DE1803636B2 - PROCESS FOR THE PRODUCTION OF ARYLOTRIAZOLES - Google Patents

Description

N = N-R

NH,

20th

(H)

wherein A and R have the meaning given above, characterized in that a thionylaniline of the general formula III is used as the oxidizing agent

R ₁ -NSO

(HI)

JO

where Ri is an optionally substituted one Phenyl radical is used.

2. The method according to claim 1, characterized in that that the reaction is carried out in inert organic solvents.

3. The method according to claim 1 and 2, characterized in that the reaction is carried out at 80-200 ° C. 4 ο

4. Process according to Claims 1-3, characterized in that one per mole of o-aminoazo compound 1 -4 moles of thionylaniline used.

The present invention is a process for the preparation of arylotriazoles, as it is in Claim 1 above is defined.

The reaction is preferably carried out at temperatures of about 80-200 ⁰ C in inert organic solvents.

Suitable radicals A in the compounds of the general formula I or I are, for example remaining members of an optionally further substituted phenylene, naphthylene or acenaphthylene radical, where as substituents in particular the following t> o his called: halogen such as chlorine and bromine, alkyl radicals with 1-12 carbon atoms, alkoxy radicals with 1 - 12 carbon atoms, dialkylamino residues such as dimethylamine and diethylamino residues, acylamino residues such as alkyl and arylcarbonylamino radicals, for example acetylamino, butyroylamino, benzoylamino radicals and arylsulfonylamino radicals, for example N-methylbenzenesulfonamido radicals, alkylsulfonates, for example Methyl and ethylsulfone residues, sulfonic acid alkyl ester residues and sulfonic acid aryl ester residues, for example Sulfonic acid methyl, ethyl and phenyl ester residues. Suitable aromatic-carbocyclic radicals R are for example optionally further substituted phenyl and naphthyl radicals, with as substituents for example halogen such as chlorine and bromine, alkyl radicals with 1-12 carbon atoms, alkoxy radicals with 1-12 Carbon atoms, dialkylamino radicals such as dimethylamino and diethylamino residues, acylamino residues such as Alkyl and arylcarbonylamino radicals, for example acetylamino, butyroylamino, benzoylamino radicals and Arylsulfonylamino radicals, for example N-methylbenzenesulfonamido radicals, alkylsulfonates, for example Methyl and ethylsulfone radicals, sulfonic acid alkyl ester radicals and sulfonic acid aryl ester radicals, for example Sulfonic acid methyl, ethyl and phenyl ester radicals, as well as nitro and azo groups, may be mentioned.

Suitable aromatic-heterocyclic radicals R are, for example, in the 7-position with the azo group linked coumarin or carbostynl residues, for example in the 3-position further substituents, in particular aromatic-carbocyclic or aromatic-heterocyclic May have radicals, such as phenyl, alkylphenyl, alkoxyphenyl and halophenyl radicals, also pyrazolyl, 1,2,3-triazolyl and 1,2,4-triazolyl radicals. Examples include tolyl, 3,4-dimethylphenyl, Methoxyphenyl, butoxyphenyl and chlorophenyl radicals.

Compounds of formulas I and II are m larger Number known from literature. In this context, we only refer to the following publications:

Belgian patent 6 33 336,

Belgian patent 6 65 688,

Belgian patent 6 81 962,

Belgian patent 6 84 677,

French patent specification 14 58 839, French patent specification 11 72 134, U.S. Patent 27 84 183,

German exposition 12 07 331, German exposition 12 13 111,

German Auslegeschrift 12 71 309. The compounds of general formula I are used for example as optical brighteners, dyes or light stabilizers.

The compounds of the formula II are generally obtained by diazotizing suitable amines R — NH ₂ and coupling onto the corresponding aromatic-carbocyclic amines in the o-position to the amino group.

With some aromatic carbocyclic amines, e.g. B. the unsubstituted aniline, is this synthetic route not possible for the preparation of the starting compounds of the general formula II. Then one goes away corresponding o-nitroazo compounds which lead to the starting compounds of the general formula II be reduced. So you get z. B. from 2-nitro-2'-hydroxy-5'-methylazobenzene (Beilstein 16, 137, II 62) after esterification with toluenesulfonic acid and reduction of the nitro group, compound no. 2 A in the table.

Suitable thionylanilines of the general formula III are, for example, thionylaniline and also, for example thionylanilines substituted by halogen, alkyl or nitro groups.

The generally applicable process, which is particularly useful for the production of arylotriazoles with Suitable alkoxy groups is generally used in the

Way carried out that 1 mol of the aminoazo compound (II) at 80-20O ⁰ C, preferably about 160-180 "C, in high-boiling inert organic solvents such as toluene, xylene, chlorobenzene, dichlorobenzene or dimethylformamide for several hours with -, about 1 - 4 moles of the thionylaniline (III) are heated. After cooling, the arylotriazo (I) generally precipitates and can be isolated by filtration.

It was already known that o-aminoazo compounds of the general formula II by oxidation in To convert arylotriazoles of the general formula I. In this context we only refer to the following publications:

US Patent 29 27 866,

Belgian patent 6 33 336, French patent 14 58 839,

A. Michaelis, G. Erdmann, Chem. Ber. 28, 2192 {1895).

For such a ring closure, copper salts (e.g. copper sulfate in aqueous ammonia or copper acetate in pyridine), sodium chloride solution, nitrobenzene, air in the presence of metallic copper or thionyl chloride is used. However, all of these methods have certain disadvantages at. For example, thionyl chloride cannot be used if sensitive to hydrogen chloride Groups, for example ether groups, are contained in the molecule. Chlorine hydroxide cannot be used if the molecule contains groups which can be substituted by chlorine. When using The complete removal of traces of copper from the reaction products often causes difficulties with copper salts. In nitrobenzene the ring closure is often too slow and the air oxidation is because of it drastic conditions for substances containing other oxidation-sensitive groups are often unsuitable.

In contrast, it was new and surprising that thionylanilines were also excellent for implementation of the ring closure are suitable. The use of thionylanilines also offers the advantage of being easier Way and high yields to deliver pure products without disruptive side reactions, with as starting compounds also those can be used which, for example, against sodium chloride solution or hydrogen chloride have sensitive groups.

The parts given in the following examples are parts by weight. The degrees are degrees Celsius.

example 1

50

26 parts of benzene- {l-azo-l) -naphthyIamin- (2), which was obtained by coupling benzene diazonium chloride to naphthylamine- (2) sulfonic acid- (l), are obtained with 39 parts of o-dichlorobenzene and 35 parts of thionylaniline Heated under reflux for an hour. The solvents are distilled off in vacuo and the residue is recrystallized from a little glacial acetic acid with the addition of activated charcoal. 20 parts of 2-phenyl-naphtho [1,2: d] -triazole, which _{melts at 100-102 ° b0} , are obtained.

Example 2

31.6 parts of 3'-nitro-4,4'-dimethoxy-2-amino-3-methyl- _M azobenzene and 38 parts of thionylaniline are heated to 170 ° in 77.5 parts of o-dichlorobenzene for 5 hours. After cooling and filtering off with suction, 20.1 parts of 2- [3-nitro-4-methoxyphenyl] -5-methyl-6-methoxy-benzotriazoi with a melting point of 214-215 ° are obtained.

Example 3

223 parts of 3-phenylcoumarin- (7-azo-5) -4amino-2n-butoxy-1-methylbenzene are heated to 185-190 ° for 4 hours with 200 parts of dichlorobenzene and 181 parts of thionylaniline. After cooling to room temperature the precipitated reaction product is suctioned off and once each from nitrobenzene and dimethylformamide re-crystallized. There are 120 parts of 3-phenyl-7- [5-n-butoxy-6-methylbenzotriazolyl- (2)] - coumarin obtained from melting point 208-210 °. The 3-phenylcoumarin- (7-azo-5) -4-amino-2n-butoxy-1-methylbenzene used as the starting material was made as described in Belgian patent specification 6 84 677.

Example 4

42.7 parts of 3-phenylcoumarin- (7-azo-5) -4-amino-2n-butoxy-1-methylbenzene with 76 parts of dimethylformamide and 36 parts of 4-nitrothionylaniline for 5 hours heated to reflux. After cooling, it is filtered off with suction, washed with methanol and at 110 ° dried. 31 parts of 3-phenyl-7- [5n-butoxy-6-methylbenzotriazolyl- (2)] -coumarin are obtained, which, after recrystallization from dimethylformamide, melts at 206 ° -208 °. The 3-phenylcoumarin- (7-azo-5) -4-amino-2n-butoxy-1 used as the starting material -methylbenzene was according to the information- in the Belgian Patent 6 84 677 produced.

Example 5

41.8 parts of 3 [pyrazolyl- (l)] coumarin- (7-azo-5) -4-amino-2n-butoxy-1-methylbenzene are refluxed for 6 hours with 65 parts of o-dichlorobenzene and 35 parts of thionylaniline. After cooling it will Sucked off, washed with methanol and dried at 110 °. 21 parts of 3- [pyrazolyl- (1)] - 7- [5nbutoxy-6-methylbenzotriazolyl- (2)] - coumarin are obtained, which, after recrystallization from dimethylformamide, melts at 205 ° -209 °. The one used as the starting product 3- [Pyrazolyl- (1)] -coumarin- (7-azo-5) -4-amino-2n-butoxy-1-methylbenzene was manufactured as described in Belgian patent specification 6 81 962.

Example 6

38.1 parts 3- [Pyrazory! - (l)] - coumarin- (7-azo-l) -naphthylamine- (2) are refluxed with 65 parts of o-dichlorobenzene and 35 parts of thionylaniline for 2 hours cooked. After cooling, it is filtered off with suction, washed with methanol and dried at 110 °. Man receives 29 parts of 3- [pyrazolyl- (l)] - 7- [naphthotriazo! yl- (2)] - coumarin, which, after recrystallization from dimethylformamide, melts at 267-270 °. That as the starting product 3- [pyrazolyl- (1)] -coumarin- (7-azo-1) -naphthylamine- (2) used was according to the information in Belgian patent 6 81 962.

According to the procedures given in Examples 1-6, also in high yields and high purity, when using the starting materials specified in column A of the following table Triazoles listed in column B obtained.

o-Aminou / m'iTbinding

Triazole

NH ₂

L _n . ν - f J> - cn cn

SO, C ₆ H ₅ N - <

^Vy 'ν SO ₂ C ₁₁ H ₅

ν oso, - ¹ C y-

■ * γ \ X ^w

CH,

CH, O -f

-NH,

QH ₅

N =

C ₂ H ₅

NH ₂

-NH ₂

CH ₃

8th /

Cl

N = N- / Vci

NH ₂

9 C ₂ H ₅ OOC

CoH ₅

7 CHjO —j

_CHi -L _N = N ^> N- _{SO, -O-CH 1}

10 1-C ₁₂ H ₂₅ - ΪΓ N = CH ₃ OL L NH ₂

C ₃ H ₅ CH ₃ ^-1

^CHj

C ₂ H ₅

N OCH ₃

CH ₃

CH ₃ O

^CH 3- \ A

Cl

χΛ /

C ₂ H ₅ OOC

// V

Cl

N Br

/ V-CH ₁

^ VBr

/ YV / VcH ₃

Ν— \ / Xxj / - ^ CH ₃ OA ^ / ^ Ί "θ

Claims (1)

Patent claims: 1. Process for the preparation of arylotriazoles of the general formula I. 10 where A for the remaining members of a mono- or polynuclear aromatic-carbocyclic ring system and R is an aromatic-carbocyclic ι-5 or aromatic-heterocyclic radical, by oxidation of an o-aminoazo compound of general formula II