DE2413223A1 - PROCESS FOR THE PRODUCTION OF DIAZONIUM SALT AND THEIR USE FOR THE FORMATION OF AZO DYES - Google Patents

Description

"Process for the preparation of diazonium salts and their use for the formation of azo dyes "

j The invention relates to a new method for the production of J Diazonium salts and azo dyes that contain a quinone residue in the MoIekill contain, from an amine, or amine salt, which has a hydro-

contains quinone residue in the molecule.

Azo dyes that contain a quinone residue in the molecule are valuable intermediates for dyes and color photography Materials referred to in U.S. Patent 3,134,764 and published JA-PA 444/63 as color developers. The synthesis however, these compounds are difficult and the only known method for doing this is described in U.S. Patents 3,222,169 and 3,307,947. This known method comprises the oxidation of the! corresponding azo dyes containing a hydroquinone radical, j in turn by O-acetylation of amines with a hydroquinone residue to protect the oxidation-sensitive hydroquinone part, the diazotization of the amines obtained, which have a 2,5-diacetoxyphenyl radical, coupling with suitable ones Azo couplers and the subsequent cleavage of the acetyl protective groups. This process thus requires at least 5 steps to convert azo dyes with a quinone residue from the starting amines

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with a hydroquinone residue and is therefore very annoying] In particular, the selective O-acetylation of one hydroquinone residue containing anines is difficult to carry out, since under normal conditions the N-acetylation predominates and in many j In some cases, a Ο, Ν-acetyl migration easily takes place. About it hinatsj the alkaline hydrolysis, which is necessary to split off the acetyl protective groups, must be carried out very carefully as hydroquinone is unstable in an alkaline medium. Thus, this stage is difficult to control and gives low yields.

An object of the invention is therefore to provide a process for the preparation of diazonrum compounds -bzw. Azo dyes that contain a ghinone residue in the molecule, from an amine, or its. Salt containing a hydroquinone residue in the molecule is available to deliver. Another task is to develop a process for the production of valuable compounds for color photo! ! graphic material, especially from color developers, for the ■ to provide that in photographic diffusion transfer j reversal processes can be used.

According to the invention it has been found that it is possible to use an azo j

A dye with a ghinone residue can be produced in good yield by using a primary aromatic amine with a hydroquinone residue in the molecule, or the corresponding ammonium salt, is diazotized and at the same time the hydroquinone part to form a Diazonium compound is oxidized with a ghinone radical and then the diazonium compound obtained with a compound converts, which is able to couple with a diazonium salt. The latter compound is commonly referred to as a coupler.

The subject of the invention is thus a method of production of diazonium salts and diazo dyes containing a quinone residue contained in the molecule, which is characterized in that one has a primary aromatic amine, or amine salt, which has a hydroquinone radical contains in the molecule, with a diazotizing agent and a Reacts oxidizing agent and optionally subjecting the diazonium salt obtained to a coupling reaction with a coupler.

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In the process of the invention, simultaneous Diazotization and oxidation of primary aromatic amines, or the corresponding ammonium salts which have a hydroquinone radical, diazonium compounds with a quinone radical. As primary aromatic Amines can e.g. Aniline, naphthylamines and their derivatives be used. The hydroquinone radical can contain 1 "to 3 substituents, since the meaning of the invention lies in the fact that the oxidation to quinone simultaneously with or successively with there? Diazotization is carried out. The bond between the hydroquinone residue and the primary amine atomic residue is not an important feature for the same reason. In other words Any divalent grouping can exist between the "two radicals "are against diazotizing and oxidizing agents is essentially inert. The hydroquinone residue can also be linked directly to the aromatic ring of the primary aromatic amine

; be linked. Preferred starting compounds "have the ^general; my formulas I and Ia

H ₂ N-Ar- (R) -) (X) ₀

OH

(D

Z ⁰ H ₃ N ®-Ar- (R)

I s

(X) ₀ ■

(Ia)

in which Ar is a benzene or naphthalene ring; X is a substituent on the Ar ring from the group consisting of alkyl radicals (C ₁ "to C ₁₀ ), halogen atoms, such as chlorine, bromine or iodine atoms, alkoxy radicals (C ₁ " to C ₁₀ ), acyloxy radicals (G ₁ "to C ₁₀ ) or hydroxyl groups "means; 1 has a value from 0 to 4; R is a divalent radical from group ■

Alkylene radicals (C ₁ to C ₅ ) and - (CH ₂ ) -R ^f - (CH ₂ ) -, where R 'means -0-, -S-, -SO ₂ -, C = O or -CO- N (R ") - j and
p + q has a value of 0 Ms 5, and R "is an alkyl radical (C. Ms C ₁ -) or a hydrogen atom; R can be linked to Ar in the 1-Ms 8 position," based on the amino group ; m is 0 or 1; Y is a substituent on the hydroquinone radical from the group consisting of alkyl radicals (Cj to C ₅ ), alkoxy radicals (Cj Ms Q ₁ -) and halogen atoms; η has a value of 0 Ms 3; and Z "an inorganic or organic anion such as Cl", Br ", HSO." (or SO.), ClO ~ or AcO ", is.

Those starting compounds which contain a Cj-Ms C ^ -alkylene radical, e.g. the group -CH ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ )., -, - (CH ₂ ) ^ -,
-CH ₂ -CH (CH " ₅ ) -CH ₂ - or - (CH ₂ ) ₅ -, as the connecting group (R), are particularly advantageous because of the easy accessibility of these compounds. In the case of connecting groups, the -S- or secondary amides of carboxylic acids is the yield
low because of the reaction with nitrous acid.

Preferred examples of primary aromatic amines which are used as starting compounds according to the invention and which contain a hydroquinone radical are
3- (Hydroquinony! Methyl) -aniline,
4- (hydroquinonylmethyl) aniline,
5-hydroquinonylmethyl-2-methylaniline,
4-Hydr ο quinonylmethyl-2-methylani1in,
5-hydroquinonylmeth.yl-2-h.ydroxyaniline,
3- (3 ^f -hydroquinonylpropyl) -aniline,
5-hydroquinonylmethyl-2-chloroaniline,
5-hydroquinonylmethyl-2-methoxyaniline,
3- ^(2!, 5-dihydroxy-4 ^{t t} methylbenzyl) aniline, or
1-amino-4-hydroquinonylmethyl naphthalene

(the production of which is described in the examples),

4- (2 ^f -hydroquinonylethyl) aniline,

1-amino-4- (2'-hydroquinonylethyl) naphthalene,

2- (p-aminophenethyl) -5-methy! Hydroquinone,

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_ 5 -

9 L 1199 * 3

2- (p-Aminophenäthyl) -5-ch.lorhydrocMnon, 4- (2 '-Hydroch.inonylath.yl) -2-methylaniline, 2- (p-aminophenethyl) -5,6-dimethylhydroquinone,

2- (p-Aminoph.enath.yl) -3,5,6-trimethylhydroquinone,

3- (2 '-hydroch.inonylath.yl) -aniline,

2- (m-aminophenethyl) -5-meth.ylh.ydroquinone,

4- (3 '-hydroquinonyl-2' -methylpropyl) -aniline, 4- (3'-Hydroch.inonylpropyl) -aniline or 4- (2 '-hydr och.inonylath.yl) -2-methoxyaniline

(the preparation of which is described in U.S. Patent 3,236,893 "), and

p-Am inophenylh.ydroch.inon,

m-Aminoph.enylh.ydroch.inon,

2- (ρ - aminophenyl) - 5 -me th.ylh.ydr ο quinone,

2- (p-aminophenyl) -5-chlorohydroquinone,

2- (3 ^! Methyl-4 ^! -Aminophenyl) -hydr ο quinone, 2- (p-aminophenyl) -5,6-dimethy! Hydroquinone, 2- (4'-aminonaphthyl) -hydroquinone,

2- (m-aminophenyl) -5-methy! Hydroquinone,

2- (4'-Amino-3 ^t -methoxyphenyl) -hydroquinone, 2- (p-aminophenyl) -6-methylhydroquinone,

2- (p-aminophenyl) -5-'bromohydroquinone,

2- (4'-amino-2,5-dimethoxyphenyl) hydroquinone, 2- (4 * -amino-2'-chlorophenyl) -hydroquinone or 2- (4'-amino-2'-methylphenyl) -hydroquinone

(the preparation of which is described in U.S. Patent No. 3,183,089 ").

Further examples of starting compounds suitable according to the invention are in U.S. Patents 3,222,169, 3,142,565, and 3,230,086 as well as in W.E. Solodar, S. Likas and M. Green "J. Chem. Eng. Data", 9, 232 (1964) described as Diacetoxyderirate, the Isicht with formation of the aromatic amines with a · hydroquinone residue can be hydrolyzed.

Here and in the following the term "hydroquinonyl group" refers and "quinonyl group" on the 2, '5-dinydroxyphenyl or 2,5 ~ DioxocyclQhexa-3,6-dienyl group.

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All of the aforementioned compounds can according to the general formula Ia can also be used as ammonium salts.

According to the invention, a simultaneous diazotization and oxidation takes place of the aforesaid amine having a hydroquinonyl group with formation of a diazonium compound of the general J-formula II

N = N-Ar- (R) f

(II)

in which Ar, X, R, Y, Z, 1, m and η have the aforementioned meaning. Since it is known that p-3ensoquinone reacts intermolecularly with a diazonium ion (G, A. Reynolds and J.A. VanAlian in "Org. Synth. Coll., Vol. 4, 15), it has been difficult to foresee the existence of such an ionic species which both a quinone nucleus and a diazonium group in the same Contains molecule. In this regard, the invention represents a new discovery. The diazonium compound of the general Formula II is stable in acidic medium, but cannot be isolated, as is generally the case with diazonium compounds the pail is. However, the expected structure of the diazonium salt can be proven from the fact that the diazonium salt with different couplers in one coupling stage to the corresponding azo dyes reacts.

The Diaaotierungsmittel used according to the invention is nitrous acid, which before the diazotization-oxidation reaction or, more preferably, in situ, by the action of acids, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or acetic acid, on inorganic Hxtrite, such as sodium -, potassium, calcium or barium nitrite. The molar ratio of nitrous acid to starting amine can be about 1: 1 to 4: 1, preferably 1; 1 Ms 1.5: 1 ».

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The reactive forms of the diazotizing agent are detailed

TJj. Z ο xl ing he discussed in the literature, ζ. B γ in "Azo and Diazo" Chemistry, Aliphatic and Aromatic 'Compounds "pp. 24 to 37 (1961), Interscience Publishers Inc., New York.

Accordingly, the term "nitrous acid" as used herein includes all of the literature derived from the diazotizing agent reactive species described.

Oxidizing agents suitable according to the invention are not only nitrous Acid itself, but also halogen-containing oxidizing agents Acids such as chloric acid, bromic acid or iodic acid, shark peracids, such as perchloric acid, hypohalous acids, such as hypochlorous acid, nitric acid, Caro's acid, chromic acid, sodium or potassium dichromate, permanganic acid, sodium and potassium permanganate, or ferric chloride, such as in Jikken Kagaku

Koza "Lecture on ExOerimental Chemistry", Vol. ' 17 (Part I), 1957, besali ri just,

besali ri,.

Maruzen Co., Ltd Λ of these oxidizers become nitrous Acid and nitric acid are particularly preferred. A stoichiometric amount or a slight excess (up to 1.5 equivalent) the oxidizing agent is used to oxidize the hydroquinone residue of the starting amine is sufficient. The use of a large excess of oxidizing agent is not desirable.

An acidic aqueous solution is expediently prepared from 1 part of the amine and diazotized by adding an aqueous solution of at least 1 part of the aforementioned inorganic nitrite, followed by the addition of a solution of the oxidizing agent in an amount necessary for the oxidation of the hydroquinone radical to form a solution of the corresponding diazonium salt is. The reverse order can also be used for the addition or can be added at the same time.!

The temperature during the diazotization-oxidation reaction is preferably approximately -20 to 20 ^° C., in particular -5 to 5 ° C.

If nitrous acid is used as the oxidizing agent, both the diazotization and the oxidation of the hydro- j quinone residues performed using the same reagent j

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will. Therefore, the use of nitrous acid is extremely advantageous from the viewpoint of reducing the number of stages required and simplifying the process. In this pail at least 3 hol nitrous acid f are required to the diazotization-oxidation reaction of 1 mole of one. To cause amine with a hydroquinone radical, since 1 mol of nitrous acid is required for the diazotization and 2 mol for the oxidation! Of the hydroquinone radical. A large excess of the reagent can reduce the yield in the subsequent azo coupling and is preferably obtained by treatment with sulfamic acid or the like It is known to use nitrous acid only as an oxidizing agent (LPFieser in "J. AmerrfSoc." 70, 3165 (1931) ), and diazotization j is also a generally known reaction for the first time the possibility of performing diazotization and oxidation simultaneously using nitrous acid.

The coupling reactions of the aforementioned diazonium salts can be carried out using conventional methods such as; are described in large numbers in the literature, e.g. in "G-osei | Senryo (Synthetic Dye) "by Hiroshi Horiguchi, Chapter 5, 1968, ι Sankyo Shuppan, Co., Ltd.," Fundamental Processes of Dye Chemistry " by H.E. Fierz-David and L. Blangey, pp. 239-297, 1949, j Interscience Publishers Inc., New York, and "The Chemistry of Synthetic Dyes "by K. Venkataraman, Chapter 11, 1952, Academic Press Inc., Publishers, New York.

So is allowed to be a solution-of a coupler in water or a water-soluble organic solvent such as methanol, ethanol, 2-metho "cyäthanol or 2-ethoxyethanol, not with- an aqueous solution of the diazonium salt at a temperature of about etv / a 50 ⁰ C, preferably not above 20 ° C. * The azo coupling is generally carried out at a pH value which is not above 9.

The azo dyes according to the invention can be prepared by all common formula III __

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KN = N-Ar- (R)
I.

^(X) "- (in)

reproduced v / earth, in which K represents the remainder of a coupler or an azo coupling component, and Ar, X, R, Y, 1, m und_.n have the aforementioned meaning. The structures of the azo dyes can also be represented by the corresponding hydrazone forms.

Examples of suitable coupling components or couplers from which K can be derived are phenolic compounds and aromatic amines that have a free o- or p-position to the hydroxyl or have an amino group, e.g. phenols, anilines, naphthols, anthrols or naphthylamines; heterocyclic aromatic Compounds containing hydroxyl or amino groups, such as pyrazolones, pyrroles, thioindoxyls, ghinolinols or amino quinols; aliphatic or alicyclic activated methylene couplers, i.e. compounds which have an aliphatic or alicyelic Have methylene group activated by two adjacent keto, aldehyde, ester or nitrile groups, which are the same or different, or a keto, aldehyde, ester or e-nitrile group in combination with an amide group, e.g. 1,3-diketones or β-keto acid arylamides; as well as substituted Derivatives of the aforementioned compounds. Examples of groups or radicals contained in such substituted derivatives are alkyl, sulfo, alkoxy, aryl, aryloxy, Amino, keto, alkylamido, carbalkoxy, carboxamido or sulfonamido groups or radicals.

Here and in the following, in connection with K, the term "radical of a phenolic coupler" means hydroxyphenyl, hydroxynaphthyl, Hydroxyanthryl, etc. radicals and substituted derivatives thereof; the term "residue of an aromatic amino coupler" Aminophenyl, aminonaphthyl, etc. radicals as well as sub-

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substituted derivatives thereof; and the terms "residue of a heterocyclic aromatic coupler "," remainder of an aliphatic activated methylene coupler "and" remainder of an alicyclisdi en activated methylene coupler "are to be understood in a similar way.

Some specific examples of those made according to the invention
Azo dyes are given below.

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N = N

CH ₂ CH ₂ -I

OCH (CH ₃ ) CH ₃

Il 0

0 Il

CH2CH2

OCH ₂ CH ₂ OCH ₂ CH ₃

Π 0

CO-C-CH n-m- / VcH ₂ CH ₂

n-CsH I ₃ NHCO-

CH ₂ CH ₂

Il 0

OH

-OCH ₃ N = N (/ ^ VCH2CH2

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-N = N- / V

CH ₂ CH ₂ -

OCH ₂ CH ₂ CH ₃ 0 II

Il 0

NH ₂

NH ₂

CH ₂ CH ₂

CH ₃ O

(10)

. 409839/1072

(ID

N = N

Il

CONHCH

OCH (CH ₃ ) CH; Z '

Il 0

(12)

(13)

i-N = N

OCH (CH ₃ ) CH; Ii

Il

'= N-NH

-CH ₂

CN

CO-C = N-NH-L ^ JL CH ₂

(15)

N = N

-CH ₂

OCH (CH ₃ ) CH ₃

(16)

N = N

OCHzCHzOCH ₃

-CH ₂

0 It

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(17)

(18)

(19)

(20)

- 14 -

n-CeHiaNHCO-

-N = N

CN ^CH3 Ji-CO-C = N-NH

CN CO-C = N-NH

CH ₃ -CHj

'-CH ₂

CH ₂

(21)

HO

CN

o J-CO-C = N-:

'-CH ₂

409839/1072 o II

- - 15 -

(22)

QoC r

HO

It

0 "CO-C = N-NH-"

CH;

Il 0

(23)

t /

N-NH-f ^^ - CHj »

Hi

H ο

(24)

NH ₂

CH ₃

-CH ₂

(25)

(26)

, CH ₂

NH ₂

N = N

'-CH ₃

, -CH ₂

. 409839/1072

The azo dyes shown above can either be in the azo or the hydrazone form, between which an equilibrium can be reached quickly ("cf. Zollinger, loc. cit., pp. 322-525).

Further examples of couplers used in the present invention are in the ÜS-PS 2 992 106, 5 134 763, .5 236 645, 3 134 764, 3 297 441, 3 134 762, 3 236 643, 3 134 765, 3 135 754, 3 173 906, 3 185 089, 3 183 093, 3 201 384, 5 208 991, 5 218 512, 5 262 924, 3 275 617, 3 077 402, 3 282 913, 3 309 199 ,. 3,252,969, 3,022,554, 5 252 990 and 5 222 169. Further suitable couplers are in Houben-Weyl "Methods of Organic Chemistry", Georg Thieme Verlag, Stuttgart, 4th ed. Vol. X / 5 (1965), p. 213 through 314 and 477 through 544.

The diazo cells made according to the invention are very useful as Zvri.schen connections, not only for the production of Azo dyes, but also for many other compounds. the Azo dyes can be used either as dyes per se or as dye intermediates. For example can different color developers obtained in a simple manner v / earth that one reduces the quinone radicals of the aforementioned azo dyes with a reducing agent such as ϊί, Ν-dialkylhydroxylamine, as described in JA-PA 52 838/73, or with hydrogen in the presence of a suitable catalyst, such as palladium-on-charcoal catalysts. About that In addition, the azo dyes indicated above are particularly valuable as a type of intermediate compound, the use of which is e.g. in U.S. Patents 3,307,947 and 3,579,334.

The examples illustrate the invention. Unless otherwise stated, All parts, percentages, proportions and other information are based on weight.

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In the examples, the reference numbers relate to those represented in the description with the same reference numbers in terms of formulas Links.

example 1 Synthesis of the compound (1):

A solution of 13.3 g (0.05 mol) of 4- (2'-hydroquinonylethyl) aniline hydrochloride in 600 ml of hydrochloric acid (2.5 percent) is stirred over the course of 20 minutes while the temperature is at -5 to ⁰ ° C., 150 ml of an aqueous solution of 11.0 g (0.16 Hol) of sodium nitrite are added dropwise; the mixture is then stirred for 1 to 2 hours. After a portion of 1.0 g of sulfamic acid has been added to the reaction mixture to destroy the excess nitrous acid, a portion of 45.0 g of sodium acetate is added in order to adjust the pH of the reaction mixture to about 4. During the aforementioned operation is added to the .Gemisch with ice chips butted not to let to rise to about 3 ⁰ C to the reaction temperature. The diazonium salt obtained i solution is added dropwise to 500 ml of an ethanolic solution of 10.1 g (0.05 mol) of 4-isopropoxy-1-naphthol at a temperature not exceeding 10 ⁰ C added. Are then added dropwise 400 ml of a saturated aqueous Natriurahydrogencarbonatlösung added and stirred the mixture for 1.5 hours at room temperature (about 20 to 30 ⁰ C). The precipitated crystals are separated off by filtration and air-dried. When recrystallizing from HO ml of a benzene-methanol mixture (4: 3 by volume), 11.2 g of the compound (1) from Έ are obtained. 168 to 170 ^G C.

Analysis,

C. 6th JS 4th 6th Ή found 73, 6th 5, 5 6th , 3 ber. 73, 5, , 4

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Example 2 Synthesis of the compound '(1) by joint use of nitrous Acid and nitric acid:

A solution of 3.0 g (0.011 mol) of 4- (2'-hydroquinonylethyl) -ani lin hydrochloride, 9 ml of hydrochloric acid (35 percent) and 150 ml of water is mixed with 0.2 ml of 2-ethyl-i-hexanol . added as defoaming agent; the mixture is cooled in a salt-ice mixture to a temperature below ⁰ ° C. The solution is then treated dropwise with 30 hjI of an aqueous solution of 2.6 g (0.038 hol) of sodium nitrite. The mixture is stirred for 50 minutes at a temperature below 3 ° C and then added dropwise with dilute nitric acid, which consists of 3 ml nitric acid (density 1.33) and 20 ml water After stirring for 20 minutes, 1.0 g sulfamic acid and then 20 g sodium acetate are added The diazonium salt solution obtained reacts with 2.0 g (0.010 hol) of 4-iso; propoxy-1-naphthol, in the same manner as described in Example 1, to give 2.6 g of the compound (1) The compound obtained is identified by comparing the results of thin-layer chromatography, the IR absorption spectrum, the UV absorption spectrum and the H-IR spectrum with those of the compounds obtained in Example 1. This shows that the joint use of nitrous acid with Nitric acid increases the yield of the compound (1) while inhibiting the formation of a hydroquinonyl group-containing by-product;

N = NV ^ CH ₂ CH ₂

OCH (CH ₃ ):

An auihaitic sample (m.p. 222 to 224 ° C) of this by-product is produced by reducing the compound (1).

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Example 3

Synthesis of compound (1) by "joint use of nitrous acid" and nitric acid:

In the procedure of Example 2, the order of addition of the sodium nitrite solution and the dilute nitric acid is reversed. A solution of 3.0 g (0.011 mol) · 4- (2 ^! -Hydroquinonylethyl) -aniline-hydrochloride in 200 ml of water is mixed with 30 ml of nitric acid (density 1.38) "at a temperature of below 3 ° C. Each 20 minutes' stirring is added dropwise to a solution of 0.8 g (0.011 mol) of sodium nitrite in 30 ml of water g sodium acetate. The diazonium salt obtained reacts with 2.0 g (0.01 mol) of 4-isopropoxy- · 1-naphthol in the same manner as in Example 1 to give 2.8 g of the compound (1).

Thin-layer chromatography and various spectral Data show that this product is similar to that obtained in Example 1 authentic sample.

Example 4

Synthesis of the compound (1) by using nitrous acid and chloric acid together;

A mixture of 3.0 g (0.011 mol) of 4- (2 ^! -Hydroquinonylethyl) aniline hydrochloride, 12 ml of hydrochloric acid (35 percent) and 150 ml of ice water is added dropwise with a solution of 0.8 ^ (0.011 mol ) Sodium nitrate is added to 30 ml of water. After 10 minutes, add dropwise 30 ml of an aqueous solution of 1.0 g (0.0065 mol) Matriumchlorat at a temperature of 0 to 2 ⁰ C and stir for another 20 minutes. After the addition of 15 g of sodium acetate, the reaction mixture is left with 2.0 g (0.01 mol) of 4-isopropoxy-1-naphthol, in the same manner as described in Example 1, to give 2.0 g of the compound (1 ) react. The identification of this product shows that it corresponds to the authentic sample of Example 1. :

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- 20 example

Synthesis of the compound (1) by, joint use of nitrous acid and Garo's acid:

7 ml of concentrated sulfuric acid are added to 150 ml of an aqueous solution of 3.0 g (0.011 mol) of 4- (2 ^{I '-hydroquinone-ethyl) -aniline hydrochloride.} Then 30 ml of an aqueous solution of 0.8 g (0.011 mol) of sodium nitrite and then 30 ml of an aqueous solution of 2.3 g (0.01 mol.) Of ammonium persulfate are added dropwise. During this time, the reaction temperature falls to below 1 ° C. 15 minutes later, a solution of 2.3 g of ammonium persulfate and 2.5 ml of concentrated sulfuric acid in 30 ml of water is added dropwise. 4-Isopropoxy-i-naphthol, described in the same way as in Example 1 ■, 0.6 g of compound (1) is obtained.

Example 6 Synthesis of the compound: (2):

According to Example 1 from 11.6 g of 4- (ß-ethoxyethoxy) -i-naphthol 12.8 g of the compound (2) of P. 148 to 149 ° C were obtained.

Analysis,

C. 5 _2 5 M " 1 found: 71 5 5, 6th 0 ber .: 71 5, 6,

Example 7

Synthesis of the compound (3):

According to Example 1, a mazonium salt solution of 3.0 g 4- (2'-Hydroquinonylethyl) aniline hydrochloride produced. These Solution is added dropwise with a solution of 1.9 g of Gj-cyano-2-acetyl-benzofuran, 200 ml of ethanol, 0.6 g of sodium hydroxide and 10 ml of water are added. After filtering off the excreted Crystals, drying in air and recrystallization from acetone gives 1.4 g of compound (3) with a temperature of 175 ° to 177 ° C.

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Analysis,

- 21st ■ H
MVM 0 24 C. 9 4, 1 N found: 70 9 4, 10.2 ber .: 70 9.9

Example 8

Synthesis of the compound (4):

According to Example 7, from 2.8 g of IT-hexyl-i-phenyl-5-pyrazalone-3-carboxamide, 0.2 g of the compound (4) from -E is grounded. 121 "to 124 ⁰ C produced.

Analysis, G ₃₀ H ₃₁ Ii ₅ O ₄ :

C. 7th 6th H
■ MM · IT 5 found: 68, 6th 5 , 0 13, 3 ber .: 68, , 9 13,

j Example 9

Synthesis of the compound (5):

According to Example 1, a diazonium salt solution is prepared from 3.0 g of 4- (2 ^l - hydroquinonyl) aniline hydrochloride. The solution obtained is mixed with a suspension of 1.3 g of m-kethoxyphenol, 10 g of sodium hydrogen carbonate and 150 ml of ethanol. After the crystals obtained have been filtered off, dried in the air and recrystallized from ethanol, 2.7 g of the compound are obtained (5) from Έ. 183 to 186 ⁰ G.

Analysis, C ₂₁ H ₁ ^ IT ₂ O .:

0
MMHW 6th 5 H ■■■■ < ■ H
■ MMYHM .f .: 69 6th 5 , 0 7th , 7 ber .: 69 , 0 7th , 7

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Example 10 Synthesis of 3- (HvdrocIinonylmethyl) -aniline:

(a) 2,5-Dimethoxy-5 ^t -nitrobenzophenon:

300 g of aluminum chloride are added to a solution of 372 g of m-nitrobenzoyl chloride and 280 g of p-dimeth-oxybenzene in 1.6 liters of dichloromethane. The mixture is stirred for 1 hour at room temperature, then left to stand overnight (15 hours) and poured into 1 liter of ice water. After separation, the organic layer obtained is washed twice with 300 ml of water and then evaporated to dryness Recrystallization of the crystalline residue from ethanol gives 470 g of 2,5-dimethoxy-3'-nitrobenzophenone as light yellow crystals from E. 98 ⁰ G.

(b) 2,5-Dimethoxy-3'-aminobenzhydrol:

A mixture of 100 g of 2,5-dimethoxy-3-nitrobenzophenone, 1.3 liters of ethanol and 1.0 g of a 10 percent palladium-on-charcoal catalyst is ^{hydrogenated in a 2 liter autoclave at 130 °} C. for 8 hours subjected to reduction at an initial pressure of 100 kg / cm. After the catalyst has been filtered off, the filtrate is concentrated to 150 ml, the desired garbinol being obtained in the form of white crystals which are separated off by filtration. 57 g of E. 132 to 134 ^° C. are obtained.

(c) 1,4-Dimethoxy-2- (3'-aminobenzyl) benzene:

A suspension of 96 g. Zinc powder and 50 g of 2,5-dimethoxy-3 ^I -aminobenzhydrol ml in 300 acetic acid is at 80 ⁰ C under vigorous stirring dropwise with 240 ml of hydrochloric acid (35 percent) was added. After stirring for 30 minutes, a further 240 ml portion of 35 percent hydrochloric acid is added, and the reaction mixture is then stirred for 2 hours. After cooling, the supernatant solution is decanted and neutralized with 30 percent sodium hydroxide solution up to pH 5. The separated oil is extracted with ethyl acetate. After the

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some of the extracts (about 500 ml) these are washed with a saturated aqueous sodium hydrogen carbonate solution and dried over anhydrous potassium sulfate. When constricting and Distilling "at the boiling point 170" to 175 ° O / 1 Torr is obtained 36 g of the desired compound in the form of white crystals with a melting point of 81 to 84 ° C.

(d) 3 - (* Hydrochir ~ onylmethyl) aniline:

A mixture of 27 g of 1,4-dimethoxy-2- (3 ^! -Aminobenzyl) -benzene and 210 ml of hydrobromic acid (4%) is refluxed at a bath temperature of IpO ⁰ C for 1 hour The resulting solution is cooled in an ice-salt bath, the hydrobromide of the desired compound precipitates and is separated off by filtration, after the hydrobromide has been dissolved in 200 ml

v / ird
WasserYmit- neutralized with 25 g of sodium acetate. This gives the corresponding free amine, which is separated off by filtration and recrystallized from ethanol-bensol (1: 3 volume mixture). 16 g of 3- (hydroquinonylmethyl) aniline from P. to 152 ^° C. are obtained.

Example 11

Synthesis of the compound (15),?

A cooled mixture ( ⁰ ° C.) of 8.4 g of 3- (hydroquinonylmethyl) aniline, prepared as in Example 10 (d), 400 ml of ice water, 27 ml of hydrochloric acid (55 percent) and 0.6 ml of 2 -Ethyl-

ιτητ, ρ. ~ ρ ΏιΊΤτρρ η? 1-hexanol (as a defoaming agent) wircnwährend a period of about 10 minutes at a temperature of below 2 ⁰ C with 100 ml of an aqueous solution of 8.4 g of sodium nitrite. After the reaction mixture ^{has been stirred at 0 to 2 °} C. for 90 minutes, the reaction mixture is treated with 1.0 g of sulfamine acid and then with 47 g of sodium acetate. This gives a solution of the 3- (quinynylmethyl) phenyldiazonium salt, which is used for azo coupling reactions will.

A solution of 7.5 g of thioindoxyl-2-carboxylic acid in 400 ml of Etna and 10 ml of an aqueous solution of 2.0 g of sodium hydroxide

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are mixed together. The mixture obtained is poured into the aforementioned diazo solution at a temperature below 15 G. The precipitated solid is separated off by filtration, dried in the air and recrystallized from 1,2-dichloroethane / ethyl acetate (1: 1 volume mixture). This gives orange crystals with a F. 189 to 190 ⁰ G.

Analysis, C ₉₁ H ₁ -IT ₀ OS:

C.
MHMH 3 H 7th found: 67, 4th 3.8 7th ber .: " 67, 3.8 2L. , 7 , 5

Example 12

Synthesis of the compound (14):

When implementing a solution of 3- (quinonylmethyl) -phenyldiazonium salt, made from 10.0 g of 3- (hydroquinonylmethyl) aniline according to Example 1, with 7.8 g of ίο -cyano-2-acetyl-benzofuran j Receives 7.0 g of the compound (Η) with a melting point of 196 to 197 ° C. j

Analysis, C ₂₄ H ₁₅ H ₅ O ₄ :

C. 5 H 8th N
mmimwmmm mm * found: 70 4th 3, 7th 10, 1 ber .: 70 ■ 3, 10, 3

Example 13 Synthesis of 5-HyIrο quinonylmethyl-2-methylaniline:

(a) 2,5-Dimethoxy-3'-nitro-4'-methylbenzophenone:

A Friedel-Crafts reaction of 68.0 g of p-dimethoxybenzene with 98.0 g of 3-nitro-4-methylben2-dyl chloride (a method similar to that described in Example 10 (a)) gives 65.0 g of 2.5- dimethoxy-3'-nitro-4'-methylbenzophenone as pale yellow crystals, melting at 109-110 ⁰ C, which is recrystallized from ethyl acetate. j

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(b) 2,5-Dimethoxy-3 ^f -amino-4'-methylbenzhydrol:

A mixture of 50.0 g "of the benzophenone prepared in Example 13 (a), 1.3 liters of ethanol and 1.0 g of a 10 percent palladium-on-charcoal catalyst is in a 2 liter autoclave for 7 hours" 80 ⁰ G with hydrogen at an initial pressure of 85 kg / cm. subject to reduction. After the catalyst has been filtered off, the Pil is concentrated to 150 ml. Hierhei obtained 40.5 g of the desired compound as white crystals, melting at 112 his 113 ⁰ C.

(c) 1,4-Dimethoxy-2- (3 «-amino-4 '-methylbenzyl) -benzene:

33.0g of 2,5-dimethoxy-3'-amino-4'-methylbenzhydrol, prepared according to Example 13 (b), ground in a manner similar to that in Example 10 (c) reduced. This gives 21.0 g of the desired compound with a boiling point of 168 to 170 ° C / 1 Torr and a P. 64 ° C.

(d) 5-Hydroquinonylmethyl-2-methylaniline:

According to Example 10 (d), from 21.0 g of the corresponding dimethoxy compound, prepared in Example 13 (c), 15.0 g the desired connection from 3 ?. 152 to 153 ° C (recrystallized from ethyl acetate / benzene, 1: 2 volume mixture).

Example 14

Syntheses of the compound (19):,

A cooled mixture ( ⁰ ° C.) of 5.0 g of 5-hydroquinonylmethyl-2-methylaniline (preparation see Example 13 (d)), 200 ml of ice water, 19 ml of hydrochloric acid (35 percent) and 0.5 ml of 2-ethyl -1-hexanol is added dropwise with 40 ml of an aqueous solution of 5.2 g of sodium nitrite. The mixture is stirred for 1 hour at a temperature below 2 G and then 19 g of sodium acetate are added. The resulting solution of the 5-quinonylmethyl-2-methylphenyldiazonium salt is used for the azo coupling.

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■ - ²⁶ '2A13223

A solution of 3.7 g of C ₃ cyano-2-acetylbenzophenone in 400 ml
Ethanol and a solution of 1.1 g sodium hydroxide in 20 ml
Water mixed with one another at room temperature. The mixture obtained is at a temperature below 15 ° C in the
Poured the aforementioned diazo solution. After filtering off the
precipitated dye, drying in air and recrystallization from 1,2-dichloroethane gives 5.7 g of yellow crystals
from P. 210 to 213 ° C.

Analysis, C ₀ P-ELr ₇ N ^ O .:

found .: ber .:

G H
■■ «■ 0 9 I.
N ^;
ι ι ι! 70.7 4, 1 9 , 6 70.9 4, , 9
¹ 1 5

example Synthesis of the compound (21):

A cooled mixture ( ⁰ ° C.) of 19.2 g of 5-hydroquinonylmethyl- ^l

2-hydroxyaniline, 1 liter of ice water, 60 ml of hydrogen chloride,

acid (35 percent) and 3 ml of 2-ethyl-1-hexahol is under resting ^:

over 15 minutes drop by drop with 100 ml of an aqueous \

Solution of 17.5 g of sodium nitrite added. One stirs the reaction -:

on mixture 80 minutes at a temperature of below 2 ⁰ C, ί

then add 1.0 g sulfamic acid and then 100 g: Sodium acetate. The resulting solution of 5-quinonylmethyl-2-

hydroxyphenyl diazonium salt is used for the azo coupling:

det. ·!

A mixture of 15.0 g «o -cyano-2-acetylbenzofuran, 1 liter:

Ethanol, 4.0 g of sodium hydroxide and 20 ml of water is incorporated into the aforementioned diazo solution at a temperature below 15 C; pour. After filtering off the precipitate and recrystalline ^! Sizing from 1,2-dichloroethane, 17.2 g of the compound (15) are obtained in the form of orange-colored crystals from P. 204 to 205 ° C. !

A * nii "l TTcsf * ΓΪ TT TT O ·

C.
■■■■ «■ • ι o ■ H «■« ■ N found: 68, 8th 3.4 9 , 6 ber .: 67, 3.6 9 , 9;

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Example 16

Synthesis of Compound (22);

A diazo solution prepared according to Example 15 from 4.6 g of 5-hydroquinonylmethyl-2-hycb: c> xyaniline is coupled with 4.0 g of al-cyano-2-acetyl-3-methylbenzofuran, 2.8 g of the compound ( 22) rom Έ, 205 to 208 ⁰ O is obtained, which is recrystallized from ethyl acetate.

Analysis,

JD H Ή
«■ Ml« « found: 68.0 3, -9 9.6 Τ} er .: 68.3 3.9 9.6

Patent claims

£ 09839/1072

Claims (1)

241327T Claims 1. A process for the preparation of diazonium salts which contain a quinone radical in the molecule, characterized in that that a primary aromatic amine or its salt which contains a hydroquinone residue in the molecule with a diazotizing agent and an oxidizing agent. 2. The method according to claim 1, characterized in that a primary aromatic amine of the general formula I OH is used in which Ar is a benzene or naphthalene ring; X is a substituent on the Ar ring from the group consisting of alkyl radicals with 1 "to 10 carbon atoms, halogen atoms, alkoxy radicals with 1" to 10 carbon atoms, acyloxy radicals with 1 "to 10 carbon atoms or hydroxyl groups; 1 is a value of 0 his 4; R is a divalent radical from the group of alkylene radicals with 1 to 5 carbon atoms and - (CH ₂ ) -R ^f - (CH ₂ ) -, where R ^{1 is} -0-, -S-, -SO ₂ -, C = O or -CO-N (R ") -, and p + q has a value from 0 to 5, and R" is an alkyl radical with 1 to 5 carbon atoms or a hydrogen atom; R with Ar can be linked in the 1- to 8-position, based on the amino group; m has the value 0 or 1; Y is a substituent on the hydroquinone radical from the group consisting of alkyl radicals with 1 to 5 carbon atoms, alkoxy radicals with 1 to 5 C atoms and halogen atoms is _/ and η has a value from 0 to 5. -3. Process according to Claim 2, characterized in that an amine of the general formula I is used in which Ar is one Phenyl nucleus, 1 the value 0, R a methylene, ethylene or trimethylene group, m is the number 1 and η is the value 0, 409839/1072 4. The method according to claim 2, characterized in that one an amine of the general formula I -used, in the Ar one Phenyl nucleus, X a methyl group, 1 the value 1, R a methylene, Ethylene or trimethylene group, m the number 1 and η the value. 0 "mean. 5. The method according to claim 2, characterized in that one uses an amine of the general formula I, in which Ar is a phenyl nucleus, I is a hydroxyl group, 1 is the number 1, R is a methylene, ethylene or trimethylene group, m is the number '1 and η is the value O mean. 6. The method according to claim 1, characterized in that one a primary aromatic amine salt of the general formula Ia (Ia) used, in which Ar, X, 1, R, m, Y and η are those specified in claim 2 Have meaning and Z ~ is an inorganic or organic anion. 7 »The method according to claim 1, characterized in that nitrous acid is used as the diazotizing agent, which by The action of an acid on an inorganic nitrite is formed. 8. The method according to claim 7, characterized in that one as acid hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or acetic acid and as inorganic nitrite sodium nitrite, Potassium nitrite, Galciuianitrite or barium nitrite are used. 409839/1072 9. The method according to claim 1, characterized in that one Nitric acid, chloric acid, nitric acid or .persulphuric acid are used as oxidizing agents. 10. The method according to claim 1, characterized in that one used as a diazotizing agent and as an oxidizing agent nitrous acid. 11. The method according to claim 1 or 10, characterized in that there is a molar ratio of nitrous acid to amine of min-, at least 3: 1 applies. 12. Use of the diazonium salts prepared according to claim 1 Ms 11 for the formation of azo dyes?] .. 13. Embodiment according to claim 12, characterized in that that the diazonium salt is reacted with a coupler. 14. Embodiment according to claim 13, characterized in that that a phenolic azo coupler is used as the coupler. j 15. Embodiment according to claim 13, characterized in that the coupler used is an aromatic aminoazo coupler. 16. Embodiment according to claim 13, characterized in that that a heteroaromatic azo coupler is used as the coupler, 17. Embodiment according to claim 13, characterized in that that the coupler used is an aliphatic activated methylene azo coupler or an alicyclic activated methylene azo coupler used. 409839/1072