US2591642A - Nondiffusing color formers comprising aryl j-acids in which the aryl radical is provided with a nondiffusing group - Google Patents

Description

Patented Apr. 1, 1952 NONDI FFUSING COLOR FORMERS COM- PRISING ARYL J-ACIDS IN WHICH THE .A-RYL RADICAL- IS PROVIDED NONDIFEUSING GROUP -Vsevolod Tulagin, Phillipsburg, N. J and Robert F. "Coles, "Easton, Pa., assignors to General Aniline &Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application-January 10, 1950, Serial No. 137,886

4 Claims.

The present invention relates to non-diffusing color formers of theqaryl-J-acid .typein which the non-diii'using group appears in the aryl radical joined to the nitrogen atom in the 6- position of the J-acid,-and the use of such color formers in the preparation of cyan azine dye The dye which is produced when using this color former has very desirable spectral char:

acteristics. The use of the color former, however, has certain disadvantages, notably its easily broken by dilute alkalies. The use of such non-diffusing color formers, therefore, limits the composition of the solutions employed in the processing of films by the azine method.

- Considerable attention has been given to improving the azine method by supplying acolor former for formation of the own image which partakes of the desirablecharacteristics of the aryl-J-acids and which are at the same time more stable than the long chain urethanes of such acids. As. a resultv of thiszstudy, it has'beendiscovered that color formers meeting these requirements can be produced by including a carboxyl group in the aromatic fradical joined to the nitrogen atom of aryl-J-acids and utilizing such carboxylic acid group for the formation of amides designed to render'the compounds fast to diffusion :in silverhalide emulsions and stable to dilute alkalies.

tendency ,todiifuse from a. silverhalideemulsion when located therein. Because: of this :the color former when used must be employed in the developer so that a multiplicity of color development steps is inevitable.

In an efiort to overcome this objection to such color former while retaining the desirable dye forming characteristics thereof and while seeking to stabilize the molecule against oxidation by photographic oxidizing agents, suchas acid or alkaline .ferri-cyanide bleach solutions, it was suggested that the aryl-Jacids be formulated as long'alkyl chain urethanes. It was felt thatsuch products which are described in United States Patent 2,480,815 would completely avoid the objections which manifest themselves in connection with the aryl-J-acids.

It has been found, however, that the long chain urethanes .of aryl-J-acids and the corresponding .carbox'amides do not meet the-.pre-

radical containing a chain of at least 10 carbon requisites of the art for the reason that the urethane and the carboxamide links are rather The preparation and use of such color formers accordingly constitute the purposes and objects of our invention.

The color formers, the preparation and use of which are contemplated herein, are represented by the following structural formula."

, in which A is a radical of aromatic character and of the benzene, naphthalene, pyridine or quinoline series, X is C'O--, --OCH2CO, -CH2CO, or --NHCH2CO, Y is an aliphatic atoms or an aromatic radical containing an aliphatic chain of at least 10 carbon atoms, M

is hydrogen or a salt forming group, such as sodium, potassium, and the like, and R is an aliphatic hydrocarbon group having less than -1- carbon atoms.

Sodium. 6- [N -propionyl-4- 3-stearoylamino-5-sulfo-o-tolylcarbamylmethyl) anilino -1-naphthol-3-'sulfonate 6.-.(N-acetyl-Euoctadecylcarbamyl-Zpyridylamino -1-. naphthol-3-sulfon1c. acid The above compoundsare prepared while utili'z'ing-carboxy aryl J-acids as 0ne-.0f theparent materials. For this purpose there may be employed":

The amidation of these acids, however is not .as simple as is the amidation of the ordinary types of acids. Thus it is not possible to prepare the acid chlorides of the aforementioned aryl-J- acids and condense these with an amine. The preparation must be efiected either (1) by. forming a phosphazo compound of the desired amineand' condensing this phosphazo compound withthe desired aryl-J-acid, or (2) by heating with phosphoroustrichloride a. mixture of the desired amine and the desired aryl-J-acid suspended in pyridine. The latter reaction proceeds quite smoothly and leads-to welldefined products and is; therefore, the operation preferred.

Theformation .of amides by: thereaction ofa phosphazo compound and an acid is described in detail; in copcnding' application Serial No. 602,154, filed, by Harry W; Grimmel et al. on June 28," 1945, and entitled Process for the Production of Organic Amides, now Patent No. 2,508,860.

The long chain amidesprepared as above are. non-diffusing color formers. A such, however,- theX cannot be used for-the preparation; of multilayer,- colonfilm because they are very easily'oxia dized; and lead to the production of an. overall brown. stain during the normal processing. of such. multilayer film. It has been found necessary to convert the amides to acylamino derivatives' which give the required. cyan dye image on color forming development, are readily-soluble in. water, compatible with photographic emulsions without the production of fog or desensitization of the silver halides: involved. The formation of the.acylami-no' derivatives can be readily effected by treating the amides with the desired acid anhydride, i. e., acetic, propionic or butyric,'while heating-the reaction mixture.

The 'colorformers of the present invention whendispersed in silver halide emulsion may be converted into; cyan azine dye; images; by develf omentwith .t-hede eopcrs of; U. s. Patent No."

2,486,440, and particularly with d-p-hydroxyethylaminq-G-phenylamino metanilic acid. Such color-formers are admirably suited; for use the processing of multilayer film by the azine method.

The dev l p rs; employ d; in suchp ocess n contain not only the desired 2,4-diamino aniline and an alkali such'as sodium carbonate, sodium hydroxide or thelike, but preferably in addition theusual adjuncts suchas an'alkali metal. bromide, i. e., potassium bromide, and an alkali metal sulfite, such as'sodium sulfite. The, best results accrue when there is present in the developer a coupling aidin-the form of an inorganic or organic base, such as pyridine, quinoline or ammonium hydroxide.

The following will serve to further illustrate the invention; but his to 'be understood .thatthe same is not restricted thereto.

PREPARATION OF CARBOXY-A-RYL-J-ACIDS EXAMPLE. 1- 6-carbo:ry-2 '-naphthyl J -a.c2'd

Into a 1-liter three-neck fiask e uipped. with an agitator-and a reflux condenser were. placed 24 g. of d-amino-z-naphthoic acid and 225 cc.

of warm water. Ammonium hydroxide. (c onc.)

- was added dropwise until a complete solution was obtained. The sodium salt of J -ac id (5j9..g. and neutral ammonium sulfite ,g. at 50%;)

and sodium metabisulfite (43, g.) were added.

The mixture was refluxed for 1% hours. The sodium salt of J -acid (40 g.) was added, and .the mixture was refluxedfor 2 hours. The. hotmixture was filtered and the solid tar. obtained was.

discarded The filtrate was. acidified with con-. centrated' hydrochloric acid. and. cooled. The solid was collected by filtration and furtherpurified by crystallization from potassium chloride solution. The material obtained was a cyan color former, giving dyes of approximately the same shade as those obtained from phenyl. J

acid.

EXAMPLE 2 7 -carbo:cy-2 -n.aphthy l J acid The "7'-carboxy-2'-naphthyl J-acid was obtained by the same procedure as that described for the 6'-carboxy-2'-naphthyl J-acid.

ExAMPLn 3 8-carbo.ry naphthoxy 2 '-naphthyl .l-aczd Into a, 1-liter 3-neck flask, equipped, with a stirrer and a reflux condenser, were placed 22 g. of 7-amino-1-naphthoxy aceticacidand. 15 0. cc. of warm water. The. mixture was stirredand treated with concentrated ammonium hydroxide.

solution until a complete solution had. taken place, The sodiumsalt ofJ-acid (58g) neutral ammonium sulfite solution (101) g.) and. sodium maceous earth. The filter medium'was washed The filtrate was treated with 250 CCuOf 30% potassium chloride. Thewith 50 cc. of Water.

oily precipitate wascollected by centrifuging, c l-issolved in 200 cc. of boiling water and the sold ti-cn was cooled. The crystalline material so EXAMPLE 4 7'-carboxy methozcy-2'-naphthyl J-acid The 7-carboxy methoXy-2'-naphthyl J-acid may be prepared in essentially the same manner as described in the preceding example by substituting 7-amino-l-naphthoxy acetic acid for the 8-amino1-naphthoxy acetic acid.

EXAMPLE 4-carbo:cy phenyl J-acid Into a 3- liter 3-neck flask, equipped with a stirrer and a reflux condenser was placed a solution of 770 g. J-acid paste (54%) in 1000 cc. of water containing 95 g. of sodium hydroxide. The mixture was heated to boiling and p-amino benzoic acid (210 g.) and sodium meta bisulfite (500 g.) were added and the mixture was refiuxed for 5 hours. The reaction mixture was diluted with 1000 cc. of water and acidified with concentrated hydrochloric acid to a pH of 1-2. The resulting suspension was filtered. The solid was washed repeatedly with water. The material was suspended in 3 liters of hot water and potassium acetate was added until a solution had taken place. Saturated potassium chloride solution (500 cc.) was added and the solution was cooled. The crystalline solid which had separated was collected by filtration and washed with potassium chloride solution. The material was further purified by repeated crystallization from 10% potassium chloride solution. A good test for the purity of the material consists of dissolving a small portion in water and acidifying with hydrochloric acid. If the substance is pure, no precipitate will be obtained while the mixture is hot; the whole mixture will set into a jelly upon cooling.

For the preparation of non-diffusing color formers, the 4-carboxy phenyl J -acid is best converted to the pyridine salt. This may be accomplished in the following manner:

The solid obtained above is dissolved in 2 liters of hot water containing pyridine (200 60.). The solution is strongly acidified with concentrated hydrochloric acid and allowed to cool. The yellow crystalline solid so obtained is collected by filtration, washed with water and dried.-

EXAMPLE 6 4-carborymethylphen'yl-J-acid Into a 1-liter E-necked flask, equipped with an agitator and a reflux condenser, were placed a solution of 10 g. of sodium hydroxide in 200 cc. of water, 66 g. of J-acid and 38 g. of p-amino phenyl acetic acid. The mixture was stirred until a solution was obtained and then 100 g. ofsodi- 8 collected by filtration and dissolved in 500 cc. of hot water. Concentrated hydrochloric acid (50 cc.) was added and the suspension so obtained was cooled to 30-40 C. The product which separated at this point was collected by filtration, washed with dilute hydrochloric acid and dried.

EXAMPLE 7 3'-carbo:cy methyl amino phenyl J-acid The 3'-earboxy methyl amino phenyl J acid may be prepared by the methods given above starting with 3-aminophenyl glycine and J -acld.

EXAMPLE 8 Z-methyl-el-carbozcy-fi-quinoline J-acid Into a 1-liter 3-necked flask, equipped with an agitator and; a reflux condenser were placed 200 cc. of water, 4 g. of sodium hydroxide, 20 g. of 2-methyl-6-amino cinchoninic acid, 39 g. of J- acid and 50 g. of sodium meta bisulfite. The mixture was refluxed for one hour and treated with an additional 13 g. of J -acid. The mixture was further refluxed for an additional three hours. The resulting suspension was cooled and filtered. The solid was collected by filtration and triturated with 3 N hydrochloric acid. The insoluble material was collected by filtration and thoroughly washed with water. The solid was dissolved in hot dilute sodium hydroxide solution; the solution was acidified with acetic acid and cooled. The crystalline solid so obtained was dissolved in hot water,- and the solution was strongly acidified with concentrated hydrochloric acid. The dark red solid thus obtained was collooted by filtration, washed with water, and dried. 7

EXAMPLE 9 4-carboxy-6-pyridino J-acz'd The procedure is the same as in Example 8 excepting that the 2-methyl-fi-amino-cinchoninic acid is replaced by an equivalent amount of .6- amino nicotinic acid.

PREPARATION OF NON-DIFFUSING ARYL J-ACIDS EXAMPLE 10 A mixture of 13 g. of 5-amino-3-stearoylamino-p-toluenesulfonic acid and 10 g. of p-carboxyphenyl J -acid in dry C. P. pyridine (150 ml.) and dry C. P. benzene ml.) is placed in a 500 ml. triple-neck flask equipped with a mechanical stirrer, dropping funnel and a reflux condenser carrying a water extractor. The mixture is heated at reflux temperature for 1 hour. The water which separates in the extractor is removed, together with a total of 100 ml. of solvents. To the stirred refluxing solution is added dropwise over a period of hour phosphorus trichloride in dry pyridine (50 ml.). The solution is heated at reflux temperature for 3 more hours.

The solvents are removed at reduced pressure, the residue dissolved in 300' ml. of hot water, filtered, and the filtrate acidified strongly with hydrochloric acid. The solid is collected and dissolved in 500 ml. of hot water, filtered through a celite pad and the filtrate treated with ml. of concentrated hydrochloric acid (or until precipitation is complete). The mixture is heated to coagulate the solid and the solid collected by filtration. The solid is extracted with 500 ml. of boiling glacial acetic acid. 20 cc. of acetic anhydride are added to the extract and the mixture is refluxed for /2 hour. a The mixture is fil- 'tered'hot, washed with petroleum etherkand thol-3-sulfonic acid.

.-EXAMPIE 1 1 EXAMPLE 12 The procedure is the same as in Example 10excepting that the p-carboxy phenyl J -acid is replaced by 7'-carboxy methoxy-2'-naphthyl J acid, and the aceticanhydride is replaced by propionic anhydride.

The product is '6-iN-propionyli-(3 stearoylamino sulfo otolyl carbamylmethyD- anilinol -l-naphth'ol-3-sul'fonicacid.

, -EXAMPLE 13 'Ina l-liter triple-'neckedflask equipped with a mechanical stirrer; dropping funnel "and reflux condenser carrying a water extractor and-heated on a m'etal bath-is placed a mixture "of l04-g.-o'f 3-amino44-octadecylamino-benzene sulfonic a'cid pyridine :salt and 88 g. of the pyridinesal'tof pcarboxyphenyl J -acid and 300 ml. of dry pyridine and 200 ml. of dry benzene. The-mixture is heated at reflux and any water-that -col 1e'cts on the separator is'taken-ofi. After the removalz'of water .is substantially "complete, a total -of 250' ml. of

solvents will be removed by the extractor. Phos-- phorus 'trichloride (13.7 g.) in dry benzene (50 m1.) is added rapidly dropwise- After the addition is complete, the solvents are removed as rapidly as possible by distillation. Theheating is continued until a sample when removed and treated with about 1 ml. of glacial acetic acid and 5 ml. of acetic anhydride and boiled for one minute andthen cooled produces a well-defined crystallinegproduct. The reaction'mixture is-then treated with'200 mlxof glacial-acetic acid and 500 m1. of acetic anhydride and heatedfonlO minutes. The solution is-then diluted with 300 ml. additional of acetic anhydride and cooled. The solid is collected, sucked as dry as possible ontheffunnel and washed with acetic anhydride and then acetone. The-product may be purified from crystallization from 50% mixture of glacial acetic-acid and absolute alcohol. It is presumably the pyridine salt of 6-iN-acetyl l-(2-octadecyl-acetaniido 5 sulfophenylcarbamyl) anilinol-l-nap'hthol-3-sulfonic acid, .-or --.of 6-p- [4-(1-octadecyl- 5 -'su1fo --2 benzimidazolyl)phenylcarbamyll- N-acetylanilino 1-naphthol-3-sulfonic acid. 5;

EXAMPLE'14 v 'In a 500 ml. triple-necked flask equipped with a'mechanical stirrer, droppingfunnel and reflux condensencarrying a water'separatorand heated on ametal bath is placed. a mixture of 52 g. of thezpyridine salt of 3-amino-4-octadecylamino benzene sulfonic acid and "36g. of m-carboxy phenyl J -acid in 150 ml. of dry pyridine and 100 m1. of dry benzene. The mixture is dried in a manner similar to the above example. A solution of phosphorus trichloride (6.9 g.) and .ben-

zene (50 ml.) is added 'dropwise with stirring at reflux. After the addition is complete, the solvents are removed by distillation and the heating of the residue is continued for one hour. The resulting syrup is treated with acetic-acid' to-obtain a solution which is diluted with acetoneand the precipitated solvent is collected. "I-he solid is refluxed with absolute ethanol and lithium--car= bonate and the resulting solution filtered "and cooled. Low boiling petroleumether isaddedito precipitate .the lithium salt. The lithiumsalt is dissolved in a mixture of glacial aceticacidaand acetic anhydride and the mixturerefluxediorhour to formthe N-acetylaminoderivative. The solution is-cooled and the precipitated'salt-istool lected by filtration.

The product is 6-[N-acetyl-3-(Z-octadecylamino sulfophenylcarbamyl)aniline] -"1'-.naphthol-"3sulfonic acid.

ExAMPLnv1-5 To a solution of 54 g. of octadecylamine'and32 g. of triethylamine in 200-cc.'of anhydrous toluene kept at '6080 -C.. is addedslowlya solutionofil i g. of phosphorus trichloride. in '35 vcc. .of.anhydrous toluene. andthe wholeisreflu'xed 'for .twoand .onehalf hours. The precipitated triethylamine.Ihy

drochloride is removed by filtration andlthephosph'azo -solution "(the.'filtrate) so obtained i's usedl withoutfurther purification.

A mixture of 10.5 g. .of potassium v (i-l8 -(ca1 boxymethoxy)-2'-naphthyl] amino-.1-n'aphthol- 3-sulfonate and 250-.cc..of anhydrousxylene-istrefluxed .under .a water'separator .until..no--more water-can be detected in the reflux. The placephazo solution prepared according-to the above 00.) is added and the mixture is kept at l25 for' 20'hours. Acetic acid (8 cc.) is add'ed and the mixture is refluxed for hour. ik'soluglacial-acetic acid is added and'themixture is refluxed for hour. Aceticanhydride (20-cc9' is added-and the mixture is-refluxed "for hour.

The resulting suspension was evaporated at -reduced pressure. Theresiduewas thoroughlyex-- cohol. The mixture was cooled and theayel-low, solid'product was collected by filtration. 1 This substance is a non-diffusing cyancolor former of the-probable constitution:

6 N..-.acetyl-8-octadecylcarbamylmethoxy 2-,

naphthylamino) -l-naphthol-.-3-sulfonic acid.

It can be further freed from 'resi'dua'1. .phos+ phoruscompoun'ds by boiling withaqueoustsodi USE OF NON-DIFFUSING COLOR FORMERS -..i'IN SILVER HALIDE EMULSIONS l EXAMPLE 1'7 A photographic silver bromide emulsion containing per kilo of emulsion 1.5 gram of the color former of Example is exposed, the latent image developed in a Metol-hydroquinone developer, re-exposed, and the residual silver halide developed for 10 minutes in a solution of the following composition: I

Potassium carbonate grams Sodium sulfite do 60 Ethylene diamine cubic centimeters 30 4 (r3 -hydroxyethylamino) -6- phehylaminometanilic acid grams 3 Water cubic centimeters 1000 The developed silver images are bleached with potassium ferricyanide and fixed in an acid hardening hypo solution. There is thus obtained a cyan dyestufi' image which is stable to acids and alkali, oxidizing agents.

. EXAMPLE 18 6 -phenylamino 4 (fi-hydroxyethylamino) metanilic acid grams 8 Potassium .carbonate do 20 Sodium sulfite do 60 Potassium bromide a do 10 Benzylamine do 5 Water to a cubic centimeters 1000 The filmafterdevelopment is washed, bleached in "a ferricyanide bleach, and fixed in an acid hardening hypo. There was thus obtained a positive dyestuif image in each of the three layers+a cyan dye image in the bottom layer, a magenta dye image in the middle layer, and a brilliant yellow dye image in the top layer.

It is to be understood that any of the color formers referred to above may be dispersed in silver halide emulsions and employed for the production of azine dye images.

Various modifications of the invention will occur to operators in this field, and we accordingly do not intend .to be limited in the patent granted exceptas necessitated by the appended claims.

We claim:

Ln photographic silver halide emulsion containing as acolor former fast to diffusion a compound of the following constitution:

N-A- x-Nn-ar wherein A is a radical of aromatic character se- 12 lected from the class consisting of those of the benzene, naphthalene, pyridine and quinoline series, X is a carbonyl containing group selected from the class consisting of those of the following formulae: --CO-, OCH2CO, CH2CO, and --NHCH2CO-, Y is a radical selected from the class consisting of those of aliphatic radicals containing a chain of at least 10 carbon atoms and aromatic radicals containing an aliphatic chain of at least 10 carbonatoms, M is selected from the class consisting of hydrogen and salt forming groups, and R is an aliphatic hydrocarbon group having less than 4 carbon atoms. 1

2. The process of producing an azine dye image which comprises developing with a 2,4-diamlnoaniline, an exposed silver halide emulsion containing as a color former, a compound of the following formula:

JOCHs wherein A is a radical of aromatic character selected from the class consisting of those of the benzene, naphthalene, pyridine and quinoline se-' ries, X is a carbonyl containing group selected from the class consisting of those of the following formulae: CO-,---OCH2CO, -CH2CO, and -NHCH2CO, Y. is a radical selected from the class consisting of those of aliphatic radicals containing a chain of at least 10 carbon atoms and aromatic radicals containing an aliphatic chain of at least 10 carbon atoms, and M is selected from the class consisting of hydrogen and salt forming groups.

3. A photographic silver halide emulsion con-.v taining as a color former fast to difiusion a com-.. pound of the following formula: s

OCH:

4. The process of producing a cyan azine dye image which comprises developing with a 2,4- diamino aniline an exposed silver halide emulsion containing as a color former fast to diffusion a;

' product of the following formula:

. Number OCH:

VSEVOLOD TULAGIN. ROBERT COLES.

Name Date Wilmanns Jan. 9, 1940' Tulagin Aug. 30, 1949

Claims (1)

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING AS A COLOR FORMER FAST TO DIFFUSION A COMPOUND OF THE FOLLOWING CONSTITUTION: