US3733335A - Indazolone magenta couplers - Google Patents

Indazolone magenta couplers Download PDF

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Publication number
US3733335A
US3733335A US00104510A US3733335DA US3733335A US 3733335 A US3733335 A US 3733335A US 00104510 A US00104510 A US 00104510A US 3733335D A US3733335D A US 3733335DA US 3733335 A US3733335 A US 3733335A
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United States
Prior art keywords
parts
group
indazolone
acetyl
compound
Prior art date
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Expired - Lifetime
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US00104510A
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English (en)
Inventor
B Anderson
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Ilford Imaging UK Ltd
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Ilford Ltd
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32Colour coupling substances
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32Colour coupling substances
    • G03C7/3231Couplers containing an indazolone ring

Definitions

  • Q is either a group -NH--R wherein R is an acyl group containing a nitrogen atom to which there is attached either directly or via a phenyl group an alkyl residue of at least carbon atoms, together with a free carboxylic acid group or a group which can liberate a free carboxylic acid group or Q is a group -N (T) wherein T is an acyl group which is attached to the nitrogen atom by a cyclic imide linkage, the group T containing an alkyl residue of at least 10 carbon atoms, the ring to which Q is attached optionally containing other substituents.
  • This invention relates to new indazolone magenta colour couplers Olf use in colour photographic material.
  • Indazolone magenta colour couplers have been known for a number of years but have not in fact been used to any great extent in colour photographic material because most of the known indazolone colour couplers are converted in part into a yellow product when they come into contact with an oxidising medium such as the bleach bath for the removal of the silver image during the processing of colour photographic material.
  • an oxidising medium such as the bleach bath for the removal of the silver image during the processing of colour photographic material.
  • a yellow product is also formed in the non image areas. It is possible to prevent the occurrence of this yellow reversal image by treating the colour developed layer with a bath containing formaldehyde before the silver is removed by bleaching. This however adds another step to the processing sequence and, further, sometimes causes unwanted side effects.
  • Q is either a group --NH-R wherein R is an acyl group containing a nitrogen atom to which there is attached either directly or via a phenyl group, an alkyl residue of at least 10 carbon atoms, and containing a free carboxylic acid group or a group which can liberate a free carboxylic acid group, or Q is a group -N (T) wherein T is an acyl group which is attached to the nitrogen atom by a cyclic imide linkage, the group T con- 3,733,335 Patented May 15,, 1973 "ice taining an alkyl residue of at least 10 carbon atoms, the ring to which Q is attached optionally containing other substituents.
  • acyl groups containing an alkyl residue of at least 10 carbon atoms and at least one carboxylic acid or a group which can liberate a free carboxylic acid group are those derived from the acylating agents described in British Pats. Nos. 830,482, 858,564, 944,838, 997,500, 1,004,075, 1,039,452 and in British patent application No. 20,003/ 69 and which contain an alkyl group of at least 10 carbon atoms.
  • the compounds of Examples 5, 6 and -8 which follow each contain a five membered cyclic inside ring and the colour couplers of Examples 2, 4, 7 and 9 which follow contain two such rings.
  • These imide rings may be converted to the amic acid having a free carboxylic acid group by treatment with aqueous alkali'in the presence Olf a solvent such as a lower alcohol, for example n-propanol followed by acidification.
  • the colour couplers of this invention are usually incorporated in a colloid silver halide emuslion by means of their alkali solubilising groups, i.e. as the salts of the amic acid.
  • the behaviour of the imide rings may be shown thus:
  • a compound of Formula I may be prepared by the reaction of a compound of the Formula II:
  • the ring-numbering of the indazolone colour couplers of the present invention is as follows:
  • indazolones are readily acylated in the l, 2 or 3 position and because of the different coupling behaviour of these derivatives it is necessary in the preparation of the acylamino indazolones of the present invention to minimise acylation occurring in the heterocyclic ring.
  • the compound of Formula II is treated with an equimolar quantity of acylating agent at a temperature preferably not greater than 65 C.
  • a readily hydrolysable group for example, an acetyl group, may be employed to protect the coupling ring of the indazolone compound before treatment with a long chain acylating agent. Subsequently the protecting group is removed by a short alkaline hydrolysis, e.g.
  • the colour coupler which comprises the l-acetyl group i.e. the compound formed after acylation and before the final alkaline hydrolysis may be isolated and stored as such.
  • the final hydrolysis may be conducted during the preparation of the colour coupler solution for coating because the initial step prior to coating is to dissolve the colour coupler in aqueous alkali.
  • the colour couplers of Formula I are incorporated in a silver halide photographic emulsion by dissolving them in aqueous alkali and most preferably in the presence of a water miscible alcohol as well, and adding this solution to the silver halide photographic emulsion.
  • the invention includes not only the new indazolone colour couplers and the methods for their preparation but also colour photographic material having a silver halide photographic emulsion layer which comprises a compound of Formula I.
  • Method 2 A mixture of 9.0 parts of l-acetyl-6-[3- carboxy 3 (N n-octadecylisobutylramido)-propionamido]-3-indazolone, 22 parts of 2 N potassium hydroxide solution, 50 parts n-propanol and 20 ml. water was heated to the boil, held at the reflux for 1 minute and acidified with acetic acid to obtain a colourless precipitate. The solid was collected by filtration, washed with water and dried at 60 C. The product was boiled with 250 parts of methanol, cooled and filtered.
  • the l-acetyl-6-aminoinrlazolone used here was prepared from 6-nitro indazolone by acetylation to 1:3-diacetyl-6-nitroindazolone, followed by partial hydrolysis to 1-acetyl-6-nitroindazolone and finally reduction by hydrogenation.
  • a photographic layer containing the colour coupler just prepared was obtained in the following manner:
  • EXAMPLE III l-acetyl-S- [3-carboxy-3- (N-n-octadecylisobutyramido) propionarnido]-3-indazoline is a'l til) (CHshCHCON-CHCHzCONH -C ⁇ A mixture of 1.91 parts of 1-acetyl-S-aminoindazolone, and 50 parts of glacial acetic acid was heated to dissolve, cooled to 60 C. and 4.37 parts of N-n-octadecylisobutyrylamino succinic anhydride was added. The whole was stirred at 60 C. for 2 hours.
  • a photographic layer containing the colour coupler derived from the above compound was prepared as follows:
  • N-( 3 dodecyloxyphenyl)pyromellitic mono-imide mono-anhydride used in this example was made by the method described in Example I of British patent specification No. 1,004,075 for N-( l-dodecylphenyl)pyromellitic mono-imide mono-anhydride.
  • a photographic layer containing the colour coupler derived from the above compound was prepared by the method of Example HI using 1.32 parts of compound and 4.0 parts of 2 N potassium hydroxide solution.
  • a photographic layer containing the colour coupler derived from the above compound was prepared by the method of Example III using 1.28 parts of compound and 3.0 parts of 2 N potassium hydroxide solution.
  • a photographic layer containing the colour coupler derived from the above compound was prepared by the method of Example III using 1.24 parts of compound and 3.0 parts of 2 N potassium hydroxide solution.
  • a photographic layer containing the colour coupler derived from the above compound was prepared by the method of Example III using 1.28 parts of compound and 4.0 parts of 2 N potassium hydroxide solution.
  • EXAMPLE VIII l-acetyl-S- [4- 3-dodecyloxyphenylcarbamoyl) phthalimido] -3-indazolone o 0N Q-NHO 0G0 N/ can boon
  • the 3.4 parts of 1 acetyl-S-[4-(3-dodecyloxyphenylcarbamoyl)phthalimido] 3 indazolone were obtained as a solid melting at 272-274 C.
  • a photographic layer containing the colour coupler derived from the above compound was prepared by the method of Example III using 1.28 parts of the compound and 3.0 parts of 2 N potassium hydroxide solution.
  • N-n-octadecyl-isobutrylamino succinic anhydride (4.37 parts) was then added and the mixture stirred at 50-60 C. for 2 hours. The solution obtained was allowed to stand overnight to allow crystallisation to take place. The colourless precipitate was filtered off, washed with ethanol and dried at C. The 7 bromo-S-[3-carboxy-3-(N-n-octadecylisobutyramido) propionamide]-3-indazolone (2.3 parts) was obtained as a solid melting at 182 C.
  • a photographic layer containing 1.33 parts of the above coupler, prepared by the method of Example I gave a bright magenta dye image.
  • a photographic layer containing the above coupler was produced by the method of Example I.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
US00104510A 1970-01-07 1971-01-06 Indazolone magenta couplers Expired - Lifetime US3733335A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB823/70A GB1285432A (en) 1970-01-07 1970-01-07 Indazole colour couplers

Publications (1)

Publication Number Publication Date
US3733335A true US3733335A (en) 1973-05-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
US00104510A Expired - Lifetime US3733335A (en) 1970-01-07 1971-01-06 Indazolone magenta couplers

Country Status (5)

Country Link
US (1) US3733335A (fr)
BE (1) BE761237A (fr)
CH (1) CH557046A (fr)
DE (1) DE2100538A1 (fr)
GB (1) GB1285432A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4040835A (en) * 1974-06-27 1977-08-09 Fuji Photo Film Co., Ltd. Two-equivalent magenta couplers with amido coupling-off groups
US4338393A (en) * 1980-02-26 1982-07-06 Eastman Kodak Company Heterocyclic magenta dye-forming couplers
US4481268A (en) * 1981-02-09 1984-11-06 Eastman Kodak Company Method of forming a photographic dye image

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3720932B2 (ja) * 1996-09-18 2005-11-30 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4040835A (en) * 1974-06-27 1977-08-09 Fuji Photo Film Co., Ltd. Two-equivalent magenta couplers with amido coupling-off groups
US4338393A (en) * 1980-02-26 1982-07-06 Eastman Kodak Company Heterocyclic magenta dye-forming couplers
US4481268A (en) * 1981-02-09 1984-11-06 Eastman Kodak Company Method of forming a photographic dye image

Also Published As

Publication number Publication date
CH557046A (de) 1974-12-13
DE2100538A1 (de) 1971-07-22
GB1285432A (en) 1972-08-16
BE761237A (fr) 1971-06-16

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