DE2226936C3 - Process for the production of lactones of basic dyes by catalytic oxidation - Google Patents

Description

20th

in which R ^{1 is} hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, cyanoethyl, carbalkoxyalkyl with a total of 2 to 5 carbon atoms, methoxyethyl, ethoxyethyl, alkanoyloxyalkyl with a total of 4 to 11 carbon atoms, Cyclohexyl, benzyl, phenylethyl, phenyl, phenyl substituted by methyl, methoxy or ethoxy, R ² hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with -> or 3 carbon atoms, cyanoethyl, methoxyethyl] or ethoxyethyl and Y hydrogen, chlorine . Methyl, methoxy or ethoxy means with benzoquinones substituted by fluorine, chlorine, bromine or cyano or phenanthrenequinones substituted by nitro groups in the presence of oxygen, oxygen-activating, complex-bound heavy metal-containing catalysts to give compounds of the formula

dehydrated.

The subject of patent 21 38 931 is a process such as R, R ^{3 the} same radicals as R ¹ . X hydrogen. ; · Production of basic dyes of the general 40 chlorine, methyl, methoxy or ethoxy, \ hydrogen,

Formula I.

R ³

Chlorine, methyl, methoxy or ethoxy, A phenyl, through chlorine, methyl, hydroxy, methoxy, ethoxy or the sulfonic acid group mono- or disubstituted phenyl, a heteroaromatic radical or a remainder of the formulas

X (D

in which, independently of one another, R is hydrogen, alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 2 or 3 carbon atoms, cyanoethyl, carbalkoxyalkyl with a total of 2 to 5 carbon atoms, methoxyethyl, ethoxyethyl, Alkanoyloxyalkyl with a total of 4 to 11 carbon atoms, benzyl, phenylethyl, phenyl, through methyl, Methoxy or ethoxy substituted phenyl or a radical of the formula

-CH,

"X

SO., H

R ^{1 is} hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, cyanoethyl. Methoxyätliyl, Athoxyäthyl or Phenyl, R ^{2 the} same radicals

R ¹

It has now been found that the method of patent 21 38 931 is also very good for manufacture of lactones of basic dyes of the general formula 1

H ^{4 is} hydrogen, chlorine, methyl, methoxy or ethoxy, R ^{5 is} hydrogen or chlorine and X is an anion. which is characterized in that compounds of the general formula 11

R R-

// ■■ /

R '(11)

with by fluorine. Chlorine, bromine or cyano-substituted benzoquinones or nitro-substituted phenanthrenequinones are dehydrogenated in the presence of oxygen and oxygen-transferring complex containing heavy metal-containing catalysts, where A ¹ is A or a radical of the formulas

R ⁵

R ¹

R ¹

Y O

^ -Y -ο

R ¹

R ²

suitable is. in which, independently of one another, R ^{1 is} hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, cyanoalkyl, carbalkoxyalkyl with a total of 2 to 5 carbon atoms, methoxyethyl. Etho'cyä'ihyl, alkanoyloxyalkyl with a total of 4 to 11 carbon atoms, cyclohexyl. Benzyl, phenylethyl. Phenyl, phenyl substituted by methyl, methoxy or ethoxy. R ^{2 is} hydrogen, alkyl having 1 to 4 carbon atoms. Hydroxyalkyl with 2 or 3 carbon atoms. Cyanoethyl. Methoxyethyl or ethoxyethyl and Y hydrogen, chlorine, methyl. Methoxy or ethoxy denotes, the process being characterized in that compounds of the general formula 2

R '

R ²

R ¹

R ²

COOH

R ¹

R ²

with by fluorine, chlorine. Substituted bromine or cyano Benzoquinones or phenanthrenequinones substituted by nitro groups in the presence of Oxygen, oxygen-activating complex-bound heavy metal-containing catalysts are dehydrated.

In addition to the substituents already mentioned individually, z. B. mentioned the following residues:

for R ¹ : methyl, ethyl, propyl, butyl, ß-hydroxy- t, _s älhyl, / i-hydroxypropyl, / y-carbomethoxy-

ethyl, / i-carboethoxyethyl;

for R ² : methyl, ethyl, propyl, butyl, / i-hydroxyethyl or / i-hydroxypropyl.

Preferred leftovers are:

for R ¹ : methyl, ethyl;
for R ² : methyl or ethyl;
for Y: hydrogen.

As heavy metals for the oxidation catalysts find z. B. copper, vanadium, molybdenum and preferably iron and cobalt to be mentioned. The metals lie The chelating agent is present in the catalysts in complex bond with nitrogen and oxygen atoms.

Examples of these are the following compounds named as oxidation catalysts:

28. hexadecachlorophthalocyanine,

29. Phthalocyanine tri (or tetra) sulfonic acid (; - diaIkylaminopropyl) amides,

30. Hematins,

31. The oxo - vanadium complex compound des Azomethines from 1,2-diaminoethane + 2 moles of 2-hydroxybenzaldehyde or

32. the dioxo - molybdenum complex compound of azomethine from 1,2 diaminoethane + 2 Mo! 2-hydroxybenzaldehyde.

Kupferkcmpiexverbindungen des

1. 2-aminoethanol,

2. i, 2-diaminoethane,

3. 1,2-diaminopropane,

Cobalt complex compounds of

2 moles

4. Azomethine from 1,2-diaminoethane
2-hydroxybenzaldehyde,

5. Azomethine from 1,2-diaminopropane
2-hydroxybenzaldehyde,

6. Azomethine from 1,3-diaminopropane + 2 moles of 2-hydroxybenzaldehyde.

7. Azomethine from 1,2-diaminobenzene + 2 mol 2-hydroxybenzaldehyde,

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

9. Azomethine from 1,2-diaminobenzene + 2 Mo! 2-hydroxy-3,5-dichlorobenzaldehyde,

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

11. Azomethine from 1,2-diaminoethyn + 2 mol 2-hydroxy-5-nitrobenzaldehyde,

12. Azomethine from 1,2-diaminoithyne + 2MoI 2-hydroxy-3-methoxybenzaldehyde,

13. Azomethines from 1,2-diaminoethyn + 2 moles of 2-hydroxy-3-ethoxybenzaldehyde,

14. Azomethines from bis (3 - aminopropyl) - amine + 2 moles of 2-hydroxybenzaldehyde,

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

16. Azomethines from 1,2-diaminoethane + 2 moles of 2-hydroxynaphthaldehyde-1,

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

IH. Azomethine from 1,2-diaminobenzene + 2 moles of 2-hydroxynaphthaldehyde-1,

19. Azomethines from 1,2-diamino-4-chlorobenzene + 2 mol of 2-hydroxynaphthaldehyde-hyd-l.

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

21. Azomethines from 1,2,4,5 - tetraminobenzene + 4 moles of 2-hydroxybenzaldehyde,

22. Formazans from cyanoacetic acid + 2 moles of diazo compound of 4-chloro-2-aminophenol-6-sulfonic acid,

23. Tetraaza [14] annulens from 1,2-diaminobenz ^ l + Malondialdehyde,

24. Tetraaza [14] annulens from 1,2-dietino-4-chlorobenzene + Malondialdehyde,

25. Phthalocyanines

Technically preferred are z. B. the catalysts 4 to 14, 23, 24, 26 or 27.

With regard to all further explanations and definitions the details of the main patent apply mutatis mutandis.

Compared to the process described in US Pat. No. 25 42 5M , the process according to the invention has the advantage of greater effectiveness: In addition, the specified reaction conditions are required. especially the reaction medium, not suitable for the production of lactones, because this would result in the corresponding amides.

Ice Complex Connections of the

26. phthalocyanines (fur),

27. phthalocyanines (FeIII),

example 1

CH,

CH,

CH,

-CO ₁ H

CH, C \ l,

CH,

CI

Complex No. 4

O ₂
Chloranil

CO

CH, CH,

A suspension of 417 parts of leuco crystal violet-o-carboxylic acid, 400 parts of glacial acetic acid, 1600 parts of chloroform, IO parts of chloranil and 10 parts of the Complex # 4 is oxidized at 50 "C with 32 parts of oxygen. The resulting suspension is concentrated to dryness under reduced pressure, the The residue was taken up in 500 parts of methanol and filtered off with suction.

Yield: 393 parts of crystalline crystal violet lactone, melting point: 172 to 174 ° C.

Example 2

A suspension of 417 parts of LeukokristallvioleU-o-carboxylic acid, 60 parts of glacial acetic acid, 1500 parts of methanol, 10 parts of complex no. 4 and 5 parts of chloranil is ^{oxidized at 50 °} C. with 32 parts of oxygen. After cooling, the resulting crystalline precipitate is filtered off and washed out with 500 parts of methanol.

Yield: 372 parts of crystal violet lactone.

Melting point: 171 to 173 ° C.

Example 3

A mixture of 473 parts of 4,4'-bisdiethylamino-4 "-dimethylamine-2" -hydroxycarbonyltriphenylmethane, 2000 parts of ethanol, 60 parts of glacial acetic acid, 10 parts of bromanil and 10 parts of complex no. 23 is oxidized with oxygen at 50.degree. After uptake of 16 parts of oxygen, the reaction mixture is cooled to 1O ⁰ C, the precipitate filtered off and washed with 500 parts of ethanol. After recrystallization from benzene, the substance melts at 17O ⁰ C.

Yield: 390 parts.

Claims (1)

Claim: Process for the preparation of lactones of basic dyes according to patent 2138931, thereby characterized in that one here compounds of the formula IO