US3282933A - Methine dyes - Google Patents

Methine dyes Download PDF

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US3282933A
US3282933A US76525A US7652560A US3282933A US 3282933 A US3282933 A US 3282933A US 76525 A US76525 A US 76525A US 7652560 A US7652560 A US 7652560A US 3282933 A US3282933 A US 3282933A
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methyl
bromide
ethyl
bromo
ether
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Nys Jean Marie
Depoorter Henri
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Gevaert Photo Producten NV
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K9/00—Arc welding or cutting
    • B23K9/14—Arc welding or cutting making use of insulated electrodes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/80—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/03—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • C07C311/49—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/51—Y being a hydrogen or a carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/10—Quaternary compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D235/08—Radicals containing only hydrogen and carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/84—Naphthothiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D293/00—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms
    • C07D293/10—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D293/12—Selenazoles; Hydrogenated selenazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups

Definitions

  • This invention relates to new methine dyes and to their preparation and use as sensitizers for photographic silver halide emulsions, and to methods of sensitizing such emulsions by means of such sensitizing dyes.
  • This staining effect is furthermore particularly objectionable in photographic papers since it is impossible, when suchdye-sensitized emulsions are used, to obtain bright whites in a black-and-white picture or a true reproduction of the colors in a color picture.
  • a light rose or yellow residual stain may further cause trouble when a finished photograph is exposed partly to full daylight, the other part being covered, so that under the influence of light the residual dye-stuff can bleach out, leaving an image which is partly white and partly colored.
  • a further object is to provide methods for preparing these new dyes.
  • Still another object is to provide silver halide emulsions sensitized with these new dyes.
  • a still further object is to provide a practical and useful method for sensitizing silver halide emulsions which has the great advantage that, when such emulsions are coated on a suitable support, the exposed photographic element after development and fixing gives a finished photograph which is essentially free from any residual stain.
  • the methine dyes are adsorbed on the silver halide crystals and on the particles of the colloid binder along the organic residue attached to the auxochrome nitrogen atom, that is the cyanine nitrogen atom which is linked through a conjugated carbon chain to another auxochrome group such as for example a nitrogen atom or a carbonyl, thiocarbonyl or cyano group.
  • sensitizing methine dyes which are adsorbed on the silver halide crystals and on the hydrophilic water-permeable colloid binder along li ateniecl Nov, 1936 an organic residue bearing a hydrophilic group containing a sulphonamide grouping generally do not leave an objectionable residual stain in the photographic layers after development and fixing of the exposed photographic element has been completed, independently of the watersolubility of the new methine dyes involved. It has been found indeed that by introducing in the molecule of the methine dye an organic residue containing a hydrophilic group according to the invention, the residual stain is avoided, although in many cases the water-solubility of the new dyes is not markedly changed and in some cases even diminished.
  • methine dycs containing electronegative groups in general are relatively poor sensitizers for photographic emulsions or even desensitizers for such emulsions and therefore not useful as practical photographic sensitizers.
  • methine dye of such an organic residue bearing a hydrophilic group containing a sulphonamide grouping may in some cases result in a shifting of the sensitization spectrum to the shorter wave-lengths.
  • this hypsochrome shifting may be very desirable to allow an extension of the spectral composition of the light in the darkroom to physiologically clearer, that is shorter wave-lengths without the risk of fogging the emulsion; such an extension is inter alia required when treating photographic elements used for copying and/or photo mechanical processes.
  • this shifting is undesirable, it can be remedied by adaption of the other elements constituting the methine dye, for example by changing a heterocyclic nucleus or by introducing a substituent in a nucleus or in the conjugated chain.
  • A represents e.g. a hydrogen atom, a hydrocarbon radical such as an alkyl group, an amino group, wherein the hydrogen atom may be substituted e.g. by an alkyL or acyl-group, an acyl-group, and an alkyl sulphonyl group
  • B represents e.g. an hydrocarbon radical such as an alkyl group, or an amino group wherein the hydrogen atom may be substituted e.g. by an aikylor acyl group.
  • the organic residue attached to the nitrogen atom may have a structure such as
  • the present invention further includes a process for preparing high-sensitive photographic silver halide emulsions which give, after development and fixing of the exposed photographic element, a finished photograph which is essentially free from any residual stain which comprises treating a photographic silver halide emulsion with a sensitizing methine dye as hereinbefore defined, and a light-sensitive photographic element containing at least one silver halide emulsion layer sensitized according to the foregoing process.
  • the present invention also includes a method of preparing the new methine dyes, which method consists in treating a quaternary salt of a heterocyclic nitrogen base bearing at the nitrogen atom an organic residue of one of the above Formulae I, II or III, by one of the methods known to be capable of converting the quaternary salt of such heterocyclic base into a methine dye.
  • the word known is to be understood as designating methods in actual use or described in literature on the subject.
  • the quaternary salts employed in the present invention can be obtained by treating the corresponding heterocyclic nitrogen base with a compound of one of the general formulae:
  • the heterocyclic nitrogen base and the compound of Formulae I", II" or III" above are merely heated together to form the quaternary halide. Crude quaternary halides prepared in this manner may be converted, if desired, into other quaternary salts before employing them to prepare our new methine dyes.
  • Boiling point 98 C. at 2 mm. Hg.
  • 3-bromo-propane sulphonyl chloride may also be prepared according to R. Adams and Campbell, I. Am. Chem. Soc. 72 (1950), 131, via the 3-b-romo-propylthiocyanate with the disadvantage, however, of considerable decomposition on distillation and with a poor yield.
  • PREPARATION 4.4-BROMOBUTANE- SULPHONYL CHLORIDE This compound is obtained from phosphorus pentachloride (212 g.) and 4-bromo-butane sulphonic acid sodium salt (212 g.) by proceeding as for preparation 1. Boiling point: 128 C. at 2.5 mm. Hg.
  • Methane sulphonamide (4 g.) is dissolved in 20 cm. of Water. After cooling at 5 C. 5 N sodium hydroxide (16.8 cm?) and 3-bromo-propane sulphonyl chloride (9 g.) are added simultaneously and drop by drop whilst stirring taking care to keep the pH at 8. This step lasts about three hours and stirring is continued for a further twenty minutes. Next the solution is acidified with strong hydrochloric acid (4.2 cm?) and evaporated under reduced pressure. The residue is extracted with acetone and after removing the solvent N-methylsulpho-3-bromopropane sulphonamide is left. Melting point: 72 C.
  • PREPARATION 15 .N- (BROMOACETYL) -N',N'- DIMETHYLSULPHAMIDE N,N-dimethylsulphamide (186 g.), bromo-acetyl bromide (309 g.) and dry benzene (2 l.) are gradually brought whilst stirring at reflux temperature and then kept at this temperature until the evolution of I-IBr stops (10 15 hours).
  • the mixture is filtered while hot and the residue extracted with two portions (500 cm?) of benzene.
  • the filtrates are cooled and hexane (3 l.) is added, first slowly until crystallization sets in, then rather quickly.
  • the product is purified by crystallization from benzene. Melting point: 84 C.
  • heterocyclic nitrogen bases known to be convertible in a polymethine dyestulf
  • the heterocyclic nitrogen bases containing in the alpha or gamma-position to the nitrogen atom of the heterocycylic ring an alkyl, thioalkyl, beta-alkylthiovinyl, betahalogenvinyl, beta(N-methylanilino)-viny1 or beta-acylanilidovinyl group, which vinyl groups may carry a substituent.
  • PREPARATION 16.--2,4-DIMETHYL 3 (OMEGA- SULPHONAMIDE-PROPYL) THIAZOLIUM BRO- MIDE 2,4-dimethyl-thiazole (4.8 g.) and 3-bromo-propaue sulphonamide (8.1 g.) are heated together for twelve hours at C. After cooling and washing with ether, the mixture is dissolved in ethanol with a little water and reprecipitated with ether. Melting point: 224 C.
  • PREPARATION 23.2-methyl 3 N-METHYLSUL- PHO CARBAMYL METHYL
  • BENZOSELENA- ZOLIUM BROMIDE N-(-bromo-acetyl)methane sulphonarnide (15 g.) and Z-methylbenzoselenazole (15 g.) are mixed and heated for twelve hours at 100 C. After cooling, the reaction mixture is washed with ether. Melting point: 104 C.
  • PREPAMTION 29.2 METHYL 3-(BETA-METH- YLSULPHONYLAMINO ETHYL) BENZOTHIA- ZOLIUM BROMIDE N-(beta-bromo-ethyl)methane sulphonamide (20 g.) and Z-methylbenzothiazole (15 g.) are heated in a sealed tube for sixteen hours at 120 C. After cooling, the solid mass is washed with ether and acetone. Melting point: 150 C.
  • PREPARATION 30.2,6-DIMETHYL 3 (OMEGA- ACETYLSULPHONAMIDO PROPYL) BENZO- THIAZOLIUM BROMIDE 2,6-dimethylbenzothiazole (10 g.) and N-acetyl-3 bromo-propane sulphonamide (14.5 g.) are heated together at C. overnight. After cooling and washing with ether, the mixture is dissolved in propanol and precipitated with anhydrous ether. Melting point: 218 C.
  • PREPARATION 36.1 BETA-METHYLSULPI-ION- YLAMINO-ETHYL -QUINALDINIUM BROMIDE Quinaldine (4.3 cm?) and N-(beta-bromo-ethyD- methane sulphonamide (6 g.) are heated together at 100 C. for 16 hours, cooled and Washed with ether. Melting point: 226 C.
  • PREPARATION 37.-2 METHYL 3 (N-DIMETH- YLAMINO-SULPHOCARBAMYL METHYL) -BEN- ZOTHIAZOLIUM BROMIDE Z-methylbenzothiazole (10 cm?) and N(bromoacetyl)- N,N'-di-methylsulphamide (13.3 g.) are heated together at 60 C. for 24 hours, cooled, pulverized, washed several times with acetone and twice with a little ethanol.
  • PREPARATION 38.2 METHYL 3 (OMEGA- ACETYLSULPHONAMIDO PROPYL) BENZO- THIAZOLIUM BROMIDE Z-methyl-benzothiazole (3 g.) and N-acetyl-4-bromopropane sulphonamide (4.8 g.) are heated together at 105 f C. for 24 hours, cooled, Washed with acetone and ether. Melting point: 260 C.
  • PREPARATZON 39.2,5 DIMETHYL 3-(N-METH- YLSULPHOCARBAMYL ETHYL) BENZOTHIA- ZOLTUM BROMIDE 2,5-din1ethyl-henzothiazole g.) and N-(beta-bromopropionyl)methane-sulphonamide (11.5 g.) are heated together at 105 C. for 24 hours, cooled, pulverized and washed with ether. Melting point: 204 C.
  • PREPARATION 40.2,5,6-TR1METHYL-3-(OMEGA- ACETYL SULPHONAMIDO BUTYL)-BENZOX- AZOLIUM BROMIDE 2,5,6-trimethyl-benzoxazole (5 g.) and N-acetyl-4- bromobutane-sulphonamide (7.74 g.) are heated together at 120 C. for 36 hours, cooled, washed with acetone and ether. Melting point: 2l3-2l4 C.
  • PREPARATION 4-1 .2 BETA ANILINO-VINYL)- 3 (OMEGA-ACETYL-SULPHONAMlDO-BUTYL)- 5,6-DIMETHYL-BENZOXAZOLIUM BROMIDE 2,5,6 trimethy1-3-(omega-acetylsulphonamido-butyl)- benzoxazolium bromide (4.2 g.) and diphenyl-formamidine (3 g.) are heated at 135 C. for minutes, cooled and washed with acetone. Melting point 187 C.
  • the new methine dyestuffs according to the present invention may be obtained starting from the new heterocyclic quaternary salts by application of the usual condensation methods known to those skilled in the art.
  • the new asymmetric cyanine dyes according to the present invention can he prepared by condensing a cyclammonium quaternary salt of the following formula:
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nitrogen nucleus containing 5 to 6 atoms in the heterocyclic ring, of the type contained in cyanine dyes, such as those selected from the group consisting of those of thi-azole series (cg. thiazole, 4methylthiazole, 4-phenylthiazole, S-methylthiazole, S-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-t'hienyl)-thiazole, etc.), those of the benzothiazole series (e.g.
  • benzothiazole 4-chlorobenzothiazole, S-chlorobenzothiazole, 6-chlorohenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole, 6-methylbenzothiazole, 5,6-dimethylbenzothiazole, S-bromohenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, 6-methoxybenzothiazole, S-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole, 4,5,6,7-tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylene-benzothiazole, S-hydroxybenzothiazole
  • benzoaxozole S-chlorobenzoxazole, S-methylhenzoxazole, 5-phenylbenzoxazole, fi-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, 6- methoxybenzoxazole, S-hydroxybenzoxazole, 6-hydroX- ybenzoxazole, etc.
  • those of the naphthoxazole series e.g. alpha-naphthoxazole, beta-naphthoxazole, etc.
  • selenazole series e.g.
  • 4-rnethylselenazole, 4-phenylselenazole, etc. those of the benzoselenazole series (e.g. benzoselenazole, S-chlorobenzoselenazole, S-methoxybenzoselenazole, S-hydroxybenzoselenazole, 4,5,6,7-tetrahydrobenzoselenazole, etc.), those of the naphthoselenazole series (e.g. alpha-naphthoselenazole, beta-naphthoselenazole, etc.), those of the thiazoline series (e.g.
  • thiazoline 4-methylthiaz0line, 4hydroxy methyl-4-methylthiazoline, 4,4-bis-hydroXymethyl-thiazoline, 4-acetoxymethyl-4-methylthiazoline, 4,4-bis-acetoxymethyl-thiazoline, etc.
  • those of the thiazolidine series e.g, 2-benzthiazolylidene 4 thiazolidon etc.
  • those of the ox azoline series e.g.
  • oxazoline 4-hydroxymethyl-4-methyl-oxazoline, 4,4-bis-hydroxyrnethyl-oxazoline, 4-acetoXymethy1-4-methyl-oxazoline, 4,4-bis-acetoXy-methyl-oxazoline, etc.
  • those of the oxazolidine series those of the selenazoline series (e.g. selenazoline), those of the 2-quinoline series (e.g.
  • quinoline 3- methylquinoline, S-methylquinoline, 7-rnethylquinoline, S-methylquinoline, 6chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroX- yquinoline, S-hydroxyquinoline, etc.), those of the 4- quinoline series (e.g. quinoline, 6-methoxyquinoline, 7- methylquinoline, S-methylquinoline, etc.), those of the l-isoquinoline series (e.g. isoquinoline, 3,4-dihydroisoquinoline, etc.) those of the 3-isoquin-oline series (eg.
  • those of the 3,3-dialkylindolenine series etg. 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.
  • those of the pyridine series eg. pyridine S-methylpyridine, etc.
  • those of the benzimidazole series e.g.
  • X represents an acid radical of the type used in the cyanine dyes such as chloride, bromide, iodide, perchlorate, benzenesulphonate, p-tolusulphonate, methylsulphate, ethylsulphate, etc.;
  • n 1 or 2;
  • R represents an organic residue containing a sulponamide grouping and corresponding to one of the Formulae I, II and III above, more particularly an organic radical of one of the formulae A represents a hydrogen atom, a lower alkyl radical such as methyl and ethyl, an amino group, a diacyl amino group such as a diacetylamino group, an acyl group such as an ecetyl group, or an alkylsulponyl group such as a methylsulphonyl group, and p represents a positive integer from 4 to 5,
  • B represents a lower alkyl group such as methyl and ethyl, or a dialkylamino group, such as a dimethyl or diethylamino group, a diacyl-amino group such as a diacetylamino group, and
  • q represents a positive integer from 2 to 3, with a cycl-ammonium quaternary salt represented by the following formula:
  • Z" represents the non-metallic atoms to complete a heterocyclic nucleus containing 5 to 6 atoms in the heteroeyclic ring of the type contained in cyanine dyes such as those described for Z;
  • n" reprwents 1 or 2;
  • X" represents an acid residue
  • R" represents a radical of the type contained in cyanine dyes as substituent on the cyanine nitrogen atom, e.g. an alkyl or substituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, allyl (vinyl methyl), beta-hydroxyethyl, benzyl (phenyl methyl), carboxybenzyl, a radical containing a sulphonamide grouping such as a radical of the same type as the radical R defined hereinbefore, a radical containing a sulpho-alkyl carbonylic ester group, etc. (e.g., an alkyl or substituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, allyl (vinyl methyl), beta-hydroxyethyl, benzyl (phenyl methyl), carboxybenzyl, a radical containing
  • D represents an alkyhnercapto, an arylmercapto, a betaarylaminovinyl, a delta-arylamino-l,3-but-adienyl, a beta-alkylmercaptovinyl, a beta-arylmercaptovinyl or a beta-acetanilidovinyl group, which vinyl groups may carry a substituent.
  • the condensations are advantageously carried out in the presence of a basic condensing agent, for example a trialkylamine such as triethylamine, a dialkylaniline, a heterocyclic tertiary amine such as pyridine, N-alkyl-pipen'dine or the like.
  • the new symmetrical cyanine dyes according to the present invention can be prepared by condensing a cyclammonium quaternary salt represented by the general Formula IV above with an ortho car boxylic acid alkyl ester, such as ethyl ortho-formate and ethyl ortho-acetate, advantageously in the presence of a carboxylic acid anhydride, for example acetic anhydride.
  • an ortho car boxylic acid alkyl ester such as ethyl ortho-formate and ethyl ortho-acetate
  • t represents an integer from 1 to 3
  • Ar represents an aryl group and L and L each represents a methine group.
  • the arylaminovinyl intermediates, or vinylene homologues thereof thus obtained can be transformed into the corresponding acetarylido derivatives by boiling with acetic anhydride, which can be condensed to unsymmetrical cyanine dyes with cyclammoniurn quaternary salts containing a methyl group in alpha or gamma positions to the nitrogen atom.
  • the condensations are advantageously carried out in the presence of a basic condensing agent as set forth above.
  • the most valuable methine dyes of the present invention are those represented by one of the following general formulae:
  • R represents a hydrogen atom or a lower alkyl radical such as methy, ethyl and propyl,
  • d represents a positive integer from 1 to 3
  • R' represents a sulphonamide group selected from the group consisting of (CH2-) p1-SO2'I T)C O-alk wherein 1 represents a positive integer from 4 to 5.
  • q represents a positive integer from 2 to 3
  • alk represents a lower alkyl radical such as methyl and ethyl, and more particularly those of one of the above general formulae wherein R represents a radical selected from the group consisting of (CH fiSONI-I wherein p, q and alk have the same specifications set forth hereinbefore
  • R" represents a lower alkyl radical such as methyl, ethyl, propyl, an alkyl radical or a benzyl radical, and a radical of the same type as the radical R, and Z and Z" are the atoms necessary to complete a heterocyclic and nucleus selected from the group consisting of a thiazoline nucleus, 21 selenazolium nucleus,
  • Example 1 The dyestufl [2-(3ethyl-benzoxazole)1- ⁇ 2-[3-(omegasulphona-mido-propyl) 4 methyl thiazole] ⁇ trimethinecyanine iodide is prepared as follows:
  • a silver bromo-iodide emulsion containing per kg. 30 mg. of this dyestufi is strongly sensitized to 600 m with broad maximum at 550 ma.
  • a silver chloride emulsion containing per kg. 20 mg. of this dyestufi' is sensitized to 500 m with a sharp maximum at 480 my.
  • Example 3 The dyes-tuft ⁇ 2-[3-(omega-acetylsulphonamido propyl) --phenylbenzoxazo1e] [2-(3-ethyl benzothiazole) trimethinecyanine iodide is prepared as follows:
  • a silver chloro-bromide emulsion containing per kg. 30 mg. of this dyestulf is strongly sensitized to 615 m with a broad maximum at 560 mu.
  • Example 4 The dyestutl ⁇ 2-[3-(omega-ethylsulphonamidobutyl)- benzoselenazole] ⁇ [2 (3-ethyl-benzoselenazole)1-mesomethyl trimethinecyanine iodide is prepared as follows:
  • a silver bromo-iodide emulsion containing per kg. mg. of this dyestuff is sensitized to 660 m with a broad maximum at 605-610 m
  • Example 5 The dyestui'f bis ⁇ 2-[3-(omega-acetylsulponamidobutyl)benzothiazole] ⁇ -trimethinecyanine bromide is prepared as follows:
  • a silver bromo-iodide emuslion containing per kg. 10 mg. of this dyestutf is sensitized to 665 ma with a broad maximum at 595 m
  • the dyestutt (2- ⁇ 3-[omega-(N-methylsul pho-sulphonamido) pro pyl] -benzothiazole ⁇ -[2-(3-ethyl-thiazoline) triethine cyanine bromide is prepared as follows:
  • a silver bromide emulsion containing per kg. 15 mg. of this dyestufr" is sensitized to 590 m with a maximum at 540 ma.
  • Example 7 The dyestufif [2-(3-methyl-naphtho-l,2,4,5-thiazole)]- ⁇ 2 [3 (N-methylsulpho-carbamyl-methyl)-benzothiazole] ⁇ monomethine cyanine bromide is prepared as follows:
  • a silver bromo-iodide emulsion containing per kg. 10 mg. of this dyestutt" is sensitized to 660 m with a broad maximum at 600 ma.
  • Example 10 The dyestuff bis (2- ⁇ 3-[beta-(N-methyl-sulpho carbamyl -e thyl] -benzo selenazole ⁇ -trimethine cyanine bromide is prepared as follows:
  • Example 13 The dyestutf ⁇ 2-[3-(N-methylsulpho-carbaimyl methyl)- phenylbenzoxazole] ⁇ [2 (3 ethylbenzothiazole)]- trirnetlhine cyanine iodide is prepared as follows:
  • a silver bromide emulsion containing per kg. 30 mg. of this dyestuff is strongly sensitized to 620 m with a broad maximum at 5 60 m
  • Example 14 The dyestufi bis ⁇ 2 [3 (beta methylsulphonylamino ethyl) benzothiazole1 ⁇ trimethine cyanine bromide is prepared as follows:
  • Example 15 The dyestufi ⁇ 2 [3 (beta methylsulphonylaminoethyl) benzothiazolej ⁇ [2 (3 ethyl thiazoli-ne)]- trimeth-ine cyanine bromide is prepared as follows:
  • Triethylamine (2.1 cm?) is added to a cooled solution of 2 methyl 3 (beta methylsulphonylamino ethyl)- benzothiazolium bromide (5.3 g.) and 2-beta-acetanilid-oviny-1)-3-ethyl thiazolinium bromide (5.3 g.).
  • the precipitated dyestult is washed with ethanol and ether and crystallized from ethanol.
  • a silver chloro-bromide emulsion containing per kg. 15 mg. of this dyestuff is sensitized to 580' m with a maximum at 540 mp.
  • Example 16 The dyestufi [2 (3 henzyl benzoxazole)] ⁇ 2 [3- (N methylsulp'ho carbamyl methyl) 4 methylth-iazol-e1 ⁇ trimethine cyanine iodide is prepared as follows:
  • a silver bromide emulsion containing per kg. 8 mg. of this dyestufi is sensitized to 585 m with a maximum at 545 mp.
  • Example 18 The dyestufi [2 (3 ethylbenzoxazole)] ⁇ 2 [1- ethyl 3 (omega acetyl sulphonamido butyl) 5,6- dichlor-o-benzimidazole1 ⁇ -trimethine cyanine iodide is prepared as follows:
  • a silver bromo-iodide emulsion containing per kg. 20 mg. of this dyestufi" is sensitized to about 675 m with a maximum at 610 m
  • the dyestuif ⁇ 2 [3 (omega acetyl-sulphoamido-propyl) 6 methylbenzothiazole] ⁇ [2 (3 ethyl selenazoline)]-trimethine cyanine iodide is prepared as follows:
  • 2,6 dimethyl 3 (omega acetyl sulphonamidopropyl)-benzothiazolium bromide (4.1 g.) and Z-(betaacetanilido-vinyl)-selenazolium ethyl iodide (4.5 g.) are treated at C. in methanol (30 cm?) with triethylamine (2.8 cm.-'*). After standing for one hour at this temperature the dyestufi is precipitated with ether, sucked off and recrystallized from ethanol and water. Absorption maximum: 510 mp.
  • a silver chloride emulsion containing per kg. 20 mg. of this dyestull' is sensitized to 570 m with a maximum at 545 mp.
  • Example 21 The dyestufi bis ⁇ 2 [3 (omega acetyl-sulphoamidopropyl) 5 phenyl benzoxazole] ⁇ meso propyl trimethine cyanine iodide is prepared as follows:
  • Example 22 The dyestufi ⁇ 2 [3 (omega diacetyl sulpho hydrazido butyl) benzothiazole] ⁇ [2 (3 ethyl thiazoline)-trimethine cyanine bromide is prepared as follows:
  • Example 23 The dyestufi ⁇ 2 [3 (omega acetyl sulphonamidobutyl) 5,6 dimethyl benzoxazole1 ⁇ ⁇ 2 [3 (N- methylsulpho carbamyl methyl) 5,6 dimethyl benzoxazole] ⁇ -trimethine cyanine bromide is prepared as follows:
  • a silver bromide emulsion containing per kg. 30 mg. of this dyestuff is sensitized to 555 m with a maximum at 520 mp.
  • Example 24 The dyestuff anhydro ⁇ 2 [3 (omega acetyl sulphonamido butyl) 5,6 dimethyl benzoxazolefi ⁇ 2- [3 (sulpho carbomethoxymethyl) benzothiazole] ⁇ -trimcthine cyanine hydroxide is prepared as follows:
  • Example 25 The dyestufi bis ⁇ 2 [3 (omega acetyl sulphonamido butyl) benzothiazole] ⁇ pentamethine cyanine bro mide is prepared as follows:
  • a silver bromo-iodide emulsion containing per kg. 30 mg. of this dyestuff is sensitized to 600 m with a maximum at 560 mp.
  • Example 28 The dyestuif bis ⁇ 2 [3 (dimethyl amino sulphonylcarbamyl-methyl)-benzothiazole] ⁇ mesomethyl trimethine cyanine iodide is prepared as follows:
  • a silver bromo-iodide emulsion containing per kg. 15 mg. of this dyestufl' is sensitized to 650 m with a maximum at 595 mp.
  • Example 29 The dyestufl ⁇ 2-[3-ethyl-4-(3-ethyl-dihydro-benzothiazolylidene-ethylidene)-5-thiazolione]) (2-[3-(be-ta-mcthyl sulphonylamino ethyl) benzothi-azolel ⁇ monomethine cyanine bromide is prepared as follows:
  • the new polymethine dyes spectrally sensitize photographic silver halide emulsions when incorporated therein.
  • the new polymcthine dies are useful especially for extending the spectral sensitivity of the customarily employed gelatino silver chloride, gelatino silver chloro-bromide, gelatino silver bromide, gelatino silver bromoiodide and gelatino silver chloro-bromo-iodide emulsions
  • photographic emulsions containing water-permeable colloids other than gelatin such as agar-agar, zeine, collodion, water-soluble cellulose derivatives, polyvinyl alcohol or other hydrophilic synthetic or natural resins or polymeric compounds, may equally well be sensitized according to the present invention.
  • the dye, or dyes can be incorporated in the photographic emulsion by one of the methods customarily employed in the art.
  • the dyes are advantageously incorporated in the finished, washed emulsions and should be uniformly distributed throughout the emulsion.
  • the concentraiion of the dyes in the emulsion can vary widely, for example from 1 to 100 mg. per kg. of fiowable emulsion and will vary according to the effect desired.
  • the suitable and most economical concentration for any given emulsion will be apparent to those skilled in the art, upon making the ordinary tests and observations customarily used in the art of emulsion making.
  • the new polymethine dyes can be incorporated in photographic emulsions the general sensitivity of which has been increased by physical and chemical ripening.
  • suitable chemical sensitiners may be mentioned the well known sulphur sensitizers such as allylisothiocyanate, allylthiourea, sodium t-hiosulphate, potassium selenocyanide and the natural sensitizers originating in the gelatin, reducing sensitizers such as the imino-aminomethane sulphinic acid and the derivatives thereof, and the salts of noble metals such as gold, platinum and palladium.
  • sulphur sensitizers such as allylisothiocyanate, allylthiourea, sodium t-hiosulphate, potassium selenocyanide and the natural sensitizers originating in the gelatin
  • reducing sensitizers such as the imino-aminomethane sulphinic acid and the derivatives thereof
  • photographic emulsions optically sensitized according to the invention may further be supersensitized and/or hypersensitized by one of the methods known to those skilled in the art.
  • the usual addenda such as antifogging agents, stabilizers, anti-bronzing agents, hardeners, wetting agents, plasticizers, development aocelerators, color couplers, fluorescent brighteners and ultra-violet screening compounds can moreover be incorporated in the emulsion in the manner customarily employed in the art.
  • the sensitivity of the silver halide emulsions sensitized according to the process of the present invention is not adversely affected but rather enhanced by the presence therein of certain fluorescent compounds.
  • Another advantage of the process for sensitizing silver halide emulsions according to the present invention is the compatibility of the new polymethine dyes with anionic wetting agents and with color couplers which is of great importance in the application of the new polymethine dyes for sensitizing the silver halide emulsions of a light-sensitive element for color photography.
  • Emulsions sensitized with the new polymethine dyes can be coated in the usual manner on a suitable support such as glass, cellulose derivative film, resin film or paper.

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Cited By (12)

* Cited by examiner, † Cited by third party
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US4578348A (en) * 1985-03-18 1986-03-25 Eastman Kodak Company Hydrolyzed azolium speed enhancing/fog-inhibiting agents for silver halide photography
US5159112A (en) * 1987-01-23 1992-10-27 Societe Nationale Elf Aquitaine (Production) Process of the production of alkanesulfonamides
US5290676A (en) * 1991-09-24 1994-03-01 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US5308748A (en) * 1992-03-23 1994-05-03 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US5310645A (en) * 1991-10-07 1994-05-10 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5364755A (en) * 1992-04-17 1994-11-15 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US5422238A (en) * 1991-08-02 1995-06-06 Fuji Photo Film Co., Ltd. Silver halide photographic material
BE1007901A3 (nl) * 1993-12-22 1995-11-14 Agfa Gevaert Nv Werkwijze voor het processen van een zwart-wit zilverhalogenide fotografisch materiaal met spectraalgesensibiliseerde emulsies.
US5604089A (en) * 1992-07-21 1997-02-18 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0794456A1 (en) 1996-03-07 1997-09-10 Agfa-Gevaert N.V. Method of reproducing an electronically stored medical image on a light-sensitive photographic material
US20040235852A1 (en) * 2003-05-20 2004-11-25 Olivero Alan G. Benzofuran inhibitors of factor VIIa
US20040242585A1 (en) * 2003-05-20 2004-12-02 Rawson Thomas E. Acylsulfamide inhibitors of factor VIIa

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JP2777949B2 (ja) * 1992-04-03 1998-07-23 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
JPH05289270A (ja) * 1992-04-15 1993-11-05 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US5464735A (en) * 1993-12-07 1995-11-07 Eastman Kodak Company Supersensitizing bis-benzothiazolocyanine dye combination for red sensitive silver halide emulsions
US5491055A (en) * 1994-12-23 1996-02-13 Eastman Kodak Company Silver halide photographic emulsions prepared and sensitized in the presence of sulfodihydroxy aryl compounds
DE19937024A1 (de) * 1999-08-05 2001-02-08 Bayer Ag Verwendung von Acylsulfonamido substituierten Polymethin-Farbstoffen als Fluoreszenz-Farbstoffe und/oder Marker

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US4578348A (en) * 1985-03-18 1986-03-25 Eastman Kodak Company Hydrolyzed azolium speed enhancing/fog-inhibiting agents for silver halide photography
US5159112A (en) * 1987-01-23 1992-10-27 Societe Nationale Elf Aquitaine (Production) Process of the production of alkanesulfonamides
US5422238A (en) * 1991-08-02 1995-06-06 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5290676A (en) * 1991-09-24 1994-03-01 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US5310645A (en) * 1991-10-07 1994-05-10 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5437972A (en) * 1991-10-07 1995-08-01 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5308748A (en) * 1992-03-23 1994-05-03 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US5364755A (en) * 1992-04-17 1994-11-15 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US5604089A (en) * 1992-07-21 1997-02-18 Fuji Photo Film Co., Ltd. Silver halide photographic material
BE1007901A3 (nl) * 1993-12-22 1995-11-14 Agfa Gevaert Nv Werkwijze voor het processen van een zwart-wit zilverhalogenide fotografisch materiaal met spectraalgesensibiliseerde emulsies.
EP0794456A1 (en) 1996-03-07 1997-09-10 Agfa-Gevaert N.V. Method of reproducing an electronically stored medical image on a light-sensitive photographic material
US20040235852A1 (en) * 2003-05-20 2004-11-25 Olivero Alan G. Benzofuran inhibitors of factor VIIa
US20040242585A1 (en) * 2003-05-20 2004-12-02 Rawson Thomas E. Acylsulfamide inhibitors of factor VIIa
US20070037814A1 (en) * 2003-05-20 2007-02-15 Genentech, Inc. ACYLSULFAMIDE INHIBITORS OF FACTOR VIIa
US20070049601A1 (en) * 2003-05-20 2007-03-01 Genentech, Inc. BENZOFURAN INHIBITORS OF FACTOR VIIa
US7250447B2 (en) 2003-05-20 2007-07-31 Genentech, Inc. Acylsulfamide inhibitors of factor VIIa
US7273886B2 (en) 2003-05-20 2007-09-25 Genentech, Inc. Benzofuran inhibitors of factor VIIa

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