of morpholine are added to the pad, and the reaction is repeated. In the first reaction 5.0 (72.7 %) N- (3,4-dichlorophenyl) - -carbamoyl-morpholine are obtained, while in the second reaction 6.35 g (92.3 %) of the same compound are separated off . Both compound fractions melt at. 152-155 ⁰ C (the authentic sample sohmeltzt at 157-158 C).

The above reaction is repeated 00 that

25 mmol of triethylamine instead of N, K-dimethy1- dodecylamine are added to the mixture. 3.05 g (44 _f 3%) of the desired end products are obtained after 24 hours of reaction.
Example 11 Manufacture of NO ^ -

-urea

A mixture of 5.50 g (25 mmol) methyl-li- {3,4- -DichlorophenyU-oarbamate, 2.18 g (25 mmol) N-butyl-methyl-

f.

amine, 4.7 g (25 mmol) of N, Nl> 1methyl-dodecylamine and 100 ml of light gasoline are reacted for 3 hours as described in Example 8. The separated pesticide is filtered off, 25 mmol of methyl N- (3,4-dichlorophenyl) -oarbamate and 2.18 g (25 mmol) of JT-butyl-methylamine are added to the Piltrate, and the reaction is repeated. In the first reaction 3 _f 70 g (53.8 %) of N- (3,4-dichlorophenyD-lf'-methyl-N'-butylurea are obtained, while in the second reaction 5.05 g (73.4%) are obtained % to be separated) of the same compound * Both fractions compound melting at 108-111 ⁰ C (the authentic sample sohmilzt at 116-117 ° C).
Example 12 Preparation of IM3.4-dichlorophenyl) -K ^> -methyl-ff »-butyl- urea

The procedure is as in Example 11, with the difference that 100 ml of xylene are used as solvent will. The port stepping of each reaction is carried out by

-X ¹ I -

Sohiohthromatography Overwhelmed. When, as evidenced by the chromatogram, about 90 % of the reaction has taken place, the mixture is evaporated in vacuo. A yellowish, Yisko RUokstand is obtained, which is readily soluble in customary organic solvents, such as aoetone or methyl ethyl ketone, and can be used in the preparation of herbicidal spray solutions. Example 13 Preparation of I ^ -f ^ chlorophenylj-IT'.fl'-diraethyl-uretoff

A mixture of 12.8 g (0.1 mol) of 4-chloroaniline,

10.3 g (0.1 mol) of methyl l ^ ir-diinethyl carbamate, 20 ml

Dimethyl-hexadeoylemin and 100 ml hoohsiedende petroleum fractions (boiling point 160-180 ⁰ C) is reacted as described in Example 12. Fig. When - as indicated by the chromatogram - about 90 % of the reaction has taken place, the reaction is ended. A solution of !! -. (^ ChlorphenyD-li ', li'-dimethy! -Urea (Monuron) is obtained, which can be used directly in the production of herbicidal compositions such as spray liquids or impregnated granules.

Claims (4)

PATENT CLAIMS 1 Method of Heratelluag of Jtf '- (inono ~ or disubstituted) N-aryl urea derivatives of general formula (I), R ¹ aryl - NH - CO - W (ι) Aryl is an optionally substituted phenyl group represents and 1 2 R and R each represent an optionally substituted alkyl, cycloalkyl, alkoxy or phenyl group stand, or 1 2 R and R together with the adjacent nitrogen atom form a nitrogen-containing heterocyclic group can form, which can enthol th another heteroatom, or 1 2
either R or R can also stand for hydrogen, 1 2 with the proviso that when either of R or R represents an optionally substituted phenyl group, dae others only hydrogen atom or an optionally substituted one May mean alkyl or alkoxy group by reacting a carbamate of the general formula R ¹ R ² N-CO-X
with an amine of the general formula (III), Aryl - BH ₂ (m) or a carbamate of the general formula (IV) Aryl - HH - 00 - I (IV) with an amine of the general formula (V) R ¹ R ² WH (Y) 12 ' wherein R and R and aryl are as defined above and X is a lower alkoxy, phenoxy or substituted phenoxy group, in the presence of a tertiary amine catalyst, characterized in that the catalyst is a tertiary alkylamine, which has a total of at least 6 carbon atoms and at least before alkyl contains a chain with at least 4 carbon atoms, or a mixture of solitary tertiary alkylemines is used 2. Method according to claim 1, characterized in that - indicates that a tertiary alkylamine, containing at least one alkyl chain with at least eight carbon atoms, or a garrison of single tertiary _: alkylamines is used as a catalyst. ; 3. The method naoh claims 1 or 2, characterized in that the tertiary alkylamine * catalyst is used in an amount of 0.05-2 mol, based on 1 mol of the reactant present in the lower molar amount. 4. The method naoh one of claims 1 to 3 »characterized in that the tertiary alkylamine catalyst is used in an amount of 0.5-1 * 2 moles, based on 1 mole of the reactant present in the lower molar amount. PCT / HU81 / OOOO3 _ 7 ty - ^{Ρ 1 48} 5 ^PGT Tf.LEPi; Oii: DACIuVJ «Ϊ 3 7 Ϊ Example 14 Manufacture of N-M-ChlorpheuyD-N'.N'-dimethyl urea 4.64 g (0.025 mol) of methyl N- (4-chlorophenyl) - carbamate and 21.3 ml of Genomin LA 302 D (a mixture of N, N-Dimet 1IyI-C _12-1 ^ alkylamines, product of Pinna Hoechst AG) are introduced into a 100 ml flask equipped with a distillation column. The mixture is heated to 150-160 ⁰ O and the mixture of gaseous dimethylamine added * In the final phase of the reaction, the Gemisoh is heated to about 160 ⁰ C, remove the methanol. The whole reaction takes about 2 hours. The yellowish brown solution obtained is allowed to cool and the almost white crystalline precipitate collected by filtering. The precipitation is washed three times with 10 ml of η-hexane each time and then dried. The Piltrat is mixed with the washing solution combined, and the Gemisoh obtained is used as the reaction medium in the next cycle. In the next Cycle 4.64 g of the above carbamate are added to the reaction medium, and the mixture is fed heated by gaseous dimethylamine. η-hexane, that Was used as detergent in the previous cycle, distilled first and was collected separately -ze- and all detergents used again. The combined mother liquor and Wasohlöaung are recirculated ten times. The results of each Cycles are summarized in Table 3 · Table 3 number
of
cycle Weight, End product
g melting point, ⁰ O Yield, % 1 2.70 168-171 54.33 2 3.05 169-171 3 4.20 170-172 * ·
84.51 4th 4.50 169-171 ^9O »54 5 4.10 167-169 62.49 CX 6th 3.50 167-169 70,42.-.'-, 7th 4.50 168-169 90.54 θ 3.95 172-173 79.48 9 3.75 172-173 75.45 10 4.55 168-169 91.55 average 3.88 78.07 Note: The melting point of N - (4-chlorophenyl) -N ', ^N> --dimethyl-urea (Monuron) is 174-175 ⁰ C. According to the literature. Example 15 Production of N-Phenyl-N » .N'-dimethyl urea The procedure is as in Example 14 with the difference that 3.78 g (0.025 mol) of methyl-N-phenyl-carbamate are used as the starting material , and the mieoh is heated long ^{at 140-180 0} C for 1.5 hours. The combined mother liquor and washing solution are recirculated eight times. The results of the individual cycles are summarized in Table 4.
Table 4 number En d product Yield, % dee
cycle Proposed, g Melting point, ⁰ C 51.20 1 2.10 127-130 83.17 2 3.41 124-127 93.90 3 3.85 125-128 91.46 4th 3.75 124-126 45.61 5 1.87 131-133 120.73 6th 4.95 124-127 74.40 7th 3.05 .. 122-126 87.80 8th 3.60 122-126 81.03 Average 3.32 Note: According to the literature, the melting point of N-phenyl-N ', N'-dimethyl-harnatoff (Phenuron) is 133-134 ⁰ C.
Example 16 Production of N- (3t4-dichlorophenyl) -N '~ methoxy - N * -inethyl - -urea 5.5 g (0.025 mol) of Kethyl-III- (3,4-JHchlorphenyl) - "-carbamate are stirred and heated in 2.3 ml (about 0.075 mol) of Genamin LA 302 D (a mixture of N, N- -Dijnethyl-C, ρ T ^ -nlkylnminon,! Product dor; · ': 1 i-jiin! Ioochnt AG) The mixture is dissolved on a Tewporotur from kept for about 200 ⁰ G, un <l?, 3 g (0.0375 WNi) of gaseous Liethoxymethylmnin been bubbled within ctv / n 3 hours through the Geraisch. The progress of the reaction is monitored by layer chromatography and is also controlled by measuring the temperature of the vapors which escape from the mixture. V.'enn the degree of implementation. about '/ I reached 90, the reaction iat terminated. A solution of Ü ~ (3,4-dichlorophenyl) ~ -N'-methoxy-N'-inothyl-hnrnatoff (Linuron) is obtained. This solution can easily be diluted with traditional organic solvents, v / ie acetone or methyl ethyl ketone, and then used directly for the production of herbicidal mixtures, such as spray liquids or impregnated grains or granules.