JPH042937B2 - - Google Patents

Description

Claim 1: A negative component comprising a light-sensitive silver halide emulsion held on a support; a positive component comprising an image-receiving layer held on a transparent support; disposed in at least one of said negative and positive components. and an aqueous alkaline processing composition comprising a light-reflecting pigment and at least one light-absorbing PH-sensitive optical filtering agent, the processing composition being distributed between said negative and said positive components. The combination of light-reflecting pigment and optical filtering agent is releasably contained in a breakable container positioned to release the composition, and the combination of light-reflecting pigment and optical filtering agent is active to the light-sensitive emulsion. The light-reflecting pigment is effective in preventing further exposure of the emulsion during processing in the presence of radiation, and the light-reflecting pigment is effective in masking the light-sensitive layer and masking the transferred image by reflected light. a light-reflecting pigment and said light-absorbing PH-sensitive optical film in a diffusion transfer photographic film unit adapted to form a transferred image visible as a reflection print, which provides after development a layer that provides a visible background; At least one of the target filter agents has the following structural formula: (wherein R is selected from alkyl, aryl, aralkyl and alkaryl, and each R' and R ^{' '} _is hydrogen, halo and _-SO2NR1R2 ^{, each R1} and ^R2 being hydrogen, alkyl, aryl,
characterized in that an alkaline aqueous solution containing a PH-sensitive indolphthalein (selected from aralkyl and alkaryl, and X represents the carbon atom required to complete the phthalide or naphthalide) is used as said treatment composition. Photographic film unit. 2. A photographic film unit as defined in claim 1, wherein said X completes naphthalide. 3. A photographic film unit as defined in claim 2, wherein said R is alkyl. 4. A photographic film unit as defined in claim 3, wherein said R ¹ is hydrogen and said R ² is alkyl. 5. A photographic film unit as defined in claim 3, wherein said R ¹ and R ² are each alkyl. 6. A photographic film unit as defined in claim 1, wherein said processing composition further contains a viscosity-imparting agent. 7. A photographic film unit as defined in claim 1, wherein said light-reflecting pigment is titanium dioxide. 8. A photographic film unit as defined in claim 1, wherein said processing composition comprises a light absorbing PH sensitive carboxynaphtholphthalein optical filtering agent. 9 Structural formula: (wherein R is alkyl, and each R' and R'' can be derived from hydrogen, halo and the -SO ₂ NR ¹ R ² with the proviso that one of said R' and R'' is -SO ₂ NR ¹ R ² _-SO2NR1R2 is substituted at the 5- or 6 ^- position of the indole ring, ^R1 is hydrogen or ^alkyl , ^R2 is alkyl, and X is selected to complete the naphthalide. (represents the required carbon atom)
A compound with 10. A compound as defined in claim 9, wherein said R ¹ is hydrogen. 11. A compound as defined in claim 9, wherein said R ¹ is alkyl. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to photography and, more particularly, to ambient light photography methods and photographic products useful in such methods. 2 Description of the Prior Art A number of diffusion transfer methods are known for creating photographic images in black and white and in color. Of particular interest are diffusion transfer processes in which the image-receiving layer supporting the transferred image is not separated from the developed photosensitive layer after processing, but both components are held together in a permanent laminate. Included as part of the stack is a layer of light reflective material, preferably titanium oxide, interposed between the image bearing layer and the developed photosensitive layer.
The light-reflecting layer separating the image-bearing component and the photosensitive component provides a white background for the transferred image and further shields the developed photosensitive layer. In addition to these layers, the laminate usually includes a dimensionally stable outer layer or support, at least one of which is transparent so that the resulting transferred image is transparent to the background made of the light-reflecting layer. It can be seen by reflection. A diffusion transfer method for forming a visible image without separating a light-sensitive component and an image-receiving component, and a film unit useful in the method, were developed in 1968, for example.
US Pat. No. 3,647,437, issued March 7, 1972, to Edwin Etsch Rand, relates to a diffusion transfer method in which the photograph produced includes a developed photosensitive layer retained with an image-receiving layer as part of a permanent stack. In the method disclosed in this patent, a film unit containing a photosensitive element is developed with ambient light, but undesirable further exposure during processing
This is prevented by light-absorbing materials or optical filtering agents carried within the treated film unit.
In a preferred embodiment, the optical filtering agent is a PH-sensitive dye, i.e. a dye with spectral absorption properties that can change reversibly in response to changes in the surrounding PH.
In particular, it is a pH-sensitive dye that becomes colored or light-absorbing at a pH above alkaline, and becomes colorless or non-light-absorbing below the above-mentioned pH. A particularly preferred embodiment of the film unit includes the above-mentioned U.S. Pat.
3415644, and consists of a sheet-like first component containing an opaque support supporting a silver halide emulsion layer and a sheet-like second component containing a transparent support supporting an image-receiving layer, which are fixed before exposure. This relationship is maintained even after processing. After exposure through the transparent support, an aqueous alkaline processing composition is distributed in a thin layer between the components. The treatment composition includes a light-reflecting pigment and at least one PH-sensitive dye, which dye is in colored form at the initial PH of said aqueous alkaline treatment composition, and which is in color after at least the first stage of treatment. is converted to a colorless form by lowering the surrounding pH, for example by an acid-reactive layer that is part of the film unit. The concentrations of light-reflecting pigments and light-absorbing optical filter agents required to sufficiently protect the photosensitive layer are:
It will vary depending on the method performed and the expected conditions, ie, light intensity, dark time, etc. Preferably, the concentration of these materials is such that the treatment composition layer containing the pigment and the optical filtering agent has a transmission density of at least about 6.
However, the reflection density is about 1 or less. Various PH-sensitive dyes have been disclosed as light-absorbing optical filtering agents to protect selectively exposed light-sensitive materials from post-exposure fog in the presence of externally projected light. Particularly useful PH
Sensitive dyes are phthaleins, i.e. 1972-11
Published on May 7th by Myron S. Simon and David
Phthalides and naphthalide dyes derived from 1-naphthols as disclosed in U.S. Pat.
Bororoa, Paul S. Whitea and Paul
Phthaloid and naphthaloid dyes derived from indoles are disclosed in U.S. Pat. No. 3,702,244 to Tay McGregor. As discussed in the latter patent, indole phthaleins that are particularly useful in photographic processes using highly alkaline media include a 2-ortho-hydroxyphenylindol-3-yl group and a 7-position such as carboxy,
a second indol-3-yl group substituted with sulfonamide or sulfamoyl, or 5-
those containing a second indol-3-yl group substituted in the 7-position with an electron-withdrawing group such as carboxy or cyano, as well as 7-carboxy-indol-3-yl groups and Indolephthalein containing a second indol-3-yl group substituted with sulfamoyl. As discussed in these and other patents, combinations of indole and 1-naphtholphthalenes are commonly used when protection from post-exposure fog across the visible spectrum is desired. Published June 26, 1984 Leon Day Selankowski, Garay S. Lapointe and Nile
U.S. Pat. No. 4,456,674 to Shi Matsuushii discloses a strong opacification system using metal cations to complex a phthalein optical filter agent, and in one embodiment, a carboxyindole phthalein complex to a complex. Certain divalent transition metal cations, such as zinc and cadmium, are used to
-600 nm). Presumably, these divalent metal cations combine with the indole nitrogen of the carboxyindole phthalein to _modify the spectral shift in the dye.
Pigmented treatment compositions in the mid-400nm region to above 500nm, in the spectral region where failure of opacification first appears due to points of thin drug spread or lower usage of treatment composition, i.e. thinner drug layers. This increases the transmission density of the material layer. SUMMARY OF THE INVENTION According to the present invention, certain 7-sulfonamides/
Sulfamoyl indole phthaleins, namely 7-sulfonamide/6-sulfamoyl and 7-sulfonamide/5-sulfamoyl indole phthaleins, have been shown to provide enhanced protection against post-exposure fog in the green region of the visible spectrum. found. At the time of filing of U.S. Application No. 752444, which is the parent application of the U.S. partial continuation application corresponding to this application (July 3, 1985).
), the sulfamoyl group is an indolyl group.
There was a mistaken belief that phthaleins were substituted at the - position, that is, phthaleins were 7-sulfonamide/7-sulfamoyl indole phthaleins. The sulfamoyl group was then actually substituted at the 6-position rather than the 7-position of the indolyl group, and the sulfamoyl-substituted indole intermediate used in the synthesis of the naphthalide dye product of the example was
-Methylsulfamoyl indole was found to be indole. This inadvertent error in positioning the methylsulfamoyl group was discovered after further confirmation of the methylsulfamoyl indole intermediate by NMR, mass spectrometry, and X-ray analysis. Also, 7-sulfonamide/5-
Sulfamoyl indole phthaleins have also been found to be useful in providing protection from post-exposure fog in the green region of the visible spectrum. 7-carboxy/7-sulfonamide Idol Phthalein and 7-sulfonamide/7
- Compared to 7-substituted indole phthaleins such as sulfamoyl indole phthalein,
The 7-sulfonamide/6-sulfamoyl and 7-sulfonamide/5-sulfamoyl indole phthaleins of the present invention have absorption spectra more spread into the green region of the visible spectrum, pronounced by their high epsilon. As such, it absorbs incident radiation more strongly in the green region. These improved spectral absorption properties make the subject indole phthalein optical filter agents suitable for the use of thinner pigmented drug layers and/or
or allow for a more efficient use, ie, a reduction in the concentration of the optical filtering agent without the need for the addition of metal salts or other materials to enhance protection in the green region of the visible spectrum. Therefore, the main object of the present invention is to use an alkaline aqueous solution of a light-reflecting pigment as a treatment composition and a light-absorbing PH-sensitive optical filter agent. An object of the present invention is to provide diffusion transfer photographic products and methods for use as at least one of the following. It is another object of the present invention to provide photographic products and methods of the type described above, in which the processing composition additionally contains an absorbing PH-sensitive carboxynaphthol phthalein optical film agent. A further object of the present invention is to provide 7-sulfonamide/5-sulfamoyl indole phthaleins and 7-sulfonamide/6-sulfamoyl indole phthaleins useful as absorbing PH-sensitive optical filtering agents. Other objects of the invention are partly obvious and partly will appear below. Accordingly, this invention includes a method comprising several steps, the relationship and order of one or more of those steps to each other, and the features, properties, and relationships of elements illustrated in the following detailed disclosure. products,
and the scope of use indicated in the claims. For a fuller understanding of the nature and purpose of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings.

[Brief explanation of drawings]

Figure 1 shows the spectral absorption characteristics of the indole phthalein optical filter agents of Examples 1, 2, and 3 of the present invention, designated as curves 1, 2, and 3, respectively, and 7-carboxy/7-sulfonamide indole.
Figure 2 is a graphical illustration comparing the spectral absorption properties of a phthalein optical filter agent (Curve C). These curves are the optical transmission density, that is, the absorbance of each optical filter agent measured in an alkaline aqueous solution in the wavelength range of 340 nm to 700 nm.
represents. Figures 2 and 3 show the wavelength range of 380n for pigmented treatment compositions.
m - A graphical illustration showing the reflection density at 700 nm, where the composition is indole phthalein.
The same except for the optical filter agent. Curves 1, 2 and 3 represent the reflection densities obtained with the optical filtering agents of the invention, namely the indole phthaleins of Examples 1, 2 and 3, respectively. curve C
and C' represent the reflection densities obtained using 7-carboxy/7-sulfonamide indole phthalein and 7-sulfonamide/7-sulfamoyl indole phthalein, respectively.

[Detailed description of the invention]

As mentioned above, the use of certain indole phthaleins as absorbing PH-sensitive optical filtering agents for the short wavelength region of the visible spectrum enhances the opacity of pigmented treatment composition layers, and particularly for the green color of the visible spectrum. It has been found that a thicker protection in the area can be achieved. These indole phthaleins are represented by the following structural formula, wherein R is selected from alkyl, ^aryl , aralkyl, alkaryl, and each R', R _' ^' is selected from hydrogen, halo and -SO ₂ NR'R'', each R ¹ , R ² is selected from hydrogen, alkyl, aryl, aralkyl, alkaryl, and X represents the carbon atom required to complete the phthalide or naphthalide. The phthalide and naphthalide moieties are represented by the following structural formulas.

[Formula] and

Preferably, X completes naphthalide. Suitable R, R ¹ , R ² substituents include branched or straight chain alkyl, usually containing 1-20 carbon atoms;
e.g. methyl, ethyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl, eicosanyl; aryl, e.g. phenyl, naphthyl; alkaryl, e.g. alkyl-substituted phenyl, where alkyl usually has 1-20 carbon atoms. Something that contains atoms, p-
Methyl phenyl, p-dodecyl phenyl, etc.; aralkyl, such as phenyl-substituted alkyl, where the alkyl usually contains 1-20 carbon atoms, such as benzyl, phenethyl, phenylhexyl, etc. If it is desired that the indole phthalein be relatively immobile in the treatment composition layer, at least one of R, R ¹ , R ² may be a long chain substitute,
Preferably long chain alkyl. R′ or
When R'' is halo, it is usually bromo or chloro. In addition to the named substituents, the title compound may be substituted with solubilizing groups such as carboxy, hydroxy, or sulfonyl to improve the compound's solubility in the treatment composition. or substitution with additional immobilizing groups such as long chain alkoxy, alkyl, or other desirable groups that do not interfere with the photographic function as an optical filtering agent should be evaluated. The subject indole phthaleins are prepared using any of the various methods previously disclosed for the synthesis of phthalides and naphthalides. A preferred method is described in Allen, published January 6, 1976. Elle
No. 3,931,228 to Bohler, in which 7-sulfonamide (or 5- or 6-sulfamoyl) indole is reacted with phthalaldehyde in the presence of a mild acid catalyst, e.g. toluene-p-sulfonic acid. acid or naphthaldehyde acid to form the corresponding phthalidyl- or naphthalidyl-indole intermediate, which can be converted into, for example, 2,3-dichloro-5,6-dicyano-
It consists of treatment with 1,4-benzoquinone and oxidation. The oxidized intermediate is then 5- or 6-
Reaction with sulfamoyl indole (or 7-sulfonamide indole) in the presence of an acid catalyst provides the desired phthalein product. The 7-sulfonamide indole used in the above process is prepared by techniques known and disclosed in US Pat. The procedures described herein for sulfamoyl-substituted indoles can be used to prepare 6-sulfamoylindoles.
The following examples are provided to illustrate the invention and are not intended to limit its scope. Example 1 Structural formula 3-(7-n-hexadecylsulfonamidoindol-3-yl)-3-(6-methylsulfamoylindol-3-yl)naphthalide was prepared as follows. (a) A mixture of naphthaldehydic acid (20 g, 0.0998 mol) and 7-hexadecylsulfonamide indole (41.9 g, 0.0998 mol) was added to 380 ml of toluene containing 0.3 g of p-toluenesulfonic acid.
and dissolved in 61 ml of acetic acid. The mixture was refluxed in a Dane-Stark trap for about 24 hours.
At that point no water was removed and thin layer chromatography with chloroform showed the reaction to be complete. The mixture was cooled and the solvent was removed under reduced pressure. Dissolve the purple oil in hot isopropanol;
The obtained crystals were collected by suction filtration. The mixture was washed with ethanol several times until the washing solution became transparent, yielding 7.3 g of naphthalidyl-indole intermediate. This reaction was carried out using naphthaldehyde acid and 7-hexadecylsulfonamide indole at 0.175
Repeating using moles at a time yielded 48.0 g of the corresponding naphthalidyl indole intermediate. (b) naphthalidyl-indole intermediate (1.0 g,
2,3-dichloro-5,6-diano-1,4-benzoquinone (0.45 g, 1.9 mmol) in 2 ml of dioxane with stirring.
added. The resulting brown solution was refluxed for 30 minutes. At that point TLC using 5% methanol/methylene chloride showed no starting material. The cooled mixture was filtered and dioxane was removed under reduced pressure. The resulting oxidized intermediate was treated with ethanol/water. This reaction was carried out with 20 g (0.033 mol) of naphthalidyl-indole intermediate and 2,3-dichloro-5,
6-dicyano-1,4-benzoquinone 9.04g
(0.039 mol) of the corresponding oxidized intermediate using
19.55g was obtained. (c) 6-
Methylsulfamoylindole (5.67g,
0.0269 mol) was added. The resulting solution was stirred at 25°C. After 36 hours TCL using 12% methanol/chloroform showed the reaction was complete. The reaction solution was carefully added to ice in a beaker and filtered with suction filtration. This was washed several times with water and dried in a vacuum oven at 75°C for 12 hours. 20.47 g of crude product was obtained. This was dissolved in chloroform, filtered through Celite, and purified by high pressure liquid chromatography using two silica gel columns to produce 3.8 liters of methylene chloride, 3.8 liters of 0.5% methanol/methylene chloride,
1% methanol/methylene chloride 7.6 liters, 1.1% methanol/methylene chloride
It eluted at 7.6 liters. 6.0 g of pure title compound was recovered as a yellowish brown small crystal compound. The 6-methylsulfamoylindole used above was prepared as follows. 3 containing 108.5g (0.911 mol) of indoline
Add acetic anhydride to a 500ml round bottom flask at a temperature of 25°C.
Added at a rate that was kept below. After addition (1 hour) the reddish slurry was poured into ice water, filtered and washed several times with water. Leave to dry overnight and use 700ml of ethanol.
116.6g of N-acetylindoline after recrystallization from
(weight yield 72.4%). N-acetylindoline in 150 ml of acetic acid in a 1000 ml three-necked flask equipped with an overhead stirrer, thermometer, and gas inlet (with sodium hydroxide trap).
116.6g (0.724mol), 32.25ml of bromine in 30 minutes
(0.68 mol) was added. Cool the mixture to 30°C in an ice bath.
I kept it. When the addition was complete, the yellow suspension was slowly poured into 1 liter of ice water and solid sodium zinc sulfate was added to destroy any residual bromine. The resulting slightly off-white solid was filtered, washed several times with water, and left to dry overnight. The obtained solid was recrystallized from 800 ml of methanol to obtain 122.86 g (weight yield: 70.7%) of 5-bromo-N-acetylindoline. 116.52 g (2.6 moles) of chlorsulfonic acid were carefully added to 122.86 g (0.51 moles) of 5-bromo-N-acetylindoline cooled in an ice bath. The mixture was stirred at 0° C. for about 30 minutes and then allowed to warm to room temperature.
The mixture was then gradually heated to about 70-90°C overnight. After cooling, the cold solution was gradually added to ice, and the solid was filtered with suction, washed several times with water, and left to dry overnight. The product was recrystallized from chloroform to yield 5-bromo-6-chlorosulfonyl-N-acetylindoline 72.5
g (weight yield 42%). 5-bromo-6-chlorosulfonyl-N-acetylindoline in tetrahydrofuran 71.83
(0.212 mol) of a 40% aqueous solution of 2 equivalents of methylamine and 2 equivalents of triethylamine was added. The mixture was heated under reflux for 1.5 hours and allowed to cool. Thin layer chromatography with chloroform showed completion of the reaction. The cooled mixture was evaporated under reduced pressure and the resulting white solid was suspended in hot methanol, filtered, washed with methanol and left to dry overnight. 5-Bromo-6-methylsulfamoyl-N
- Obtained 65.12 g of acetylindoline (weight yield
92%). 5-bromo-stirred in 200 ml of dioxane
A suspension of 65.11 g (0.195 mol) of 6-methylsulfamoyl-N-acetylindoline contains 146
ml (1.75 mol) was added. Stir the mixture to 1.5
The mixture was refluxed for hours and allowed to cool. The mixture was concentrated under reduced pressure, cooled in an ice bath and neutralized to PH7 with 10% sodium hydroxide solution. The resulting white precipitate was filtered, washed several times with water, and left to dry overnight to give 55.92 g of 5-bromo-6-methylsulfamoylindoline (weight yield:
98%). 55.92 g (0.19 mol) of 5-bromo-6-methylsulfamoylindoline in 150 ml of dioxane
While stirring the solution of 2,3-dichloro-5,6
-dicyano-benzoquinone 41.79g (0.184mol)
was added at 25°C. Thin layer chromatography using chloroform showed the reaction to be complete when the resulting brown solution was heated at 80° C. for 2 hours. The reaction mixture was allowed to cool, filtered through Celite, and the filtrate was concentrated under reduced pressure. The resulting brown solid was stirred in a 50/50 methylene chloride/ether mixture and filtered. Perform this operation two more times,
35.2 g (weight yield 63.9%) of 5-bromo-6-methylsulfamoylindole was obtained. A solution of 8.68 g (0.299 mol) of 5-bromo-6-ethylsulfamoylindole in ethanol was degassed with nitrogen for 15 minutes. Triethylamine (0.036 mol) was then added followed by 1.09 g of palladium catalyst. The mixture was hydrogenated (40 psi) for 3 hours.
Thin layer chromatography (2.5% methanol/methylene chloride) showed the reaction to be complete. The mixture was filtered to remove the catalyst and concentrated under reduced pressure. The residual oil was extracted with chloroform and concentrated under reduced pressure four times to remove traces of ethanol solvent. The oil was chromatographed on a silica gel column and eluted with 2.5% ethanol/methylene chloride. The golden solution was concentrated in vacuo to give an oil. The oil was mixed with water to give a tan solid precipitate. After cooling overnight, the tan solid was separated by vacuum filtration and washed with water. After the solid was air-dried, it was ground to a powder and further dried. 6-methylsulfamoylindole 5.76g (weight yield 91.2%)
I got it. M/e210 ¹ H-NMR: (DMSO) δ7.859
(m, 1H), 7.728 (d, 1H), 7.63 (t, 1H), 7.39
(dd, 1H), 7.25 (q, 1H), 6.57 (t, 1H), 2.37
(d, 3H). Example 2 Structural formula 3-(7-n-hexadecylsulfonamidoindol-3-yl)-3-(5-methylsulfamoylindol-3-yl)naphthalide was prepared as follows. (a) A stirred solution of 4.32 g (0.0205 mol) of 5-methylsulfamoylindole in 200 ml of glacial acetic acid is dissolved in 4.104 g (0.0205 mol) of naphthaldehydic acid.
mol) was added. The mixture was heated to reflux. Add p-toluenesulfonic acid 7 to the reaction mixture.
Added ml. The solution was refluxed for 3 hours. Thin layer chromatography with 2% methanol/methylene chloride showed the reaction to be complete. The solution was allowed to cool and then added to 2 liters of ice water. The brown solid was collected by suction filtration and air-dried in air to obtain 6.854 g (0.0174 mol) of naphthaldyl-indole intermediate (85% weight yield). (b) 3.412 g (0.015 mol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is added to a stirred solution of 5.965 g (0.015 mol) of the naphthalidyl-indole intermediate in 200 ml of dioxane.
added. The mixture was refluxed for 6 hours. 3/1
Thin layer chromatography with ethyl acetate/hexane showed the reaction to be complete. Allow the solution to cool;
Filtered through Celite and concentrated under reduced pressure. The dried residue was covered with chloroform and then dissolved in acetone. The product was precipitated by adding hexane to the chloroform-acetone solution. The pink solid was collected by suction filtration and air-dried to give 4.962 g (0.0127 g) of the naphthalidyl oxide-indole intermediate.
mole) was obtained. (c) 4.883 g (0.0125 g) of oxidized intermediate in 100 ml of glacial acetic acid
5.25 g of 7-n-hexadecylsulfonamide indole while stirring a solution of
(0.0125 mol) was added. 100 ml of trifluoroacid was added to the mixture. The reaction mixture was incubated at room temperature for 24 hours.
Stir for hours. Thin layer chromatography with 2% methanol/methylene chloride showed the reaction to be complete. The solution was poured onto 2 liters of ice water. Pink crystals were collected by suction filtration and purified by high pressure liquid chromatography eluting with 1% methanol/methylene chloride. The impure fraction was chromatographed on silica gel and eluted with 500 ml of 1% methanol/methylene chloride, 500 ml of 1.5% methanol/methylene chloride, and 500 ml of 2% methanol/methylene chloride.
7.49 g (0.00923 mol) of the title compound (weight yield 74
%) was obtained. The 5-methylsulfamoylindole used above was prepared as follows: 213 ml (3.21 mol) of ice-cold chlorsulfonic acid.
100g (0.680mol) of N-formylindoline
was added in portions over 20 minutes. The reaction mixture was heated to 65° C. for 20 minutes under mechanical stirring in an oil bath. The solution was then allowed to cool to room temperature. The solution was carefully added to 2 liters of ice and filtered with suction. The brown solid was washed with water and air-dried to give 62.67 g of 5-chlorosulfonyl-N-formylindoline (weight yield:
38%). N-formyl-5-chlorosulfonylindoline in 400 ml of ice-cold methylene chloride
Triethylamine in a solution of 31.07 g (0.126 mol)
37 ml (0.252 mol) and a 40% aqueous solution of methylamine
30 ml (0.252 mol) was added in portions over 20 minutes. The mixture was allowed to warm to room temperature and then heated to reflux in an oil bath with mechanical stirring for 1 hour. Thin layer chromatography with chloroform showed completion of the reaction. The aqueous layer was removed, and the methylene chloride layer was washed with water and dried with sodium sulfate. The solution was concentrated under reduced pressure and the residue was dried in air to give 23.74 g of 5-methylsulfamoyl-N-formylindoline.
(0.0988 mol) (weight yield 75%) was obtained. 23.42 g of 5-methylsulfamoyl-N-formylindoline in 500 ml of methanol (0.0975
40 ml of concentrated hydrochloric acid was added to the solution of mol). The solution was heated under reflux for 1 hour. Thin layer chromatography with chloroform showed completion of the reaction. After the solution was allowed to cool, methanol was removed under reduced pressure. The remaining aqueous slurry was dissolved in ice water and neutralized by adding sodium hydroxide solution. The precipitate was extracted with methylene chloride and washed with water and saturated brine. The solution was dried with Glauber's salt and concentrated under reduced pressure. The residue was dried in air to give 5-methylsulfamoylindoline.
17.02 g (0.08 mol) (82% weight yield) was obtained. A stirred solution of 12.87 g (0.0605 mol) of 5-methylsulfamoylindoline in 200 ml of dioxane was dissolved with 15.11 g (0.0666 mol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone.
added. The mixture was heated to 75°C in an oil bath for 2 hours. Thin layer chromatography with 3/1 hexane/acetone showed the reaction to be complete. The solution was allowed to cool, filtered through Celite, and concentrated under reduced pressure.
The black residue was chromatographed through silica gel, eluting with 2.5% methanol in methylene chloride. Thin layer chromatography showed a mixture of compounds. The residue was then chromatographed through a silica gel column, eluting with 3/1 hexane/acetone. It was found that the purple compound could not be separated from the 5-methylsulfamoylindole product. 4.42 g (0.021 mol) of purple solid (weight yield
35%). The compound of Example 1 was also synthesized using the above procedure by reacting 6-methyl-sulfamoylindole with naphthaldehyde acid. Example 3 Structural formula 3-(7-n-hexadecylsulfonamidoindol-3-yl)-3-(5-dimethylsulfamoylindol-3-yl)naphthalide was reacted with an oxidized naphthalidyl-indole intermediate. Prepared according to the procedure set forth in Example 2, except that the huamoylindole was 5-dimethylsulfamoylindole. This indole was prepared in the same manner as 5-methylsulfamoylindole using dimethylamine. Example 4 The structural formula is 3-(7-methylsulfonamideindol-3-yl)-3-(5-n-hexadecylsulfamoylindol-3-yl)naphthalide, 5-n-hexadecylsulfamoylindole It was prepared according to the procedure set forth in Example 2 above, except that it was reacted with an oxidized naphthalidyl-indole intermediate synthesized from 7-methylsulfonamide indole. Example 5 The structural formula is 3-(7-hexadecylsulfonamideindol-3-yl)-3-(5-bromo-6-
Methylsulfamoylindol-3-yl)naphthalide was prepared according to the procedure set forth in Example 2, except that 5-bromo-6-methylsulfamoylindole was used as the sulfamoylindole intermediate. As noted above, the present invention is particularly suited to facilitate non-camera processing of diffusion transfer units that are maintained as a permanent stack after processing, with the final transferred image viewed through one surface of the stack. ing. Such film units have a light reflective layer disposed between the developed photosensitive layer and the layer supporting the transferred dye image. These essential layers are preferably a pair of dimensionally stable external supports, at least one of which is transparent and allows the transferred dye image to be viewed in reflection against a background created by the reflective layer. , is trapped between. Commonly available image dye-providing materials are either (1) initially soluble or diffusible in the processing composition but rendered selectively unable to diffuse within the image-like pattern as a result of development; (2) having the property of being initially insoluble or non-diffusible in the processing composition, but which, as a function of development, is rendered selectively diffusible in an image-like distribution or provides a diffusible product; . These materials are finished dyes or dye intermediates, ie color couplers. The necessary differentiation in mobility or solubility can be obtained, for example, by chemical reactions such as redox reactions or coupling reactions. Examples of initially soluble or diffusible materials and their application to color diffusion transfer methods include, for example, US Pat.
Reference is made to those disclosed in Nos. 3230082; 3345163; 3443943. As examples of initially non-diffusible materials and their use in color transfer systems, US Pat.
Reference is made to the materials and systems disclosed in Nos. 3227550; 3227552; 4076529. Both types of image dye-providing materials and film units also useful therein are discussed in the aforementioned U.S. Pat. No. 3,647,437, to which reference is made. A particularly useful system for forming color images by diffusion transfer uses a dye developer (a dye that is also a silver halide developer) as the image dye supply material as described in U.S. Pat. No. 2,983,606. be. In such systems, a light-sensitive element comprising at least one silver halide layer (in the same or adjacent layer) with a dye developer in combination is developed by application of an aqueous alkaline processing composition. It is. Development of the exposed silver halide results in oxidation of the dye developer to give an oxidized product that is considerably less diffusive than the unreacted dye developer, and thereby from the point of view of the unexposed areas of the silver halide layer. A diffusible dye developer with an image-like distribution is now obtained, which image-like distribution is then transferred, at least in part, by diffusion to a thin dyeable layer in which the positive dye is deposited. A transferred image is provided. In such diffusion transfer systems, the color transfer image, sometimes referred to as the "negative component," is formed by combining an image dye-providing material in the same or adjacent layer with at least a light-sensitive layer, such as a silver halide gelatin emulsion layer. forming a developable image by exposing the photosensitive element comprising a photosensitive element; developing the exposed element with a processing composition to form an image-like distribution with a diffusible image dye supply material; transfer this image-like distribution, at least in part by diffusion, to a superimposed image-receiving layer, sometimes referred to as a "positive component", consisting of at least a thin dyeable layer; This gives a color transferred image. The negative and positive components may initially be kept on separate supports, combined during processing and then held together as a final integrated negative-positive reflection print, or they may be initially kept together in a unitary structure, e.g. No. 3,415,644 is an integrated negative-positive film unit in which the negative and positive components are held together in a physically overlapping relationship before, during and after imaging. (The manner in which the positive and negative components form a film unit in which they are temporarily layered prior to exposure is described, for example, by Albert Gier-Basselder and Frederik Gier, published March 28, 1972.
In both cases (as described in U.S. Pat. No. 3,652,281 to Binder and U.S. Pat. No. 3,652,282 to Edwin Etsch Rand, issued on the same day), the positive component is not subtracted from the negative component for viewing purposes. These components may be stacked together or otherwise brought into close contact by physical juxtaposition. In order to provide a multicolor image, the film unit consists of two or more selectively sensitized silver halide layers, each layer being associated with a suitable image dye supply material, which has an associated halogen The present invention provides an image dye having spectral absorption characteristics that are substantially complementary to the light beams exposing the silver oxide. The most commonly used negative elements for forming polychromatic images are of three-pack construction, each layer containing silver halide layers sensitive to blue, green, and red, each containing yellow in the same or adjacent layer. , magenta and cyan image dye supplies. An insertion layer or spacer layer is provided between each silver halide layer and the associated image dye supply material or between other layers. Indeed, a light reflective spacer layer placed between the silver halide layer and the associated image dye supply layer is used to increase the effective film speed as a result of reflecting light back to the silver halide. A particularly suitable light-reflecting spacer layer consists of a light-reflecting pigment dispersed with inert polymer particles that are virtually non-alkaline swollen and virtually non-film-forming. Such a group was published in the published European patent application no. 8 December 1982.
This is the title of issue 0066341. In addition to the aforementioned layers, such film units may further include a reflective layer between the dyeable thin layer and the negative component to effectively shield the silver image formed as a result of development of the silver halide layer. Also included are methods of shielding the undiffused image dye supply material and providing a background, preferably white, so that the color image formed in the thin dyeable layer can be viewed in reflected light without separation. Preferably, this reflective layer is provided by including a reflective agent in the treatment composition. The dye diffusion image can be viewed through the dimensionally stable layer or support against the background of the reflective layer. As mentioned above, the most preferred further dimensionally stable layer or support is placed on the opposite surface of the essential layer, so that said essential layer is between a pair of dimensionally stable layer or support members; One of them is transparent, allowing the color diffusion image to be seen through it. Known breakable containers contain the necessary processing compositions and, upon application of pressure, release their contents to transfer the exposed film unit, e.g. By uniformly distributing it, it is suitable for development. The dye developer (or other image dye-providing material) is preferably selected from those capable of providing the colors useful for performing subtractive color photography, namely cyan, magenta, and yellow. These are incorporated into each silver halide emulsion, in a preferred embodiment in a separate layer behind each silver halide emulsion. Thus, since the dye developer is, for example, in a coating or layer behind each silver halide emulsion, such a layer of dye developer has a calculated density which gives the desired dye developer application per unit area. in,
It is applied using a coating solution containing the respective dye developer dispersed in a film-forming natural or synthetic polymer, such as gelatin, polyvinyl alcohol, etc., which is compatible with the penetration of the processing composition. The dye developer is a compound having the development performance of silver halide of the coloring system of the dye as described above. "Silver halide development performance" means a formulation suitable for developing exposed silver halide. A preferred silver halide developing property is a hydroquinonyl group. Other suitable development properties include ortho-dihydroxyphenyl, ortho- and para-amino substituted hydroxyphenyl groups. Generally, the developability includes benzenoid developability, ie, aromatic developable groups that are oxidized to produce quinoid or quinone materials. The image-receiving layer is preferably one containing a color fixing agent for the transferred image dye, such as polyvinyl alcohol, gelatin, etc. as known in the art. If the color of the diffused image dye is affected by changes in PH, the PH of the image layer is adjusted to the PH that gives the desired color. In various color diffusion transfer systems using aqueous-alkaline processing solutions as described above, acid-reactive agents are used in the layers of the film unit to lower the ambient PH and improve image stability subsequent to substantial dye transfer. It is well known to increase or adjust the PH from a first PH at which image dyes diffuse to a second (lower) PH at which they do not diffuse. For example, US Pat. No. 3,415,644 discloses a system in which the desired pH reduction is achieved by providing a layer of polymerized acid adjacent to a thin dyeable layer. These polymerized acids are polymers containing acid groups capable of forming salts with alkalis, such as carboxylic and sulfonic acid groups, or potential acid-forming groups such as anhydrides or lactones. Preferred acid polymers are those containing free carboxyl groups. Instead, the acid-reactive agent is placed in the layer adjacent to the silver halide furthest from the image-receiving layer, as disclosed in U.S. Pat. be. Another system for delivering acid-reactive agents is disclosed in U.S. Pat. No. 3,576,625 to Edwin Etsch Rand, issued April 27, 1971. An inert interlayer or spacer layer is used in combination with the polymerized acid layer to control or "time" the PH drop so that it does not interfere with the development process too early. A spacer or "timing" layer suitable for this purpose is described in U.S. Pat.
3362819; 3419389; 3421893; 3455686; 3575701
Details are given in the issue. It is known that liquid processing compositions for carrying out multicolor diffusion transfer processes consist of an aqueous solution of at least an alkaline substance and have a pH of at least 12, as described, for example, in the previously cited patents. Preferably, the alkaline substance used in the subject invention is an alkali metal hydroxide. The treatment composition also preferably includes a viscosity-imparting agent, which comprises a film-forming material that causes the composition to form a relatively firm and relatively stable film when applied and dried. The agent is, for example, a cellulosic polymer such as hydroxyethyl cellulose or sodium carboxymethyl cellulose, an oxime polymer such as polydiacetone acrylamide oxime, or other alkali-stable high molecular weight polymer. A viscosity-imparting agent is preferably included in the treatment composition, the appropriate amount of which imparts a viscosity to the composition of greater than 100 cps at about 24°C, preferably approximately 100,000 cps to 200,000 cps at that temperature. As previously mentioned, absorbing PH-sensitive filtering materials that absorb in the long wavelength region of the visible spectrum, typically carboxynaphtholphthalein, are used in combination with the subject indolephthaleins to provide additional protection throughout the visible spectrum. . “Carboxynaphtholphthalein” used here is 3,3
-di(4'-hydroxy-1'-naphthyl)-phthalides and 3,3-di(4'-hydroxy-1'-naphthyl)-naphthalides;
One of the substituents is intended to be a 3'-carboxy-4'-hydroxy-1'-naphthyl moiety such as the phthaleins disclosed in the aforementioned US Pat. No. 3,702,245. The PH-sensitive phthalein dyes used as light-absorbing optical filtering agents are preferably initially included in colored form together with a light-reflecting substance, such as titanium oxide, in the treatment composition. The concentration selection of phthalein dyes, in combination with other intervening layers and incident radiation, can be used to prevent non-image exposure, i.e. fogging caused by incident active radiation during special photographic processes. It is designed to provide the required light transmission density. The transmission density and concentration of the phthalein dye to provide the necessary protection from incident light are determined by the film speed or sensitivity, the thickness of the opacifying layer, the processing time, and the expected Factors such as the intensity of the incident light can be readily determined for any photographic method by routine experimentation. Rather than requiring a particular transmission density for all parts of the spectrum, it has been found that lower densities are sufficient in wavelength regions corresponding to the lower sensitivity of particular photographic materials. It can be seen that mixtures of phthalein dyes, as described above, are used to obtain absorption in the entire visible and near-visible critical region to which the silver halide emulsion used is exposed. If a light-absorbing phthalein optical filtering agent is present in the processing composition, a surface of the image-receiving component that is adapted to decolorize the optical filtering agent adjacent the interface between said component and the processing composition layer. It is advantageous to use a material with layers. Suitable bleached layers include Edwin Etsch Land, Leon Day Selankowski, Nail C.
U.S. Patent No. 4298674 to Matsushii, U.S. Patent No. 4298674 to Reyna Bronstein-Bonte, Edward P. Lindholm, and Lloyd Day Taylor.
No. 4,294,907, and US Pat. No. 4,367,277 to Charles K. Chiklis and Nail C. Matsushii. To further illustrate the invention, Examples 1, 2,
The permeation density of each compound in 3 was determined by measuring the permeation density of each compound in a solution of 1:4 mixture of ethanol in 10% aqueous sodium hydroxide solution.
Measurements were made spectrophotometrically at a concentration of x10 ^-5 M over a wavelength range of 340 nm to 700 nm. The obtained curves are named curves 1, 2, and 3 and are shown in FIG. For comparison, 3-(7-carboxindol-3-yl)-3-(7-n-hexadecylsulfonamidoindol-3-yl)naphthalide was prepared at the same concentration in 1:4 ethanol/10% aqueous sodium hydroxide. Measurements were made in the same manner. The resulting curve is named curve C in FIG. As can be seen from FIG. 1, the indolphthaleins of the present invention are 7-
Carboxy/7-sulfonamide absorbs more strongly in the green region of the visible spectrum than indole phthalein. λ _nax and epsilon measured by λ _nax were 533 (32200) and 533 for the compounds of Examples 1, 2, and 3, respectively, compared to 467 (15300) for the 7-carboxy-7-sulfonamide compound.
(30860), 530 (31100). The transmission densities measured under the _same conditions for the compounds of Examples 4 and 5 were 532 (30020) and 532 (34450) for λ _nax and epsilon, respectively. Ten%
When similarly measured using 5% aqueous sodium hydroxide instead of aqueous sodium hydroxide, λ _nax and epsilon for the compounds of Examples 1-5 were 518 (25150) and 512, respectively.
(25250), 526 (26200), 525 (22750), 525 (30470)
)
, while λ _nax and epsilon of the 7-carboxy/7-sulfonamide compound are 466-467
(12600). The enhanced protection in the green region afforded by the subject indolephthaleins is shown in the reflectance spectra for pigmented treatment compositions containing the same components except for the indolephthalein optical filtering agent used as a short frequency absorber. , will be further explained in FIGS. 2 and 3. Curves 1 and 2 in FIG. 2 represent pigmented treatment composition layers containing the compounds of Examples 1 and 2, respectively, and curves C and C' represent 3-(7-carboxindol-3-yl)-3- (7-n-hexadecylsulfonamidoindol-3-yl)naphthalide and 3-(7-n-hexadecylsulfonamidoindol-3-yl)-3-(7-methylsulfamoylindole-3- Figure 3 represents a pigmented treatment composition layer containing naphthalide. In FIG. 3, curves 2 and 3 represent Examples 2 and 3, respectively.
Curve C represents a pigmented treatment composition layer containing the compound 3-(7-carboxindole-3-
1 represents a pigmented treatment composition comprising (1)-3-(7-n-hexadecylsulfonamidoindol-3-yl)naphthalide. In addition to each indolphthalein short wavelength absorber, the aqueous alkaline treatment composition contains a viscous aqueous solution of an alkali metal hydroxide containing titanium dioxide as a light-reflecting pigment, and an optical filter for absorbing the long wavelength region of the visible spectrum. The agent includes carboxynaphtholphthalein having the following structural formula. 3-(3′-carboxy-4′-hydroxy-1′-naphthyl)-3-(3″-carboxy-4″-hydroxy-7″-octadecyloxy-1″-naphthyl)naphthalide treatment compositions The reflection density of each layer was measured over a wavelength range of 380-700 nm by coating approximately 0.0028 inch thick between two transparent polyethylene terephthalate plates. As is clear from the comparison between curves 1 and 2 in FIG. 2 and C and C' and the comparison between curves 2 and 3 and curve C in FIG. The composition layer allows more effective protection in the green region of the visible spectrum, as evidenced by the significant increase in reflection density above 500 nm, especially in the 520-550 nm region. It will be appreciated that the present invention can be utilized in a variety of photographic processes using a variety of image supply materials and in which image transfer is silver or dye based. Such methods are well known and need not be described in detail. It is clear that in these photographic systems, the transferred image with respect to the photographic subject matter as a unique imaging feature may be positive or negative, and the silver halide emulsion may be negative working or positive working. Similarly, the image-receiving layer and other negative and positive component layers can be modified according to the methods given. Since certain changes may be made in the above heading without departing from the scope of the present invention, all matter contained in the above description or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense. It should be construed that there is no.