Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
  • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
  • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
  • C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
  • C07C205/26—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups and being further substituted by halogen atoms
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/34—Couplers containing phenols
  • G03C7/346—Phenolic couplers

Definitions

• the present invention relates to a group of phenolic compounds which have been found to particularly favor reaction with oxidized primary aromatic amines such as phenylene diamines to obtain stable cyan dyes in excellent yield.
• the group of compounds within this invention enjoy an unusual spectrum of additional functional characteristics which uniquely qualify them as Z-Equivalent Cyan Dye-Forming Color Photographic Couplers.
• colored photographic images are obtained in the photographic art by coupling the development product (i.e., oxidized primary aromatic amino developing agents) with a color-forming or coupling compound.
• the subtractive process of color formation is ordinarily employed and the resulting image dyes are usually of the complementary primary colors such as cyan, magenta or yellow.
• Coupler compounds employed to produce the above three dyes generally contain color-forming groups of the phenolic hydroxyl, pyrazolone or benzoyl acetamide classes, capable of reacting with the oxidation product of the primary aromatic amino developing agent on photographic development.
• color-forming coupler compounds containing acetoacetanilides, S-pyrazolones, phenolic or naphtholic configuration also customarily have active methylene groups which will react with an oxidized color developer during color development to produce a dye.
• a majority of color photographic couplers of the above types are known and described as 4Equivalent couplers and are characterized in requiring the development of four light-exposed silver halide molecules in order to ultimately produce one molecule of dye by a coupling reaction with oxidized developer.
• coupler compounds there are other classes of coupler compounds, however, including Z-Equivalent couplers in which non-chromophoric coupling oif groups are substituted in coupling positions. Such couplers are functionally characterized by requiring the development of only two exposed silver halide molecules during development to obtain one molecule of dye.
• couplers which may be homogeneously incorporated into silver halide emulsions in carefully controlled amounts without adversely affecting-viscosity, adhesion, or the unity of any particular emulsion layer during modern high speed multilayer application onto a film backing.
• Undesired changes in viscosity of melted gelatin photographic emulsions may be caused by additives such as Wetting agents, color components, etc., and these changes directly affect the coating characteristics of a photographic emulsion. This fact is indicated, for instance, on page 250 of the text by Zelikman and Levi, entitled Making and Coating Photographic Emulsions; The Focal Press.
• a coupler-containing layer in such an element is also important, and depends upon the absorption properties of the particular dye to be obtained upon reaction of coupler and oxidized developer. For this reason, an optimal spectrum of characteristics for yellow, cyan and magenta dye-producing couplers may dilfer to some extent. Also to be considered, in this connection, is the fact that a cyan dye is generally not required in the same amount as a yellow photographic.
• a further desired characteristic of a coupler compound is substantial solubility in highand/or low-boiling organic solvents as described and utilized, for instance, in Julian, U.S. Pat. 2,949,360, in the light of earlier disclosures in Mannes, U.S. Pat. 2,304,939; Jelley et al., U.S. Pat. 2,322,827; Vittum, U.S. Pat 2,801,170; and Fierke, U.S. Pat. 2,801,171. It is much to be desired that a modern coupler require only minimal amounts of solvent since the thickness, durability and optical opacity of the resulting photographic element is substantially affected by the amount required. This, in turn, aifects image definition and resolution properties of the resulting photographic element. Limitation in the use of competing couplers also helps, to a lesser extent, provided cyan dye couplers in the existing solvent or vehicle produce a D value commensurate with good color balance and having a lower parameter of not less than about 1.8 for reflective photographic purposes
• R and R are individually defined as hydrogen or alkyl of 1-4 carbon atoms;
• R is defined as an aryloxy-substituted alkylcarbonamido group such as a phenoxy alkyl carbonamido and including alkyland dialkyl-substituted phenoxy-alkylcarbonamido groups.
• substituents may be conveniently and specifically expressed in formula form as follows:
• R is defined as 1) an alkyl-substituted phenoxy-lower alkyl in which the alkyl group of the alkyl-substituted phenoxy contains about l-20 carbon atoms and (2) as a di-alkyl substituted phenoxy-lower alkyl, preferably a (t)-alkyl phenoxy-lower alkyl in which the (t) alkyl group contains up to 10 carbon atoms.
• R is exemplified as di-tertiary pentyl phenoxy propyl, di-tertiary pentyl phenoxy butyl, di-tertiary pentyl-phenoxy pentyl, n-octadecyl phenoxy propyl, n-pentadecyl phenoxy propyl, and n-pentadecyl phenoxy ethy p;
• R is defined as an arylor alkyl-carbonamido group, such as polyfluoro phenyl carbonamido, a :fiuoroalkyl carbonamido, an alkyl substituted phenoxy-lower alkyl car bonamido, also an aryl ureido group such as a chlorophenyl ureido, and may be conveniently expressed, for instance, as
• X and X are defined as halo radicals, inclusive of chloro and fluoro groups, and n is an integer of 0-5,
• n preferably being 5 when X is defined as fluoro
• the above compounds may be obtained from commercially available para-fluoro phenols obtainable, for instance, from the corresponding p-amino phenols.
• the p-fiuoro phenol may then be converted into a 2- nitro derivative by adding HNO in glacial acetic acid, and this intermediate converted to the corresponding 2 methyl-5-fluorobenzoxazole by catalytic reduction followed by cyclization with triethylorthoacetate.
• the resulting Z-methyl-S-fluoro benzoxazole is then nitrated with a HNO and H acid mixture and hydrolyzed to obtain 2-amino-4-fluoro-5-nitro phenol.
• Alk. is defined as an alkyl or lower alkyl group, and n is an integer of 1-2.
• the corresponding bis compound of Formula H may be obtained, for instance, by treating the product of step (D) supra with phosgene to obtain a ureido linkage under conditions permitting further reaction with a compound having the desired para-fluoro phenol moiety.
• Compounds having the above-defined configurations are generally of the ballasted non-diffusing type and are usefully incorporated into photographic silver halide emulsion layers as part of singleor multi-layer color photographic materials by methods (i.e., the solvent and Fisher fat-tail methods) described earlier in part, for instance, in Mannes et al. in US. Pat. 2,304,939/40; and Jelley et al. US. Pat 2,322,027 (June 1943), in which highboiling organic solvents are used to dissolve the coupler.
• a further procedure is also described in Vittum et al. US. Pat. 2,801,170; Fierke et al. US. Pat. 2,801,171 (July 1957); and Julian US. Pat.
• the present compounds may be incorporated into a layer adjacent to a red-sensitive silver halide emulsion layer and/or within such layer and may optimally utilize no high boiling solvent.
• Hydrophilic colloid-silver halide emulsion layers suitable for purposes of incorporating the instant group of 2- Equivalent Couplers include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc., within gelatin, colloidal albumin, a cellulose derivative or synthetic resin such as described in US. Pat. 2,286,215 or 2,327,808, a water-soluble ethanol amine cellulose acetate as described in US. Pat.
• Emulsions utilized in the present invention may also include those chemically or optically sensitized by known means as demonstrated, for instance, in U.S. Pats. 1,574,- 944, 1,623,499, 2,410,689, 2,448,060, 2,566,245, 2,566,- 263, 2,399,083, 2,597,856, 2,597,915, 2,487,850, 2,518,- 698, 2,521,926, 1,942,854, 1,990,507, 2,493,748, 2,519,- 001, 2,666,761, 2,734,900, 2,739,149 and British Pat. 450,958.
• the emulsions may also contain speed-increasing compounds of the quaternary ammonium and polyethylene glycol type as found in US. Pats. 2,271,623, 2,288,226, 2,334,864 and 2,708,162.
• support layer and film base, as used herein, constitute a layer suitable for purposes of coating photographic emulsions thereon within the scope of the present invention.
• Such layers include cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, polyethylene film, polypropylene film and related films of resinous materials as well as paper, glass, and others.
• the terms also include paper or other fibrous material coated with a hydrophobic film or surface which repels and does not absorb or adsorb water.
• a support layer having a hydrophobic surface also may include hydrophobic resin layers which have been electron bombarded as described, for instance, in British Pats. 971,058. 1,060,526 and US.
• Pats. 2,864,755 and 2,864,756 to improve adhesion of hydrophilic colloid layers coated over them.
• Such resin layers or films may be either self-supporting or may be coated over another support layer.
• Specific supports having useful hydrophobic surfaces include polyethylene terephthalate films electron-bombarded to have a contact angle less than 45 C. (U.S. Pat. 2,220,842), an electronbombarded surface comprising a chromium halide (U.S. Pat. 2,117,865), or electron-bombarded hardened gelatin coated papers (Belgian Pat. 671,661), etc.
• a support layer may also contain various functional additives such as titanium dioxide pigments and an antistatic agent as described, for instance, in US. Pat. 3,253,922.
• photographic emulsions within the present invention are coated on support layers in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support.
• the support is usually coated in succession with a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer, either with or without a Carey Lea filter layer between the blueand green-sensitive layers.
• the three differently color sensitized layers may be arranged in any other order over one layers are arranged on the same side of the support layer.
• the above light-sensitive layers are arranged on the same side of the support layers.
• EXAMPLE -1 (A) 2-nitro-4-fluorophenol: To a stirred solution of 22.4 g. (0.2 mole) of p-fluorophenol in ml. of glacial acetic acid is added at room temperature 14 ml. (0.22 mole) of concentrated nitric acid. The obtained mixture is stirred for 30 minutes, then poured into 500 ml. of icewater. A yellow precipitate is formed, collected, washed with water, and dried. Yield 20 g. (64%); M.P. 72- 74 C.
• a precooled (10 C.) nitrating mixture consisting of 9 ml. of concentrated sulfuric acid and 6.5 ml. (0.1 mole) of concentrated nitric acid is added slowly from a dropping funnel.
• the reaction temperature is maintained at 20-25 C., and after being stirred at this temperature for 1.5 hrs., the mixture poured into 200 ml. of ice-water. The resulting precipitate is removed, washed with water,
• the acid chloride reactant of step (G) is prepared, for instance, by reacting the sodium salt of the corresponding alkyl-substituted phenol and an appropriate u-bromophenoxy alkanoic acid (i.e.,
• EXAMPLE 2 .2 mole of p-fluorophenol is reacted in accordance with steps (A)-(F) of Example 1 and the resulting product 8 reacted with .05 mole of a ballasted acid chloride of the formula prepared in the manner of Example 1, and the resulting product recovered as in step (G) of Example 1 (CptLlI) OH F 1
• EXAMPLE 6 Para-chloro phenol is reacted in accordance with steps (A)(E) of Example 1, using as the acid chloride, to effect placement of the o-substituent on the phenol ring.
• the remaining steps (F)-(G) of Example 1 are then followed, using o,p-ditertiary pentyl as the ballasted phenoxy hexanoic acid chloride as the acid chloride of step (G).
• a compound of the formula p OH H CsHuQ-O-Z-C 0NH is obtained having a melting point of 170-l71 C.
• Phenol is reacted in accordance with steps (A)(G) of Example 1 to obtain a compound of the formula (Cpd. VII) Phenol is reacted in accordance with steps (A)-(G) of Example 1 wherein step (E) is effected with and step (G) effected with di(t)-pentyl phenoxy-hexanoic acid chloride to obtain a compound of the formula (Cpd. VIII 4 n( having a melting point of 154-155 C.
• Photographic test strips are coated with standard gelatinous silver bromo-iodide emulsion coating to obtain 136 mg. silver, 450 mg. gelatin, 78 mg. of one of the abovedescribed coupler compounds 1-10, and 39 mg. di-n-butyl phthalate as coupler solvent in accordance with the technique described in the Example 1 of US. Pat. 2,949,360.
• the coated strips are sensitometrically exposed through a graduated-density test object and processed in the usual manner at 20 C., one duplicate being treated with Color Developing Solution A, as hereinafter described.
• the strips are then stop-fixed, washed, silver bleached, washed, fixed, washed, stabilized and dried in the usual manner, thereafter tested as explained below, and evaluated to determine their maximum image dye density, also light and heat fading characteristics, and the results set forth in Table I.
• Heat Fade The extent to which the image dyes fade under the influence of heat and humidity is determined by subjecting 1 1 coatings to a temperature of 60 C. at a relative humidity of 70% for 1 week. The resulting decrease in image dye density is termed Heat Fade (HR) and is measured in terms of decrease in dye density in density units.
• the effect of heat on unreacted coupler is determined and 7.5 grams of B-ethoxyethyl acetate at 138 C.
• a gelatin solution is prepared containing 34 grams of 10% gelatin solution in water, ml. of 7.5% alkanol B solution and grams of B-ethoxyethyl acetate dissolved at 49 C.
• the coupler solution is poured into the gelatin by subjecting coatings to the above heat and humidity con- 5 solution, stirred for about one minute and passed through ditions, and determining the increase in density (i.e. yela colloid mill five times.
• the dispersion was set up on a lowing) in a D area (420 me) of the coating, and rechill plate at 5 C., noodled and washed for 6 hours in cording this in terms of percent density increase. cool water to substantially remove all auxiliary solvent TABLE I Yellow- Devel- SANS Heat lng Print oper 21 day fade percent out, solu- (light (HF) density per- COmpOlmd NO- tion mn. max, fade) (1 week) increase cent 3.40 0. 77 .09 +0 0 3 3.32 6.70 .00 +.03 4 2 3.20 6.54 .08 +.03 5 1 3.53 0.
• a cyan are prepared utilizing, as coupler compound, yellow dyedye image having a ,Dmx value of 340 is obtained producing compounds of the following formula prepared (B)
• Five grams of Compound 1 of Example I are m accordance with Us Pats- 3,369,895 and 31409439' incorporated in a system free of high-boiling coupler sol- NHC O RI RI vent and substantially free of low-boiling coupler solvents, x 40 obtained by initially dissolving into 10 grams of a 1:1 R--C 0-dH-CONII mixture of B-ethoxyethyl acetate and methyl-n-propyl I ketone.
• the resulting solution is then dispersed in a 10% Y gelation solution, chilled, noodled, washed and dried as TABLE nr described above and thereafter melted and incorporated Compound into a gelatino-silver halide emulsion.
• the resulting emul- No. R x Y R, R1 sion is applied to test strips as before, the concentration of silver, gelatin and coupler being identical, to obtain 0;) Bum C1 C1 'i1 h iio (0112) a cyan dye image having suitable D value of 1.92 for reflective purposes.
• the thickness of the test strips is i I... XIIB (t) F 01 do (CH2): observed to be about /1 of the test strip of Example 13A lcmpling 905mm substiwentand also substantially more resistant to scratching and TABLE IV abrasion.
• Example 13A Five grams of Compound VII of Example 7 are dissolved, incorporated into a gelatino-silver halide emulsion and coated onto a test strip as in Example 13A to Compound obtain a cyan dye having a D value of 2.85.
• R Y Five grams of Compound VII are initially disxII,o c-Meth- 01 H 1,3dl(t)pentyl- H solved in auxiliary solvents and dispersed into a 10% gfi' Phemxyf gelatin solution followed by chilling, noodling and washing as described in Example 13.
• EXAMPLE 13 We claim: (A) Five grams of Compound 1 of Example I are 1. A color photographic element having a film base, dissolved in a solution of 2.5 grams of di-n-butyl phthalate a light-sensitive silver halide emulsion applied thereto,
• cyan dye-forming coupler compound a compound having the formula Ru-CO-HN R3 wherein the formula NH-CO-Ra Ra-CO-N wherein R is defined as a halophenyl, a halo-phenylamino or phenylamino group; and R is an alkyl substitutedor dialkyl-substituted-phenoxy-lower alkyl group.
• n being defined as 5 when X is fluoro and as 1 when X, is defined as chloro.
• a color photographic element having a film base, and light-sensitive silver halide emulsion applied thereto and having incorporated therein as cyan dye forming coupler compound a compound of the formula wherein R is defined as a halophenyl, a halo-phenylamino or phenylamino group; and R is an alkyl substitutedor dialkyl-substituted-phenoxy-lower alkyl group.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

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• 1971
  • 1971-02-18 US US00116624A patent/US3758308A/en not_active Expired - Lifetime
• 1972
  • 1972-02-15 IT IT20578/72A patent/IT947573B/it active
  • 1972-02-17 BE BE779512A patent/BE779512A/xx unknown
  • 1972-02-17 FR FR7205286A patent/FR2125969A5/fr not_active Expired
  • 1972-02-17 GB GB733672A patent/GB1377233A/en not_active Expired
  • 1972-02-17 DE DE2207468A patent/DE2207468C2/de not_active Expired
  • 1972-02-18 JP JP1661772A patent/JPS5521335B1/ja active Pending
  • 1972-02-18 CH CH233972A patent/CH553430A/fr not_active IP Right Cessation

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