DE1794301C3 - Chromium complex developer dyes - Google Patents

Description

Cr * OH,

R "is H, - CH ₃ , - CN,

- CO - NH - C. _ ₆ Hj _, 3 or

- CO —NH-A ',

A 'is - Y - G, - O - Y - G or - G, Y is an alkylene radical with up to 5 carbon atoms or a phenylene radical, G is the remainder of the hydroquinone or hydro

cliinon-dibenzyläthcrs,

X are the atoms required to complete a benzene, cyclopentene or cyclohexene ring, it being possible for the benzene nucleus to contain a methoxy group as a substituent, with the proviso that at least one of the radicals R ₅ or R ₆ bears a substituent A '.

Il

-CR ₁

R,

R ₅ -AN = NBR ₁ ,

Cr * OH ₂

μ The invention relates to chromium complex developer dyes, which compared to the known 2: 1 complexes by greater stability against color degradation by actinic rays, moisture and warmth. In addition, these Cr complexes have a deeper and clearer color than the well-known 2: 1 complexes.

The chromium complex developing dyes of the present invention are dyes which have a single coordination chromium contained per dye molecule.

They are characterized by the general formula

R ₅ -AN = NBR _n

C = C C-R,

where the substituents have the following meanings:
A is a benzene or naphthalene nucleus or a divalent naphthalimide radical, B is a benzene or napthalene nucleus, a pyrazolone nucleus which is connected to the azo group in position 4 and a phenyl group which is substituted by nitro or A 'in position 1 can, and in 3-position carries _{the ReStR 6;} or the barbituric acid residue; where the residues A and B are each bound to the chromium complex via an oxygen bridge,

R is CH ₃ -, C ₂ H ₅ -, F ₃ CC ₆ H ₅ -NH- or CrI ₃ -O-CH ₂ -,

R, is CH ₃ -, C ₂ H ₅ -, F ₃ C-, or CH ₃ -O — CH ₂ -, C ₆ H ₅ NH-,

R ₂ is H or phenyl,

R ₃ is H, a lower alkyl group or - OH,

R ₄ is H, a lower alkyl group, -CH ₂ -COOH,

35

40

RC = C CR ₁

(A)

or

R ₅ -ANNBR ,,

or A ',

R ₅ is H, -CN
-SO ₂ N (RJ ₂ ,

Ci

or -SO ₂ A 'A',

(B)

r> o

SO ₁ H,

-SO ₁ -NH

in which the substituents have the following meanings: A is a benzene or naphthalene nucleus or a divalent naphthalimide radical, B is a benzene or naphthalene nucleus, a pyrazolone nucleus which is connected to the azo group in 4-position and which is a phenyl group in 1-position, the can be substituted by nitro or A ', and in 3-position carries the radical R ₆ ; or

the barbituric acid residue; where the residues A and B

each via an oxygen bridge to the chromium

are complex bound,

IStCHi-X ₂ H ₅ , FjC-, CH ₅ -NH- or

CH ₃ -O-CH, -,

IS CH ₃ -, CH ₅ -, F ₃ C-, or

CH ₃ -O- CH ₂ -, C ₆ H ₅ NH-,

is H or phenyl,

is H, a lower alkyl group or - OH,

is H, a lower alkyl group,

- CH ₂ - COOH,

The new dyes are characterized by the spectral absorption values that they are suitable for color photography Make it appear particularly suitable when reproductions of the correct color are desired.

A preferred group of dyes according to the invention contains the hydroxynaphthylazo-pyrazolone building block, in which the abovementioned substituents are directly in the para position on the naphthyl nucleus to the azo substances. As chromium complexes, they represent purple dyes, as follows characteristic building blocks contain:

or A ',

is H, --- CN or - SO ₁ A ', - SO ₃ H,
-SO ₂ N (R ₄ J ₂ , -A ',

SO, -NH

R _h is H, -CH ₃ , -CN,

- CO - NH - C ₁ _ "H ₃ _ ₁₃ or

- CO —NH-A ',

A 'is - Y - G, - O - Y - G or - G,
Y is an alkylene radical with up to 5 carbon atoms or a phenylene radical,
G is the remainder of the hydroquinone or hydroquinone dibenzyl ether,

X are the atoms required to complete a benzene, cyclopentene or cyclohexene ring, where the benzene nucleus can contain a methoxy group as a substituent,

With the proviso that at least one of the radicals R ₅ ider R _h bears a substituent A '.

HY - N - O, S

> —N - · - ■ N ■ - B —A '

OH

/ Λ

OH

Λ '- Y - N - 0-, S-

and

N = C ■ - <

OH

> -N N- B

OH

OH

> ■ - N NBA ¹

OH

Examples of these and other useful dye building blocks are the following substances

C ₂ H ₅ N

-A '

(1)
(submitted later)

OH

HO

CO-NH-CH ₃

OH

(CH ₂ I ₃ -ι

OH

CO-NH-CH ₃

CH ₂ CH, -

OH CH ₃ O ₂ S- Λ-CH ₂ - -CH- τ OH < -N - I. CH, > OH

HO

H-CH ₃

N = N

HO

CO —NH-

OH

- N = N

CH,

OH

OH

IK)

N = C-

OH

N = N-

HO

CO-NH-CH ₃

(CH ₂ J ₂

OH

CH ₃

OH

/ VcH ₂ -NO ₂ S- <>

-N = N-

OH

OH

HO (8)

(9)

OH

M = N-Tr-T-CO-NH-C ₂ H ₅

HO

OH

CH ₂ CH ₂ π

OH

OH (10)

(12)

709 636/75

CH, <

CH ₃ -CH ₂ -CH ₂ -CH ₂ -N-SO ₂

π—

1 N

10

CN

HO

CH ₂ CH ₂

OH

N = N-

-CO-NH-C _A H.

OH

HO

(CH ₂ J ₂

The connections! to 14 are dye developers 35 A preferred ligand is Acrylacetom: winder, ie dyes that have a silver halide developer group, e.g. B. contain a dihydroxyphenyl radical, such as a hydroquinonyl group, and as a result q q whose dyes as well as silver halide are developing substances. 40 (^ j ₃ - C-CH C CH (15)

The ligands or compounds that make up the 23-

Contributing to both oxygen atoms bound to the chromium atom can be defined as

/ J-hydroxy-a ^ -unsaturated carbonyl compounds Examples of other preferred ligands which

or as compounds which in such a structure 45 the new 1: 1 chromium complex dyes of the formulas can tautomerize. (A) and (B) are:

O O

Il Il

CHj - CH ₂ - C - CH ₂ - C - CH,

(16)

O O

Il Il

CFj - C - CH ₂ - C - CF ₃

(18)

ο ο

Il Il

CH ₃ - CH ₂ - C - CH ₂ - - C - CH ₂ - CFI ₃ (17)

9 oo

NH-C- CH ₂ -C- CH ₃ CHj -C- CFI ₂ -C- CF, ( ¹⁹ > (20)

OH

CHO

CHO

(22)

O
C-CH ₃

(21)

11th O 1 7th 94 30 1 ο 12th ο
Il Il
—C- ο pC-CHj CHjO-CH ₂ C. H ₂ Il
-C-CM ₃ (25) (24)

Examples of I: l-chromium complex color plates according to the invention are:

CH ₃ -C = CH C-CH

CO-NH-CH ₃

CO-NH-CH

CH ₂ CH ₂

(26)

O O

I Il

CH ₃ -C = CH - C-CH ₃ (27)

N = C

CO-NH-CH ₃

CH ₂ CH ₂ - ,,
O \ _{/ y}

CH ₃ -C = CH C-CH ₃

OH

Λ — CH ₂ —CH — N —SO ₂

OH

O

I Il

CH ₃ -C = CH C-CH ₃

CO-NH-CH ₃

C ₂ H ₅ -C = CH-C-CH

14th

CO-NH-CH ₃

CO-NH-C ₂ H

₂ H ₅

H ₂ O> Cr

/ \ CH ₂ CH ₂

O O

I Il

(T, -C = CH-C-CH ₃ OH

OH

15th

16

_{N =} N- CO-NH-C ₂ H ₅

H, O -> Cr

Γ /

(CH ₂ ), _{ι (} OH

(34)

OH

CH ₃ -C = CH - C - CH, - OCH,

NH-CO — CH ₂ CH, - (

(35)

O O

CH ₃ -C = CH - C-CH,

—IpCO — NH-C ₂ H ₅

OH

CO-NH-C ₂ H ₅

CF ₃ - C == CH - C - CF ₃

CN

OCH ₂ - \ y

CH ₃ -C = CH - C-CH ₃ OCH,

CHj - C = CH - C - CH

CO-NH-C ₆ H ₁

A '

CH ₃ -C = CH C -CHj

(39)

(40)
(submitted later)

One method of producing the new chromium complex dyes is that one does not complexed dye with the desired ligand, e.g. B. a ligand of formulas 15 to 25 with an inorganic chromium salt such as chromium acetate. The reaction runs off when you get one Mixture of the above-mentioned ingredients in an inert organic solvent such as dimethylformamide, heated to reflux.

The term "inert organic solvent" denotes an organic one; Solvent that both is chemically inert towards the Reaktson partners as well as towards the reaction product.

After the complex formation, further reactions can be carried out on the dye molecule, to form an analogous chromium complex thereof.

The new chromium complex dyes according to the invention can also be prepared by a chromium complex dye, e.g. B. the dye Color Index 18810, with at least one substituent A 'converted into a chromium complex dye

HO

leads, which has the desired chemical and / or physical properties, whereupon him subjected to a complex formation reaction with the desired ligand. This creates a Chromium complex dye of formula A or B. The chromium complex dyes can also be prepared by turning the complex of a metal other than chromium into the desired chromium complex dye convicted.

Production example 1

20.0 g of benzenesulfonazide were dissolved in 50 ml of tetrahydrofuran, ^{cooled to about 0 °} C. and flushed through with nitrogen. To this solution, a mixture of 5.0 g of sodium hydride (50% in oil) and 46.2 g of a pyrazolone of the formula was added dropwise over the course of one hour, while the reaction was maintained at 0 to 5 ° C. and under a nitrogen atmosphere

COOC ₂ H ₅

CH ₂ CH ₂

in 1.5 l of tetrahydrofuran (the entire system must be protected from air by nitrogen). After the dropwise addition was completed. the mixture was stirred in an ice bath under the protection of nitrogen for ¹ liter for _{2 hours.} A solution of! 4, Og ^ -naphthol in 50.0 ml of tetrahydrofuran was added and the resulting

OCOCHj

The mixture was stirred under nitrogen for 1 hour at room temperature, whereupon it was treated with 21.0 g of p-toluenesulfonic acid has been acidified. The mixture was then filtered and the filtrate was in vacuo concentrated to about 150 ml, cooled, and 17.1 g of a crystalline orange dye were obtained isolated with a melting point of 168 to 172 C.

It had the following structural formula:

Π 94

N = N

COOC ₂ H ₅

OH

(CH ₂ ) ₂

OCOCH,

15.0 g of this dye were mixed with 200.0 ml of methanol and the resulting solution with Flushed with nitrogen. 40.0 ml of 40% aqueous monomethylamine was added and the mixture refluxed on a steam bath for 3 hours. She was then with Ethanol Hydrochloric acid acidified to give a viscous Ul which solidified on standing. The fixed one The mass was filtered off and washed thoroughly with water. It was then made from 600.0 ml of ethyl acetate recrystallized, giving 9.47 g of a dye developer with a melting point of 164 to 166.degree received. He had the following formula:

| T-CO-NH-CH ₃

Production example 2

143.0 u-naphthylamine were dissolved in 250.0 ml of dimethyl

\ formamide was dissolved, and this solution was added to 294.0 ml of hydrochloric acid in 3000 ml of water while stirring given. The resulting white precipitate («-naphthylamine hydrochloride) was cooled to 0 ° C in a dry ice bath. 69.0 g sodium nitrite in 750.0 ml Water was then added with vigorous stirring, the temperature being maintained at 0 to 2 ° C would. The resulting dark brown diazonium solution was stirred for 10 minutes, with the Temperature was maintained between 0 to 2 ° C; then the solution was filtered. A second (coupler) -

■ 5 solution was prepared by dissolving a pyrazolone of the following formula in 15 1 acetone:

HO

25th

Then 336.0 g of sodium bicarbonate and enough ice were added that the temperature at IOC

vs was held. The dark brown diazonium solution was then second (coupler) solution with stirring over 30 minutes while the temperature was maintained at 10 ⁰ C. The resulting mixture was then stirred for an additional 90 minutes. A red-orange solid was collected on a Buchner funnel. It was washed with 3 liters of a 1: 1 acetone-water solution (at room temperature), 31 water and 21 isopropanol. It was then dried overnight in einerr vacuum oven at 40 ⁰ C, where mar 518.0 of a red-orange solid product g of Forme

50

6.7 g of this dye developer and 13.0 g of acetylacetone were dissolved in 10.0 ml of dimethylformamide and the resulting solution was flushed with nitrogen, 12.7 g of finely powdered chromium acetate were dissolved in 60.0 ml of boiling dimethylformamide, and this hot solution was added to the dye developing solution. The resulting mixture was then heated to reflux under nitrogen for 15 to 20 minutes. It was then chilled and thin Poured stream with vigorous stirring into 600.0 ml of water containing 10.0 ml of concentrated acidic acid. This mixture was then filtered and the solid portions washed thoroughly with water and recrystallized from 400.0 ml of acetone, 6.95 g of a chromium complex developer dye of the 6s Formula 40 received.

This compound has an X _max at 520 and 555 ηΐμ in methylcellosoiv: r = 17,000; 20 500.

-N = N

HO

CO ₂ CH ₂ CH ₃

OCOCH ₃

01, CH ₃ CH

OCOCH,

received. A mixture of 57.8 g of the above dye, 25, Og copper (II) acetate and 1000.0 ml of Di methylformamide was stirred at room temperature until the solution was complete. That reaction!

mixture was then filtered and the filtrate was cooled to O'C with dry ice, water and a methanol cooling bath. Then 25.0 ml of hydrogen peroxide (30% solution) was added with stirring in an amount such that the temperature of the reaction was maintained at 0 to 2 ° C while the cooling was maintained at about -5 ° C. The mixture

was then stirred at 0 to 2 ° C for a further hour and precipitated in 3 1 of 0.2% strength hydrochloric acid with vigorous stirring. The resulting solid mass was then collected on a Buchner funnel, washed with water and in vacuo at room temperature dried to constant weight: 48.0 g of a copper complex of the formula were obtained

CO ₂ -CH ₂ CH ₃

H ₂ O-Cu

CH ₂ CH ₂ CH ₂

OCOCH ₃

OCOCH ₃

22.0 g of this compound was dissolved in 330.0 ml of dimethylformamide, and the resulting solution was then filtered to remove traces of undissolved material. 5.5 g of dithiooxamide were added with stirring, and the resulting mixture then became another at room temperature Stirred for hour. The reaction mixture was filtered to remove the copper complex of the preceding Step to remove thioxamide formed. The filtrate was then slowly added a vigorously stirred 0.1% hydrochloric acid solution, a brick-red solid precipitate precipitated, collected on a Büchner funnel with water

jo washed, collected again and overnight at Room temperature dried in vacuo: 19.1 g of a dye of the formula were obtained

OCOCH ₃

The reaction of the above dyestuff with the manner described in aq Monomethylamine followed by acidification with a substance developer of the formula of ethanolic hydrochloric acid in the

CO-NH-CH ₃

CH ₂ CH ₂ CH ₂

7 94

Treatment of this compound with acetylacetone and chromium acetate as described in Preparation I resulted in the chromium complex developer dye of formula 26.

This connection has a /. _max at 520 and .534 ηΐμ in methyl cellosolve: f = 16,400; 19 400.

Production example 3

5.0 g of 4-cyano-naphthalene-1-diazo-2-oxide were added to a solution of 14.0 g of l- [p- (2 ', 5'-diaceloxyphenylethyl) phenyl] -3-carbaldoxy-5 · pyrazolone in 100.0 ml of ethanol, 250.0 ml of water and 5.0 g of sodium carbonate given. The mixture was heated to about 30 ° C. and, after one hour, with hydrochloric acid acidified, giving a rubber-like product, which was then dissolved in 200.0 ml of ethanol and taken under Nitrogen was refluxed with 50.0 ml of 40% aqueous methylamine for 2 hours. It was cooled and neutralized with 20.0 ml of hydrochloric acid in 50.0 ml of ethanol. Crystallizing from methyl cellosolve and water brought 3.6 g of a dye developer of the formula

CO-NH-CH ₃ ίο

100.0 ml of water and enough ice to make the Temperature was kept below 5 ° C. The resulting yellow diazonium salt became dropwise with stirring in the course of 30 minutes> a mixture of 43.5 g of 1-phenyl-S-melhyl-S-pyrazolone. 160.0 ml of pyridine, 200.0 ml of water, 500.0 ml of ethanol and enough ice were added that the temperature of the Reaction mixture was kept below 5 C. After stirring for an additional 15 minutes

• Suck off the reaction product and discard the filtrate. The precipitate was with water washed to remove the pyridine and then dried in a vacuum oven. Recrystallization from 3000.0 ml of 50% methyl cellosolve and

'5 Water led to 89.4 g of l-phenyl-3-methyl-4- (4'-naphthalenesulfonic acid-l'-azo) -5-pyrazolone with / _moI in methylcellosolv = 435 ηΐμ:

40 24.5 g of this compound, 12.5 g of phosphorus pentachloride and 100.0 ml of 1,1,2-trichloroethane were refluxed for 5 hours and the reaction mixture was filtered while it was hot. 16.0 g of red-orange crystals with a melting point of 243 to 247 ° C. were obtained. Recrystallization from toluene gave 11.5 g of 1-phenyl-3-methyl-4- (4'-naphthalenesulfonyl chloride-1'-azo) -5-pyrazolone with /. "," = 422 ηΐμ: / = 28 2 (X). The compound has the following structural formula:

3.0 g of this compound, 5.6 g of chromium acetal and 14.0 g of acetylacetone in 60 ml of dimethylformamide were Heated to reflux for 20 minutes. The mixture was then dissolved in 600.0 ml of water containing 10.0 ml of hydrochloric acid contained, poured. The solution was collected and stirred with 100.0 ml of acetone. About 50.0 ml Methanol was added after 2 hours and the product formed was filtered off and washed with methylene chloride washed to give 1.5 g of Formula 28 developing dye.

This compound has a ) “ _ax at 536 and 576 ηΐμ in methyl cellosolve:, = 21,000; 25 400.

Preparation example 4

55.6 g of 4-amino-1-naphthalenesulfonic acid were in Dissolved 700.0 ml of water and 20.0 g of 50% strength aqueous sodium hydroxide. 17.5 g of sodium nitrate were made added with stirring until the solution was complete. The resulting solution was then added dropwise with stirring for 10 minutes a mixture of 83.5 ml of concentrated hydrochloric acid.

45 ClO ₂ S

HO

- CH,

34.4 g of this compound. 100.0 ml of pyridine and 19.8 ml of 2-N-methylamino (2.5 -dimcthyloxyphynyl): propane were stirred at room temperature for 45 minutes. The mixture was then heated on a Vl _{steam bath for 2} hours. It was then slowly poured into dilute hydrochloric acid and ice with stirring, filtered, and dried in a vacuum oven to give 49.0 g of the product. This substance was recrystallized from 150.0 ml of acetic acid and dried at 50 ° C. in a vacuum oven. 23.9 g of an A / ofarbsloffcs were obtained. Sdimp. 148 to 150 C: /. _{m ()} , == 428 m> i: > - 23 (XX).

709 636/75

ocn.,

cn.,

CH ₂ -CH-NO ₂ S

OCH.,

CH,

22.3 g of this azo dye was dissolved in 160.0 ml of trichloromethane, and to the resulting mixture was added dropwise 22.0 ml of boron tribromide in 60.0 ml of trichloromelhanum at room temperature with stirring over a period of 30 minutes. The mixture was stirred for an additional hour during which time a red precipitate formed. HXU) ml of methanol was added dropwise with stirring to the reaction mixture, which was then heated on a steam bath for 2 hours. The orange precipitate was filtered off and dried. 15.0 g of a developer dye were obtained, melting point 249 to 250 ° C .; Z _1111x 425 mu; f = 23 200:

OH

CH ₃
i
CH ₂ -CH-NO ₂ S- ^

CH ₃

A mixture of 15.0 g of this compound, 30.0 ml of acetic anhydride, 2.0 ml of pyridine and 120.0 ml of dimethylformamide was heated on a steam bath for 2 hours with stirring. The reaction mixture left to stand overnight. It formed bright red crystals, which filtered off and

were washed with dilute hydrochloric acid and water. They were dried over potassium hydroxide in vacuo, giving 13.7 g of bright orange-colored crystals with a melting point of 195 to 197 ° C:) . _max = 426 ηΐμ: / = 23,600; the substance corresponds to the formula /

OCOCH ₃
j [\ - CH ₂ -CH-NO ₂ S

OCOCH ₃

CH ₃

12.0 g of this compound were dissolved in 160.0 ml of dimethylformamide and 140.0 ml of tetrahydrofuran dissolved. A solution of 5.47 g of copper (II) acetate was used for this purpose given in 160 ml of dimethylformamide. This mixture was cooled to 4 C and then became them with 22.46 g (20.0 ml) of 30% hydrogen peroxide

(j- V-CH ₂ -CH-NO ₂ S CH ₃

offset. After thorough stirring, the mixture was precipitated in 400.0 ml of 3η hydrochloric acid and ice, filtered and washed with water. The resulting solid was over potassium hydroxide overnight dried in vacuo, giving 10.0 g of a dye with a melting point of 80 to K) O C:

N = N-

HO

ti

A mixture of 4.0 g of this compound, 60.0 ml of deaerated methyl cellosolve and 4.0 ml of 50% aqueous sodium hydroxide was stirred at room temperature under a nitrogen atmosphere for 45 minutes. Then 20.0 ml of concentrated hydrochloric acid in 20.0 ml v / water were added with cooling and stirring. The resulting red-orange precipitate was filtered and dried over phosphorus penoxide overnight. It was then washed with 100.0 ml of boiling trichloroethane, 3.0 g of a dye developer being obtained: mp 233 to 235 C; λ _ηαχ 474 ιτίμ: <- = 23 800:

OH

CH,

Aj-CH ₂ -CH-NO ₂ S- ^ ^ -N =

Y CH _{1 OH}

OH

HO

2.76 g of this dye developer and 4.70 g of acetylacetone were dissolved in 9.0 ml of dimethylformamide. 4.3 g of chromium acetate was dissolved in 20.0 ml of boiling dimethylformamide and then that described above Solution added. The mixture was refluxed for 15 to 20 minutes, in dilute hydrochloric acid and ice precipitated and then washed thoroughly with water. It then became dissolved in 30.0 ml of hot methanol, cooled, filtered and evaporated to dryness. The residue was Stripped in a Soxlat extractor with methyl chloride; the extracts were cooled and filtered, the chromium complex developing dye of Formula 29 was obtained.

This compound has a k _max at 530 and 565 mti in methyl cellosolve: * · = 21,500; 22 700.

The other chromium complex dyes (Formein 30 to 40 can also be determined using the method of represent the above production examples.

The spectral absorption properties of these chromium complex dyes in methyl cellosolve are in of the following. Table compiled.

Formula No. 520 ί 16 900 30th 554 20,000 520 17000 31 555 20 400 530 18 390 32 565 18 800 534 12400 33 558 12 800 520 16 300 34 556 19 500 543 23 600 35 572 21 300 520 16600 36 554 19 800 535 19 400 37 562 17600 533 12 900 38 572 14 800 522 16 200 39 556 19 200 553 40 592

The chromium complex developing dyes described above: can be used for photographic processes Production of color images can be used where a true color reproduction is required. This means that in addition to the advantages of increased stability over the 2: 1 chromium complexes new chromium complex developer dyes according to the invention particularly sharp spectral absorption curves with minimal light absorption in undesired Showing areas of the spectrum. As a result, they are particularly useful in subtractive Color photography to create accurate color reproductions of an object.

Claims (1)

Claim: Chromium complex - developer dyes, characterized by the general formula R ₅ -AN = NBR ,, I \ I o \ o