DE2152703C3 - Process for the production of basic dyes by catalytic oxidation - Google Patents

Description

[ι 4-R ⁵

^N

R ³ 'R ⁴

or

N
R ¹ 'R ²

R ³ and R ⁴ independently of one another are hydrogen. Alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, cyanoethyl, methoxyethyl or ethoxyethyl, R ³ and R ⁴ together with the N atom are a heterocyclic radical or R ³ or R ⁴ linked to the o-position of the benzene ring is a condensed heterocycle, R ^{5 is} hydrogen, chlorine, methyl, methoxy, ethoxy, acylamino. Hydroxycarbonyl. Alkoxycarbonyl or hydroxysulfonyl and X is an anion.

it. characterized in that the subject of patent 21 38 931 is a method

ier compounds of the formula for the preparation of basic dyes of the general

Formula I.

R ¹ R ¹

\ / = v / 40 RR ²

/ W \ i / \ NN

R ² Y YR ² / ^V \ A, / \ / '

lit compounds of the formula AH to compounds of the formula

msetzt, where R ^{1 is} hydrogen, alkyl with 1 to C atoms, hydroxyalkyl with 2 or 3 C atoms, 'yanäthyl. Carbalkoxyalkyl with a total of 2 to 14 carbon atoms, methoxyethyl, ethoxyethyl, alkaoyloxyalkyl with a total of 4 to 11 carbon atoms, yclohexyl, benzyl, phenylethyl, phenyl, phenyl substituted by methyl, methoxy or ethoxy, R ² hydrogen, alkyl with 1 to 4 C atoms, iydroxyalkyl with 2 or 3 C atoms, cyanoethyl, ethoxyethyl or ethoxyethyl, Y hydrogen, chlorine, methyl, methoxy or ethoxy, A one

R ¹

R ^J

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, methyl, methoxy or ethoxy-substituted phenyl or a radical of the formula

_ SO ₃ H

R ^{1 is} hydrogen. Alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, cyanoethyl, methoxyethyl, ethoxyethyl or phenyl, R ^{2 the} same radicals as R, R ^{3 the} same radicals as R ¹ , X hydrogen, chlorine, methyl, methoxy or Ethoxy, Y hydrogen, chlorine, methyl, methoxy or ethoxy, A phenyl, through chlorine. Methyl. Hydroxy, methoxy, ethoxy or the sulfonic acid group mono- or disubstituted Phe-

nyl, a heteroaromatic radical or a radical where A ¹ is A or a radical of the formulas
of the formulas

R ¹

R ⁵

Y ⁴

R ¹

R ⁵

f: i '

or

R- '

N-CHj

R ¹

N-CH,

is.

R ¹

ί ¹ Η j!

R ²

R ³

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

R ^:

R ¹

R ²

R ¹

R ⁴ 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 II

X (1)

R ¹

y c

Y X

Λ ¹

suitable is. in which, independently of one another, R ¹ 50 is hydrogen. Alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms. Cyanoethyl, carbalkoxy alkyl having 2 to 5 carbon atoms, methoxyethyl. Ethoxyethyl, alkanoyloxyalkyl with a total of 4 bi? R ² 11 carbon atoms, cyclohexyl, benzyl, phenylethyl, Phe-

55 nyl. phenyl substituted by methyl, methoxy or ethoxy, R ² hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms. Cyanoethyl R- '(II) methoxyethyl or ethoxyethyl.Y hydrogen. chlorine

Methyl. Methoxy or ethoxy. A is a heteroaromatic Remainder or a remainder of the formulas

¹ R ⁵

with by fluorine. Chlorine. Bromine or cyano substituted ß / ochinoncn or substituted by nitro Phenanthrenequinone in the presence of oxygen and oxygen-transferring complex bound Heavy metal containing catalysts dehydrogenated,

R ⁴

Examples of heteroaromatic radicals A are:

1 -Methyl ^ -phenyl-indolyl-S, 2-methyl-indolyl-3, 2-phenyl-indolyl-3, 1-cyanoethyl-2-methyl-indolyl-3, 1 - phenylpyrazolyl-4,

R ¹

R-

R 'and R ⁴ independently of one another are hydrogen. Alkyl with 1 to 4 carbon atoms. Hydroxyalkyl with 2 or 3 carbon atoms. Cyanoethyl, Methoxyälhyl or Äthoxyälhyl. R ³ and R ⁴ together with the N atom are a heterocyclic radical or R ³ or R ^{4 are} linked to the o-position of the benzene ring to form a condensed heterocycle. R ^{5 is} hydrogen. Chlorine, methyl. Methoxy. Ethoxy. Acylamino. Hydroxycarbonyl. Alkoxycarbonyl or hydroxysulfonyl and X is an anion, the process being characterized. that one compounds of the general formula 2

R ¹

R-

1.

R ¹

R ²

(21

with by fluorine. Chlorine. Bromine or cyano substituted benzoquinones or substituted by nitro groups Phenanthrenequinones in the presence of oxygen, oxygen-activating complex bound Heavy metal-containing catalysts and a nucleophilic compound of the general formula 3

AH

(3)

30th

35

40

5 °

dehydrated.

Besides the individually already mentioned Suhstituenten z. B. mentioned the following residues:

for R ¹ :

Methyl. Ethyl. Propyl. Butyl. , i-hydroxyethyl. , .'-hydroxypropyl. , .'-carbomethoxyethyl. , .- carboethoxyethyl;

for R ² , R ³ , R ⁴ :

Methyl. Ethyl propyl, butyl, ^ -hydroxyethyl or / i-hydroxypropyl;

for a heterocyclic radical consisting of R ³ and R ⁴ and the N atom:

the remainder of the morpholine, piperidine, piperazine or pyrrolidine;

Door a condensed heterocycle. if R ³ and R * are linked to the o-position:

1,2,2,4-tetramethyl-1,2-dihydroquinoline,
1,2,2,4-tetramethyl-1,2,3,4-tetrahydroquinoline,
2,2,4-trimethyl-1,2-dihydroquinoline.
1 ^ dimethyl ^ dihydroindole.
1-Butyl-a-hydroxy-T-methyl-1.2.3,4-t-tetrahydroquinoline.

1,4-perimidin-yl-4 or
Perimidon-yl-4.

Preferred leftovers are:
for R ¹ :

Hydrogen, methyl, ethyl, cyanoethyl, phenyl, p-methoxyphenyl or p-ethoxyphenyl;

for R ² :

Hydrogen, methyl or ethyl; for R ³ :

Hydrogen, methyl, ethyl or cyanoethyl; forR ⁴ :

Hydrogen. Methyl or ethyl; forR ⁵ :

Hydrogen, methyl. Methoxy. Ethoxy. Acetylamino. Carboxyl. Carbomethoxy. Carboethoxy or hydroxysulfonyl:

for Y:

Hydrogen;
for heteroaromatic residues A:

the indolyl radicals mentioned.

Anions X are for example: bromide. Tetrafluoroborate. Formate, methosulphate or ethosulphate and especially chloride. Nitrate, acetate or tetrachlorozincate.

The heavy metal for the oxidation catalysts are, for. B. Copper. Vanadium. Molybdenum and preferably To mention iron and cobalt. The metals are in a complex bond with the catalysts Nitrogen and oxygen atoms of the chelating agents

45 before.

60

65 For example, the following compounds may be mentioned individually as oxidation catalysts:

Copper complex compounds of

1. 2-aminoethanol,

2. 1,2-diaminoethane,

3. 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 1,3-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

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

609 650/200

11. Azomethine from 1,2-diaminoethane

+ 2 moles of 2-hydroxy-5-nitrobenzaldehyde,

12. Azomethine from 1,2-diaminoethane

+ 2 moles of 2-Hydroxy-3-methoxybenzaldehyde,

13. Azomethine from 1,2-diaminoethane

+ 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. 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. Azomethines from 1,2-diamino-4-chloro-benzene
4- 2 moles of 2-hydroxynaphthaldehyde-1,

20. Azomethine from 1,2-diaminobenzene
4- 2 moles of S-FormyM-methyl-S-cyano-2,6-dihydroxypyridine,

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

22. Formazans from cyanoacetic acid

4- 2 moles of diazo compound of 4-chloro-25 bis-diphenyl

2-aminophenol-6-sulfonic acid, game methane

23. Tetraaza [14] annulens from 1,2-diaminobenzene

+ Malondialdehyde,

24. Tetraaza [14] annulens from 1,2-diamino-4-chlorobenzene 4- malondialdehyde,

25. phthalocyanine,

Iron complex compounds of

26. phthalocyanine (Fe "),

Phthalocyanine (Fe ¹ "), hexadecachlorophthalocyanine,
Phthalocyanine tri (or tetra) sulfonic acid (; <-dialkyiaminopropyl) amides,
Hematins,

the oxo-vanadium complex compound of azo methine from 1,2-diaminoethane + 2 moles of 2-Hy droxybenzaldehyde or

32. the dioxo-molybdenum complex compound des
Azomethines from 1,2-diaminoethane
4- 2 moles of 2-hydroxybenzaldehyde.

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

The compounds of the formula 2 can be used as such, but they can also be used in the reaction mixture from the associated starting materials (e.g. formaldehyde 4-dialkylaniline) among those according to the invention Reaction conditions are formed.

With regard to all further explanations and definitions, the information in the main patent applies accordingly.

Compared to the catalytic processes known from US Patents 16 94 057 and 25 42 544 For the production of basic dyes, the new process is much better Yields from, it can also be compared to conventional methods for the production of basic 6 the same Perform dyes in a very environmentally friendly way.

In US Pat. No. 1,8 05,925, the oxidation of leuco compounds described, in contrast, it enables the method according to the invention to often to dispense with complex production of the Lcukoverbinder and instead of easily accessible Starting materials.

_s B eis ρ ie 1 1

A mixture of 254 parts of 4,4'-bisdimethyl aminodiphenylmethane, 121 parts of dimethylaniline 10 parts of chloranil, 10 parts of complex no. 23 1480 parts of chloroform and 360 parts of glacial acetic acid

ίο the at 50 ° C with vigorous stirring in a closed NEN apparatus treated with oxygen. The acidic substance uptake comes after a consumption of 22.4 almost to a standstill. The chloroform is removed from the reaction mixture by distillation. De The residue is dissolved in 1200 parts of water at 80 ° C., the solution is filtered and then treated with a little conc Hydrochloric acid added. After adding conc. NaCl solution precipitates the dye (Basic Violet 3). Out booty 343 g.

In the same way, the following Diphenylme thane and compounds of the formula 3 to triaryl oxidize methane dyes.

Connection of the r-formula 3

2 4,4'-bisdimethyl-
amino

3 the same

-

45

50

55

60

4 the same.

yield

CH ₃ CH ₃

5 the same.

N CH ₃ ^X CH ₃

OC ₂ H ₅

11th

continuation

Example diphenyl compound of formula 3 play methane

7 4,4'-bisdimethylamino

8 the same.

9 the same.

10 the same.

11 the same.

12 desfel.

13 the same.

NHCOCH ₃

N CH ₃ CH ₃

CO ₂ H

/ \ CH ₃ CH ₃

OC ₂ H ₅

Ν— Η

CH ₃

N HOH ₄ C ₂ C ₂ H ₅

5 at
game Diphenyl
methane Compound of formula 3 HOH ₄ C ₂ N
C ₂ H ₄ OH Au
beu Out
prey (% IO CO ₂ C ₂ H ₅ 90 15th 14th 4,4-bisdi
methyl-
amino 7th
N
CH ₃ CH ₃ 41 15th the same ( 59 20th . J about
30th Y

16 the same

35

17 the same.

45

18 the same.

19 the same.

55

6o

20 the same

N-CH ₃

N-CH ₃ CH,

Λ / \

NH

CH,

/ \ / N-CH ₃ ON

Ph

continuation

Example of a diphenyl game methane

13th

Connection of the Formet

22 the same.

23 the same

24 desel.

25 the same.

CH,

/ γ

! H ! H

\ ί: Η H ₃ CH

<i

14th

Out-
bcule at
game 5 Diphenyl
methane Vei compound of formula 3 Out
dent
1%) Ι ^ϋ ,, ι 30th
in 67 4.4'-to-
cyanithyl
meihyl-
amino 0
CH ₃ CH ₃ 81 A.

the same

35

N C ₂ H ₅ V ₁ H ₅

32 4.4'-to- Il dimethyl \ '■■''' amino 2.2-di- N methvl- CH ₃ CH ₃ 30 33 descl. : i

C ₂ H ₅ C ₂ H ₅

CH ₃

26 4.4'-bisdiethylamino

27 the same.

28 desel.

29 of the «!.

N CH,

C ₂ H ₅ H

ü ^H

H ₅ C ₂ O

If complex no. Is replaced by other complex compounds in Example 1, the following is obtained Exploit:

Complex no.

45

>
6th
7th
8th
9
10
H
12th
13th
14th
15th
16
17th
18th
19th
20th

55

60

Yield 1%)

31 91 89 88 92 91 90 86 85 90 92 84 87 81 79 88 87 85

continuation Bulging Complex no. 79 2t 88 24 91 27 Example 34

example

38

aniline

C ₂ H ₅ CH ₂ -

yield

68

IO

A mixture of 254 parts of 4,4'-bisdimethylamino-diphenylmethane, 121 parts of dimethylaniline, 5 parts of chloranil, 5 parts of complex No. 23, 25 parts of sperm oil alcohol condensed with 20 moles Ethylene oxide, 20 parts of triisobutyl phosphate, 175 parts of glacial acetic acid and 700 parts of water is 8 hours in a circulating apparatus through a gas injection nozzle at 50 C with air. To the reaction solution then 1500 parts of water are added, the mixture is heated to 80 ° C., filtered off, and a little conc. Hydrochloric acid to and the dye falls by adding conc. NaCl solution. Yield 377 parts of dye.

39

CH ₃ CH ₃

H CH, 71

ί Ί

2: 1

Example 35 ^ ₀

A mixture of 447 parts of diethylaniline, 30 parts of paraformaldehyde, 10 parts of chloranil, 10 parts of complex No. 4, 500 parts of glacial acetic acid and 1500 parts Ethylene chloride is gassed with air at 50 C with vigorous stirring. After 7 hours the ethylene chloride is removed by distillation, the residue dissolved in 1500 parts of water at 80 ° C., the solution filtered off. slightly conc. to the filtrate. Hydrochloric acid was added and the dye (CI. Basic Violet 4) with conc. NaCl solution precipitated. Yield 377 parts of dye.

The following anilines can be converted into triphenyl methane dyes in the same way:

example

aniline

CHj CH,

CH, C ₂ H ₄ CN

Example 40

A mixture of 254 parts of N.N'-bisdimethylamino-diphenylmethane, 121 parts of dimethylaniline, 10 parts of bromanil, 10 parts of complex no. 27 applied to activated carbon (weight ratio 1: 1). 1480 parts of ethanol and 360 parts of propionic acid are closed at 50 C with vigorous stirring Apparatus treated with oxygen. The oxygen uptake comes after a consumption of 22 1 almost to a standstill. The ethanol is removed from the reaction mixture by distilling off, the residue is dissolved in 1200 parts of water, the solution is filtered off, with a little conc. Hydrochloric acid added and the Dye by adding conc. NaCl solution precipitated.

Yield: 337 parts.

Example 41

A mixture of 254 parts of N.N'-bisdimethylamino-diphenylmethane. 121 parts of dimethylaniline. 10 parts of tetrachlorohydroquinone, 10 parts of the condensation product from 1 mole of o-phenylenediamine with 2 moles of salicylaldehyde. 5 parts of Co-acetate. 2000 Part-Auslen Ethyl chloride and 172 parts of p-toluenesulfone

^{Hculc acid is heated in} air for 8 hours with vigorous stirring

Col 50 fumigated. Obtained after work-up according to Example 1 349 parts of dye.

Example 42

291 parts of N-ethyl-N-benzylaniline-3-sulfonic acid are concentrated in 1600 parts of water in a little. Sodium hydroxide solution dissolved. 25 parts of the adduct of 1 mol of sperm oil alcohol and 20 mol are then added Ethylene oxide and 25 parts of triisobutyl phosphate are added and then a mixture of 254 parts 4,4-bis-dimethylamino-diphenylmethane. 400 parts of glacial acetic acid, 10 parts of chloranil and 10 parts of the complex No. 23. The reaction mixture is gassed with air at 50 ° C. for 12 hours. then with 2000 parts Water added, erhil to 90 C / l and nitrated. the Dye is then used with kon /. NaCl solution fallen. Yield: 249 parts.

Claims (1)

Claim: Process for the preparation of basic dyes of the formula I according to Patent 21 38 931 where, independently of one another, R is hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, cyanoethyl, carbalkoxyalkyl i hl Ethoxyethyl, alkanoyloxyalkyl with a total of 4 to 11 carbon atoms, benzyl, phenylethyl, phenyl, through Methyl, methoxy or ethoxy substituted Phei R d Fl with a total of 2 to 5 carbon atoms, methoxyethyl, 20 nyl or a radical of the formula SO ₃ H -CH, - / "^ R ^{1 is} hydrogen, alkyl with 1 to 4 carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, cyanoethyl, methoxyethyl, ethoxyethyl or phenyl, R ^{2 is the} same as R, R ^{3 is the} same as R ¹ , X is hydrogen, chlorine, Methyl, methoxy or ethoxy, Y hydrogen, chlorine, methyl, methoxy R ¹ or ethoxy, A phenyl, by chlorine, methyl, hydroxy, methoxy, ethoxy or the sulfonic acid group mono- or disubstituted phenyl, a heteroaromatic radical or a radical of Formulas R ^{4 is} hydrogen, chlorine, methyl, methoxy or ethoxy, R ^{5 is} hydrogen or chlorine and X ^{e is} an anion, by catalytic oxidation, in which compounds of the general formula II R ² N N R ¹ III Ij R ³ (Π) Y X A ¹ dehydrogenated with benzoquinones substituted by fluorine, chlorine, bromine or cyano or phenanthrenequinones substituted by nitro in the presence of oxygen and oxygen-transferring complex-bound heavy metal-containing catalysts, where A ¹ is A or a radical ler formulas N-CH ₃ y \ Ij V ! H R- heteroaromatic radical or a radical of the formulas