Claims
- 1. A compound of the formula ##STR49## wherein: A represents the atoms necessary to complete a benzene or naphthalene radical;
- D is an anthraquinone dye moiety;
- Z.sup.1 is hydrogen or a substituent replaceable by an oxidized aromatic amino color developer in elimination-coupling reactions; said substituent being selected from the group consisting of chloro, bromo, carboxy, sulfo, hydroxy, alkoxy and hydroxyalkyl;
- Y is the residue of an acid forming an amide with and reducing the basic character of the nitrogen atom to which it is bonded and is selected from the group consisting ##STR50## X.sup.1 is hydroxy or a primary, secondary or tertiary amino of the formula ##STR51## wherein each R.sup.3 is hydrogen, alkyl, phenyl, naphthyl, or each R.sup.3 may be alkylene so that the R.sup.3 's together with the nitrogen atom provide a heterocyclic ring having 5 or 6 carbon atoms or each R.sup.3 may be a lower alkyl having a substituent chosen from the group consisting of a hydroxy substituent, a methoxyethoxy substituent, a polyglycoloxy substituent, a carboxy substituent, an ethoxycarboxy substituent, a benzyl substituent, a phenyl substituent, a sulfo-phenyl substituent, an acetylaminophenyl substituent, a succinylaminophenyl substituent or a furane substituent;
- R is an anchoring substituent rendering the compound non diffusible said substituent containing a higher alkyl radical bonded to a single carbon atom of said aromatic nucleus formed by said A moiety;
- R.sup.1 is hydrogen or alkyl; and
- n is 2 or n may be 1 when X.sup.1 is a secondary or tertiary amino comprising an anchoring moiety rendering said compound non diffusible or R.sup.1 is an alkyl radical providing such an anchoring moiety.
- 2. A compound as defined in claim 1 wherein R.sup.1 is hydrogen, and n is 2.
- 3. A compound as defined in claim 1 wherein R comprises a higher alkyl linked directly to said aromatic nucleus or indirectly through a --CONH-- substituent.
- 4. A compound of the formula ##STR52## wherein: each of A and A.sup.1 represents the atoms necessary to complete a benzene or naphthalene radical;
- D is an anthraquinone dye moiety;
- Y is the residue of an acid forming an amide with and reducing the basic character of the nitrogen atom to which it is bonded and is selected from the group consisting ##STR53## X and X.sup.2 each is the substituent R, hydrogen, hydroxy, a primary, secondary or tertiary amino of the formula ##STR54## wherein each R.sup.3 is hydrogen, alkyl, phenyl, naphthyl, or each R.sup.3 may be alkylene so that the R.sup.3 's together with the nitrogen atom provide a heterocyclic ring having 5 or 6 carbon atoms or each R.sup.3 may be a lower alkyl having a substituent chosen from the group consisting of a hydroxy substituent, a methoxyethoxy substituent, a polyglycoloxy substituent, a carboxy substituent, an ethoxycarboxy substituent, a benzyl substituent, a phenyl substituent, a sulfo-phenyl substituent, an acetylaminophenyl substituent, a succinylaminophenyl substituent or a furane substituent provided that at least one of X and X.sup.2 must be hydroxy or amino;
- R and R.sup.4 each represent an anchoring substituent rendering the compound non diffusible, said substituent containing a higher alkyl radical bonded to a single carbon atom of said aromatic nucleus formed by said A or A.sup.1 moieties respectively;
- R.sup.1 is hydrogen or alky; and n and n.sup.1 each is 1 or 2 and each n and n.sup.1 may be 1 when one X or X.sup.2 is the substituent R or a secondary or tertiary amino comprising an anchoring moiety rendering the compound non diffusible or when R.sup.1 is an alkyl substituent providing such an anchoring moiety but when said substituents do not contribute an anchoring moiety, at least one of n and n.sup.1 must be 2.
- 5. A compound as defined in claim 4 wherein each of R and R.sup.4 comprises a higher alkyl linked directly to said aromatic nucleus or indirectly through a --CONH-- substituent.
- 6. A compound of the formula: ##STR55## wherein: each of R and R.sup.4 comprises an amide of at least 13 carbon atoms, said amide being bonded directly to a nuclear carbon atom of the shown benzene moiety or linked thereto through a phenylene or alkylene substituent;
- each of n and n.sup.1 is 1 or 2 provided that at least one of said n and n.sup.1 is 2; and
- D is an anthraquinone dye moiety.
- 7. A compound of the formula: ##STR56## wherein: D is an anthraquinone dye moiety;
- Z.sup.1 is hydrogen or a substituent replaceable by oxidized aromatic amino color developer in elimination-coupling reactions, said substituent being chloro, bromo, carboxy, sulfo, hydroxy, alkxoy or hydroxyalkyl;
- R.sup.1 is hydrogen or alkyl;
- X.sup.1 is hydroxy or amino;
- R is an anchoring moiety which renders the compound nondiffusible and comprises a higher alkyl of at least 10 carbon atoms bonded to a nuclear carbon atom of the shown benzene moiety by a linking group which is --CONH--; and n is 2.
- 8. A compound of the formula: ##STR57## wherein: D is an anthraquinone dye moiety;
- R.sup.1 is hydrogen;
- one of X.sup.1 or X.sup.2 is hydroxy or amino and the other is hydrogen or the substituent R;
- each R is an anchoring moiety rendering the compound nondiffusible and comprises a higher alkyl of at least 10 carbon atoms bonded to a nuclear carbon atom of the shown benzene moiety by a linking group which is --CONH--; and
- one of n and n.sup.1 is 2 and the other is 1 unless X.sup.1 or X.sup.2 is R, in which case both n and n.sup.1 are 1.
- 9. The compound: ##STR58##
- 10. The compound: ##STR59##
- 11. The compound: ##STR60##
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of application Ser. No. 318,227 filed Dec. 26, 1972, now abandoned, which is a Division of U.S. Patent application Ser. No. 655,338 filed July 24, 1967 which is now U.S. Pat. No. 3,751,406.
The copending application of Stanley M. Bloom and Howard G. Rogers, now U.S. Pat. No. 3,443,940, filed concurrently, relates to novel photographic systems for preparing color images. In these systems, a photosensitive element including at least one light-sensitive silver halide emulsion is developed in the presence of a compound which is immobile and non-diffusible in the processing fluid, but which, upon development, undergoes a ring-closing reaction to split off a mobile and diffusible color-providing material. Color image formation is predicated upon the resulting differential in diffusibility, whereby an imagewise distribution of the more diffusible color-providing material split off as a function of development may be transferred to an image-receiving layer, e.g., a dyeable stratum of the character heretofore known in the art, to provide a color transfer image thereon.
The present invention relates to novel compounds which may be employed in the various photographic products and processes described and claimed in this copending application.
These compounds may be defined as being compounds which are immobile and non-diffusible in an aqueous alkaline processing medium and where are capable of reacting with an oxidized silver halide developing agent of the type known as "color developers" or which are capable of providing an oxidation product which may auto-react intramolecularly in such a way as to form a new heterocyclic ring, and as a function of such reaction and ring formation to split off a mobile and diffusible color-providing material.
They may also be defined as being within one of the following groups of compounds:
(1) RELATIVELY IMMOBILE AND NON-DIFFUSIBLE COMPOUNDS CAPABLE OF COUPLING WITH THE OXIDATION PRODUCT OF AN AROMATIC PRIMARY AMINO COLOR DEVELOPER DURING DEVELOPMENT OF AN EXPOSED SILVER HALIDE EMULSION WITH SUBSEQUENT RING CLOSURE TO PRODUCE A NEW HETEROCYCLIC RING AND AS A FUNCTION OF SUCH REACTION TO SPLIT OFF A MOBILE AND DIFFUSIBLE COLOR-PROVIDING MATERIAL; OR
(2) RELATIVELY IMMOBILE AND NON-DIFFUSIBLE SILVER HALIDE DEVELOPING AGENTS WHICH ARE CAPABLE OF PROVIDING, UPON DEVELOPMENT OF AN EXPOSED SILVER HALIDE EMULSION, AN OXIDATION PRODUCT WHICH CAN AUTO-REACT INTRAMOLECULARLY TO FORM A NEW HETEROCYCLIC RING AND AS A FUNCTION OF SUCH REACTION TO SPLIT OFF A MOBILE AND DIFFUSIBLE COLOR-PROVIDING MATERIAL.
As was mentioned previously, this invention is directed to novel compounds including a color-providing moiety and which are of particular use in the photographic systems described and claimed in the aforementioned copending application now U.S. Pat. No. 3,443,940
A primary object of this invention, therefore, is to provide a novel class of compounds of the foregoing description and methods for preparing the same.
Another object is to provide a novel class of compounds which are partiicularly useful in color photography.
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 compounds of this invention may be represented by the following formula: ##STR1## wherein:
A represents the atoms necessary to complete an aromatic ring, e.g., a benzene or naphthalene nucleus, which nucleus may be further substituted;
d is a color-providing moiety, e.g., a complete dye such as a monoazo, disazo or anthraquinone dye, which may, if desired, be metallized in known manner;
Z may be hydrogen, any of the substituents heretofore known in the art which are replaceable by oxidized aromatic amino color developer in so-called elimination-coupling reactions (see, for example, Mees, "The Theory of the Photographic Process", Revised Edition, 1954, pp. 599-601), e.g., chloro, bromo, carboxy, sulfo, hydroxy, alkoxy, hydroxyalkyl, etc.; or an aromatic amino radical, e.g., an anilino substituent, including substituted anilino radicals, particularly of the p-hydroxy-anilino series or the substituted anilino radical of a color developer of the p-phenylene diamine series, e.g., ##STR2## wherein:
each R.sup.2 is hydrogen or a lower alkyl radical, and including the known substituted derivatives of the aforementioned anilino radicals having a free position ortho to the --NH-- substituent, a para-amino or a parahydroxy-naphthylamino radical, including substituted derivatives thereof having a free position ortho to the --NH-- substituent, which derivatives may contain an anchoring moiety to be described with more particularity hereinafter;
Y is any substituent which completes or forms an amide with, and reduces the basic character of the amino group in the 3-position, such as the residue of an acid, linking the color-providing moiety D to the 3-nitrogen atom, and which is capable of being eliminated during the ring formation to be described with more particularity hereinafter, e.g., ##STR3##
X is hydroxy or amino, e.g., a primary, secondary or tertiary amino substituent of the formula: ##STR4## wherein:
each R.sup.3 may be hydrogen, a hydrocarbon radical, e.g., alkyl, such as methyl, ethyl, butyl, dodecyl, etc., aryl such as phenyl or naphthyl attached through a carbon atom thereof to the nitrogen atom, a cyclic alkyl such as cyclopentyl or cyclohexyl, i.e., where both R.sup.3 's are alkylene comprising together with the nitrogen atom a heterocyclic ring, a substituted alkyl, such as hydroxyethyl, methoxyethoxyethyl, polyglycoloxyethyl, carboxymethyl, carboxyethyl, ethyl-carboxymethyl, benzyl, phenylethyl, sulfo-phenylethyl, acetylaminophenylethyl, succinylaminophenylethyl, furanemethyl, etc.; or a substituted aryl such as methylphenyl, ethylphenyl, etc.; or when Z is one of the described anilino or naphthylamino radicals containing a para-amino or para-hydroxy substituent, X may be hydrogen or the substituent R;
R is an "anchoring" or immobilizing substituent rendering the compound non-diffusible, e.g., higher alkyl such as 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--, ##STR5## etc., an aromatic ring, e.g., of the benzene or naphthalene series, or a heterocyclic ring, 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 R may be a plurality of short chain radicals which together provide the anchoring moiety, each of said short chain radicals being linked directly or indirectly to a different carbon atom of the aromatic nucleus formed by the A moiety;
R.sup.1 is hydrogen, an alkyl such as methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cyclohexyl, etc.; or a substituted alkyl, e.g., a hydroxyalkyl, such as 2-hydroxyethyl, 3-dihydroxypropyl, etc., carboxyalkyl such as carboxymethyl, carboxyethyl, carboxybutyl, carboxydecyl, etc., hydroxyethyl-ether, polyglycoloxyethyl, furanemethyl, benzyl, phenylethyl, carboxyphenylethyl, sulfo-phenylethyl, acylamino-phenylethyl, etc.;
and n is a positive integer from 1 to 2, provided that when R.sup.1 or R.sup.3 alone or together comprise one of those named substituents rendering the compound non-diffusible, i.e., an "anchoring" substituent, and/or when Z comprises an aromatic nucleus contributing an anchoring moiety alone or in conjunction with said R.sup.1 and/or R.sup.3 moieties, n may be 1, but when R.sup.1, R.sup.3 or Z alone or together do not provide such a substituent, n must be 2.
The various substituents described above which may provide the R, R.sup.1, R.sup.2, R.sup.3 , Z and/or Y moieties and illustrative compounds containing the same are disclosed, for example, in one or more of the following U.S. patents: Nos. 2,414,491; 2,486,440; 2,522,802; 2,536,010; 2,543,338; 3,227,550; 3,227,551; 3,227,552; 3,227,554; 3,243,294; and 3,245,795.
As was mentioned previously, Z may be a substituted anilino radical of a color developer of the p-phenylene diamine series. As examples of color developers of this series which may contribute the aforementioned radical, mention may be made of the following:
Also as was mentioned previously, the colorproviding moiety D is not restricted to complete dyes and is intended to include within its scope materials which are initially colorless or of a color other than that ultimately desired in a particular environment, but which provide the desired color during or subsequent to use in the aforementioned photographic procedures, e.g., upon a change in environment and/or upon subsequent chemical reaction. This change of environment may, for example, be a change in pH, e.g., to an acid environment. Color-providing materials of this nature include indicator dyes, leuco dyes and carbonyls of basic dyes. Also included within the scope of this invention are incomplete dyes or color formers which may react with another substance to form a dye image. However, an incomplete dye or a color former of this description must not be reactable with the oxidized color developer so as to preclude ring-closure and release of the diffusible color-providing moiety.
In general, compounds within the scope of formula A may be readily synthesized by appropriate reaction between an acid salt of the desired dye and the 3-amino substituent of the aromatic ring, as follows: ##STR6##
Where X is amino, it may be necessary or desirable to employ the corresponding 1-nitro analogues in the aforementioned reaction, followed by reduction, e.g., with hydrogen in the presence of a Raney nickel catalyst, to form a 1-amino compound within the scope of formula A. It may also be desirable, in some instances, to have the 1-amino substituent protected during reaction, e.g., by an appropriate blocking group, to insure reaction between the acid salt and the 3-amino substituent.
The compounds wherein Z is a coupling position may be represented by the following formula: ##STR7## wherein A, R, R.sup.1, n, Y and D have the meanings heretofore noted;
X.sup.1 is hydroxy or an amino substituent as heretofore noted in connection with the description of the X moiety; and Z.sup.1 is hydrogen or any of the substituents such as heretofore mentioned which are replaceable by oxidized aromatic amino color developer to effect ring-closure in a manner similar to that described in certain of the aforementioned patents and in the aforementioned copending application Ser. No. 655,440 filed July 24, 1967 now U.S. Pat. No. 3,443,940.
As examples of useful compounds within the scope of formula (B), mention may be made of the following: ##STR8##
The compounds of Formula A wherein Z is an aromatic amino substituent may be represented by the following formula: ##STR9## wherein:
X.sup.2 is hydrogen, hydroxy, an amino group of the formula: ##STR10## such as may be contained by said X moiety, as previously described, or the substituent R.sup.4, provided that at least one of said X and X.sup.2 moieties must be hydroxy or amino;
A.sup.1 represents the atoms necessary to complete a benzene or naphthalene ring, which ring may be further substituted:
R.sup.4 has the same meaning as R;
n.sup.1, like n is a positive integer from 1 to 2, provided that when R.sup.1 or R.sup.3 alone or together comprise one of those heretofore named substituents rendering the compound non-diffusible, either or both n and n.sup.1 may be 1, but when R.sup.1 and R.sup.3 alone or together do not provide such an anchoring moiety, at least one of n and n.sup.1 must be 2.
The compounds of formula (C) may be prepared by coupling a dye of the formula:
Where X and/or X.sup.2 is hydroxy, it may be necessary or advisable for the hydroxy moiety to be present as a protected derivative, e.g., as an alkoxy substituent, during coupling, in which event the desired hydroxy analogue may subsequently be obtained by hydrolysis.
The preferred compounds of formula (C) may be represented by the formula: ##STR12## wherein the anchoring moiety R or R.sup.4 comprises a long chain amide, e.g., of at least 13 carbon atoms, said amide being bonded directly to a nuclear carbon atom of the designated benzene moity or being linked thereto through a phenylene or alkylene linking substituent; and nuclear substituted derivatives thereof, e.g., where any of the nuclear carbon atoms of the respective benzene moieties not containing one of the specifically designated substituents may contain a carboxy, alkyl, alkoxy, amino, chloro, hydroxyl, or amide substituent, etc.
The preferred subclass of formula (F) may be prepared by coupling in the manner described with regard to the broader class of formula (C) followed by dealkylation of the protected hydroxy group. Where the starting materials are not readily available, they may be prepared by the steps set forth in the following sequence of reaction steps: ##STR13##
They may also be prepared by coupling of any of the protected derivatives of the known p-aminophenol developers, with an ortho-fluoro-nitrobenzene, followed by reduction of the nitro group, coupling of the dye-containing moiety D--SO.sub.2 --Cl, and hydrolysis in the aforementioned manner, according to the procedure described and claimed in the copending application of Harris L. Curtis, Ser. No. 655,304 filed July 24, 1967 and now abandoned.
As examples of useful compounds contemplated by formula (C) mention may be made of the following: ##STR14##
Compounds 24 and 25 contain a color-shifted yellow dye moiety; and compounds 28, 29, and 31 contain a color-shifted magenta dye moiety. These compounds are initially substantially colorless but upon hydrolysis, e.g., in an alkaline photographic processing fluid, provide the desired color. Color-shifted yellow dyes and magenta dyes and their advantages in photography are described with more particularity in U.S. Pat. Nos. 3,230,085 and 3,307,947, respectively.
US Referenced Citations (8)
Divisions (1)
|
Number |
Date |
Country |
| Parent |
655338 |
Jul 1967 |
|
Continuation in Parts (1)
|
Number |
Date |
Country |
| Parent |
318227 |
Dec 1972 |
|
Patent Grant
4110355
