DE2243322A1 - PROCESS FOR THE PREPARATION OF BIS-P-N-SUBSTITUTED DIPHENYLMETHYL DERIVATIVES - Google Patents

Description

Our reference: 0.Z. 29 577 Bg / ah

6-700 Ludwigshafen, September 1st, 1972

Process for the preparation of bis-p-N-substituted diphenyl

methy! derivatives

The invention relates to a process for the production of compounds of formula I.

I,

12 3 4
in which Z, Z, Z and Z independently of one another are hydrogen, optionally substituted alkyl, cycloalkyl, aralkyl or aryl,

-ι ρ -ζ. U

Z ^ and Z or Z ^ and Z together with the nitrogen form a heterocycle or in each case one of the radicals linked to the o-position of the benzene ring is a condensed heterocycle, Z ^ hydrogen, halogen, alkyl or alkoxy, Z hydrogen, halogen, alkyl or alkoxy and Z denotes optionally substituted aralkylamines, cycloalkylamino, arylamino, a radical bonded via heterocyclic nitrogen or arylsulfonyl,

which is characterized in that compounds of the formulas

II

with benzoquinones substituted by fluorine, chlorine, bromine or cyano or phenanthrenequinones substituted by nitro with oxidation potentials> O.W in the presence of oxygen and Oxygen-activating complex-bound heavy metal containing

5 ^ 1/72 -2-

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Tending catalysts are oxidized to the carbinols and these with compounds of the formula ZM, where M is hydrogen, sodium, Potassium or ammonium means converts.

In the compounds of formula I, the substituents have, for example following meanings:

Z is hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or j5 carbon atoms, cyanoethyl, carbalkoxyalkyl'mit a total of 2 to 5 carbon atoms, methoxyethyl, ethoxyethyl, alkanoyloxyalkyl with a total of 4 to 11 carbon atoms, cyclohexyl, benzyl, phenylethyl, Phenyl or phenyl substituted by methyl, methoxy or ethoxy,

Z is hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, cyanoethyl, methoxyethyl, ethoxyethyl or phenyl,

7? the same radicals as Z;

4 2

Z is the same as Z;

Z ^J hydrogen, chlorine, methyl. Methoxy or ethoxy; Z ° hydrogen, chlorine, methyl, methoxy or ethoxy; Z phenylamino, phenylamino, benzylamino, phenylethylamino, cyclohexylamino, tetramethyleneamino, pentamethyleneamino, morpholino, piperazino, N-methylpiperazino, naphthylamino, chlorine, methoxy, methyl, chlorine, methoxy, methyl, mono- or disubstituted by chlorine, methyl, hydroxy, methoxy or ethoxy , Ethoxy or acetylamino substituted phenylsulfonyl or a radical of the formula

ö.

^ JL / ^Or

In addition to the substituents already mentioned individually, are for example the following remains are called:

for Z ¹ : methyl, ethyl, propyl, butyl, ß-hydroxyethyl, ß-hydroxypropyl, ß-carbomethoxyethyl, ß-carboethoxyethyl, ii-acetoxyethyl, ß-propionyloxyethyl or ß- (2-ethylhexanoyl) -oxyethyl, ß-carbethyl; _-,

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for Z ² ; Methyl, ethyl, propyl, butyl, ß-hydroxyethyl or

β-hydroxypropy1;

1 2 for a heterocyclic radical consisting of Z and Z and the N atom:

the rest of the morpholine, piperidines, piperazines or pyrrolidines,

1 2 for a condensed heterocycle, if e.g. Z or Z with

the o-position is linked: l ^^^ - Tetramethyl-l ^ -dihydroquinoline, ! ^^, ^ - Tetramethyl-l ^^^ - tetrahydroquinoline, 2,2,4-trimethyl-l, 2-dihydroquinoline, -l, 2-dimethyl-2,3-dihydroindole, l-butyl - ^ - hydroxy ^ -methyl-l ^^^ - tetrahydroquinoline.

Preferred leftovers are:

For Z: methyl, ethyl, cyanoethyl, phenyl, p-methoxyphenyl, p-

Methoxyphenyl or p-ethoxyphenyl, for Z: methyl or ethyl,

for Z ^: hydrogen, chlorine, methyl, methoxy, for Z: hydrogen, chlorine, methyl, methoxy, for Z: phenylamino, by chlorine, bromine, methyl or methoxy

substituted phenylamino, and the phenylsulfonyl radicals mentioned.

^{The compounds with Z 1} and Z methyl or ethyl and τΡ and Z hydrogen hydrogen are of particular technical importance.

Quinones, which act as oxidizing agents, are e.g. tetrafluoro, Tetrachloro, tetrabromo, dichloro-dicyano or tetracyano-1,4-benzoquinone, 2-nitro-, 2,7-dinitro- or 4,5-dinitrophenanthrenequinone, Tetrachloro- or tetrabromo-1 ^ -benzoquinone. Preferred tetrachloro- and tetrabromo-1,4-benzoquinone are used.

The quinones can be used as such or in the form of the hydroquinones will. Nitrophenanthrenequinones and the haloquinones can be used in pure form or as those obtained during the synthesis Mixtures are used. ^

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Heavy metals for the oxidation catalysts are e.g. copper, Vanadium, molybdenum and preferably iron and cobalt should be mentioned. The metals are in a complex bond with the catalysts Nitrogen and oxygen atoms of the chelating agents.

The following compounds may be mentioned in detail, for example: Copper complex compounds of

1) 2-aminoethanol

2) 1,2-diaminoethane
J>) 1,2-diaminopropane

Cobalt complex compounds of

4) Azomethine from 1,2-diaminoethane + 2 moles of 2-hydroxybenzaldehyde

5) Azomethine from 1,2-diaminopropane + 2 moles of 2-hydroxybenzaldehyde

6) Azomethine from 1, J5-diaminopropane + 2 moles of 2-hydroxybenzaldehyde

7) Azomethine from 1,2-diaminobenzene + 2 moles of 2-hydroxybenzaldehyde

8) Azomethine from 1,2-diamino-4-chlorobenzene + 2 moles of 2-hydroxybenzaldehyde

9) Azomethine from 1,2-diaminobenzene + 2 moles of 2-hydroxy-3,5-dichlorobenzaldehyde

10) Azomethines from 1,2-diamino-4-chlorobenzene + 2 moles of 2-hydroxy-3,5-dichlorobenzaldehyde

11) Azomethine from 1,2-diaminoethane + 2 moles of 2-hydroxy-5-nitrobenzaldehyde

12) Azomethine from 1,2-diaminoethane + 2 moles of 2-hydroxy-j5-methoxybenzaldehyde

13) Azomethine from 1,2-diaminoethane + 2 moles of 2-hydroxy-j5-ethoxybenzaldehyde

Ik) azomethines from bis (j5-aminopropyl) amine + 2 moles of 2-hydroxybenzaldehyde

15) Azomethine from 1,2-diaminobenzene + 2 moles of 2-hydroxy-5-nitrobenzaldehyde

16) Azomethine from 1,2-diaminoethane + 2 moles of 2-hydroxynaphthaldehyde-1

17) Azomethine from 1,2-diaminopropane + 2 moles of 2-hydroxynaphthaldehyde-1

18) Azomethine from 1,2-diaminobenzene + 2 moles of 2-hydroxynaphthaldehyde-1

19) Azomethine from 1,2-diamino-4-chloro-benzene + 2 moles of 2-hydroxynaphthaldehyde-l

-D-

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20) Azomethines from 1,2-diaminobenzene + 2 moles of 3-formyl-4-methyl-5-cyano-2,6-dihydroxypyridine

21) Azomethins from 1,2,4,5-tetramino "benzene + 4 moles of 2-hydroxybenzaldehyde

22) Formazans from cyanoacetic acid + 2 moles of diazo compound from
4-chloro-2-arainophenol-6-sulfonic acid

25) Tetraaza [14J annulens from 1,2-diaminobenzene + malondialdehyde

24) Tetraaza [l4jannulens from 1,2-diamino-4-chlorobenzene "+
Malondialdehyde

25) phthalocyanine

Iron complex compounds of

26) phthalocyanine (fur)

27) phthalocyanine (FeIIl)

28) hexadecachlorophthalocyanine

29) Phthalocyanine tri (or tetra) sulfonic acid (jT-dialkylaminopropyl) amides

30) hematins

31) tetraphenylporphins

32) the oxo-vanadium complex compound of azomethine
1,2-diaminoethane + 2 moles of 2-hydroxybenzaldehyde or

33) the dioxo-molybdenum complex compound of azomethine
1,2-diaminoethane + 2 moles of 2-hydroxybenzaldehyde c

Technically preferred are, for example, the "catalysts 4 to 14, 23, 24, 26, 27 or 31.

It can be advantageous to use the catalysts applied to supports. Z = B, activated carbon, kieselguhr, aluminum oxide or ceramic materials are suitable as carrier material. The preparation of such catalysts is -from the literature, for example
for fuel cells, known.

The new process is expediently carried out in such a way that the compounds of the formula II are in solution or suspension in
neutral to acidic pH range at a temperature between about 0 ° and 15O ⁰ C, preferably 30 to 60 ⁰ C * with about 10 "^ to 10 moles of quinone, relative to the molar amount of compound II,

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oxidized, the catalysts being expediently added in one to four times the amount of the quinones. The complex catalysts can be added as such to the reaction mixture or formed from the individual components in the reaction mixture will.

Purely the feeding and mixing of the material used for the oxidation Oxygen, usually pure oxygen or air, with the mixture to be oxidized are usually suitable for the Mixing of gas and liquid suitable devices, as described for example in Houben-Weyl, Vol. 4/2, pages 26l to 276 are. Working under pressure is of course also possible.

Suitable solvents for the oxidation reaction are e.g .: methanol, ethanol, propanol, butanol, glycol, methylglycol, dimethylglycol, Tetrahydrofuran, dioxane, ethyl acetate, chloroform, 1,2-dichloroethane, carbon tetrachloride, methylene chloride, chlorobenzene, Dichlorobenzene, benzene, toluene, xylene, acetic acid, propionic acid or lactic acid and mixtures of such solvents. the Oxidation reaction can also be carried out in aqueous suspension with the addition of emulsifiers, such as sperm oil alcohol, condensed at 28 moles Ethylene oxide, and, if necessary, defoamers such as triisobutyl phosphate, can be carried out. Preferred solvents are chlorinated hydrocarbons, low molecular weight aliphatic ^ carboxylic acids and alcohols.

The oxidation can depend on the compounds of the formula II can be carried out in the neutral to acidic pH range, usually the acidic pH range, in particular between 2 and 4, is advantageous.

Low-molecular water-soluble carboxylic acids such as formic acid, lactic acid, chlorine, Dichloroacetic acid, trichloroacetic acid, sulfonic acids such as benzenesulfonic acid or sulfuric acid and especially acetic acid, propionic acid or toluenesulfonic acid.

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The compounds of the formula II to be oxidized are expediently in concentrations in the solutions or suspensions between 5 and 60, preferably 10 to 40 percent by weight, based on the weight of the solution or suspension.

The reaction of the carbinols formed as an intermediate with the compounds of the formula

ZM

is advantageously carried out immediately after the oxidation. For the conversion of the amines ZH, the approximately neutral pH range is preferred, i.e. the pH of the reaction mixture is expediently increased after the oxidation. It is not necessary to change the pH value to produce the sulfonyl derivatives, However, it arises when not the sulfinic acids ZH but their alkali or ammonium salts are used for the reaction will.

The compounds of the formula I which can be prepared according to the invention are suitable e.g. as reactive dyes for carbon-free copying processes.

In the following examples, parts and percentages are based on weight, unless otherwise stated.

example 1

A mixture of 5-08 parts 4,4 '-Bisdimethylaminodipheny! Methane, 10 parts of chloranil, 20 parts of the complex number. 4, I9OO parts of methanol and l40 parts of glacial acetic acid is treated at 50 ⁰ C with vigorous stirring in a closed apparatus with oxygen . After 32 parts of oxygen have been absorbed, the oxidation is terminated, 193 parts of sodium ptoluenesulfinate * 2H ₂ O are added to the reaction mixture and the suspension is refluxed for 2 hours. After cooling, it is filtered off with suction, the residue is washed out with water and, after drying, recrystallized from benzene.

Yield: 550 parts ($ 75)

Melting point 184 to 185 ⁰ C.

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If complex 4 is replaced in example 1 by other complex compounds, the following yields are obtained:

example

If in Example 1 the Na p-toluenesulfinate is replaced by others Na sulfinate, the corresponding compounds are obtained with the specified melting points and in the yields:

Example sulfinic acid m.p. Yield in %

8 ci ^ \ so ₂ H. 184-186 ° C 68

Complex no. Yield in % 5 72 6th 74 7th 73 8th 67 23 58 31 51

H ₃ CCONH- / 'y-SOgH 174-176 ^O C 59

Example 10

A mixture of 620 parts of 4,4'-Bisdiäthylaminodiphenylmethan, 20 parts of bromanil, 20 parts of the complex number. 4, I9OO parts of ethanol and l40 parts of glacial acetic acid is treated at 50 ⁰ C with vigorous stirring in a closed apparatus with oxygen. After 32 parts of oxygen uptake, the oxidation is terminated, 193 parts of sodium p-toluenesulfinate »2HpO are added to the reaction mixture, and the suspension is then refluxed for 2 hours. After cooling, it is filtered off with suction, the residue is washed with ethanol and then with water and, after drying, recrystallized from ethyl acetate.

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Yield: 495 parts (59 % of theory)

Melting point I ^ to 145 ° C

Example 11 - - -

A mixture of 508 parts of 4,4'-bisdimethylaminodiphenylmethane, 10 parts of chloranil, 20 parts of complex no. 4, 1900 parts of methanol and 140 parts of glacial acetic acid at 50 ° C under strong Stirring treated with air. After an oxygen intake of 32 parts, the oxidation is terminated, the loss of methanol balanced and the reaction mixture with 190 parts 50 percent Sodium hydroxide solution neutralized. Then 255 parts of 2-methyl-5-chloroaniline are added and the reaction mixture is heated 4 hours under reflux. After cooling down, it is sucked off, the residue was washed out with methanol and recrystallized from benzene.

Yield: 424 parts (61 % of theory)

Melting point 1? 4 Ms 176 ° C »

If the aniline derivative is replaced by other amines in Example 11, the following yields are obtained:

Example amine yield in %

12th o-chloroaniline 65 15th 2-methyl-5-bromo-aniline .64 14th 2,4-dichloroaniline 59 +) 15 N-methylpiperazine 41 +) 16 Morpholine 58

+) Reaction time 40 hours under an Ng atmosphere

■ -10-

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Claims (1)

Claim Process for the preparation of bis-p-N-substituted diphenylmethy! Derivatives of formula I. in Z ¹ , Z ² , 3 4
Tr and Z independently of one another are hydrogen, optionally substituted alkyl, cycloalkyl, aralkyl or aryl, ι 2 3 4
Z ^x and Z or Z- ^ and Z together with the nitrogen form a heterocycle or in each case one of the radicals linked to the o-position of the benzene ring is a condensed heterocycle, Z is hydrogen, halogen, alkyl or alkoxy, Z is hydrogen, halogen, alkyl or alkoxy and Z denote optionally substituted aralkylamines, cycloalkylamino, arylamino, a nitrogen-bonded heterocyclic radical or arylsulfonyl, which is characterized in that one compounds of the formula II, with benzoquinone substituted by fluorine, chlorine, bromine or cyano or phenanthrenequinones substituted by nitro and having oxidation potentials > 0.4V in the presence of oxygen and oxygen-activating complex-bound heavy metal-containing catalysts oxidized to the carbinols and these with compounds of the formula ZM, where M is hydrogen, sodium, potassium or Ammonium means, converts. Badische Anilin- & Soda-Fabrik AG ^ p 409812/1048