US3597474A

US3597474A - Aminoalkylene sulfonic acid containing phenols

Info

Publication number: US3597474A
Application number: US810403*A
Authority: US
Inventors: Stanley M Bloom; Paul S Huyffer
Original assignee: Polaroid Corp
Current assignee: Polaroid Corp
Priority date: 1967-07-24
Filing date: 1968-09-16
Publication date: 1971-08-03
Anticipated expiration: 1988-08-03

Abstract

THIS INVENTION RELATES TO NOVEL IMMOBILE REDUCING AGENTS OF THE P-AMIOPHENOL TYPE WHICH MAY BE DEFINED AS ZWITTERIONIC (INNER) SALTS OF P-AMINOPHENOLS CONTAINING AN ANCHORING OR IMMOBILIZING MOIETY.

Description

United States Paten O1 fice 3,597,474 Patented Aug. 3, 1971 3,597,474 AMHNOALKYLENE SULIFONIIC ACID CONTAlNlNG PHENOLS Stanley M. Bloom, Waban, and Paul S. Huylfer, Lynnfield, Mass, assignors to Polaroid Corporation, Cambridge, Mass.

No Drawing. Original application July 24, 1967, Ser. No. 655,309, now Patent No. 3,459,548, dated Aug. 5, 1969. Divided and this application Sept. 16, 1968, Ser. No, 810,403

lint. Cl. C07c 143/52, 143/64 US. Cl. 260-507R 8 Claims ABSTRACT OF THE DISCLOSURE This invention relates to novel immobile reducing agents of the p-aminophenol type which may be defined as zwitterionic (inner) salts of p-aminophenols containing an anchoring or immobilizing moiety,

This application is a division of copending U.S. Ser. No. 655,309 filed July 24, 1967 and now US. Pat. 3,459,- 548 issued Aug. 5, 1969.

BACKGROUND OF THE INVENTION The copending application of Stanley M. Bloom and Howard G. Rogers, Ser. No. 655,440 filed concurrently (Pat. No. 3,443,940) describes and claims certain photographic procedures for forming positive color transfer images wherein a photosensitive element containing at least one light-sensitive silver halide emulsion and an associated layer of color-providing material is exposed and then developed with an aqueous alkaline processing composition including a silver halide solvent and a silver halide developing agent. As a function of development, an imagewise distribution of soluble silver complex is formed, and this imagewise distribution migrates to the associated color-providing material where it is reduced and the color-providing material is in turn liberated for transfer to a superposed stratum to impart thereto a positive color transfer image.

In the practice of this photographic procedure, care must be taken to avoid a redox reaction between oxidized developing agent formed as a function of development and the color-providing material, since this redox reaction interferes with the system upon which selective transfer of color-providing material to the superposed stratum to form the desired image is predicated.

One system for obviating this redox reaction is to incorporate in the photosensitive element a reducing agent or scavenger for the oxidized developer which will reduce the latter before it has had opportunity to react with the color-providing material. The scavenger should ideally provide an immobile reaction product so that it will be unable to migrate to the superposed stratum where it might adversely affect the color and/or stability of the desired color image.

SUMMARY The present invention is directed to a novel class of reducing agents which are of particular use in the aforementioned photographic processes and in procedures generally where it is desired that the reducing agent be immobile or non-migratory. The reducing agents of this invention are also silver halide developing agents.

The novel reducing agents of this invention contain an immobilizing or anchoring substituent which effectively precludes unwanted migration of the compound from its layer in the photosensitive element, which migration may adversely affect image formation by the previously described photographic system.

As was mentioned previously, the present invention is directed to novel reducing agents.

A primary object of this invention, therefore, is to provide a novel class of reducing agents.

Another object is to provide a novel class of reducing agents or scavengers of the foregoing description.

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 components which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description.

The novel reducing agents of this invention may be represented by the following formula:

Ann-i) B (n) A represents an anchoring or immobilizing substituent rendering the compound non-diffusible, e.g., higher alkyl, e.g., of at least eight carbon atoms, such as octyl, decyl, dodecyl, stearyl, oleyl, etc. linked directly to the aromatic nucleus or linked indirectly thereto through an appropriate linking group, e.g., -CONH; -alkylene-CONH:

etc., an aromatic ring, e.g., of the benzene or naphthalene series which rings may be either bonded to a single carbon atom of the aromatic nucleus or fused thereto, i.e., bonded to a pair of adjacent carbon atoms, or A may be a plurality of short chain radicals which together provide the anchoring moiety, each of the short chain radicals being linked directly or indirectly to a different carbon atom on the benzene nucleus;

B is carboxy, alkoxy, alkyl, chloro or an amide substituent; n is a positive integer from 1 to 3;

The alkylene moiety contains at least two carbon atoms, e.g., from 2 to 18 carbon atoms, and preferably from 2 to 4 carbon atoms, and may be a straight or a branched chain; and

m is a positive integer from 1 to 2, provided that where the alkylene moiety alone or together with said B substituent provides an anchoring or immobilizing substituent 121 may be 1, but when it does not, then 111 must be 2.

The compounds of this invention may be prepared by the following sequence of steps:

Where the alkylene moiety contains from 2-4 carbon atoms, the desired compound may also be obtained by employing as step II, the following reaction:

B (011 Product The particular reaction conditions, e.g., time, temperature, pressure, etc. are not critical and will be readily apparent to those skilled in the art.

As examples of novel reducing agents contemplated by this invention, mention may be made of the following:

Because of the anchoring moiety rendering the compound non-diffusible from the layer in which it is present, migration of the compound to the layer containing the color-providing material is effectively precluded, thereby in turn precluding unwanted competition between scavenger and color-providing material for reduction of the soluble silver complex formed as a function of development.

The inner salt or zwitterionic form of the p-aminophenol-type compound affords significant advantages over p-aminophenols in general in that the latter are not stable in the photosensitive element and, upon contact, will desensitize the emulsion; whereas the inner salt form of this invention is highly stable and does not so desensitize the emulsion.

The following examples show by way of illustration and not by way of limitation the practice of this invention.

Example 1 38.6 g. of 6-nitrodehydrocoumarin was dissolved in 400.0 cc. of methyl Cellosolve. 28.4 g. of n-octylamine were added and the mixture was heated on a steam bath for 30 minutes and then cooled. Filtration yielded 40.2 g. of a light yellow compound, M.P. l79-180 C. of the formula:

40.2 g. of the last-named nitro compound 15.8 g. of

propane sultone 200.0 cc. of methanol and 5% palladium/barium sulfate were placed in a pressure vessel. Hydrogen was introduced and the reaction mixture was shaken for four hours after theoretical hydrogen uptake. 100.0 cc. more of methanol were then added and the mixture was boiled and then filtered. Cooling of the filtrate yielded 23 g. of the pure white compound of Formula 1, M.P. 196197 C.

Example 2 11.0 g. of 6-nitrodehydrocoumarin was dissolved in 100.0 cc. of methyl Cellosolve. 12.0 g. of n-dodecylamine were then added. (The reaction was exothermic and a yellow solid separated out.) The mixture was heated until a clear solution was obtained and then cooled to give 14.0 g. of light yellow crystals, M.P. 168-170" C., an amide of the formula:

l lo:

27.5 g. of the above amide (prepared in the foregoing manner) and 9.28 g. of propane sultone (10% excess) were placed in a pressure vessel. 200.0 cc. of methanol and 5% Pd/BaSO were added and the mixture was then hydrogenated at 40 p.s.i. The reaction mixture was shaken for four hours after theoretical hydrogen uptake. An additional 100.0 cc. of methanol were then added and the mixture was heated. to boiling, filtered and cooled. After cooling, 11.65 g. of the compound of Formula 2 were obtained, a white solid, M.P. 207-208 C. An additional 2 g. of this compound were obtained after concentration of the filtrate.

Example 3 A photosensitive element of the type disclosed in the aforementioned copending application Ser. No. 655,440 was prepared by coating on a cellulose acetate support a gelatin layer containing a colloidal silver silver-preeipitating agent and non-ditfusible color-providing compound of the formula:

to provide a calculated coverage of 136 mgm. per square foot of each of the color-providing compound and the silver precipitating agent; applying over this a layer containing a calculated coverage of 136 mgm. per square foot of gelatin and the same amount of a compound of Formula 1; and finally coating on a light-sensitive gelatino silver iodobromide emulsion. This element was then exposed and developed by spreading between the thus exposed element and a superposed dyeable sheet material at a gap of .0026 a processing composition containing the following proportions of ingredients:

G. Hydroxyethyl cellulose 3.9 Sodium hydroxide 5.0 Sodium thiosulfate 2.0 Sodium sulfite 2.0

Metol 1.6

Water-l00.0 cc.

After an imbibition time of about two minutes, the elements were separated to reveal a positive dye transfer image.

Example 4 A similar photosensitive element containing no scavenger was exposed and developed in the manner described in Example 3. When the elements were separated following imbibition, dye had transferred in both exposed and unxposed areas so that no image formation was observable.

Example 5 A photosensitive element was prepared as in Example 3, except that the compound of Formula 1 was included in the silver halide emulsion layer at a calculated coverage of 68 mgm. per square foot. This photosensitive element was exposed and developed in the manner described in Example 3 with a developing composition containing the following proportions of ingredients:

G. Hydroxyethyl cellulose 3.9 Sodium hydroxide 5.0 Sodium thiosulfate L 1.0

Water100.0 cc.

The gap employed was .0016. After two minutes the elements were separated to reveal a positive dye image.

From the procedure described in Example 5, it will be observed that the compounds of this invention may be employed as silver halide developing events. While they are primarily intended for use in the processes described above, and illustrative Example 5 so indicates their usefulness in such processes, it will be apparent that they may find use as silver halide developing agents in other photographic processes, e.g., processes wherein the use of an immobile or relatively immobile developer is desirable. Ac-

cordingly, it is to be expressly understood that the photographic utilization of the compounds of this invention is not restricted to products and processes such as were described in Examples 3-5.

By way of recapitulation the compounds of this invention are particularly useful in the photographic systems described and claimed in the aforementioned Ser. No. 655,440 wherein a photosensitive element including at least one light-sensitive silver halide emulsion having associated therewith a non-diffusible color-providing material which is capable of providing an oxidation product which can auto-react intramolecularly to effect ringclosure and to eliminate the color-providing moiety of said material for transfer is exposed and then developed with an aqueous alkaline processing composition including a silver halide solvent and a silver halide developing agent the oxidation product of which is reducible by a redox reaction with the color-providing material; and imagewise distribution of soluble silver complex is formed in terms of unexposed areas of the emulsion; the non-diifusible colorproviding material is contacted with the imagewise distribution of soluble silver complex where, in the presence of silver-precipitating nuclei, the complex is reduced and as a function thereof an imagewise distribution of oxidized color-providing material is formed; the oxidized material is allowed to auto-react intramolecularly to eliminate the color-providing moiety to provide an imagewise distribution of diffusible color-providing moiety in terms of unexposed areas of the emulsion; and this imagewise distribution of color-providing moiety is transferred, at least in part, by imbibition, to a superposed stratum to impart thereto a positive color transfer image. In one procedure described in this copending application, a scavenger for oxidized developer is positioned in a layer in the photosensitive element between the emulsion layer and the layer of color-providing material, so that oxidized developer formed as a function of development is reduced before it can migrate to the layer of color-providing material and there undergo an undesired redox reaction with the colorproviding material.

Since the novel compounds of this invention are effectively immobile in their reduced form, they cannot migrate to the layer of color-providing material where they would compete with the color-providing material as reducing agents for the soluble silver complex, which competing would be deterimental to proper image formation.

Since certain changes may be made in the above product and process 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.

What is claimed is:

1. A compound of the formula NH -alkylene-SOa wherein, A is an anchoring substituent rendering the compound non dilfusible, said substituent being a higher alkyl of from 818 carbon atoms linked directly to the aromatic nucleus or linked indirectly to said nucleus through a linking moiety chosen from the group consisting of or A is the moiety which, when bonded to the 2,3 nuclear carbon atoms of said pictured benzene nucleus, can provide a naphthalene nucleus.

8 B is a substituent chosen from the group consisting of 6. CH OCH and COOH; n is O or 1 and alkylene con- OH tains from 212 carbon atoms. I

2. A compound as defined in claim 1 wherein said alkyl- E JL ene moiety contains from 2 to 4 carbon atoms. 5 C N 9 NHzcH c1-I -CH2-s03 1 0 H n 10 CHz-CHz-CNGaH 7-I1 0H I? HO 0 O CIIT-CHzON-C8H17 NH2-CI{2CH2CH2-S 03 15 4. 1 11Iz-oII2--0H -so3 OH I i 20 OH @OHzCH CNO H -n I Q i 9 NHPoHPcHr-om-sm 19 NH CHzCH CH SOa References Cited OH UNITED STATES PATENTS H 2,319,078 5/1943 McNally et a1. 260409 H -oo H N DANIEL D. HORWITZ,P1-1mary Examiner U.S. Cl. X.R.