US1969445A - Photographic emulsion containing neothiazolocarbocyanines - Google Patents

Photographic emulsion containing neothiazolocarbocyanines Download PDF

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Publication number
US1969445A
US1969445A US548026A US54802631A US1969445A US 1969445 A US1969445 A US 1969445A US 548026 A US548026 A US 548026A US 54802631 A US54802631 A US 54802631A US 1969445 A US1969445 A US 1969445A
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United States
Prior art keywords
dye
neothiazolocarbocyanines
dyes
iodide
mols
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Expired - Lifetime
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US548026A
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English (en)
Inventor
Leslie G S Brooker
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US548025A priority Critical patent/US1994562A/en
Priority to US548026A priority patent/US1969445A/en
Priority to GB18533/32A priority patent/GB408273A/en
Priority to FR739314D priority patent/FR739314A/fr
Priority to DEK137917D priority patent/DE642278C/de
Priority to DEK126064D priority patent/DE668380C/de
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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
    • C09B23/12—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being branched "branched" means that the substituent on the polymethine chain forms a new conjugated system, e.g. most trinuclear cyanine 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 a new composition of matter and particularly to a new class of photographic sensitizing dyes known as neothiazolocarbocyanines vand photographic emulsions con- 5 taining them.
  • An object of the present invention is to provide a process for the preparation of photographic sensitizers of a new type containing the thiazole nucleus.
  • These dyes may be termed neothiazolocarbocyanines, by analogy with, neocyanine, which is thought to contain a similar linkage connecting its three heterocyclic nuclei.
  • Another object of the invention is to provide such photographic sensitizing dyes as may be added to photographic emulsions or coated thereon as an overcoating, thereby increasing the spectral sensitiveness of the emulsion.
  • a further object is to provide a gelatino silver halide' emulsion in which is incorporated one or more of the new dyes disclosed herein and a photographic element comprising such an emulsion. Other objects will hereinafter appear.
  • the thiazole ring is usually numbered in the following manner, and this system of numbering is used in the present application:
  • the Z-methyl thiazoles also yield such dyes as thiazoloiso-cyanines l'and thiazolo-vf-cyanines. These are dealt with in my co-pendingapplication Serial No..619,960 led ⁇ June 29, 1932.
  • dialkylsulfates and more especially-alkyl p-toluenesulfonates are used for the preparation of the thiazole alkylquaternary salts, and these when treated with an excess of ethyl orthoformate in anhydrous pyridine yield the neothiazolocarbocyanines of the instant application in preponderating amounts.
  • a Small amount of simple thiazolocarbocyanine frequently accompanies the neothiazolocarbocyanine, but as a rule the latter dyes are less soluble than these simple thiazolocarbocyanines and can readily be isolated in a pure state.
  • a and B represent univalent atoms or groupings such as hydrogen, alkyl or aryl; R stands for alkyl and X represents a suitable acid radical.
  • I 3,3'dialkyl7 (thiazyl 2 alkyl salt) methyl thiazolocarbocyanine salt and that for II is 3,3dialkyl7 [(thiazyl2 alkyl salt) vinyll-thiazolocarbocyanine salt.
  • consideration of atoms or groups A and B is omitted for the sake of simplicity. Since these new dyes are believed to be structurally related to the known dye neocyanines, it is logical to call them "neothiazolocarbocyanines been done herein.
  • the quaternary alkyl thiazyl group which is linked through the vinylene chain in the above formulae, has the alkyl group and the acidic radical both linked to the nitrogen atom of the thiazyl nucleus.
  • This nitrogen atom is numbered 3 but since it is the only position in this thiazyl nucleus for such linkage, the number need not appear in the name of the dye.
  • Formula Lone molecule of ethylorthoformate is supposed to have reacted with three molecules of quaternary salt, whilst Formula II may be arrived at by supposing that two molecules of ethylorthoformate react with three molecules of the alkyl quaternary salt.
  • Formula II isv the more probable one, and the analytical evidence favors it in most cases.
  • the utility of my invention is not affected by theoretical considerations relating to the exact structure of the molecule.
  • Step I Ihe thiazole base containing a reactive methyl group is first converted into an appropriate alkyl quaternary salt, by heating withffor instance, an alkyl sulfonic ester, such as an alkyl p-toluene sulfonate. 'Ihe dialkyl .sulfates may also be 'employed, but the yields are usually lower.
  • -A and B are hydrogen atoms or substituent atoms or groups
  • R stands for alkyl
  • X stands for a suitable acidic radical such as p-toluene sulfonate (-O.SOz.C1H'1) or alkyl sulfate (--O.SO2.OR)
  • Step II l' ' The thiazole alkyl quaternary salt is heated In these two general names which has.
  • step' III 11 This is a simple step and consists of dpuble decomposition.
  • the reaction mixture, concentrated'or otherwise, or the solution of the dye in some other solvent is treated with an aqueous solution of an alkali salt of the acid whose anion it is desired to introduce into the dye.
  • an alkali salt of the acid whose anion it is desired to introduce into the dye.
  • the p-toluene sulfonate of a dye may be treated with an aqueous solution of potassium iodide or sodium iodide or ammonium bromide. Thisv alkali salt is conveniently employed in considerable excess.
  • the dye iodides for example,
  • the iodideof the dye so produced was filtered off and washed and the more; soluble neothiazolocarbocyanine was removed by treatment with a hot mixture of acetone and methyl alcohol.
  • the dye was puried by crystallization from methyl alcohol and was nally obtained as a dull purplish-black felted crystalline mass and gave a Violet solution in methyl alcohol.
  • the dye was boiled with acetone and ltered hot but the filtrate was quite bluish and little or no crimson thiazolocarbocyanine seemed to be present in the preparation:
  • the dye was crystallized from methyl alcohol and gave beautiful greenish-bronze plates which imparted a violet coloration to methyl-alcohol.
  • the iodide of the dye consisted of a greenish-grey l powder. Most of the more soluble crimson thiazolocarbocyanine was removed by boiling the dye with a mixture of methyl alcohol and acetone and v alcohol.
  • the crude quaternary salt was refluxed for 41/2 95 hours with 60 cc. pyridine and 22.2 cc. ethyl hot distilled water.
  • the dye was ltered oi when cold and washed.
  • the air-dried dye consisted of EXAMPLE V Iodide of the neothiazolocarbocyam'ne from 2,4- dimethylthiazole etho-p-toluenesulfonate 4,4- dimethyl 3,3' Methyl-7 [-(4-methylthiaeyl- 2 ethiodz'de) -m'nyll -thz'aeolocarbocyamne iodide 11.3 g.
  • 2,4-dimethylthiazole (3 mols.) was heated overnight at 115-120 C. with 20 g. ethyl p-toluenesulfonate (3 mols.).
  • the crude quaternary salt which was a light brown viscous liquid, was rei'iuxed for 5 hours with 40 cc. pyridine and @.2 cc. ethyl orthoformate (4 mols.).
  • the reaction mixture was concentrated in vacuo and the residue mixed with hot distilled water and an excess of potassium iodide added.
  • the dye was allowed to crystallize out and was then filtered oi and washed.
  • the air-dried dye consisted of small, dark bluish-green crystals.
  • the dye was boiled with methyl alcoholand stood to cool somewhat I and was then filtered before it was quite cold. 135
  • the dye left on the iilter was almost pure normal thiazolocarbocyanine and consisted of small purple needles which gave a crimson solution.
  • the mother liquor . was concentrated somewhat and was then cooled in a freezing mixture.
  • 140 Bluish-green crystals of the neothiazolocarbocyanine iodide were obtained.
  • the mother liquor and Washings were again concentrated and a third crop of crystals obtained, and similarly a fourth and iifth crop.
  • 'Ijhese crops consisted of 145 tolerably pure neothiazolcarbocyanine.
  • the dye was. crystallized from methyl alcohol into beautiful greenish needles which became dull on drying and which gave a violet-blue solution in methyl alcohol.
  • the air-dried dye consisted of a purplish-brown crystalline powder.
  • the crimson normal thiazolocarbocyanine was removed by boiling with a mixture of methyl alcohol and acetone. The dye was then recrystallized from methyl alcohol and when dried consisted of a dull greenishbrown powder. The color -of the methyl alcoholic solution was blue.
  • the dye was precipitated as the iodide by adding a hot solution of an excess of potassium iodide in water and"stood aside to cool. The dye was filtered off and as it was somewhat tarry it was boiled with acetone, cooled, and filtered.l The dye when dried consisted of a dull bronze colored powder. The dye was boiled with a mixture of methyl alcohol and acetone and filtered hot,'but the solution was quite blue, as though little or no normal thiazolocarbocyanine were present. The dye was nally crystallized from methyl alcohol and consisted of small coppery crystals which .gave a blue solution in the solvent.
  • neothiazolocarbocyanines are produced by the condensation of thiazole alkyl quaternary salts, containing reactive methyl groups (Z-methylthiazole alkyl quaternary salts) with ethyl orthoformate in some suitable solvent such as anhydrous pyridine.
  • thiazole alkyl quaternary salts containing reactive methyl groups (Z-methylthiazole alkyl quaternary salts)
  • ethyl orthoformate in some suitable solvent such as anhydrous pyridine.
  • 3 molecules of the quaternary salt condense together with one, or more probably two, molecules of ethyl orthoformate.
  • the dyes may also be described as a particular type of 7-substituted thiazolocarbocyanine. ⁇
  • the diagrammatic spectrograms constituting the accompanying drawing illustrate the regions of the spectrum to which the various types of dyes herein disclosed ,will sensitize a gelatinosilver-halide emulsio Ktand the extent of the sensitization at various ⁇ ave lengths.
  • the figures of this drawing and the dye, the sensitizing properties of which each of the Figs. 1 to 6 illustrates, are listed, respectively, at the top of each spectrogram. These figures were all taken from silver. bromide emulsions in which the respective dyes were incorporated as herein described; corresponding ones taken from chloride emulsions vary somewhat but areromparable in region and density.
  • the dye may be dissolved in methyl alcohol and a volume of solution diluted with water and containing from 5 to 100 milligrams of dye added to 1000 cc. of, for instance a owable photographic gelatino-silver-halide emulsion, which may then be coated upon a suitable glass or cellulose derivative, transparent support and allowed to dry, the details of which are well known to emulsion experts. While it may not be necessary to add some of the sensitizers in a large amount, it may be necessaryto add others in amounts larger than those given above; generally about 10 to 20 milligrams is suicient to obtain the maximum sensitizing effect with a dye having good sensitizing power.
  • a gelatino-silver-halide emulsion which contains a sensitizing dye having most probably the following structure Lid in which A and B represent hydrogen atoms, or aliphatic or aromatic groupings, R represents an alkyl group and X represents a suitable acid radical.
  • a photographic element comprising a supporting surface coated with a gelatine-silverhalide emulsion which contains a sensitizing dye having most probably the following structure in which A and B represent' hydrogen atoms, or aliphatic or aromatic groupings, R represents an alkyl group and X represents a suitable acid radical.
  • a gelatino-silVer-halide emulsion which contains a 3,3dialkyl'7[(thiazyl2 alkyl quaternary salt) vinyl]-thiazolocarbocyanine salt.
  • Av gelatino-silver-halide emulsion which contains a 4,4diphenyl3,3' -diethyl-7 4phe ny1thiazyl-2 ethyl quaternary salt) vinyll-thiazolocarbocyanine salt.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Cosmetics (AREA)
  • Plural Heterocyclic Compounds (AREA)
US548026A 1931-06-30 1931-06-30 Photographic emulsion containing neothiazolocarbocyanines Expired - Lifetime US1969445A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US548025A US1994562A (en) 1931-06-30 1931-06-30 Neothiazolocarbocyanine dye and method of preparing it
US548026A US1969445A (en) 1931-06-30 1931-06-30 Photographic emulsion containing neothiazolocarbocyanines
GB18533/32A GB408273A (en) 1931-06-30 1932-06-30 Manufacture of carbocyanine dyes
FR739314D FR739314A (fr) 1931-06-30 1932-06-30 Nouveaux composés chimiques, applicables comme colorants et comme sensibilisateurs photographiques, et leur procédé de fabrication
DEK137917D DE642278C (de) 1931-06-30 1932-07-01 Verfahren zur optischen Sensibilisierung von Halogensilberemulsionen mit Hilfe von Carbocyaninfarbstoffen, die von einfachen Thiazolen abgeleitet sind
DEK126064D DE668380C (de) 1931-06-30 1932-07-01 Verfahren zum optischen Sensibilisieren photographischer Halogensilberemulsionen

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US548026A US1969445A (en) 1931-06-30 1931-06-30 Photographic emulsion containing neothiazolocarbocyanines

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DE (2) DE668380C (de)
FR (1) FR739314A (de)
GB (1) GB408273A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2427177A (en) * 1944-08-16 1947-09-09 Gen Aniline & Film Corp Sensitizing silver halide emulsions
US2461137A (en) * 1946-09-04 1949-02-08 Eastman Kodak Co Photographic emulsions sensitized with n, n-alkylenecyanine dyes
US3044875A (en) * 1957-08-16 1962-07-17 Agfa Ag Cyanine dyes derived from thienylbenzoxazoles and silver halide emulsions sensitized therewith
US3194805A (en) * 1960-09-02 1965-07-13 Eastman Kodak Co Merocyanine and holopolar dyes containing arylene-chain substitution

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1069289B (de) * 1959-11-19

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2427177A (en) * 1944-08-16 1947-09-09 Gen Aniline & Film Corp Sensitizing silver halide emulsions
US2461137A (en) * 1946-09-04 1949-02-08 Eastman Kodak Co Photographic emulsions sensitized with n, n-alkylenecyanine dyes
US3044875A (en) * 1957-08-16 1962-07-17 Agfa Ag Cyanine dyes derived from thienylbenzoxazoles and silver halide emulsions sensitized therewith
US3194805A (en) * 1960-09-02 1965-07-13 Eastman Kodak Co Merocyanine and holopolar dyes containing arylene-chain substitution

Also Published As

Publication number Publication date
DE642278C (de) 1937-03-06
GB408273A (en) 1934-04-03
FR739314A (fr) 1933-01-09
DE668380C (de) 1938-12-02

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