DE1172386B - Process for the preparation of dye-developing substances - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school KL: C 09 b;

H03i
German class: 22 b -3/02

Number: 1172 386

File number: J 11460 IVc / 22 b

Filing date: March 9, 1955

Opening day: June 18, 1964

The invention relates to a process for the preparation of dye developing agents which, for. B. are suitable for the implementation of photographic transfer processes, according to which colored Direct positives can be produced by the silver salt diffusion process.

The products of the process are capable of not only a color image on an image-receiving one To produce film, but also a latent silver halide image in an exposed silver halide layer to develop a photosensitive film.

The dye developing agents have the general formula

Y (8-m) —A— N —Z —D '

in which A represents an anthraquinone nucleus in any bond and D 'represents an organic radical containing hydroxyl, amino or alkylamino groups which has a developing effect on exposed silver halide, Q represents hydrogen, an alkyl group or an aliphatic or aromatic acyl group, Z represents a direct bond or an organic radical containing at least one methylene group, m an integer from 1 to 4 and Y hydrogen and / or an amino, alkyl, aryl, nitro group, halogen, an alkylamino, arylamino, aryloxy, alkoxy, Oxy, sulfonamido, carboxamido or sulfo group or processes for the preparation of dye developing agents

Applicant:

International Polaroid Corporation, Jersey, N.J.

(V. St. A.)

Representative:

Dr.-Ing. H. Ruschke, patent attorney,

Berlin 33, Aüguste-Viktoria-Str. 65

Named as inventor:
Allan Rogers Blout, Belmont, Mass.,
Myron Sydney Simon, Newton Center, Mass.,
Marilyn Ruby Cohler, Brooküne, Mass.,
Milton Green, Newton Highlands, Mass.,
Robert Burns Woodward, Belmont, Mass.,
Richard Stancliffe Corley, Wellesley Hills, Mass.
(V. St. A.)

Claimed priority:

V. St. v. America March 9, 1954 (415 073) -

have different atoms, e.g. B. Alkylene radicals, such as -CH ₂ - —CH ₂ -CH ₂ - -CH ₂ -CH-

CH ₃

and alkaryl radicals, such as

-N - Z - D '-

-CH ₂

and are obtained by using a corresponding compound of the anthraquinone series, the at least one substitutable for amino groups in any position contains, with an amine of the general formula

D ' - Ζ - Ν - Η

reacted and optionally acylated at least one of the amino groups of the product obtained.

In general formula I, Z refers to organic radicals which have two free valences on ver-The radicals can be saturated and unsaturated and substituted by chlorine or OH groups. Experience has shown that where Z is an alkylene group, the best results are obtained using a lower alkylene group having fewer than 6 carbon atoms and preferably an ethylene (- CH ₂ CH ₂ -) group. However, alkylene groups containing more carbon atoms can also be used provided that the resulting dye developer is soluble in the liquid processing agent and its oxidation product is immobilized in the developed emulsion layer.

409 600/286

The acylation of the amino nitrogen atoms, which are part of the chromophoric system, causes the visible absorption band of the compounds to be shifted to higher frequencies (shorter wavelengths). Thus, the acylation of an amino nitrogen atom of the blue-green 1,4-bis - [ß - (2 ', 5' - dioxyphenyl) - ethylamino] -anthraquinone causes a color shift to purple and the acylation of both amino nitrogen atoms a shift in color to orange-yellow.

The invention is illustrated by the examples.

example 1

7.2 g of leucoquinizarin, 4.2 g of aminoethylsulfonic acid and 60 ecm of ethanol were refluxed under nitrogen for 12 hours. Then 10.3 g Aminohydrochinonmonobenzoat, 9 g of boric anhydride and 15 cc of cresol were added, the mixture heated for 1 hour under nitrogen and then 1 hour in air at 120 ⁰ C. A white, solid substance precipitates here. On cooling, the mixture hardens to a dark, semi-solid mass that is boiled with trichlorethylene, which contains some dichloroacetic acid. The resulting mixture is filtered, the filtrate treated with methanol, then heated under a stream of air and concentrated. The solution takes on a dark green color. After standing for 12 hours, 8.4 g of a reaction product with a melting point of 248 to 251 ^° C. crystallize out. On further standing, a further 1.6 g of the reaction product crystallize out. Recrystallization from trichlorethylene gives a compound of the formula

OH

OCOC ₆ H ₅

OCOC ₆ H ₅

Cl ₂ CHCOOH

35

40

45

with a melting point of 253 to 254 ° C. The free 1,4-bis (2 ', 5'-dioxyanilino) -anthraquinone is obtained by adding 5.0 g of the above product in 100 ecm of ethanol and 250 ecm of 10% sodium hydroxide heated under nitrogen on the steam bath for 10 minutes. The mixture is concentrated in Hydrochloric acid filtered. Vacuum drying at room temperature gives 3.3 g of the desired product, which is a dark blue, solid substance mixed with benzoic acid, for example. The application this dye developing agent in a transfer process gives a blue-green positive Color image.

The above synthesis can optionally be carried out by direct reaction of the leucoquinizarin with aminohydroquinone monobenzoate be modified.

65 Example 2

1 mole of leucoquinizarin and 4 moles of 4 - (/ S-aminoethyl) pyrocatechol hydrobromide are refluxed in butanol for 4 hours under nitrogen in the presence of 4 moles of sodium bicarbonate. The reaction mixture is then acidified with dilute hydrochloric acid (in the presence of sufficient methanol to prevent separation) and filtered. The precipitate is oxidized by dissolving it in pyridine with admission of air and boiling until no further change in color occurs. By crystallization from ethyl acetate-petroleum ether gives 1,4 - bis - [beta - (3 ', 4' - dioxyphenyl) - ethylamino] anthraquinone with a melting point 159-161 ⁰ C. This compound is dissolved in acetone, ethanol, ethyl acetate and pyridine soluble, insoluble in water and petroleum ether, stable in neutral or acidic solutions, but inconsistent in bases in the presence of air. The use of this dye developing agent in transfer processes produces a green-blue positive color image.

Example 3

1,4-bis [/ H3 ', 4'-dioxyphenyl) ethylamino] anthraquinone and benzoyl chloride in a molar ratio of 1: 1 become acetone in about 10 parts by volume refluxed until the color change from blue-green to purple is complete. The acetone solution is then concentrated and the residue is recrystallized twice from acetone-chloroform. In this case, N-monobenzoyl, 4-bis - [/ M3 ', 4'-dioxyphenyl) ethylamino] anthraquinone is obtained in 32% yield obtained that sinters at 221 to 223 ° C and melts at 229 to 232 ° C. It's in watery Soluble in alkali, moderately soluble in methanol and acetone, and easily soluble in pyridine. In solution it has an intense, light purple color. The application of this dye developer substance in a transfer process gives a positive purple color image.

The acylated dye developing agents as prepared in Example 3 are preferred by heating the appropriate amino compounds with the appropriate acid halide or acid anhydride. Other known methods of acylation can also be used such as the application of an ester or amide of the acid. Through appropriate control the reaction conditions and the ratios of acylating agent to amino compound the acylation of one or more amino nitrogen atoms can be effected. It can also be different Acyl groups into a compound with more than one amino nitrogen atom in the chromophore System to be introduced.

Example 4

5.5g5,8-bis-benzenesulfonamidoquinizarin (0.01Mol), 9.95 g / J-amino-u-methyl-ethylhydroquinonyl hydrobromide (0.04 mol), 1.8 g sodium carbonate, 3.4 g sodium bicarbonate and 3, 75 g of phenol was added in a vented flask having a vented with nitrogen solution of 17 cc of 95% ethyl alcohol and 11.5 cc of water were mixed and reacted for 101 hours under nitrogen at a temperature of 105-107 ⁰ C. The reaction mixture was precipitated in 2% hydrochloric acid solution, filtered and the resulting precipitate was redispersed in a 2% hydrochloric acid solution. The precipitate was then filtered off and washed with 2% hydrochloric acid solution until the wash waters

were colorless. The product was then dissolved in ethylene glycol monomethyl ether and precipitated by adding dilute hydrochloric acid, filtered and dried. It was precipitated even further by twice precipitating from ethyl acetate by adding hexane. The resultant 5,8-bis-benzenesulfonamido - 1,4 - bis - (ß - hydroquinonyl - a - methyläthylamino) anthraquinone sintered at 142 ° C and resulted in the spectrographic analysis in ethylene glycol monomethyl ether

ε672ηΐμ = 19,200, ε 622 ηΐμ = 14,000, ε580πΐμ = 11600.

Example 5

2.3 g leuko-IAS ^ -tetrahydroxyanthraquinone, 5.6 g 2-aminopropylhydroquinone hydrobromide and 1.9 g sodium bicarbonate were in 50 ecm pyridine and Dissolved 2 ecm of water and refluxed for 64 hours. The solution was at its boiling point Vented for 1.2 hours and then left to stand at room temperature for an additional 18 hours. The product was precipitated in 10% hydrochloric acid solution and taken up in 300 ecm of methanol. This methanol solution was evaporated until crystallization started and then left to stand overnight. The resulting 1,4-bis (/? - hydrochmonyl-a-methylethylamino) -5,8-dihydroxyanthraquinone had a melting point of 224 ° C and found on spectrographic analysis

ε 620 πΐμ = 20 600, ε 675 πΐμ = 30,000.

Example 6

36.0 g quinizarine (0 ^ 15MoI) and 50 g phenol were added to 180 ecm of ethyl alcohol and 120 ecm of water and deaerated with nitrogen. It 5 g of sodium carbonate and 13.4 g of 2-amino-1-butanol (0.15 mol) were then added, whereupon the mixture was refluxed under nitrogen for 40 minutes. Then there was 37.2 g of 2-aminopropylhydroquinone hydrobromide (0.15 mol) and 12.6 g of sodium bicarbonate added and the boiling on Reflux continued under nitrogen for an additional 22 hours until the reaction was complete. That The reaction mixture was then poured into 10% hydrochloric acid to give a gummy mass. This gummy mass was made twice from acetone by adding dilute hydrochloric acid and then deposited from ethylene glycol monomethyl ether by adding dilute hydrochloric acid. she got further purified by separating twice from ethyl acetate by adding hexane and then dried in a vacuum dryer. The resulting 1 - (a-hydroxymethylpropylamino) -4 - (/ S-hydroquinonyl-a-methylethylamino) anthraquinone showed the following values in the spectrographic analysis:

ε640πΐμ = 19,000,

ε594ηΐμ = 16 400,

ε558ΐημ = 8,800.

Example 7

The procedure described in Example 4 was repeated, only instead of the 5,8-benzenesulfonamidoquinizarin 3.09 g of 6,7-dichloroquinizarin (0.01 mole) used. After 100 hours of implementation the reaction mixture was cooled under reflux and added to 160 ecm of 10% hydrochloric acid, to precipitate the product. This product was then diluted once from acetone by adding Hydrochloric acid and deposited a second time from warm acetone by adding hexane. The resulting 1,4-bis (/ S-hydroquinonyl-a-methylethylamino) -6,7-dichloroanthraquinone resulted in the ίο spectrographic analysis

ε 657 ηΐμ = 21 400.

The nitrogen analysis showed: calculated 4.63%, found 4.4%.

As explained, D 'is an organic radical that bears substituents, which means that the radical is opposite Obtains silver halide developing properties. In some of the above explanations one can think of the remainder D 'derived from hydroquinone, d. i.e., 'D' consists of the hydroquinonyl group

OH

OH

There are various other organic radicals that contain substituents that make them opposite Obtained silver halide developing properties, such as 3,4-dioxyphenyl, l-oxy-4-aminophenyl, 1-oxy-4-methylaminophenyl, 1,2,3-trioxyphenyl and 1-oxy-2-aminonaphthyl. These evolving residue examples are illustrative only, and other substituents can be used which act as well. In a preferred embodiment D 'contains an aryl nucleus, e.g. B. a benzene or naphthalene nucleus. If D 'has a benzene nucleus contains, the silver halide developing property in a known manner by in o or p-position to each other arranged amino, alkylamino and / or oxy groups are effected.

For the chemical constitution of the silver halide developing groups, reference is made to "The Theory of the Photographic Process", CEK Mees (1942), The Macmillan Co., New York, NY, pp. 342 ff. It should also be noted that D may contain substituents other than those which cause a silver halide developing property, if these substituents do not destroy the silver halide developing effect. Examples of such substituents are alkyl, oxy or amino groups or halogen. Please note z. B. the use of toluhydroquinonyl or aminohydroquinonyl groups.
The terms alkyl, aryl and amino radicals mean both unsubstituted and substituted groups. In the same way, sulforestates also mean the salts, e.g. B. sodium sulfonate.

In certain cases it may be appropriate to use the oxy or amino groups in the radical D ' to protect the dye developer substance by suitable acylation during the synthesis. These protecting groups can be removed by hydrolysis before use.

Claims (3)

Patent claims: 1. Process for the preparation of dye developer substances of the general formula Y (S-I ■ A— N —Z —D ' in which D 'is an organic radical containing hydroxyl, amino or alkylamino groups which has a developing effect on exposed silver halide, A is an anthraquinone radical in any bond, Q is hydrogen, an alkyl radical or an aliphatic or aromatic acyl group, Z a direct bond or an organic radical containing at least one methylene group, m is an integer from 1 to 4 and Y is hydrogen and / or an amino, alkyl, aryl or nitro group, halogen, an alkylamino, arylamino, aryloxy , Alkoxy, oxy, sulfonamido, carboxamido or sulfo group or - N - Z - D ' is, characterized in that a corresponding compound of the anthraquinone series, the at least one substitutable for amino groups in any substituent Contains position, with an amine of the general formula D '- Ζ - Ν - Η in which D ', Z and Q have the meaning given, reacted and optionally at least acylated one of the amino groups of the product obtained. 2. The method according to claim 1, characterized in that there is a leuco derivative of Anthraquinone compound is used as a starting material and the reaction product is then oxidized. 3. The method according to claim 1 and 2, characterized in that there is an amine of the general formula D '- Z - N - H in which D 'denotes a hydroquinonyl group, is used. 409 600/286 6.64 © Bundesdruckerei Berlin