US2689849A - Cyanine dyes containing the triazolo[4, 3-alpha] quinoline or tetrazolo[alpha] quinoline nucleus - Google Patents

Cyanine dyes containing the triazolo[4, 3-alpha] quinoline or tetrazolo[alpha] quinoline nucleus Download PDF

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US2689849A
US2689849A US308908A US30890852A US2689849A US 2689849 A US2689849 A US 2689849A US 308908 A US308908 A US 308908A US 30890852 A US30890852 A US 30890852A US 2689849 A US2689849 A US 2689849A
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those
series
dyes
quinoline
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Leslie G S Brooker
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Eastman Kodak Co
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Eastman Kodak Co
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    • 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
    • C09B23/14—Styryl dyes
    • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
    • 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

Definitions

  • dyes of the cyanine dye series are known to extend the sensitivity of photographic silver halide emulsions.
  • Dyes which have been found useful for this urpose include those which contain a quinoline nucleus. Such dyes have been long known, although they have not been particularly eflicacious for such purposes as sensitizers for photographic emulsions. While dyes of the above mentioned type are classed as weak sensitizers, I have now found a new class of dyes,
  • a further object is to provide photographic silver halide emulsions sensitized with such dyes.
  • a still further object is to provide a process for preparing photographic silver halide emulsions containing these new dyes.
  • Thenew dyes of the cyanine series of my invention can be represented by the following general formula:
  • R and. R1 each represents an alkyl group, such as methyl, ethyl, n-propyl, isopropy1,n-butyl, benzyl (phenylmethyl) etc.
  • D represents the non-metallic atoms necessary to complete a carbocyclic nucleus of the benzene series
  • X represents an acid radical, such as chloride, bromide, iodide, perchlorate, thiocyanate, benzenesulfonate, p-toluenesulfonate, ethylsulfate, methylsulfate, etc.
  • Q represents a nitrogen atom or a methine group
  • d and n each represents a positive integer of from 1 to 2
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from five to six atoms in the heterocyclic ring, such as those selected from the group consisting of those of the thiazole
  • benzoxazole 5-chlorobenzoxazole, 5-methylbenzoxazole, 5- phenylbenzoxazole, G-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5- methoxybenzoxazole, 5-ethoxybenzoxazole, 5- chlorobenzoxazole, G-methoxybenzoxazole, 5-hydroxybenzoxazole, G-hydroxybenzoxazole, etc.), those of the naphthoxazole series (e. g. a-naphthoxazole, B-naphthoxazole, etc.), those of the selenazole series (e. g.
  • quinoline 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, G-chloroquinoline, 8-ch1oroquinoline, 6- methoxyquinoline, d-ethoxyquinoline, B-hydroxyquinoline, 8-hydroxyquinoline, etc.
  • 4-quinoline series e. g. quinoline, G-methoxyquinoline, 7-methylquinoline, 8-methy1quinoline, etc.
  • those of the l-isoquinoline series e. g. isoquinoline, 3,4-dihydroisoquinoline, etc.
  • 3-isoquinoline series e. g.
  • those of the 3,3-dialkylindolenine series e. g. 3,3-dimethy1indolenine, 3,3,5-trimethylindolenine, 3,3,T-trimethylindolenine, etc.
  • the pyridine 4-(Z-thienyDthiazole, etc.) those of the benzoseries (e. g. pyridine, 5-methylpyridine, etc.), etc.
  • the cyanine dyes represented by Formula I above (d is 1) can advantageously be prepared by condensing a cyclammonium quaternary salt selected from those represented by the following wherein R, D, Q and X eachhave the values set forth above, together with a cyclammonium quaternary salt selected from those represented by the following general formula:
  • the organic tertiary amines such as triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, etc., N-methylpiperidine, N-ethylpiperidine, N,N-dimethylaniline, N',N-diethylaniline, etc.
  • the condensations can advantageously be effected in the presence of an inert solvent, e, g. ethanol, isopropanol, 1,4-dioxane, etc. Heating accelerates the condensations and temperatures varying from room temperature (about 20 C.) to the temperature of the steam bath can be used.
  • cyclammonium quaternary salts selected from those represented by Formula II above can advantageously be prepared by heating the corresponding free base together with an alkyl salt, e.,g.
  • R and .X each have the values given above.
  • the free bases can be prepared in accordance with the method described by Marckwald et al. in Berichte (1900), volume 33, pages 18854899. Quaternization can be effected by simply heating the free base together with the alkyl salt on an oil bath or a steam bath until the mass sets to a solid (generally -20 hours).
  • the cyclamrnonium quaternary salts can have substituents on the oarbocyclic ring, such as halogen (e. g. chlorine, bromine, etc.), hydroxyl, alkoxyl, etc.
  • the carbocyanine dyes represented by Formula I above can advantageously be prepared by condensing a cyclammonium quaternary salt selected from those represented by the following general formula:
  • R1,,X1, n, and Z each have the values given above
  • R3 represents an acyl group (e. g. acetyl, propionyl, benzoyl, etc.)
  • R4 represents an aromatic group (e. g. phenyl, tolyl, naphthyl, etc), together with a cyclammom'um quaternary salt selected from those represented by Formula II above.
  • the condensations can advantageously be effected'in the presence of a basic condensing agent, such as those set forth above for the condensation of the compounds of Formula II with those of Formula III.
  • condensations can advantageously be effected in the presence of an inert solvent, such as those set forth above for the condensation of the compounds of Formula II with those of Formula III. Heating accelerates the condensations and temperatures varying from room temperature (about 20 C.) to the temperature of the steam bath can be used.
  • room temperature about 20 C.
  • Example 4.-3,3-diethyZ-5-tetraaolo [a] quz'nothiacyam'ne iodide 0.92 gram (1 mol.) of 5-methyltetrazolaEalquinoline and 1.50 grams (1 mol+50% excess) of ethyl p-toluenesulfonate were heated together on an oil bath at 140 C. for 15 hours. After coolin the fused mass to room temperature, 2.00 grams (1 mol.) of 2phenylmercaptobenzothiazole ethiodide, 1.11 grams (2 mols.+5% excess) of triethylamine and 15 cc.
  • Example 5.1 ',3-dz'ethyZ-5-tetrazolo[a] quz'no-T-cyam'ne iodide 0.92 gram (1 mol.) of 5-methyltetrazoloEalquinoline and 1.50 grams (1 mol.+50% excess) of ethyl ptoluenesulfonate were heated together on an oil bath at 140 C. for 15 hours. After cooling the fused mass to room temperature, 1.97 grams (1 mol.) of 2-phenylmercaptoquinoline ethiodide, 1.11 grams (2 mols.+5% excess) of triethylamine and 15 cc.
  • Example 7.3'-ethyZ-3-methyZ-5-tetrazololal qumothiacyanine p-toluenesulfonate 0.92 gram (1 mol.) of 5-methyltetrazolofalquinoline and 1 gram (1 mol.
  • the intermediates represented by Formula 11 above can be condensed with a p-aminoaromatic aldehyde to produce dyes of the styryl class.
  • Useful aldehydes include, for example, p-dimethylaminobenzaldehyde, p diethylaminobenzaldehyde, etc.
  • the condensations are advantageously eifected in the presence of a basic condensing agent, e. g. piperidine, etc.
  • the condensations can be carried out in the presence of an inert solvent, e. g., ethanol, propanol, isopropanol, n-butanol, etc.
  • Heating accelerates the condensations and temperatures varying from room temperature (about 20 C.) to the temperature of the steam bath can be used.
  • the styryl dyes thus obtained have been found to be particularly useful in the preparation of filter layers, overcoating layers, and the like in photographic elements.
  • the reaction mixture was cooled and extracted twice with ether. The residue was dissolved in ethyl alcohol and treated with an aqueous solution of sodium iodide. After cooling, the crystals were filtered off and-washed with ethyl alcohol. After two recrystallizations from methyl alcohol (100 cc./ gram) the yieldwas 17% of the theoretical. The reddish-brown crystals melted at 278-280 C. dec.
  • Example 9.5-p-dimethylaminostyryl 3 ethyltetrazolo [al quinolim'um iodide was 50% of the theoretical.
  • the maroon needles melted at 259-261 C. dec.
  • my new cyanine dyes (Formula I) spectrally sensitize photographic silver halide emulsions'when-incorporated therein.
  • the dyes are especially'useful for extending the spectral sensitivity-of the customarily employed gelatino-si1verchloride, gelatino-silver-chlorobromide, gelatino silver bromide and gelatinosilver-bromiodide developingout emulsions.
  • To prepare emulsions sensitized with one or more of my new dyes it is only necessary to disperse the dye or dyes-in the emulsions.
  • the methods of incorporating dyes in emulsions are simple and are known to those skilled in the art.
  • the concentration of the dyes in the emulsions can vary widely, e. g. from 5 to mg. per liter of fiowable emulsion.
  • concentration of the dyes will vary according to the type of emulsion and according to the effect desired.
  • suitable andmost 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.
  • A-quantity of dye is dissolved in methyl alcohol or acetone (or a mixture of acetone and pyridine) and a volume of this solution, which may be diluted with water, containing from 5 to 100 mg. of dye, is slowly added to about 1000 cc. of gelatinosilver-halide emulsion, with stirring. Stirring is continued until the dye is thoroughly dispersed in the emulsion.
  • the dyes can be incorporated in photographic emulsions by any of the other methods customarily employed in the art, e. g. by bathing a, plate or film upon which an emulsion is coated in a solution of the dye in an appropriate solvent. However, bathing methods are ordinarily not to be preferred.
  • Emulsions sensitized with the dyes canbe coated on suitable supports, such as glass, cellulose iderivativefilm, resin film or paper in the usual manner.
  • styryl dyes obtained according to my invention from 50 mg. to mg. ofstyryl dye is'dissolved in from 2 to 5 cc. of water-miscible solvent. Methanol or acetone is suitable for this purpose, but pyridine or fi-ethoxyethanol can also be used.
  • the solution is then added to about 25 cc. of a 5% gelatin solution at about40 C.:and .the mixture coated on the support.
  • R5 represents an alkyl group, e. g. methyl, ethyl, etc.
  • Rs-X2 an alkyl salt
  • V (a) ?Ha wherein R has the values given above, ,Rc represents an alkyl group, e. g. methyl, ethyl, etc., and X2 represents anacid radical, e. g. chloride, bro- .mide, iodide p-toluenesulf.onate, etc.
  • R1, Ra, Ra, X2, n, and Z each have the values given above.
  • the condensations can advantageously be effected in the presence of a basic condensing agent, e. g. triethylamine, tri-n-butylamine, etc.
  • R1, R6, n and Z each have the values given above.
  • the dyes represented by Formula VII above give colors in solution that are considerably deepened on adding a solution of silver nitrate, indicating the formation of the isomer represented as Formula VII (b) above. dyes are, accordingly, excellent indicators for the presence of the silver ion. Some of the new dyes represented by Formula VII are also useful in extending the sensitivity of photographic silver halide emulsions.
  • Example 1 0.-1 ',3-dzethyl-2' -ethylmercapto-oma- 4-carbocyanine perchlorate (2 mols, excess) of triethylamine and 70
  • These dyes likewise, have Inert sol-y vents can also be employed in the condensations,
  • Example 11.1,3-diethyl-Z'-ethylmereaptothia- 4-carbocyanine perchlorate 12.0 grams (1 mol.) of 2-ethylmercaptolepidine ethoethylsulfate, 16.6 grams (1 mol.) of 2-18- acetanilidovinylbenzothiazole ethiodide, 8.2 grams (2 moles. +10% excess) oi. triethylamine and '75 cc. of ethyl alcohol were mixed and refluxed 20 minutes and the dye precipitated with an excess of aqueous potassium perchlorate.
  • Example 13.1 ethyl 4 (3 ethyl 2(3H) benzothz'aeolylidene) propenylthiocarbostyril 2.60 grams (1 mol.) of 1-3-diethyl--2'-ethylmercaptothia-4-carbocyanine perchlorate, 0.98
  • R and R1 each represents an alkyl group containing from 1 to 4 carbon atoms, d and n each represents a positive integer of from 1 to 2,
  • X represents an acid radical
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the naphthothiazole series, those of the thianaphtheno-7',6,4,5-thiazole series, those of the oxazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the selenazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the thiazoline series, those of the 2-quino1ine series, those of the l-quinoline series, those
  • a cyanine dye selected from those represented by the following general formula:
  • R and R1 each represents an alkyl group containing from 1 to 4 carbon atoms, at and n each represents a positive integer of from 1 to 2, X represents an acid radical, and Z represents the nonmetallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring.
  • R1 represents an alkyl group containing from 1 to 4 carbon atoms
  • R2 represents a member selected from the group consisting of an alkyl group containing from 1 to 2 carbon atoms
  • R3 represents an acyl group of a carboxylic acid
  • R4 represents a mononuclear aromatic group
  • n represents a positive integer of from 1 to 2
  • X1 represents an acid radical
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus seiected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the naphthothiazole series, those of the oxazole series, those of benzoxazole series, those of the naphthoxazole series, those of the selenazole series, those of the benzoselenazole series,
  • a process according to claim 9 wherein the basic condensing agent is triethylamine.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
US308908A 1952-09-10 1952-09-10 Cyanine dyes containing the triazolo[4, 3-alpha] quinoline or tetrazolo[alpha] quinoline nucleus Expired - Lifetime US2689849A (en)

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GB24924/53A GB736266A (en) 1952-09-10 1953-09-09 Improvements in and relating to cyanine dyes

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2770620A (en) * 1954-01-21 1956-11-13 Hoechst Ag Sensitizing dyestuffs
US2786054A (en) * 1954-08-19 1957-03-19 Eastman Kodak Co Cyanines from triazolo bases
US2870014A (en) * 1957-01-09 1959-01-20 Eastman Kodak Co Cyanines from triazolo bases
US3337540A (en) * 1962-04-13 1967-08-22 Gevaert Photo Prod Nv Methine dyes
US3449335A (en) * 1966-01-03 1969-06-10 Gaf Corp Merocyanine dyes containing the carbostyril nucleus
US3909275A (en) * 1970-01-15 1975-09-30 Minnesota Mining & Mfg Cyanine dye salts, merocyanine dyes, and their use in silver halide photographic emulsions
US4003750A (en) * 1973-05-03 1977-01-18 Eastman Kodak Company Silver halide emulsion containing photographic sensitizing dyes
JP2007291403A (ja) * 1994-10-27 2007-11-08 Molecular Probes Inc 選択された透過性を有する置換非対称シアニン色素

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2443136A (en) * 1946-04-11 1948-06-08 Gen Aniline & Film Corp Photographic elements containing 1, 3, 4-triazaindolizine cyanine dyes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2443136A (en) * 1946-04-11 1948-06-08 Gen Aniline & Film Corp Photographic elements containing 1, 3, 4-triazaindolizine cyanine dyes

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2770620A (en) * 1954-01-21 1956-11-13 Hoechst Ag Sensitizing dyestuffs
US2786054A (en) * 1954-08-19 1957-03-19 Eastman Kodak Co Cyanines from triazolo bases
US2870014A (en) * 1957-01-09 1959-01-20 Eastman Kodak Co Cyanines from triazolo bases
US3337540A (en) * 1962-04-13 1967-08-22 Gevaert Photo Prod Nv Methine dyes
US3449335A (en) * 1966-01-03 1969-06-10 Gaf Corp Merocyanine dyes containing the carbostyril nucleus
US3909275A (en) * 1970-01-15 1975-09-30 Minnesota Mining & Mfg Cyanine dye salts, merocyanine dyes, and their use in silver halide photographic emulsions
US4003750A (en) * 1973-05-03 1977-01-18 Eastman Kodak Company Silver halide emulsion containing photographic sensitizing dyes
JP2007291403A (ja) * 1994-10-27 2007-11-08 Molecular Probes Inc 選択された透過性を有する置換非対称シアニン色素
JP2009280820A (ja) * 1994-10-27 2009-12-03 Molecular Probes Inc 選択された透過性を有する置換非対称シアニン色素

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