DE2800111A1 - PROCESS FOR THE PRODUCTION OF AMINOPHENYLURA AND AMINOCARBANYLATES - Google Patents

Description

Our no. 21 433 Pr / br

Aziende Colori Nazionali Affini - ACNA S.p.A. Milan / Italy

Process for the preparation of aminophenylureas and aminocarbanylates

The invention relates to a particularly simple and selective process for the preparation of aminophenylureas and aminocarbanylates.

Such products are of great interest in the fine chemicals field, and mainly in the The field of dyes, as they are basic intermediates for the synthesis of colorants. In particular, they are suitable as Herbicides and as coupling agents in the manufacture of azo dyes as described, for example, in BE-PSS 694 733, 702 400 and 694 633.

The inventive method is carried out by the Phenylureas or the carbanylates in suitable acidic solvents such as sulfuric acid, trifluoroacetic acid or mixtures of which with acetic acid with a suitable N-halogenamine and with a redox system that contains salts such as ferrous, Contains titanium III or cupro salts, at more or less low levels Temperatures, for example around room temperature, treated.

The phenylureas and the carbanylates can be substituted on the nitrogen by, for example, optionally substituted

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Alkyls, aralkyls, cycloalkyls or aryls.

The phenyl can also be substituted by, for example, halogens, alkyls, a nitro group, a cyano group, a Hydroxyl group or an optionally substituted alkoxyl group.

The object of the invention was to provide a particularly simple, large-scale To provide a process that allows the achievement of products, their synthesis by conventional methods usually very is difficult.

The reaction takes place in a very breiteriTemperaturbereich: from -60 to +100 ⁰ C. Good results are obtained, for example,

between 0 and 40 ° C.

The molar ratios between N-chloramine and the aromatic Substrate (phenylureas or carbanylates) fluctuate as puncture of synthesis. Generally they are between 1: 3 to 3: 1

The catalyst may vary depending on between with respect to N-chloramine 1: 1 and 1: 100 mol, preferably 1: 1.2 and 1:50 mol, vary.

Also with regard to the acid mixture it is possible to have the most varied Ratios based on the aromatic substrate to be used.

A high selectivity and good yields can be achieved in some cases by using 300 to 1000 ml per mole of this aromatic Achieve substrate.

When using H ₂ SO ₁ , the bed results will be obtained at a concentration of at least 25 wt. HpSOj, scored.

The procedure can be carried out as follows:

One with a stirrer, thermometer, funnel, and one

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Cooler equipped reactor comes with the following components

loaded:

the acid mixture, the phenylurea or the carbanylate,

the N-Thhlorandn dissolved in an acid mixture and

the catalyst.

After the reaction has ended, the reactor components are poured onto ice with stirring and the starting product, if any still present, is removed from the acidic solution with the help of a suitable solvent, for example chloroform, CCl ^, ethyl acetate, Ethyl ether, toluene, chlorobenzene, dichlorobenzene, nitrobenzene or Cyclohexane, extracted.

After making it alkaline with a concentrated alkaline solution, for example 3O # sodium hydroxide, becomes the reaction product extracted. The most suitable solvent is used in each case. The choice is essentially based on the distribution coefficient of the product bound between solvent and aqueous solution.

Some suitable solvents are, for example, chloroform, carbon tetrachloride, ethyl ether, toluene or cyclohexane.

After distilling off the solvent, the finished products are generally obtained in a degree of purity such that they are already suitable for further processing. In In some cases it may be appropriate to use a crystallization from a suitable solvent or a fractional To carry out precipitation such as hydrochloride, sulfate or phosphate.

Suitable N-haloamines are, for example:

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N-chloromethylamine

N-chlorodimethylamine

N-chloromethylethylamine

N-chloromethylbenzylamine

N-chlorodiethylamine

N-chloromorpholine or

N-chloropiperidine.

Suitable phenylureas are, for example:

N-phenylurea,
N-methyl-N-phenylurea, N-phenyl-N ^! -methylurea, N-phenyl-N ', N'-dimethylurea, N-methyl-N-phenyl-N'-methylurea, N-methyl-N-phenyl-N ¹ , N ¹ -dimethyl urea, N-phenyl- N'-ethylurea, N-Ethy1-N-phenylurea,
N-Phenyl-N ¹ , N'-diethylurea, N-Ethy1-N-phenyl-N ¹ -ethylurea, N-Ethyl-N-pheny1-N ', N'-diethylurea, N-phenyl-N'- phenylurea, N-methyl-N-phenyl-N'-phenylurea, N-methyl-N-phenyl-N -methyl-N'-pheny! urea, N-ethyl-N-pheny1-N'-phenylurea, N- Ethy1-N-pheny1-N'-ethy1-N'-phenylurea, N-Pheny1-N'-ethy1-N'-phenylurea, N-Methy1-N-pheny1-N ', N'-diethylurea, N-methyl- N-phenyl-N'-methyl-N ¹ -ethylurea, N-Ethy1-N-pheny1-N -methyl-N'-ethylurea, N-ethyl-N-phenyl-N ', N'-dimethylurea, N- Ethy1-N-phenyl-N'-methyl-N'-ethylurea, N-phenyl-N'-pheny1-N'-methylurea,

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N-Pheny1-N'-ethy1-N'-phenylurea, N-methyl-N-phenyl-N'-methyl-N'-ethylurea, N-methyl-N-phenyl-N-methyl-N'-phenylurea, N-methyl-N-phenyl-N'-ethy 1-N '-phenylharr.stoff, N-Ethyl-N-phenyl-N '-methyl-N' -ethy lh arr-sroff, N-Ethyl-N-phenyl-N'-methyl-N'-phenylharnsvoff, N-ethyl-N-phenyl-N'-ethyl-N'-phenylurea, N-2-nitrophenylurea,

N-2-chlorophenylurea,

N-2-broraphenylurea,

N-2-iodophenylurea,

N-2-methylphenylurea,

N-2-isopropylphenylurea, N-2-chlorophenyl-N-methyl-N ^t -ethylurea, N-2-methylphenyl-N ', N'-dimethylurea, N-2-methylphenyl-N'-2-methylphenylurea, N- 2-cyanophenylurea,

N-2-acetoaminophenylurea, N-2-methoxyphenylurea,

N-2-Methoxypheny1-N ·, N · -dimethylurea, N-2-methoxyphenyl-N'-ethylurea, N-2-methoxypheny1-N ·, N'-diethylurea, N-methyl-N-2-ethoxyphenylurea, N-2-hydroxyphenylurea,

N-3-chlorophenylurea,

N-3-methylphenylurea,

N-methyl-N-3-chlorophenylurea, N-ethyl-N-3-chlorophenylurea, N-methyl-N-3-chloropheny1-N'-dimethylurea, N-3-chlorophenyl-N ', N'-diethy! Urea, N-3-methylphenyl-N ', N'-diethylurea,

N-3-ethoxyphenylurea or N-3-methoxyphenylurea,

N-3-hydroxyphenylurea, N-2-tert-butylphenylurea, N-3-methoxyphenyl-N ', N'-diethylurea, N-methyl-N-3-methoxyphenylurea, N-4-chlorophenylurea, N-4-methylphenylurea , N-4-hydroxyphenylurea, N-4-methoxyphenylurea, N-4-ethoxyphenylurea, N-4-acetaminophenylurea, N-4-ureidophenylurea, N-ethyl-N-4-chlorophenyl-N ', N' diethylurea, N-methyl-N-4-methoxyphenylurea, N-4-methoxyphenyl-N ·, N'-dimethylurea, N-4-methoxyphenyl-N'-ethylurea, N-ii-methoxyphenyl-N'-methyl urea, N-methy 1-N- ¹ I-methoxyphenyl-N ' _S N ^f -dimethylurea, N-methyl-N-4-methoxypheny1-N ^f , N ^f -diethylurea, N-4-ethoxyphenyl-N' -ethy! urea, N-4-ethoxyphenyl-N ·, N '-dimethylurea ·; N-Ethyl-N-4-ethoxyphenyl-N ^f , N'-diethylurea N-2,5-dimethoxyphenylurea, N-2,5-dimethylphenylurea, N-4-methoxyphenyl-N'-4'-methoxyphenylurea N-4- ethoxyphenyl-N'-4'-ethoxyphenylurea, N-phenyl-N'-3 ', 5'-dinitrophenylharnstoff, N-4-methylphenyl-N'-3', 5 '-dinitrophenylharnstoff, N-4-ethoxyphenyl-N' -3 ', 5'-dinitrophenylurea, N-4-methoxyphenyl-N'-3', 5'-dinitrophenylurea, N-phenyl-N'-3 ', 5'-dicyanophenylurea, N-4-methylphenyl-N'- 3 ', 5'-dicyanophenylurea, N-4-methoxyphenyl-N'-3', 5'-dicyanophenylurea,

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N-4-ethoxyphenyl-N'-3 ', 5'-dicyanophenylurea, N-phenyl-N'-3'-nitro-5'-cyanophenylurea, N-phenyl-N'-chloroethylurea, N-phenyl-N · - cyanoethylurea, N-phenyl-N'-sulfopropylurea, N-phenyl-N'-hydroxypentylurea, N-phenyl-N'-ethoxyvalerylurea, N-phenyl-N'-aminobutylurea, N-methyl-N-phenyl-N'-hydroxypropylurea , N-Ethyl-N-4-ethoxyphenyl-N ¹ -sulfopropylurea, N-4-ethoxyphenyl-N -cyanoethylurea, N-4- (2-hydroxyethoxy) -phenyl-N'-hydroxyethylurea, N-methyl-N- 4-methylpropionatoxypheny1-N'-chloroethylurea, N-4- (2-hydroxyethoxy) -phenylurea, N-4-methylpropionatoxyphenylurea, N-4-cyanoethoxyphenylurea, N-4-cyclohexoxyphenylurea, N-4-methoxypropylionylo ( 2-ethoxyethoxy) phenylurea, N-4-isopropoxyphenylurea, N-4-t-butoxyphenylurea,
N-methyl-N-4-cyclohexoxyphenylurea, N-methyl-N-4- (2-hydroxyethoxy) -phenylurea, N-ethyl-N-4-methylpropionatoxyphenylurea, N-ethyl-N-phenyl-N'-cyclohexylurea , N-phenyl-N'-cyclohexylurea, N-4-methoxyphenyl-N'-cyclohexylurea, N-methyl-N-4-ethoxyphenyl-N'-cyclohexylurea, N-ethyl-N-4-methoxyphenyl-N'-cyclohexylurea , N-4-Cyclohexoxypheny1-N'-cyclohexylurea, N-ethyl-N-4- (2-hydroxyethoxy) -pheny1-N'-cyclohexylurea, N-methyl-N-phenyl-N ^f -ethylharnstoff.

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Suitable carbanylates can be the derivatives of methyl or ethyl carbanylate be such as:

N-methyl methyl carbanylate, 4-methoxymethyl carbanylate, N-methyl-4-ynethoxymethylcarbanylate, N-ethylraethylcarbanylate, N-ethyl-4-methoxymethylcaPbanylate, 2-nitromethylcarbanylate, 2-chloromethyl carbanylate 2-broramethylcarbanylate, 2-iodomethyl carbanylate, 2-methylmethylcarbanylate, 2-ethylmethylcarbanylate, 2-isopropylmethylcarbanylate, 2-tert-butylmethylcarbanylate, . •, "- methyl 2-chloromethylcarbanylate, N-ethyl-2-methylmethylcarbanylate, 2-cyanomethylcarbanylate, 2-methoxymethyl carbanylate, 2-hydroxymethyl carbanylate, 2-ethoxymethylcarbanylate, N-ethyl-2-ethoxymethylcarbanylate, N-methyl-2-acetylaminomethylcarbanylate, 3-chloromethyl carbanylate, 3-methylmethylcarbanylate, J-methoxymethylcarbanylate, 3-kydroxymethylcarbanylate, J-ethoxymethyl carbanylate, N-methyl-O-methoxymethylcarbanylate, N-methyl 1-3-methylmethylcarbanylate, N-ethyl-S-ethoxymethylcarbanylate, N-ethyl-3-niethoxymethylcarbanylate, il-chloro diethyl carbanylate, A-methoxymethyl carbanylate, 4-methylmethylcarbanylate,

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2300111

4-Ethoxymethylcarbanylat, 2,5-Diraethoxymethylcarb anylat, 2,5-Dimethylmethylcarbanylat, 4- (ß-hydroxy) ethoxymethylcarbanylat, -Methoxypropionyloxymethylcarbanylat ^, ^ - (ß-GyanoJethoxymethylcarbanylat, Ii-Cy clohexyloxymethylcarb any lat, ¹ I- (.beta. ethoxy) ethoxymethy lcarb anylat, 4-Isopropyloxyniethylcarbanylat, 4-t-Butyloxymethylcarbanylat ₃ N-Cyclohexylmethylcarbanylat, N-ethyl-4-ethoxymethylcarbanylat, N-cyclohexyl-4-methoxyraethylcarbanylat, N-ethyl - ^ - cyclohexyloxymethylcarbanylat, ^N-methyl-i t - (ß-cyano) -ethoxymethylcarbanylate _> N-ethyl-4- (ß-hydroxy) -ethoxymethylcarbanylate _> N-methyl-4-methoxypropionyloxymethylcarbanylate, N-ethyl-4- (ß-ethoxy) -ethoxymethylcarbanylate.

In the compounds listed above, the methyl of the ester group can be exchanged for an ethyl.

Other suitable carbanylates are, for example:

ß-chloroethyl carbanylate, ß-cyanoethyl carbanylate, Propyl carbanylate, isopropyl carbanylate, tert-butyl carbanylate, cyclohexyl carbanylate, ß-hydroxyethyl carbanylate,

2300111

ß-chloroethyl-N-methylcarbanylate,
Cyclohexyl-N-ethylcarbanylate,
Cyclohexyl-N-cyclohexylcarbanylate,
ß-cyanoethyl-N-methylcarbanylate,
Propyl 4-methoxycarbanylate,
tert-butyl-4-methoxycarbanylate,
Isopropyl-N-methyl- ^ - methoxycarbanylate, N-cyclohexyl- ^ - cyclohexyloxycyclohexylcarbanylate, N-ethyl-H-ethoxy-ß-cyanoethylcarbanylate.

The procedure for aminating phenylureas can be as follows represent as follows:

R. O R. + Cl R, - N R. -i- / 3 \ • 4 N - <(A)>

R or

\ Il I ²

R and R _{1 can be} identical or different and are hydrogen or an optionally substituted alkyl, cycloalkyl, aryl or aralkyl radical,

Rp hydrogen or an optionally substituted alkyl, Cycloalkyl, aryl or aralkyl radical,

R- and R ^ can be identical or different and an optionally substituted alkyl, cycloalkyl or aralkyl radical and one of the two radicals R-. or R ₁ . Mean hydrogen. R, and R ₁ . can also together represent an optionally substituted cyclic radical which optionally contains other heteroatoms.
A denotes an optionally substituted benzene ring with

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ORfG / NAL IKZr ~: -TD

at least one vacant position.

The substituents on

and A can, for example

Halogen, nitrile, sulfonic acid or carboxylic acid groups and their Esters, amino hydroxyl, alkyl, substituted alkyl, alkoxyl, substituted alkoxyl, acylamino, cycloalkyloxy or uric acid groups represent. In particular, the substituents on the alkyl and alkoxyl groups, for example halogen, hydroxyl, Carboxylic acid or sulfonic acid groups and their esters, a nitrile or an alkoxyl.

', ienn R ₁ , R ₂ * R? and R ₁ . denote an alkyl or an alkoxyl, their alkyl groups preferably contain 1 to 5 carbon atoms.

The procedure for aminating the carbanylates with N-chloramines can be represented as follows:

R.

R.

C-N-

wherein

R ₁ and Rp, for example, an optionally substituted alkyl,

Cycloalkyl, aryl or aralkyl and R ₂ also denotes hydrogen and

R, and Rk, for example, an optionally substituted alkyl, Cycloalkyl or aralkyl and also one of the two hydrogen

mean or

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_{R 1} and R 1 ^ represent an optionally substituted cyclic radical which optionally has heteroatoms, and A denotes a benzene nucleus with at least one free position.

The substituents on R ₁ , R ₂ , R ₁ , R 1. and A can be, for example, halogen, nitrile, sulfonic acid or carboxylic acid groups and esters thereof, amino, hydroxyl, alkyl, substituted alkyl, alkoxy1, substituted alkoxyl, acylamino, cycloalkyloxy or uric acid groups, and the substituents of the alkyls or alkoxyls can also be, for example, halogen, hydroxyl , Carboxylic acid or sulfonic acid groups and esters thereof, nitrile or oxygen alkyl.

If R ₁ , R ₂ , R, and R ₁ ^ are alkyl or alkoxyl, their alkyl chain preferably contains ibis 5 carbon atoms.

The Process for Synthesizing N-Alkyl Aromatic Amines by Amination of aromatic substrates with N-chloramines in the presence of a reducing salt in an acidic reaction medium has been described in US Pat. No. 3 ^ 83,255, in which unsubstituted or substituted with chlorine, bromine, iodine or -OCH aromatic compounds are alkylaminated.

It was to be expected that when working according to this method, N-chloroureas and chlorination products of the side chains in the substituted ureas would form.

With the carbanylates, when working according to this method, it was also to be expected that by-products would be formed, such as, for example, N-chlorocarbanylates, chlorination products of

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Side chains in the substituted carbanylates, and also that the carbanylates hydrolyzed under the reaction conditions would be.

Surprisingly, it has now been found that the new synthesis method causes no formation of the above products and furthermore with high yields and high selectivity both when using pheny! ureas as well as carbanylates or the use of phenyl-substituted phenyl ureas and carbanylates.

For example, if starting compounds such as N-phenylurea, N-phenyl-N'-ethylurea, N-methyl-N-phenyl-N ¹ , N'-dimethylurea or N-methyl-N-phenyl-N ¹ -ethylurea are used, a selective binding in the para position, based on the nitrogen in A, achieved.

If the phenyl is substituted in the para position, ie if products of the following types are used: N-4-methoxyphenylurea, Ν-Ί-methoxyphenyl-N'-ethylurea, N-4-ethoxyphenyl-N'-ethylurea, N-4- Hydroxyphenylurea, N-4-cyclohexoxyphenyl-N ¹ , N'-dimethylurea, N-methyl 1-N-chlorophenylurea or N-4-ethoxyphenyl-N, N'-dimethylurea, a selective bond is achieved in the meta position, based on on N in A.

Conversely, if phenyl is substituted in the ortho position, ie if products of the following type are used: N-2-methylphenylurea, N-2-methylphenyl-N ¹ , N'-dimethylurea, N-2-chlorophenyl-N'-ethylurea or N-methyl-N-2-bromophenylurea, a selective bond in the para position, based on the nitrogen in A, is achieved.

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When regarding the carbanylate starting compounds like Methyl carbanylate, ethyl carbanylate, N-methyl ethyl carbanylate or N-ethylmethylcarbanylate will be used selective binding in the para position, based on the nitrogen in A, achieved.

When the phenyl is substituted in the para position, i.e. when compounds of the following kind are used: 4-methoxymethylcarbanylate, ^ -ethoxymethylcarbanylate, 4-methoxyethylcarbanylate, JJ-ethoxyethylcarbanylate or N-methyl - ^ - methoxymethylcarbanylate, a selective binding in the meta position, based on the nitrogen in A, is achieved.

Conversely, if the phenyl is substituted in the ortho position, i.e. when compounds of the following type are used: 2-methylmethylcarbanylate, 2-chloroethylcarbanylate or 2-methylethylcarbanylate, a selective bond in the para position, based on the nitrogen in A, is achieved.

The following examples serve to further illustrate the invention. In these examples the term "parts" means Parts by weight, unless otherwise specified. For the examples relating to phenylureas, the yield is calculated on the amount of N-chloramine used, while for the examples relating to carbanylates, the yield on the amount of carbanylate converted is calculated.

A) Production of aminophenyl ureas Example 1

A reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel was made with 60 parts

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concentrated HpS (K and while keeping the temperature below 10 ° C was charged with 8.2 parts of N-phenyl-N'-ethylurea.

Gradually, while stirring, 41.7 parts of a 9.65% sulfuric acid solution of N-chlorodimethylamine were added, which corresponds to 4 parts at 100 % .
7 parts of FeSO ^ 7HpO were then added batchwise.

The mixture was allowed to react for 2 hours, followed by the contents of the reactor was poured onto 150 parts of chopped ice. After extraction with chloroform, the solvent was distilled off and man

received 2.4 parts of the starting product.

> and after the mother liquids were made alkaline with 30% NaOH / extraction with chloroform, the solvent was distilled off, 7.7 parts of Np-dimethylaminophenyl-N ¹ -ethylurea with a titer of 93.4 % being obtained. Yield about 69.5 %. Melting point = 154 to 156.5 ° C.

Example 2

A reactor as in Example 1 was filled with 23.8 parts of a 25.2 strength sulfuric acid solution of N-chloropiperidine corresponding to about 6 parts at 100 % _t 60 parts of concentrated HpSO ^ and, while the temperature was kept below 0 ° C., 8 , Charged 2 parts of N-phenyl-N'-ethylurea. 7 parts of FeSO ₁ I * 7HpO were then added batchwise. The mixture was allowed to react for 2 hours after which time the reactor contents were poured onto 150 parts of chopped ice. After extraction with chloroform, the solvent was distilled and 2.9 parts of the starting material were obtained. 8.9 parts of Np-piperidinophenyl-N'-ethylurea with a titer of 90.2 % were obtained. Yield = 65 J; Melting point = 162.5 to 164.5 ⁰ C.

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Example 3

A reactor as in Example 1 was charged with 150 parts of concentrated H ₂ SO ₂₁ . While the temperature was kept below 20 ° C., 19.4 parts of N-4-methoxyphenyl-N'-ethylurea were added. 37.5 parts of a 21.2% strength sulfuric acid solution of N-chlorodimethylamine, which corresponds to about 8 parts at 100 % , were then added with stirring. Gradually, 14 parts of FeSOj. * 7H_O were added batchwise. The mixture was allowed to react for 2 hours after which the reactor contents were poured onto 300 parts of chopped ice. After extraction with chloroform, the solvent was distilled and 1.7 parts of the starting material were obtained. After making alkaline with 30% NaOH, extracting with chloroform and distilling off the solvent, 22.3 parts of N-3-dimethylamino- ¹ l-methoxyphenyl-N · -ethylurea with a titer of 94 % were obtained. Yield about 90 Ϊ; Melting point 111.5 to 115.5 ° C.

Example 4

A reactor as in Example 1 was charged with 60 parts of concentrated HpSO ^ ₁ and, while maintaining the temperature below 10 ⁰ C, with 9 parts of N-4-ethoxyphenylurea charged. 40 parts of a 9.94 strength sulfuric acid solution of N-chlorodimethylamine, which corresponded to about 4 parts at 100 % , were then added with stirring. 6 parts of FeCl_ were then added intermittently. The further procedural measures of Example 1 gave 9 parts of N-3-dimethylamino-4-ethoxyphenylurea with a titer of 94.7 * · yield 76.4 %; Melting point = 134-137 ° C

Example 5

A reactor as in Example 1 was made more concentrated at 50 parts

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HpS (K and, while the temperature was kept below -5 ° C., charged with 10.4 parts of N-4-ethoxyphenyl-N ', N'-dimethylurea. Gradually, k parts of N-chlorodimethylamine, which were dissolved in 35 parts concentrated H _? SO ^ was added with stirring, then 3.5 parts of PeSO ^. 7HpO was added in batches, and by proceeding as in Example 1, 9.6 parts of N-3-dimethylamino-4-ethoxyphenyl-N were obtained ¹ , N'-dimethylurea with a titer of 9.4 %. Yield = 72 %; melting point = 129 to 131.5 ° '

'C.

The procedure was analogous to Example 3 and the following products were obtained:

at
game
No. acid
mixture catalyst formula I.
N 2
y
2 Chromatographic
see analysis 6th 96 $ H SO
2 4 FeSO, .7H ₀ O
4 2 OCH CH ₂ -CH
lOj> CH ₂ -CH
h '% = o _v elution
• ^CH 2 medium No. 1
RF = 0.5
uniformly *
H

^OC 2 ^H 5 ι CH 96% H SO ₁ FeSO ^ yH ^ O ^ -W 2 5 Eluierungsmit-

^{24 4 2} lOJ ^N c H tel No. 1

2 5! R.F. = 0.1

O uniform

Il NH I

96> S H SO FeSO..7H 0 2 4 4 2

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R.F. = 0.1 uniform

Example acid catalyst game mixture

Formula chromatographic analysis

96% H SO FeSO
.24 4

Eluent # 2 R.F. = 0.2 uniform

10 96SiH ₂ SO ₄ -FeSO ₄ .7H ₂ O ^

H C = O

^CH 3 ^CH 3

HSO ₁ - FeSO, .7H _o 0 2 4 4 ί

CH

"^ O ^N S ^H 5

Eluant No. R.F. = 0.1 uniform

Eluent No. 1 R.F. = 0.65 uniform

^CH

^12th conc 'H ₃

FeSO ₄ .

N-C-N

Eluent No. 1 R.F. = 0.65 uniform

ch ' ^x ch

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At-acid catalyst

game mix

Formula chromatographic analysis

conc-, H-SO FeSO .7H 0 2 4 4 2

H /

H C-N

W ° ^C 2 ^H 5

Eluent No. 1 R.F. = 0.2 uniform

conc

^H ₂ ^S0 _4th

Cl

H C-N

Eluent No. 1 R.F. = 0.2 uniform

^CH

conc. η SO

2 — r4

acetic acid

SO FeSO, .7H O 20 4 2.

Hr ^

\ / Ä ^N

N ^o

LOI _n / 3

¹ p

0CH ^ ^CH ₃

Eluent No. 2 R.F. = 0.1 uniform

conc

TiCl

0 H \ Il /

N-C-N

CK. CH.

Eluent No. 1 R.F. = 0.2 uniform

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- ^2k - 2800711

All products were diluted over silica. Eluent No. 1: benzene = 79 parts, methanol = 14 parts,

Acetic acid = 7 parts.

Eluent No. 2: toluene = 50 parts, ethyl acetate = 50 parts The product of Example 15 showed the same melting point and spectrum as the product obtained in Example 3. The product of Example 16 showed the same melting point and spectrum as the product obtained in Example 1.

B) Production of aminocarbanylacenes

example 1

A reactor equipped with a stirrer, a condenser, a thermometer and a dropping funnel was concentrated with 60 parts of HpSO. and, while the temperature was kept below 0 ^° C., charged with 9.75 parts of M-methoxyethylcarbanylate. The following ingredients were added with stirring:

19.1 parts of a 20.8% strength sulfuric acid solution of N-chlorodimethylamine, corresponding to about 4 parts at 100 %. 7 parts of PeSO ₁₁ ^ HpO were then added batchwise. The mixture was allowed to react for 2 hours after which time the reactor contents were poured onto 150 parts of chopped ice. After extraction with chloroform, the solvent was distilled and 3.68 parts of unreacted product were obtained. The mother liquors were made alkaline with 30% NaOH, and after extraction with chloroform, the solvent was distilled off to obtain 7.26 parts of 3-N, N-dimethylamino-M-methoxyethylcarbanylic acid having a titer of 90.7 % . Yield> 95?

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The product eluted on silica showed a R.P. from 0.5> where the eluent consists of 50 parts of toluene and 50 parts Ethyl acetate and a R.P. of 0.5, the eluent being consisted of 79 parts of benzene, 14 parts of methanol and 7 parts of acetic acid.

The procedure of Example 1 was followed, but the starting materials varied, i.e. the kind of carbanylate and chloramine, and obtained the following products.

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Example no.

Acid mixture

catalyst

FeSO

H ₂ SO ₄

FeSO

FeSO

formula

Chromatography before analysis

CH

NH
\;

OCH,

.0

Eluent # 2

RP: 0.4
uniformly

NH.
C = O

/ ^CH 3 ^X CH.

Eluent # 2

RF: 0.6
uniformly

[δ]

, CII. 'CIL

^OCH 3

Eluent # 2

RF: 0.6
uniformly

CXD

O CD

Case-Acid Catalyst Formula Chromatographic

game mix analysis

No.

co O CS CO

CO O

H SO 96 $ ^FeS0 / t HC eluent

* ■ * VJ / O Λ

I R.F .: 0.35

[OJ uniformly

<*> 6 ^Η ο ⁵⁰ , 90 $ ί ^FcS0 A \ 2 ς Ν CH eluent

" ⁴ I -" ^ ' 2 No. 2

R.F .: 0.7 uniform

! Ό

00 CD CD

Example no.

Acid gel mi β ch

catalyst

formula

Chromatographic analysis

H ₉ SO ₄

FeSO

4th

OCH,

ch:

I ²

CH

^N f ^H 2

N .CH,
^N CH,

H'

C = O ι

Eluent # 2

R.P .: 0.65 uniform

H ₀ SO, 9H

ό -4

FeSO

? ^C1I 3

II

• c * o

OCH,

CH

^CH

Eluent N 2

R.F .: 0.65 uniform

H SO 2

FeSO

CH.

OCH,

Eluent # 2

R.F .: 0.75 uniform

K)

00

O O

Example no.

Acid gel mis ch

catalyst

formula

Chromatographic analysis

α »ο co

10

11

H ₀ SO. 905S 2

FeSO

FeSO

CH

CH

N O I

.N

CH

Bluing agent No. 1

RP: 0.6
uniformly

Eluent # 2

RP: 0.7
uniformly

12 ILSO 96% - £ 5

CH COOH

15th

FeSO

Eluent # 2

RP: 0.5
uniformly

QD O O

Example no.

Acid mixture

catalyst

formula

Chromatography before analysis

CO OO IS>

13th

14th

H-SO. 98J6 2

H ₀ SO. 2

^TiC1 3. '

FcSO

H-

.CH

C = O ÖCH "

.CII

3 CH,

C = O OCH ₃ .

Eluent No. 2 R.P .: 0.4 uniform

Eluent No. 2 R.P .: 0.5 uniform

15th

96%

FeSO

ίο

.CH.

'2' 5

C = O OClI,

Eluent No. 2 R.P .: 0.45 uniform

ho co

Example no.

Acid gel mi β ch

catalyst

formula

Chromat ographisehe analysis

ο co co rx> co

16

17th

96 *

^H 2 ^S ° 4

FeSO

FeSO

, C-OC ₂ H ₅

LOJ " ^CH 3

N CH ₃ "^ CH ₃ .H.

Eluent No. 1

RP: 0.4
uniformly

Eluent No. 1

R.P .: 0.45 uniformly

All products were diluted over silica,

Eluent No. 1: 79 parts of benzene * Ik parts of methanol, 7 parts of acetic acid

Eluent No. 2: 50 parts of toluene, 50 parts of ethyl acetate,

For: Aziende Colori Nazionali Affini - ACNA S.p.A. Milan / Italy

Di * Vh. ff. Wolff Lawyer

809828/0799

Claims (1)

;, WOLFF & BEIL? Αηηΐ1 RECHTSANWÄLTE ^ ^U _; [ '. ADELON3TRAS5E 53 6230 FRANKFURT AM MAIN 80 Patent claims: 1. Process for the preparation of substituted aminobenzenes, v_ characterized in that one substituted Benzenes with N-chloramines ir. A redox system and aminated directly in an acidic reaction medium. 2. The method according to claim 1, characterized in that phenylurea is used as substituted benzene. 3 · The method according to claim 1, characterized in that as substituted benzene esters of carbanyl acids used. k. Process according to Claim 1, characterized in that N-chloramines of the general formula are used Cl-N wherein R, an optionally substituted alkyl, cycloalkyl or Aralkyl radical,
Rh is hydrogen or an optionally substituted one Alkyl, cycloalkyl or aralkyl radical and R 1 and R j together represent an optionally substituted cyclic radical Radical which may optionally contain heteroatoms. 5. The method according to claim 2, characterized in that one uses phenylureas of the general formula 809820/0799 wherein R and R are identical or different. know and hydrogen or an optionally substituted alkyl, cycloalkyl, aryl or aralkyl radical, R _{2 is} hydrogen or an optionally substituted alkyl, Cycloalkyl, aryl or aralkyl radical and A an optionally substituted benzene nucleus with at least mean a free position. 6. The method according to claim 2 for the preparation of aminophenylureas the general formula wherein R, R, Rp, R, R ^ and A have the preceding meaning, thereby characterized in that a pheny! urea of claim 5 with an N-chloramine of claim 4. 7. The method according to claim 3, characterized in that a carbany acid ester of the following general formula used 809828/0799 worxn R is an optionally substituted alkyl, cycloalkyl, Aryl or aralkyl radical, Rp hydrogen or an optionally substituted alkyl, Cycloalkyl, aryl or aralkyl radical and A denotes an optionally substituted benzene nucleus with at least one free position, where the substituents of R., R "and A halogen, nitrile, sulfonic acid groups and their esters, the carboxylic acid group and their esters, amino, hydroxyl, alkoxyl, substituted alkoxyl, alkyl, substituted Alkyl, acylamino, uric acid or cycloalkyloxy groups represent. 8. The method according to claim 3 for the preparation of esters amino-substituted Carbany acids of the following general formula ^R i wherein R., R, R, R ₁ ^ and A have the above meaning, characterized in that a carbanyl acid residue of claim 7 is reacted with an N-chloramine of claim * J. 9. The method according to claim 1, characterized in that a reaction medium is used, the sulfuric acid, trifluoroacetic acid and mixtures thereof with acetic acid as the strong acid and a ferrous, cuprous and titanium III salt. 809828/0799 10. The method according to claim 9, characterized in that an acidic reaction medium is used which contains ferrous sulfate. 11. The method according to claim S _3, characterized in that an acidic reaction medium is used, the concentrated HpSOi, or mixtures thereof with solvents, wherein the H ₂ SO. is present in a concentration of at least 25 wt. 12. The method according to any one of the preceding claims, characterized in that the N-chloramine is used in a molar ratio between 1: 3 and J>: 1, based on the phenylurea. 13. The method according to any one of the preceding claims, characterized in, that the Perrosulfat in a molar ratio between 1: 1 and 1: 100, preferably 1: 1.2 and 1:50, based on N-chloramine, are used. 809828/0799 \