CH632525A5 - Process for preparing new azamethine-copper complexes - Google Patents

Description

The invention relates to a process for the preparation of new azamethine-Cu complexes of the formula I.

(I), £ 10

in which X is hydrogen, chlorine, bromine, alkyl or alkoxy, each having 1 to 4 carbon atoms, nitro, trifluoromethyl or a group of the formula -COOY, where Y is hydrogen or alkyl having 1 to 5 carbon atoms, and R1 and R2 is hydrogen or one of the radicals R1 and R2 is hydrogen and the other is -COOY, with the proviso that at least one of the radicals X, R1 and R2 is -COOY, characterized in that 20 azamethines of the formula II

R

(I).

n = ch r ho '

25th

(II),

in which X is hydrogen, chlorine, bromine, alkyl or alkoxy, each having 1-4 C atoms, nitro, trifluoromethyl or a group of the formula -COOY, where Y is hydrogen or alkyl having 1-5 C atoms, and R1 and R2 is hydrogen or one of the radicals R1 and R2 is hydrogen and the other is -COOY, with the proviso that at least one of the radicals X, R1 and R2 is -COOY.

If Y is alkyl, it is, for example, ethyl, N-propyl, isopropyl, n-butyl, isobutyl, n-amyl or isoamyl, but preferably methyl.

The process according to the invention is characterized in that azamethines of the formula II

30th

in which R is hydrogen or methyl, metallized with a copper-donating compound.

2. The method according to claim 1, characterized in that

that you can metallize at temperatures from 20 to

180 ° C. 35

3. Process according to claims 1 and 2, characterized in that azamethines of the formula II, in which R is hydrogen, are metallized at temperatures of 20 to 150 ° C.

4. The method according to claim 3, characterized in that one works in the temperature range from 80 to 110 ° C.

5. Process according to claims 3 and 4, characterized in that metallized in water or in an aqueous-organic solvent.

6. The method according to claims 1 and 2, characterized 45- characterized in that azamethines of the formula II, in which R is methyl, metallized at temperatures from 120 to 180 ° C.

7. The method according to claim 6, characterized in that

that you metallize in an inert organic solvent.

8. The method according to claims 5 and 7, characterized in that an alcohol, a glycol ether, glacial acetic acid, formamide or a dipolar aprotic solvent is used as the solvent.

9. The method according to claims 1 to 8, characterized in that metallized with a copper salt.

10. The method according to claim 9, characterized in

that a copper (Il) salt is used as the copper salt.

11. Use of the compound of formula I for pigmenting substrates.

12. Use according to claim 11 for pigmenting lacquers, high molecular weight plastic masses and coloring agents, such as printing pastes.

13. Pigmented substrates obtained according to claim 11 65.

14. Substrates according to claim 13, which are obtained according to claim 12.

n = ch or ho

(II),

50

55

in which R is hydrogen or a methyl group with a copper donating compound, e.g. an inorganic or organic, preferably divalent copper salt metallized. Suitable copper salts are, for example, copper (II) chloride, copper (II) sulfate, copper formate, copper (II) acetate or copper ferrous stearate.

The compounds obtained are used for pigmenting substances.

The copper plating of compound II, in which R represents hydrogen, can be carried out in water or organic solvents or aqueous-organic solvents at temperatures between 20 and 180 ° C., preferably 20 to 150 ° C., in particular 80 to 110 ° C. Suitable solvents for copper plating are, for example, alcohols, in particular lower alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol or isobutanol; Glycol monomethyl ether; Glacial acetic acid; Formamide or dipolar aprotic solvents such as dimethylformamide, N-methylpyrrolidone or tetramethylene sulfone. The same solvent in which the copper salt was previously dissolved is preferably used for the copper plating. The copper plating can be carried out in the presence of a basic compound such as sodium acetate.

The copper plating of the anisole derivatives (R = CH3) is expediently carried out in the presence of a copper plating agent in an inert organic solvent at temperatures between 120 and 180 ° C., and the alkylation to give the azamethine compound of the formula I.

The azamethine compound of formula II is either prepared separately or the azamethine-Cu complex of formula I is synthesized in a one-pot reaction.

The compounds of formula II are generally prepared by condensation of the corresponding 2-aminophenol or anisole or their hydrochlorides with, if appropriate

3,632,525

oils or polypropylene, polystyrene, polyvinyl chloride, polyacrylic-2-hydroxynaphthaldehyde- (l) substituted by the group -COOY in 3- or 6-position, where Y also includes a cation, nitrii, polyacrylic acid ester, rubber, casein, silicone and silicone, for example Alkali metal can mean forth. Resin is suitable. It does not matter whether the mentioned advantageously equivalent amounts of the two starting high molecular weight compounds as plastic masses, melt bonds in water, organic solvents or aqueous 5 or in the form of spinning solutions, lacquers or printing pastes organic solvents at temperatures between 20 and present. Depending on the intended use, it turns out to be pre-150 ° C, preferably 80-110 ° C. partial, the new pigments as toner or in the form of prepa-

The reaction can also be used in the presence of an inert gas such as guess. The pigments of formula I are characterized in nitrogen. If the reaction is carried out using high color strength, a pure color, high tempera water, then it is advisable to add surface-active resistance to stoving enamels and plastics, agents such as cationic, anionic or non-ionic, but especially excellent varnish, light and Weather constraints. If the hydrochloride is used, the authenticity, especially among the extreme Bedin-4-carbomethoxy-2-aminophenols or anisols, should be based on an aluminum metallic paint base, an external compound such as sodium acetate, sodium hy - There is always good light and weather fastness.

bicarbonate or potassium carbonate can be added. As 15 In the following examples, percentages of organic solvents are mentioned, for example: lower by weight, unless stated otherwise.

Alcohols with 1 to 6 carbon atoms, glacial acetic acid, dimethylformamide or glycol monomethyl ether. After isolation and washing of example 1, the compound of formula II obtained can then be coppered as described above in 17.2 g of 2-hydroxynaphthaldehyde (1) in 200 ml. After another suspension of 20% ethanol, with 21.5 g of 4-carbomethoxy-2-aminophe embodiment of the process, the azamethine-copper-com-hydrochloride and 10 g of anhydrous sodium acetate in plex of formula I can be prepared directly in a grinding unit - 200 ml of ethanol warmed to boiling temperature and the reac in which the starting compounds, for example 4-Carbo mixture kept at this temperature for one hour. methoxy-2-aminophenol and 2-hydroxynaphthaldehyde- (l), in During the reaction time, nitrogen is passed over the water together with a coppering agent, such as 25. The precipitated orange-red precipitate of azamethine, for example copper (II) sulfate, is suctioned off in the presence of an acid buffer and washed with ethanol and water. Grinded-out like sodium acetate. 29.4 g (91.6% of theory) of loot (after drying) are suitable as grinding units.

for example ball mills, pearl or sand mills. The grinding 16 g of the azamethine obtained in this way is dissolved in 150 ml of dime-can also be in the presence of a salt and / or a surface-formamide and is carried out for 3 hours at 100 ° C. with 10 g of copper active. 30 (Il) acetate treated. The mixture is allowed to cool to 50 ° C. and is suctioned off. The azamethine-copper complexes of the formula I are valuable and are washed with the yellow pigment with ethanol and water. After full properties as pigments. drying gives 17.8 g of the compound of the formula

In order to achieve optimal coloristic properties of the pigments produced according to the invention, it is sometimes advantageous to convert the finished pigment into a finely divided form by heating in a solvent, if appropriate in the presence of water or salt solutions.

Suitable solvents for this purpose are those in which the pigment is insoluble, but which allows a certain amount of dissolving under the finishing conditions, for example aliphatic alcohols, in particular lower alkanols such as ethanol, isopropanol,

Iso- or n-butanol, chloroaromatics, such as chlorobenzene and -to-oxynaphthaldehyde- (l) are mixed in 100 ml of water for 5 minutes

toluene or dichlorobenzenes and dipolar aprotic solvents. Then 50 ml of 2N sodium hydroxide solution and 30 ml of, for example, dimethylformamide, dimethylacetamide, dime 40% sodium hydrogen sulfite solution are added and the ethyl sulfoxide, N-methylpyrrolidone, polyalkylureas such as Te 45 mixture are stirred at 95 ° C. for 15 minutes. The precipitate of tramethylureas and phosphoric acid amides such as hexamethyl is suction filtered and washed with cold water. The press cow

phosphoric acid trisamide. is then mixed in 200 ml of water with a quick stirrer

Also a fine distribution by grinding with salts or stirring.

Solvents can be advantageous, in which case a solution of 27.5 g of copper (II) sulfate is then added.

preferably dry grinding on vibrating mills and then pentahydrate in 100 ml water and 50 g concentrated ammonium

The salt is dissolved with water and the antigen solution is added, the mixture heats up to 95 ° C and keeps it wet, if necessary, or heat treatment at this temperature for an hour. The pigment is removed hot

Can connect solvents. sucks, washed with hot water and dried. One

The salts used are essentially alkali and alkaline earth 32.9 g of the compound of Example 1.

salts of hydrohalic acids or sulfuric acid in 55

Consider, for example sodium or potassium chloride and Example 3

Sodium or magnesium sulfate. A mixture of 16.7 g of 4-carbomethoxy-2-aminophenol,

The solvents which can be used for wet grinding are in 17.2 g of 2-hydroxynaphthaldehyde (l) and 200 ml of water. The above-mentioned, for example alcohols, acid are substantially in a ball mill with 200 g ceramic balls (diameter amide or dimethyl sulfoxide. 10 mm ) 24 hours. After adding 25 g Na

The new compounds represented valuable pigments, trium acetate trihydrate, 26 g copper (II) sulfate pentahydrate and which are suitable for printing inks, emulsion paints, lacquer colors and 100 ml water will be ground for a further 80 hours. That get

for pigmenting high molecular weight organic material, the ground product is washed with water and dried,

such as. Cellulose ethers and esters, polyamides, polyurethane yield 35.7 g of the yellow pigment of Example 1.

or polyesters, acetyl cellulose, nitrocellulose, natural 65

resins or synthetic resins, e.g. Aminoplasts, in particular Example 4

urea and melamine-formaldehyde resins, alkyd resin- 16.7 g of 4-carbomethoxy-2-aminophenol and 17.2 g of 2-hydride

Zen, phenoplasts, polycarbonates, polyolefins such as polyethynoxynaphthaldehyde (l) are mixed with 400 ml of water with a coco = ch ^ />

3 ^ r \ i °

.o-cu-0

Example 2

16.7 g of 4-carbomethoxy-2-aminophenol and 17.2 g of 2-hydr

632 525

4th

High speed stirrer dispersed and the dispersion after heating to 95-98 ° C for 4 hours at this temperature.

It is suctioned off, washed with hot water and the moist presscake is stirred with 400 ml of water in which 26 g of copper (II) sulfate pentahydrate and 25 g of sodium acetate are dissolved, and the mixture is heated to boiling temperature. After 5 hours of heating to 100 ° C., the product is suctioned off hot, washed with water and dried. 34.9 g of the yellow pigment from Example 1 are obtained.

Example 5

18.1 g of 4-carbomethoxy-2-aminoanisole and 17.2 g of 2-hydroxynaphthaldehyde (l) are heated to 100 ° C. in 400 ml of diethylene glycol monomethyl ether and kept at this temperature for two hours. Nitrogen is passed over the batch during the reaction time. 10 g of copper (II) acetate, dissolved in 100 ml of diglycol monomethyl ether, are added to the hot reaction mixture. The mixture is heated to 150 ° C. and kept at this temperature for 4 hours. After cooling, the yellow pigment is filtered off, washed thoroughly with ethanol and water and dried. 31.9 g of the compound of the example are obtained.

Example 6

11.2 g of 2-hydroxy-l-naphthaldehyde are suspended in 700 ml of n-propanol. Then 24.3 g of n-propyl 3-amino-4-hydroxybenzoate as hydrochloride and 10 g of anhydrous sodium acetate are added. The mixture is heated under reflux under a nitrogen atmosphere for 2 hours. The yellow azamethine of the formula n-C3H7OOCX ^^ j --- N

oh is suctioned off hot, washed with n-propanol and water and dried. Yield 33 g.

17.45 g of the azamethine thus produced are suspended in 250 ml of n-propanol. 12.5 g of copper sulfate pentahydrate, dissolved in 30 ml of water, are then added dropwise within 15 minutes. The pH is kept at 5 with about 25 ml of a 4N sodium acetate solution. The mixture is heated under reflux under a nitrogen atmosphere for 3 hours, then the product is suctioned off hot, washed with n-propanol and water and dried. 23.3 g of the green pigment of the formula are obtained, filtered off hot, washed with ethanol and water and dried. Yield 28.4 g.

16.75 g of the azamethine thus produced are suspended in 250 ml of ethanol and, as described in Example 6, manufactured in copper. 24 g of the green pigment of the formula c2h5ooc are obtained

Example 8

17.2 g of 2-hydroxy-1-naphthaldehyde are suspended in 500 ml of 15 n-butanol, then 25.75 g of 3-amino-4-hydroxybenzoic acid n-butyl ester hydrochloride and 10 g of anhydrous sodium acetate are added. The mixture is heated to 90 ° C. and kept at this temperature for 2 hours. It is then suctioned off at about 70 ° C., washed with n-butanol and water and dried. Man-20 holds 26.55 g of the orange azamethine of the formula n-c.ho00c 4 9

n =

Oh

30th

18.15 g of the azamethine thus obtained are suspended in 250 ml of n-butanol and coppered as described in Example 6. 19.95 g of the yellowish-green pigment of the formula are obtained

35

-c.hnooc 4 9

The following 40 pigments were obtained in accordance with Examples 6 to 8:

yooc ^^ ä ^ / n = ch

x cu '

n-C3H7OOC

n = ch o \ / o cu

Example Y

50

10th

55

Example 7

17.2 g of 2-hydroxy-1-naphthaldehyde are suspended in 500 ml of ethanol. Then 23 g of 3-amino-4-hydroxy-11-benzoic acid ethyl ester hydrochloride and 10 g of anhydrous sodium acetate are added. The mixture is boiled under reflux for 2 hours under a nitrogen atmosphere. The failed orange azamethine of formula * 2

H

H3C \

CH-H.C /

H3C \

CH-CH, -H3C- "

CH3

I.

CH, -CH, -CH-

Nuance in letterpress greenish-yellow greenish-yellow redish-yellow brownish-yellow c_hcooc

2. D

65

13 CH3-CH2-CH2-CH2-CH2- reddish yellow

CH3

I.

14 CH3-CH2-CH-CH2- brownish yellow

5

632 525

Example 15

21.6 g of 2-hydroxy-1-naphthaldehyde-3-carboxylic acid are boiled together with 11.4 g of o-aminophenol in 300 ml of ethanol under reflux in a nitrogen atmosphere. Then the precipitate of the azamethine is suction filtered while hot, washed with ethanol and water and dried.

After suspension in 300 ml of ethanol, 10.2 g of the orange azamethine thus produced are boiled with 7 g of copper acetate and kept at the boiling point for 3 hours. The pH is kept at 6.5 by adding 25 ml of 4N sodium acetate solution. It is suctioned off hot, washed with ethanol and water and dried. Yield 11.7 g of the greenish-yellow pigment of the formula n = ch

à

cooh

Example 16

21.6 g of 2-hydroxy-1-naphthaldehyde-6-carboxylic acid are suspended together with 11.4 g of o-aminophenol in 300 ml of glacial acetic acid. It is heated to boiling and kept at this temperature for 3 hours. It is suctioned off hot, washed with ethanol and water. After drying, 30.5 g of the orange azamethine of the formula are obtained

20 g of the azamethine are dissolved in a mixture of 150 ml of dimethylformamide and 150 ml of diethylene glycol dimethyl ether and heated to 100 ° C. with 13.5 g of copper sulfate pentahydrate and kept at this temperature for 3 hours. It is then suctioned off 5 hot, washed with ethanol and water and dried.

Yield 22.5 g.

12 g of this crude pigment are ground together with 50 g of sodium sulfate and 50 g of sodium acetate in a porcelain ball mill with 800 g of porcelain balls of 10 mm in diameter for 10 hours. The contents of the mill are then stirred in hot water, and the greenish-yellow pigment is isolated, which is washed and dried salt-free.

Example 18

15 If the procedure is as described in Example 17, but replacing the 2-hydroxy-l-naphthaldehyde-6-carboxylic acid methyl ester with 24.8 g of 2-hydroxy-l-naphthaldehyde-3-carboxylic acid ethyl ester, 31.5 g of the Azamethine of the formula

20th

25th

cooc2h5

n = ch oh cooh

15.35 g of the azamethine thus produced are dissolved in 100 ml of dimethylformamide and heated to 100 ° C. with 100 ml of diethylene glycol dimethyl ether and 15 g of copper acetate and kept at this temperature for 3 hours. 16.7 g of the greenish-yellow pigment of the formula are obtained

15.4 g of the azamethine thus produced are heated to 100 ° C. with 100 ml of dimethylformamide and 100 ml of diethylene glycol dimethyl ether 30 and 9 g of copper acetate and kept at this temperature for 3 hours. It is then suctioned off hot, washed with dimethylformamide, ethanol and water and dried. 16.3 g of the yellowish-green azamethine-Cu complex of the formula cooh are obtained

40

c00c2h5

Example 17

If the procedure is as described in Example 16, but 23.2 g of the corresponding methyl ester are used instead of 2-hydroxy-1-naphthaldehyde-6-carboxylic acid, 29.7 g of the orange azamethine of the formula cooch are obtained,

The following 45 further azamethine-Cu complexes are obtained in accordance with Examples 15-18:

Ex.

R1

R2

nuance

19th

20th

21st

22

COOCH3 CQO-nC3H7 COO-n-C4H9 / CH3

COOCH.

\ CH,

H H H

H

greenish-yellow greenish-yellow greenish-yellow yellow

CH,

23

COOCH-CH, CH,

H

yellow

632 525

24th

25th

26

27th

28

29

COO-n-C5Hn COO-CH2 CH-CH2-CH3

h h h h

ch.

h h

COOC2H5

COO-n-C3H7

COO-n-C4H9

COO-CH

-CH3

\

CH,

greenish-yellow yellow greenish-yellow greenish-yellow greenish-yellow greenish-yellow

30th

31

32

h h h co o-n-c5h; j ch3 I

cooch-ch2-ch3

cooch2ch-ch2-ch3 I

ch3

greenish yellow yellow greenish yellow

Example 33

21.6 g of 2-hydroxy-1-naphthaldehyde-6-carboxylic acid are suspended in 300 ml of glacial acetic acid together with 21.5 g of methyl 3-hydroxy-4-aminobenzoate hydrochloride. It is heated to boiling and kept at this temperature for 3 hours. It is suctioned off hot, washed with ethanol and water. After drying, 35.2 g of the orange azamethine of the formula h3cooc are obtained

N = CH

oh ho h3coocv ^ ä ^ 'n = ch 0 \ 0

cooh

Cu '

12 g of this crude pigment are ground together with 50 g of sodium sulfate and 50 g of sodium acetate in a porcelain ball mill with 800 g of 10 mm diameter porcelain balls for 10 hours. The contents of the mill are then stirred into hot water, and the greenish-yellow pigment is isolated, which is washed and dried salt-free.

25 Example 34

If the procedure is as described in Example 33, but the 2-hydroxy-l-naphthaldehyde-6-carboxylic acid is replaced by 2-hydroxy-l-naphthaldehyde-3-carboxylic acid, 35.75 g of the azamethine of the formula h3cooc ooh are obtained 35

40

n = ch oh ho cooh

20 g of the azamethine are dissolved in a mixture of 150 ml of dimethylformamide and 150 ml of diethylene glycol dimethyl ether and heated to 100 ° C. with 15 g of copper sulfate pentahydrate and kept at this temperature for 3 hours. It is then suctioned off hot, washed with ethanol and water and dried. Yield 23.5 g of the greenish-yellow pigment of the formula

18.3 g of the azamethine thus produced are heated to 100 ° C. with 100 ml of dimethylformamide and 100 ml of diethylene glycol dimethyl ether and 10 g of copper acetate and kept at this temperature for 3 hours. It is then suctioned off hot, washed with dimethylformamide, ethanol and water and dried. 17.3 g of the yellowish green azamethine-Cu complex of the formula are obtained

50 h, cooc = ch cooh

55

The following further azamethine-Cu complexes are obtained in accordance with Examples 33 and 34:

60

65

rl

Ex.

x

7

ri r2

nuance

35

Cl

COOH

H

reddish brown

36

Cl

H

COOH

yellow

37

no2

COOH

H

reddish-yellow

38

no2

H

COOH

reddish-yellow

39

Br

COOH

H

greenish-yellow

40

Br

H

COOH

brownish-yellow

41

COOC2H5

COOH

H

yellowish green

42

COOQHj

H

COOH

green

43

COOC3H7 (n)

COOH

H

brownish green

44

COOC3H7 (n) / CH3

H

COOH

yellowish green

45

COOCH

xCH3

COOH

H

brownish green

/ CH3

COOCH

xch3

46

H

COOH

yellowish green

47

COOC4H9 (n)

COOH

H

yellowish green

48

COOC4H9 (n)

H

COOH

bluish green

49

ch3

COOH

H

reddish-yellow

50

ch3

H

COOH

reddish-yellow

51

cf3

COOH

H

yellowish green

52

cf3

H

COOH

yellow

53

och3

COOH

H

brownish-yellow

54

och3

H

COOH

reddish-yellow

55

Cl cooch3

H

reddish-yellow

56

no2

H

COOCH3

reddish-yellow

57

co2ch3

H

cooch3

yellow

58

COOH

COOH

H

greenish-yellow

59

COOH

H

COOH

greenish-yellow

Claims (2)

632 525 2nd PATENT CLAIMS 1. Process for the preparation of new compounds of formula I. 15. Substrates according to claim 14 in the form of coloring agents.