US3262924A - Phenyl carboxamido monoazo dyes - Google Patents

Description

United States Patent 3,262,924 PHENYL CARBOXAMIDO MONUAZO DYES Milton Green, Newton Center, Mass., assignor to Polaroid Corporation, Cambridge, Mass, a corporation of Delaware No Drawing. Filed Feb. 15, 1962, Ser. No. 173,349

a 7 Claims. (Cl. 260-163) This application is a continuation-in-part of application Serial No. 703,515 filed December 18, 1957, and now abandoned.

This invention relates to chemistry and, more particularly, to novel chemical compounds which are useful in preparing monochromatic and multichromatic photographic images.

U.S. Patent No. 2,983,606, issued on May 9, 1961, to Howard G. Rogers, discloses diffusion transfer processes wherein a photographic negative material such as a photographic element comprising an exposed silver halide emulsion layer containing a latent image, is processed using a compound which is both a dye and a silver halide developer and designated as a dye developer, thereby imparting to the image-receiving element a reversed or positive dye image. In carrying out the process of this patent, a photosensitive element containing a silver halide emulsion is exposed and permeated with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, and the thus permeated exposed photosensitive element is brought into superposed relationship with an image-receiving layer. In a preferred embodiment, the photosensitive element contains a layer of dye developer and the liquid processing composition permeating the photosensitive element provides a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated, in situ, with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. At least part of the imagewise distribution of unoxidized dye developer is transferred, by imbibition, to the superposed image-receiving layer or element to form the dye transfer image. While the dye developer may be utilized in the photosensitive element, for example, in, on, or behind the silver halide emulsion, it may also be utilized in the image-receiving element or in the liquid processing composition.

The present invention relates to novel dye developers which are particularly useful in photographic processes, products and compositions, such as described above and disclosed with more particularity in the aforementioned US. Patent No. 2,983,606.

One object of this invention, therefore, is to provide novel chemical compounds and novel syntheses for preparing these novel compounds.

Another object of the invention is to provide novel chemical compounds useful in photographic products, processes and compositions in which color developing agents are used to develop a latent image.

Yet another object of the invention is to provide novel chemical compounds useful in preparing monochromatic and multichromatic photographic images.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the product possessing the features, properties and the relation of comice ponents which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

For a further understanding of the nature and objects of the invention, reference should be had to the following detailed descriptioni The novel compounds of this invention are azo dye developers, that is, azo dyes containing at least one and not more than two silver halide developing functions, or derivatives thereof having a protecteddeveloping function, that is, one or two aromatic groups which upon hydrolysis form a developing function. In other words, the novel compounds of this invention comprise an azo dye having at least one and not more than two substituents of the following formula:

wherein R is hydrogen or an alkyl group, preferably a lower alkyl group, such as for example, methyl, ethyl, etc.; and R and R may be the same or different or may be hydroxyl or acyloxy groups. The term acyloxy as used herein is meant to signify the grouping i R (JO- wherein R is an aryl, alkyl, aryloxy, or alkoxy group, and the term dye developer as used herein is intended to signify the compounds of Formula A wherein both R and R are hydroxyl groups.

It will be apparent that the novel compounds of this invention may also be represented by the formula:

wherein R the represents the radical of an azo dye molecule wherein R, R and R have meanings previously noted;

Y may be -N=NQ, or a pyrazolone dye radical linked to the phenylene radical of said substituent through the free nitrogen atom of said pyrazolone nucleus; and Q represents an azo coupler, such as, for example, a pyrazolone or naphthol azo coupler radical.

As illustrations of azo dyes within the scope of this invention, mention may be made of the following compounds:

1 OH O H 4- (4'- [p- 2 ,5 -dlhydroxyphenyl) -phenylcarboxamido phenylazo)-3-methyl-1-phenyl-5-pyrazolone 3) OH 0 H OH l N=N 6 63 6E 60H,

2- (4-[p-(2",5"-dlhydroxyphenyl) -pl1enylcarboxamldo phenylazo) -4-meth0xy-1-naph th-ol 2- 4'- [p- 2 ,5 -bls-cuthyloxyphenyl) -phenylcarboxamido phenylazo) -4-methoxy-1-naphtho1 3-curbethoxy-4- 4'- [m- 2",5 -dihydroxyphenyl) -phenylcarboxamldo] -phenylaz0) -1-pheny1-5-pyrazo1one 0 on, NN ('5 N/ F n 0 N C a H N/ on 0 ll HNC 1 (4' [m (2",5"-dihydroxyphenyl)-benzamido]-phenyl)- 3 N,N dimethylcarboxamido 4 (2,4,6-trlmethylphenylaZo)-5-pyraz01one The compounds of this invention containing an amino or substituted amino group may also be present in the form of acid addition salts such as, for example, the hydrochloride.

One method of preparing the novel compounds of this invention comprises reacting, in the presence of a suitable halogen acid acceptor such as, for example, quinoline, anhydrous pyridine, etc., a compound of the formula:

( acyloxy i C-halogen acyloxy with an azo dye containing not less than one and not more than two reactive primary or secondary amino groups, such as for example, 4-(p-aminophenylazo)-3- methyl-l-phenyl-S-pyrazolone; 2 (p-aminophenylazo)-4 phenylazo-S-pyrazolone, etc.

Another method of preparing the novel compounds of this invention comprises reacting, in the presence of a suitable halogen acid acceptor, a compound of Formula D with a compound of the formula:

( R N ArX wherein R has the same significance as previously noted; Ar is an arylene nucleus, i.e., phenylene; and X is a group convertible to a primary amino group subsequent to reaction such as, for example, a nitro group. The resulting primary amine may be diazotized and coupled according to conventional methods to provide suitable compounds within the scope of this invention.

After reaction and prior to use as a photographic dye developer, the respective acyloxy groups may be removed by deesterification such as for example, by hydrolysis in the presence of alkali to form the hydroquinonyl developing function.

However, it is to be noted that where desired the respective acyloxy groups of the aforementioned intermediate products, which may be represented by the formula:

(F) acyloxy a cyloxy wherein Ar and R have the meanings heretofore given and X is a nitro or a primary amino group; may also be removed by deesterification and the resulting dihydroxyphenyl products thereof may then be utilized as photographic developing agents.

As examples of compounds contemplated within the scope of Formula F and the free hydroquinonyl forms thereof, mention may be made of:

I OH

4- (p [2,5'-dihydroxyphenyl]-phenylcarboxamido)-an1line 4- (p- [2 5-bis-cathyloxypl1enyl] -phenylcarboxamido -aniline 9 O H H I O H 4- (19- [2',5'-dihydroxypheny1] -phenylcarb0xamid0)- nitrobenzene 4-(p-[2,5-bis-cathyloxypheny1] phenylcarboxamido)- nitrobenzene The invention will be illustrated in greater detail in conjunction with the following specific examples which set out representative preparations of the novel compounds of this invention, which however are not limited to the details therein set forth and are intended to be illustrative only.

Example I To a hot solution of 7 g. of p-carboxyphenylquinone, prepared according to the procedure of Kvalnes in JACS 56, 2478 (1934), in 350 cc. of 95% ethanol is added a solution of 10 g. of sodium hyposulfite in 40 cc. of water. The original amber color discharges, and a white precipitate forms which is removed by filtration. The filtrate is acidified with 10 cc. of concentrated hydrochloric acid and a White precipitate forms which is removed by filtration. The resultant filtrate is then evaporated to dryness and the residual solid yellow residue crystallized from 250 cc. of water containing a trace of ethanol after clarification with charcoal. The resultant product, 2.5 g. of a white solid, p-(2,5-dihydroxyphenyl)-benzoic acid, exhibits an M.P. at 222 C. Concentration of the mother liquor to 50 cc. results in an additional yield of 0.3 g. of the desired product exhibiting an M.P. at 218 C.

A solution of 2.16 g. of sodium hydroxide in 40 cc. of water is deaerated with nitrogen for 10 minutes. 3.1 g. of p-(2,5-dihyd1'oxyphenyl)-benzoic acid is added to the solution and the mixture chilled for 10 minutes. To the chilled mixture, 5.1 cc. of ethyl chloroformate is added portionwise over an interval of 30 minutes. The resultant mixture is stirred for 30 minutes during which time a While solid precipitates. The mixture is then acidified with 11 cc. of 3 N. hydrochloric acid, causing a guru to separate. Contact of the gum with small amounts of aqueous ethanol results in solidification. The solid product is crystallized from aqueous ethanol and then recrystallized from a benzene-hexane mixture yielding 2.5 g. of a white solid, .p-(2,5-bisoathyloxyphenyl)-benzoic acid, exhibiting an M.P. at 174 to 175 C.

Analysis 0 this pr0duct.Calculated as C H O C., 61.0%; H, 4.8%. Found: C, 61.2%; H, 5.0%.

2.5 g. of p-(2,5-bis-cathyloxyphenyl)-benzoic acid are refluxed with 10 cc. of thionyl chloride for 2.5 hours. Excess thionyl chloride is evaporated in vacuo and the residual oil mixed with benzene. The benzene is then evaporated and the residual oil further purified by a second benzene treatment. The resultant product, an oil, p- (2,5-bisoathyloxyphenyl)-benzoyl chloride, may be utilized in the subsequent reaction without further purification.

To the above product, 0.94 g. of p-nitroaniline and 0.55 cc. of pyridine in 20 cc. of benzene are added and the mixture refluxed for 1 hour. The mixture is then cooled, extracted with water and the organic layer separated, dried over magnesium sulfate and filtered into 15 0 cc. of hexane. An orange gum separates which solidifies upon standing overnight and is crystallized from 215 cc. of ethanol yielding 2.5 g. of a White solid, 4-( p-[2,5-bis-cathyloxyphenyl] phenylcarboxamido nitrobenzene [Formula 10], melting at 138 to 139 C.

Where desired the product of the above reaction may be deesterified, for example, by hydrolysis in the presence of alkali, to yield, 4-(p-[2',5'-dihydroxyphenyl]-phenylcarboxamido)-nitrobenzene [Formula 9].

A mixture of 2.5 g. of 4-(p-[2',5'bis-cavthyloxyphenyl]phenylcarboxamido)-nitrobenzene [Formula 10], cc. of ethanol and 5 g. of 7% palladium/barium sulfate catalyst is hydrogenated at 30 p.s.i. of hydrogen. Theoretical uptake occurs in 1 hour. The catalyst is removed by filtration and the filtrate evaporated to dryness. Triturating the residual oil with 20 cc. of cold 1:1 hydrochloric acid yields a white solid product which is crystallized from 40 cc. of ethanol yielding 1.7 g. of a white amorphous solid, 4-(p[2,S bis-cathyloxyphenyl]-phenylcarboxamido)-aniline hydrochloride, [the hydrochloride acid addition salt of Formula 8], which decomposes at 203 C.

Where desired the product of the above reaction may be deesterified, such as for example, by hydrolysis in the presence of alkali, to yield 4-(p-[2,5-dihydroxyphenyl]- phenylcarboxamido)-aniline [Formula 7].

Example 2 1.7 g. (.00344 mol) of 4-(p-[2,5-bis-cathyloxyphenyl]phenylcarboxamido)-aniline hydrochloride [the hydrochloride acid addition salt of Formula 8 as prepared in Example 1], are dissolved in a warm solution of 20 cc. of glacial acetic acid and 0.27 cc. (.00344 mol) of 12.5 N. hydrochloric acid. The solution is cooled, diazotized at 10 C. with sodium nitrite and poured into a 50 cc. icewater mixture. The mixture is then added, over a 30 minute interval, to a mixture of 0.59 g. (.0034 mol) of 3- methyl-l-phenyl-S-pyrazolone, 50 cc. of acetone and 10 cc. of pyridine. 245 cc. of 10% sodium carbonate solution are added portionwise concurrently with the diazo solution to maintain a pH of 7 to 8. The resultant orangered slurry is stirred for 1 hour, filtered and the filter cake washed with water yielding 1.7 g. (dry weight) of 4-(4'- [p (2",5" bis-oathyloxyphenyl)-plieny'lcarboxamido]- phenylazo)-3-methyl-1-phenyl-5-pyrazolone [Formula 2].

' Example 3 1.7 g. of 4-(4'-[p-(2",5"-bis-cathyloxyphenyl)-phenylcarboxamido] phenylazo) 3-rnethyl-l-phenyl-S-pyrazolone [Formula 2 as prepared in Example 2], are treated in vacuo with a mixture of 2 g. of potassium hydroxide, 30 cc. of ethanol and 10 cc. of water with intermittent warming on a steam bath for 3 minutes. The product is precipitated with a dilute hydrochloric acid solution, the resultant slurry filtered and the filter cake washed with water. The dye is further purified by dissolving it in a methylcellosolve solution, precipitating with a 1% hydrochloric acid solution and washing with hot water. A yield of 0.9 g. (dry weight) of 4-(4'-[p-2",5-dihydroxyphenyl) phenylcarboxamido] phenylazo) 3-methyl-1- phenyl-S-pyrazolone [Formula 1], is obtained which decomposes at 258 to 260 C. The spectral absorption curve of this product exhibits a A at 425 my in ethanol; e=33,000.

As previously mentioned, the novel dihydroxyphenyl compounds of this invention, that is compounds in which the terms R and R of Formula 1 are both hydroxlyl groups, are useful dye developers. In the following examples all parts are given by weight except where otherwise noted, and all operations involving light-sensitive materials are carried out in the absence of actinic radiation. These examples are intended to be illustrative only of the photographic use of the dye developers and should not be construed as limiting the invention in any way.

Example 4 A photosensitive element is prepared by coating a gelatin-coated film base with a solution containing 3% of 4-(4'-[p-(2",5-dihydroxyphenyl) phenylcarboxamido]- phenylazo)-3-methyl-l-phenyl-S-pyrazolone [Formula 1 as prepared in Example 3], in a 4% solution of cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran. After this coating has dried, a silver iodobromide emulsion is applied. This photosensitive element is exposed and processed by spreading an aqueous liquid processing composition comprising:

Percent Sodium carboxymethyl cellulose 4.5 l-phenyl-B-pyrazolidone 0.2 Sodium hydroxide 5.0 Potassium bromide 0.2

between said photosensitive element and an image-receiving element as said elements are brought into superposed relationship. The image-receiving element comprises a cellulose acetate-coated baryta paper which has been coated with a solution comprising 4% Nylon Type F8 (trade name for N-methoxymethyl polyhexamethylene adipamide) in 80% aqueous isopropanol. After an imbibition period of approximately one minute, the imagereceiving element is separated and contains a yelloworange positive dye image of the photographed subject.

The following example illustrates the use of the dye developer in the silver halide emulsion, instead of placing it in a layer behind the photosensitive emulsion.

Example Percent Sodium carboxymethyl cellulose 4.5 1-phenyl-3-pyrazolidone 0.2 Sodium hydroxide 1.0 Potassium bromide 0.2

between said photosensitive element and an image-receiving element as said elements are brought into superposed relationship. The image-receiving element comprises a cellulose acetate-coated baryta paper which has been coated with a solution comprising 4% Nylon Type F8 in aqueous isopropanol. After an imbibition period of approximately one minute, the image-receiving element is separated and contains a yellow-orange positive dye image of the photographed subject.

The dye developers of this invention are also useful in integral multilayer photosensitive elements for use in multicolor diffusion transfer processes. As an example of such photosensitive elements, mention may be made of the photosensitive elements disclosed and claimed in the copending U.S. application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13, 1956, wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed, simultaneously and without separation, with a single common image-receiving element. A suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a greensensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames. The photosensitive elements of this invention are especially useful in composite roll film intended for use in a Polaroid Land camera, or a similar camera structure such, for example, as the camera forming the subject matter of U.S. Patent No. 2,435,717, issued to Edwin H. Land on February 10, 1948. In general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution. The rolls and pods are so associated with each other that, upon processing, the photosensitive element may be superposed on the image-receiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and construction of the pods used in such units are well known to the art. See, for example, U.S. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol); benzylaminophenol; hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenylhydroquinone, or 4'-methylphenylhydroquinone; or a 3-pyrazolidone such as l-phenyl-3-pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.

In addition, development may be effected by the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in the copending application of Milton Green and Howard G. Rogers, Serial No. 50,851, filed August 22, 1960, and now Patent No. 3,173,786.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black and white, monochromatic or toned prints or negatives. By way of example, a

developer composition suitable for such use may comprise an aqueous solution of approximately 1-2% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline Washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained With the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are self-sufiicient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction between a color former or coupler and the oxidized developing agent, as Well as socalled auto-coupling processes in which color is obtained by a reaction of the oxidized developing agent with unoxidized developing agent.

It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of imagereceiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in US. Patent No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, mention may be made of nylon, e.g., N-methoxymethyl-polyhexamethylene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine. The imagereceiving element also may contain a development restrainer, e.g., 1-phenyl-5-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849, filed August 22, 1960.

The dye developers herein set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in US. Patent No. 2,968,554, issued to Edwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyes for textile fibres, such as nylon.

In the preceding portions of the specification the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black.

Since certain changes may be made in the above product Without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

I ll Z-N-O I B n is the residue of a monoazo dye molecule R Zita] and wherein Z represents the azo dye molecule other than the amino group or groups; R is a member of the group consisting of hydrogen and lower alkyl radicals; R and R each are selected from the group consisting of hydroxy and carbethoxy; and n is a positive integer from 1 to 2.

2. 4-(4'-[p-(2",5-dihydroxyphenyl) phenylcarboxamido] phenylazo -3 -methyll-phenyl-S -pyrazolone.

3. 4-(4-[p-(2,5-bis cathyloxyphenyl) phenylcarboxamido] -phenylazo )-3-methyl-1-phenyl-5-pyrazolone.

4. 2-(4-[p-(2,5-dihydroxyphenyl) phenylcarboxamido] -phenylazo) -4-methoxy-1-naphthol.

5. 2-(4'-[p-(2,5-bis cathyloxyphenyl) phenylcarboxamido] -phenylazo) -4-methoxy-l-naphthol.

6. 3-carbethoxy-4-(4-[m (2",5" dihydroxyphenyl)- phenyloarboxamido] -phenylazo) -1-phenyl-5-pyrazolone.

7. 1-(4'-[m-(2,5 di-hydroxyphenyl) benzamido]- phenyl)-3,N,N-dimethylcarboxamido-4-(2',4,6-trimethylphenylazo)-5-pyrazolor1e.

wherein References Cited by the Examiner UNITED STATES PATENTS 2,715,120 8/1955 Ruegg et al 260-162 2,816,103 12/1957 Schmid 260-162 2,983,606 5/ 1961 Rogers 96-29 2,997,390 8/1961 Land 96-29 3,009,958 11/1961 Green et al. 96-29 3,019,107 1/1962 Blout et al. 96-66 3,036,128 5/1962 Moffett 260-559 3,047,627 7/1962 Greenlee 260-559 3,134,764 5/1964 Blout et al. 260-162 3,135,734 6/1964 Green et al 260-162 FOREIGN PATENTS 554,212 7/1957 Belgium. 1,047,620 12/ 1958 Germany.

OTHER REFERENCES Lubs, The Chemistry of Synthetic Dyes and Pigments, Reinhold, New York, 1955, page 670.

Venkatoraraman, The Chemistry of Synthetic Dyes," vol. 1, Academic Press, Inc., New York, 1952, pages 358 and 359.

CHARLES B. PARKER, Primary Examiner. L. ZITVER, Examiner.

REYNOLD I. FINNEGAN, D. M. PAPUGA,

Assistant Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,262,924 July 26, 1966 Milton Green It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, lines 25 to 39, the lower left-hand portion of the formula should appear as shown below instead of as in the patent:

O- C-OC H column 4, lines 40 and 41, for "Z-(p-aminophenylazo) 4- phenylazo-S-pyrazolone, etc." read 2(p-aminophenylazo) 4methoxylnaphthol; l-(p-aminophenyl) 3-N,N-dimethylcarboxamido-4phenylaz0-5pyrazolone, etc, column 7, lines 10 and 11, for "4(4 -[p2' ,5-dihydroxy" read 4- 4 2, 5 dihydroxycolumn 8, line 65, for "by" read in column 10, line 23, for "carbethoxy" read cathyloxy lines 24 and 25, for "-phenylcarboxamido1" read -phenyl carboxamido] Signed and sealed this 5th day of September 1967.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. A MONOAZO DYE OF THE FORMULA: