US3836370A - Merocyaninic dyes and their use in silver halides photographic emulsions containing the same - Google Patents

Merocyaninic dyes and their use in silver halides photographic emulsions containing the same Download PDF

Info

Publication number
US3836370A
US3836370A US00232724A US23272472A US3836370A US 3836370 A US3836370 A US 3836370A US 00232724 A US00232724 A US 00232724A US 23272472 A US23272472 A US 23272472A US 3836370 A US3836370 A US 3836370A
Authority
US
United States
Prior art keywords
ethyl
furfuryl
thiohydantoin
methyl
max
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00232724A
Other languages
English (en)
Inventor
P Beretta
L Magnani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Application granted granted Critical
Publication of US3836370A publication Critical patent/US3836370A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • G03C1/22—Methine and polymethine dyes with an even number of CH groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • 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
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/0025—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being bound through an oxygen atom
    • 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
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/0033—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being bound through a sulfur atom
    • 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
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • 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
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • 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
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/107—The polymethine chain containing an even number of >CH- groups four >CH- groups

Definitions

  • ABSTRACT Merocyanine dyes comprising a heterocyclic nitrogenous nucleus and a heterocyclic ketomethylene nucleus, and silver halide emulsions containing such dyes.
  • the present invention relates to merocyaninic dyes and to silver halides emulsions containing the same and to photographic elements containing such dyes.
  • Silver halides by themselves, are substantially insensitive to the visible radiations with the exception of those having a lower wave length.
  • the sensitivity of the silver halides emulsions has been extended to higher wave lengths by the introduction into them of various dyeing sensitizers such as those of the merocyaninic class.
  • These dyes are now of common use in the black and white photographic emulsions and in the colored photographic emulsions.
  • a useful photographic element for colored photography may contain layers of silver halides emulsion which have been sensitized to the red, green and blue light.
  • the dyeing sensitizers used in the above photography must exhibit, according to what hereinabove said, the sensitization characteristics required and moreover they must be completely removable from the photographic elements during the processing so as to impart the least residual coloration possible to the final colored image.
  • the present invention relates to merocyaninic dyes comprising on one side a heterocyclic, nitrogeneous nucleus and on the other one of a heterocyclic ketomethylenic nucleus.
  • merocyaninic dyes are characterized by the ketomethylenic group containing at least a nitrogen atom, carrying, as a substituent, a furfurylor a tetrahydrofurfuryl group.
  • the invention relates moreover to photographic silver halides emulsions containing such dyes, as sensitizers and desensitizers, and to photographic elements prepared with them.
  • the presentinvention refers to merocyaninic dyes representatable by the following formula:
  • R represents a substituted and a non substituted alkyl having from one to eight carbon atoms such as for ex- LII ample methyl, ethyl, hydroxyethyl, sulphoethyl, car- Z represents the non metallic atoms required to complete a heterocyclic nucleus.
  • Q represents the non metallic atoms necessary to completea heterocyclic nucleus comprising at least a nitrogen atom carrying, as a substituent, a furfuryl or a tetrahydrofurfuryl group.
  • heterocyclic rings which are completed by the non metallic atoms represented by Z in the hereinabove formula (1) are those of the thiazole series (thiazole, 4-methyl-thiazole, 4-phenylthiazole, 5- methyl-thiazole, S-phenyl-thiazole, 4,5-dimethylthiazole, 4,5-diphenyl-thiazole); those of the benzothiazole series (benzothiazole, 4-chlorobenzothiazole, 5- chloro-benzothiazole, 6-chloro-benzothiazole, 7- chloro-benzothiazole, 4-nitro-benzothiazole, S-nitrobenzothiazole, 6-nitro-benzothiazole, 5-chloro-6-nitrobenzothiazole, 5-bromo-o-nitrobenzothiazole, 4-methyl-benzothiazole, S-methyl-benzothiazole, 6- methylbenzothiazole, S-bromo-lbenzothiazole, 6- bromo-benzo
  • those of the imidazole series for example imidazole, l-alkyl-imidazole, 1-alkyl-4- phenyl-imidazole, l-alkyl-4,5-dimethyl-imidazole, ctc.
  • those of the henzimidazole series for example bcnzimidazolc, l-alkyl-bcnzimidazolc, l-alkyl-5,6- dichloro-benzimidazole, l-phenyl-benzimidazole, lhydroxyethyl,5,6-dichloro-benzimidazole, l-ethyl-S- chloro-benzimidazole, l-acetoxyethyl-S ,6-dichlorobenzimidazole, l-ethyl-5-chloro-6-aminobenzimidazole, l-ethyl-5-chloro-6-bromobenzimidazole, l
  • nuclei which are completed by atoms represented by Q in the hereinabove formula (1) are the nucleus of the thiazole, for example 2,4-thiazoledione, 4-thiazolidone, 2-thio-2,4-thiazole-dione (roda' nine); nuclei of the oxazolone type, for example 2-thio- 2,4-oxazole-dione and 2-imino-2,4 oxazole-dione (pseudo-hydantoin); nuclei of the imidazolone type, such as the 2,4-imidazole-dione (hydantoin, for example 2-thio-2,4-imidazolo-dione (2-thio-hydantoin); nuclei of the pyrazolone type, oxindole (2,3- dihydroketoindole), 2,4,6-triketohexahydropyrimidine (barbituric or thiobarbituric acid
  • the merocyaninic dyes of the present invention represented by the general formula l wherein d is equal to I, can be prepared by reacting an ammonium salt chosen among those known to the skilled in the art, represented by the formula:
  • R represents an alkyl group (such as for example methyl, ethyl, etc.) or an aryl group (such as for example phenyl, o-, m-, p-tolyl, etc.);
  • X represents an acid anion such as chloride, bromide, iodide, thiocyanate, sulfamate, methylsulfate, ethylsulfate, perchlorate, benzensulfonate, p-toluenesulfonate, etc. with a compound chosen among those represented by the following formula:
  • the dyes according to the invention represented by the general formula l where d 2, 3 can be prepared by condensing a compound of the general formula (3) with a compound chosen among those known to the skilled in the art, represented by the general formula:
  • R, R,, X, Z and n have the meaning hereinabove reported and R is equivalent to monovalent alkyl group such as methyl, ethyl, etc.
  • Another method to prepare the merocyaninic dyes of the general formula (1), where d 2 and L is equal to non substituted methinic group consists of reacting a quaternary salt belonging to the class of the compounds known to the skilled in the art, represented by the following formula:
  • R R have the hereinabove cited meanings.
  • the condensations of which hereinabove, can be ad vantageously performed by heating the reacting mixture at temperatures ranging between room tempera-' where R, L, Z, n and d have the meanings hereinabove reported and where at least one among the substituents R and R is a furfurylor tetrahydrofurfuryl group, while the other one is an alkyl group (for example methyl, ethyl, n-propyl, n-butyl, n-amyl, n-hexyl, nheptyl, benzyl (phenylmethylene), allyl, cyclo-penty], cyclo-hexyl, etc.; a substituted alkyl group such as car- 'boxyethyl, carboxymethyl, sulfo-propyl, dialkylaminoalkyl, etc.; an aryl group such as phenyl, 0-, m-, ptolyl.
  • R and R have the hereinabove reported mean- 6 ings, obtained in a known way, for example according to Wheeler and Al, J.A.C.S. (1911), 45, 456-474, and from compounds not known before the present invention, having the formula obtained in a way known to the skilled in the art from compounds having the formula (10) as it results from the following examples.
  • R, L, Z, n, d have the hereinabove said meanings W is equal to S and O and R represents a furfuryl or tetrahydrofurfuryl radical.
  • W and R have the hereinabove reported meanings, obtained in a way known to the skilled in the art, for example according to Holberg and Al in K. Prakt, Chemie, 81 (1910) 451 and Andreasch and Zizsser in monatschr. fur Chemie 24 (1903) 504 and 25 (1904) 167 and according to A. Ahlquist in Journ. Prakt. Chemie [2], 84 (1911), 662-675, and from compounds, not known before the present invention, having the formula:
  • the sensitizers of the present invention introduced into the silver halides photographic emulsions have the advantage of imparting to them and to the photographic element containing them a more extended spectral sensitization (and therefore a greater sensitivity) and of not presenting any residual coloring.
  • Example 2 furfuryl-senfol This compound has been prepared similarly to the preceeding one by using 50 g of furfurylamine, 22.8 g of NaOH in l 14 cc of water, 60.3 g of CS and a solu tion of 240 g of lead acetate in 600 cc of water. At the end a dark dense oil was obtained which was immediately used without further purification, since it decomposed very easily (even if stored under vacuum).
  • Example 4 l-carboxymethyl-3-tetrahydrofurfuryl-2- thiohydantoin
  • 37.6 g of the iminoacetic acid diethyl ester were introduced in a flask supplied with reflux and dropper. From the latter 28.5 g of tetrahydrofurfuryl-senfol (example 1) were allowed to drop in and then the mixture was boiled for 10 minutes.
  • the reaction mixture was poured in a vessel containing 200 cc of cold water; an oil was separated which was extracted with ethyl ether.
  • the ethereal solution was treated with bone black, dried with Na SO and evaporated ultil dryness.
  • a dark oil (9.5 g) was obtained, which was used immediately for the synthesis of the dyes without further purification.
  • N-tetrahydrofurfuryl-rodanine 18 g of tetrahydrofurfuryl-senfol, 32 g of absolute alcohol and 16 g of thioglycolic acid were introduced into a 250 cc flask and placed on an oil bath at l 10C. After 1 hour, 2 cc of acetic anhydride were added and the heating was continued for 24 hours. A yellow solution was obtained which was concentrated under vacuum until the formation of a solid which was filtered on a buckner.
  • the yield was 10.7 g of dried product.
  • the raw product was crystallized from 425 cc of ligroin and 9.4 g of pure product having a M.P. 88-89C was obtained.
  • Example 6 Acetamidofurfurylamine hydrochloride g of furfurylamine, 486.4 g of chloroacetamide and 1600 cc of absolute alcohol, were heated at 5050C on a steam bath for 2 hours and then at reflux for 4 hours. The mixture was cooled and allowed to stand. A brown solid was separated and was filtered on a buckner. The solid was mashed with acetone several times until it became white; it was collected on a buckner and washed with ethyl ether. The flaky white product obtained was dried and gave a yield of 186 g M.P. l80.5 l8l.5C.
  • Example 7 1-furfuryl-3-(y-dimethylaminopropyl )-2- thiohydantoin
  • a refluxing flask placed in an oil bath at 100C 52.5 g of acetamido-furfurylamine hydrochloride, 100 cc of methyl alcohol and 39 g of -di-methylaminopropyl-senfol were introduced.
  • a vivacious reaction occurred which was quenched by immerging the flask into a bath of water and ice.
  • Example 8 N-furfuryl-rodanine The reaction was performed similarly to that one of Example 5. The amounts used were 40 g of furfurylsenfol, 73 cc of ethyl alcohol, 4.5 cc of acetic anhydride and 36 g of thioglycolic acid. The obtained yield was 7.2 g of oil which was distilled under reduced pres sure. B.P. ll6l20C/l mm Hg.
  • Example 9 l-furfuryl-3-propyl-thiohydantoin 52.5 g of acetamido-furfurylamine hydrochloride, 300 cc of methyl alcohol, 27.8 g of propyl-senfol and 16.6 g of KOH dissolved in 110 cc of water, were mixed in a l l flask. The mixture was boiled for 3 hours then I37 cc of concentrated HCl were added after cooling the flask with water and ice. The mixture was then boiled for half an hour and then 200 cc of solvent were distilled off.
  • the mixture was diluted with 200 cc of water and was extracted with ethyl ether, drying the ethereal solution with Na SO After evaporation of the ether, 53 g of a dark yellow oil remained which was distilled under vacuum collecting the fraction distilled at 168l70C/l mm Hg. The yield was 45.5 g ofa slightly yellow oil.
  • Example 10 N-furfurylglycine ethyl ester 30 g of furfurylamine, together with cc of absolute ethyl alcohol, were introduced in a flask and from a reflux 54 g of ethyl bromo-acetate were added. A dark solution was obtained and 32 g of triethylamina were added to it. A white solid separated. The mixture was brought to ebullition and was allowed to react for 15 hours while the solid went completely into solution. By cooling and standing a solid tri-ethylamine hydrobromide separated, which was separated from the solution by filtration on a buckner. To the: solution was added more ethyl ether to complete the triethylamine hydrobromide precipitation. The ethereal solution was concentrated under reduced pressure and the remained dark oil was diluted under vacuum collecting the fraction having a HP. l60l 70C/2 mm Hg. The obtained yield was 33.6 g.
  • Example 1 l l-furfuryl-3-carboxymethyl-2-thiohydantoin oH,--N-orn-o of this product were boiled for minutes with 82 cc of a 10 percent sodium hydroxide. The dark yellow solution obtained was cooled and acidified with HCI. Then it was extracted with ether, the ethereal solution was dried with anhydrous sodium sulfate and then was evaporated under vacuum. The residual yellow oil by standing a few days in the dessiccator, solidified and was crystallized from ethyl alcohol. Yield 23 g M.P. l25126C.
  • Example 12 l-tetrahydrofurfuryl-3-ethyl-2thiohydantoin JaHr 9.8 g of N-tetrahydrofurfuryl-glycine-ethyl ether (Example 11) and 4.45 g of ethylsenfol were heated at 150C for 36 hours. The obtained dense liquid was distilled under vacuum and a yellow oil having a B.P. 168l 72C/ 1 2 mm Hg was obtained. The yield was 7.1
  • Example 14 N-furfuryl-2-thio-oxazolidone 26.1 g of furfuryl-amine and a solution consisting of 21.19 g of potassium hydroxyde dissolved in 81.8 cc of water were mixed in a keller. Under fast stirring 57 g of acetamido-carbodithioloneglycolic acid (prepared according to what has been reported in J. Prakt. Chem./2/99 (1919) p. 45 and following), were added in small portions. The mixture was allowed to stand overnight, was diluted with 271 cc of water and was stirred again for 2 hours then was acidified with HCl.
  • acetamido-carbodithioloneglycolic acid prepared according to what has been reported in J. Prakt. Chem./2/99 (1919) p. 45 and following
  • Example 16 -acetanilido methylene-3-furfuryl-2-thiooxazolidone.
  • Example 17 5-acetanilido-methylene-3-tetrahydrofurfuryl-2-thiooxazolidone It was prepared analogously to the intermediate 16, using the N-tetrahydrofurfuryl-Z-thio-oxazolidone instead of the N-furfuryl-2-thio-oxazolidone. At the end of the operation, 3,5 g of crystallized product having MP. l74 -175C were obtained.
  • Example 18 5 -acetanilido methylene-1-furfuryl-3 -propyl-2-thiohydantoin
  • the reaction was analogous to that of Example 16.15 g of l-furfuryl-3-propyl-2-thiohydantoin, 12.3 g of diphenyl-formamidine and 45 cc of kerosene were used.
  • the 5-anilino-methylene-l-furfuryl-3-propyl-2- thiohydantoin obtained (8.5 g M.P. l24-5C) was boiled with acetic anydride and triethylamine.
  • the yield of the crystallized product was 3.5 g, MP. l67-9C.
  • Example 19 5-( 3 -ethyl-thioazolidine-Z-ylidene-ethylidene )-3- tetrahydroiu rfuryl'rodanine 1,39 g of tetrahydro-furfuryl-rodanine, 2 g of 2-(wacetanilido-vinyl)thioazoline-iodo-ethylate, 15 cc of ethyl alcohol and 1 cc of triethylamine, were boiled for 20 minutes obtaining an orange solution. The solution was cooled and precipitated with water. A fluid pitch separated and it hardened after standing. It was boiled twice with water and crystallized from ethyl alcohol. Shining violaceous scales were obtained having M.P. 148C.
  • Example 20 5-( 3-methylbenzoxaline-2-ylidene-ethylene-)-3- tetrahydrofurfuryl-rodanine as t. 5H3 EH2 2.78 g of N-tetrahydrofurfuryl-rodanine, 4.2 g of 2-(wacetanilidovinyl)benzoxazole-iodo-methylate, cc of ethylic alcohol and 3 cc of triethylamine, were boiled for 20 minutes, obtaining an orange solution. By cooling it separated the dye which was crystallized from a mixture of pyridine and ethyl alcohol in the ratio 2:1.
  • Example 21 CH ⁇ N/ (in.
  • the orange dye separated out in the hot and was filtered and washed with ethyl alcohol and ethyl ether.
  • the product was boiled with water and crystallized from ethyl alcohol and needlelike crystals having golden reflexes were obtained.
  • the yield was 1.7 g, the M.P. 1945C.
  • Example 27 l-2-dihydro-1 -methyl-pyridin-2-ylidene )-3-furfuryl- 2-thiooxazolidone 1.97 g of N-furfuryl-2-thio-oxazolidone, 2.67 g of 2- methylmercapto-pyridine-iodoethylate, 25 cc of ethyl alcohol 2.5 cc of triethylamine were boiled for min utes. By cooling the orange solution thus obtained, the raw dye separated out; the dye was crystallized from ethyl alcohol. Yellow needles were obtained.
  • Example 28 5-( 3-methyl-benzothiazoline-2-ylidene)-3-furfuryl-2- thiooxazoliclone 0.98 g of N-furfuryl-2-thio-oxazolidone, 1.61 g of 2- methylmercapto-benzothiazole-iodo-methylate, cc of ethyl alcohol, 2 cc of triethylamine were boiled for 5 minutes. The dye separated immediately and was crystallized from N,N-dimethyl-formamide. Yellow needles having a M.P. 280-1C were obtained.
  • Example 29 5 3'ethyl-5 ,6-dimethyl-benzoxazoline-2-ylideneethylene)-2-thio-3-furfuryl oxazolidone 0.98 g of 3-furfuryl-2-thio-oxazolidone, 2.23 g of 2-(wacetanilidoviny1)-5,6-dimethyl-benzothiazole-iodoethylate, 10 cc of ethyl alcohol and 1 cc of triethylamine were boiled for 30 minutes. The mixture was filtered and the product was crystallized from pyridine. An orange amorphous product having M.P. 276-7C was obtained.
  • Example 30 5 3 -ethyl-benzothiazoline-2-ylidene-isobutilidene- 3 tetrahydrofurfuryl-2-thio-oxazolidone H Cz O 0.4 g of N-tetrahydrofurfuryl-2-thio-oxazolidone, 0.8 g of 2-( 2 -ethylmercapto-3-butenyl )-benzothiazole-iodoethylate, 8 cc of ethyl alcohol, 0.8 cc of triethylamine were boiled for 10 minutes. The mixture was cooled and diluted with acidified water. A dark pitchy material with violaceus reflexes separated out. It was crystallized from ethyl alcohol and red violaceus crystals having MP. l34135C were obtained.
  • Example 31 5-(3-ethylbenzothiazoline-Z-yIidene-isopropylidene 3-furfuryl-2-thio-oxazolidone 0.4 g of N-furfuryl-2-thio-oxazolidone, 0.87 g of 2-(2- ethylmercapto-propenyl)-benzothiazole-ethylparatoluenesulfonate, 8 cc of ethyl alcohol, 0.8 cc of triethylamine were boiled for 5 minutes. The dye separated out and was crystallized from pyridine. Red violet crystals 5 having M.P. 224-5C were obtained.
  • Example 33 5-(3-ethyl-benzothiazoline-2-ylidene-isobutylidene)-3- furfuryl-2-thio-oxazolidone 0.4 g of N-furfuryl-2-thio-oxazolidone, 0.8 g of 2-(2- ethylmercapto-butenyl)-benzothiazole-iodoethylate, 8 cc of ethyl alcohol and 0.8 cc of triethylamine, were boiled for 5 minutes. By standing the dye separated out and was crystallized from ethyl alcohol. Purplish pink crystals of the dye, having M.P. l67-9C were obmined.
  • Example 36 5-( 3-ethyl-naphthol ,2-4,5-oxazoline-2-ylideneethylidene )-3-furfuryl-2-thiooxazolidone o s N N i JJ'HS din Zll 1.97 g of N-furfuryl-2-thio-oxazolidone, 4.84 g of 2-(wacetanilidovinyl)-B-naphthooxazole-iodo-ethylate, 40 cc of ethyl alcohol and 4 cc of triethylamine, were boiled for 10 minutes. The orange dye separated in the hot. It was filtered and crystallized from pyridine. Red orange crystals having MP. 285-6C;
  • the hot mixture was poured into hot water then decanted and the washing was repeated several times.
  • the product was dissolved in boiling ethyl alcohol and was allowed to stand.
  • the obtained dye weighed 2.3 g and had a M.P. l73-5C (Purplish pink crystals).
  • ZCI' QCHS 45 2.39 g of l-furfuryl-3-propyl-2-thiohydantoin, 4.96 g of Z-(w-acetanilidovinyl)-5-phenyl-benzoxazole-iodomethylate, 80 cc of butyl alcohol, 8 cc of piperidine were boiled for 1 hour. The dye separated by cooling and was crystallized from piperidine. A light brown amorphous product having M.P. 2624 C was obtained.
  • Example 46 3-ethyl-5,6-dimethyl-benzoxazoline-Z-ylideneethylidene)-1-furfuryl-3-carboxymethyl-2- thiohydantoin thiohydantoin, 0.892 g of Z-(A-acetanilidovinyl)-5,6- dimethyl-benzoxazole-iodo-ethylate, 7 cc of pyridine and 1 cc of trimethylamine were boiled for 10 minutes. After cooling water was added and the mixture was slightly acidified with acetic acid. Purple pink crystals of the dye having M.P. 258260C. were obtained (A max of absorption in ethanol: 490 nm).
  • Example 47 5-( 3-ethyl-5-phenyl-benzoxazoline-2-ylideneethylidene-1-furfuryl-3(y-dimethylamino-propyl)-2- thiohydantoin 1.4 g of 1-furfuryl-3-('y-dimethylaminopropyl)-2- thiohydantoin, 2.55 g of 2-(w-acetanilidovinyl)-5- phenyl-benzoxazole-iodoethylate, cc of ethyl alcohol and 1.5 cc of piperidine were boiled for minutes. The dye separated out and was crystallized from pyri- 5 dine.
  • the compound was prepared analogously to Example 48 using the S-methyl derivative of the benzoxazole instead of the 5-chloro derivative. Red orange crystals. M.P. 192-4C.
  • Example 50 5 5 5-( 3-ethyl-5-acetylamino-benzoxazoline-Z-ylideneethylidene)-1-furfuryl-S-(y-dimethylaminopropyl)-2- thiohydantoin 011.10 ONIlmn- -N (Illa).
  • the compound was prepared analogously to Example 48 using the 5-acetylamino derivative of the benzoxazole instead of the 5-chloro derivative. Violet crystals. M.P. l5l-2C.
  • Example 5 1 5-( 3-ethyl 5-metoxy-benzoxazoline-2-ylideneethylidene l -furfuryl-3-(y-dimethylaminopropyl )-2- thiohydantoin
  • the compound was prepared analogously to Example 48, using the 5-methoxy derivative of the benzoxazole instead of the 5-chloro derivative. Orange amorphous product. M.P. 227-8C.
  • Example 52 5-( 3-ethyl-5,6-dimethyl-benzoxazoline-2-ylideneethylidene l -furfuryl-3-(-y-dimethylaminopropyl)-2- thioydantoin The compound was prepared analogously to Example 48, using the 5,6-dimethyl derivative instead of the 5- chloro derivative.
  • Example 53 5-( 3-ethyl-5 ,7-dimethyl-benzoxazoline-2-ylideneethylidene)-1-furfuryl-3-(-y-dimethylaminopropyl)-2- thioydantoin
  • the compound was prepared according to what reported for Example 48, using the 5,7-dimethyl derivative of the benzoxazole instead of the -chloro derivative.
  • Example 55 5-( 3-ethyl-5-phenyl-benzoxazoline-Z-ylideneethylidene l -m ethyl-3-tetrahydrofurfuryl-2- thiohydantoin The compound was obtained analogously to Example 54, using the S-phenyl derivative of the benzoxazole. M.P. 218-9C. Purple pink crystals.
  • the compound was obtained analogously to Example 54 using the 5-chloro derivative of the benzoxazole.
  • the product was orange and amorphous, with M.P. 250.5251.5C.
  • Example 58 5-(3-ethyl-5 ,7-dimethyl-benzoxazoline-2-ylideneethylidene l -methyl-3-tetrahydrofurfuryl-2- thiohydantoin The compound was prepared analogously to Example 54 using the 5,7-dimethyl derivative of the benzoxazole; the product was in orange crystals with M.P. 239.5-240C.
  • Example 59 5-( 3-ethyl-5-acetylamino-benzoxazoline-Z-ylideneethylidene )-l -methyl-3-tetrahydrofurfuryl-2- thiohydantoin HaCC ONH 1r 2 ⁇ O JEEP-dim
  • the compound was prepared analogously to Example 54, using the S-acetylamino derivative of the benzoxazole, in red orange microcrystals having M.P. 280-lC.
  • Example 62 5-(3-ethyl-naphtho-2'. l '-4.5-oxazoline-2-ylideneethylidene l -furluryl-3-('y-dimethylaminopropyl )-2- thiohydantoin Ulla 1.4 g of 1-furfuryl-3-(y-dimethylaminopropyl)-2- thiohydantoin, 2.42 g of 2-(w-acetanilidovinyl)- napththo-2',l '-4,5-oxazole-iodo-ethylate, 8 cc of ethyl alcohol, 2 cc of piperidine were boiled for 20 minutes.
  • Example 64 5 3-ethyl-naphtho.-l ,2 -4,5-oxazoline-2-ylideneethylidene l -methyl-3-tetrahydrofurfuryl-2- thiohydantoin l lltl llr
  • the compound was prepared analogously to Example 54 using the naphtho-l ',2-4,5-oxazole. (A max of absorption in ethanol: 502 nm).
  • Example 65 (3-ethyl-naphtho-l ,2-4,5-oxazoline-2-ylideneethylidene l -furfuryl-3-('y-dimethylaminopropyl )-2- thiohydantoin naphtho-l,2-4,5-oxazoleiodo-ethylate, 5 cc of pyridine, 1 cc of triethylamine were boiled 20 minutes. A crystalline solid separated out and was crystallized from pyridine.
  • Example 67 5-(3-methylnaphtho-l ,2'-4,5-oxazoline-2-ylidene- 1.14 g of l-(tetrahydrofurfuryl)-3-ethyl-2- thiohydantoin, 2.35 g of 2-(w-aldehydomethylene)- naphtho-l',2-4,5-oxazoleiodo-ethylate. 5 cc of ethyl alcohol and 0.5 cc of triethylamine were boiled for 10 minutes.
  • Example 68 5-( 3-methyl-naphtho-4,5-oxazoline-2-ylideneethylidene l furfuryl )-3-propyl-2-thiohydantoin 0.239 g of l-(furfuryl)-3-propyl-2-thiohydantoin, 0.47 g of 2-(w-acetanilidovinyl)'-naphtho-4,5-oxazole-i0doethylate, 3,5 cc of butyl alcohol, 0.5 cc of piperidine were boiled for 15 minutes. The dye separated out and was crystallized from pyridine. The dye dried in the oven has M.P. 2535C. Dark red crystals.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US00232724A 1971-03-09 1972-03-08 Merocyaninic dyes and their use in silver halides photographic emulsions containing the same Expired - Lifetime US3836370A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT4891971 1971-03-09

Publications (1)

Publication Number Publication Date
US3836370A true US3836370A (en) 1974-09-17

Family

ID=11269033

Family Applications (1)

Application Number Title Priority Date Filing Date
US00232724A Expired - Lifetime US3836370A (en) 1971-03-09 1972-03-08 Merocyaninic dyes and their use in silver halides photographic emulsions containing the same

Country Status (5)

Country Link
US (1) US3836370A (enrdf_load_stackoverflow)
BE (1) BE780443A (enrdf_load_stackoverflow)
DE (1) DE2211200A1 (enrdf_load_stackoverflow)
FR (1) FR2128737B1 (enrdf_load_stackoverflow)
GB (1) GB1385030A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976640A (en) * 1975-02-18 1976-08-24 Polaroid Corporation Bis-type quaternary salts including benzothiazole and benzimidazole rings and process for preparing dye therewith
US5418126A (en) * 1992-11-19 1995-05-23 Eastman Kodak Company Furan or pyrrole substituted dye compounds and silver halide photographic elements containing such dyes
US6066443A (en) * 1994-05-18 2000-05-23 Eastman Kodak Company Blue sensitizing dyes with heterocyclic substituents

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2265908A (en) * 1938-10-06 1941-12-09 Ilford Ltd Manufacture of sensitizing dyestuffs
US3384486A (en) * 1964-05-04 1968-05-21 Eastman Kodak Co Merocyanine dyes for photographic elements containing an extracyclic tertiary amino group
US3632349A (en) * 1969-04-09 1972-01-04 Fuji Photo Film Co Ltd Silver halide supersensitized photographic emulsion
US3718476A (en) * 1970-10-23 1973-02-27 Eastman Kodak Co Silver halide element containing merocyanine dyes with a 3-pyrrolinylalkyl group

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2265908A (en) * 1938-10-06 1941-12-09 Ilford Ltd Manufacture of sensitizing dyestuffs
US3384486A (en) * 1964-05-04 1968-05-21 Eastman Kodak Co Merocyanine dyes for photographic elements containing an extracyclic tertiary amino group
US3632349A (en) * 1969-04-09 1972-01-04 Fuji Photo Film Co Ltd Silver halide supersensitized photographic emulsion
US3718476A (en) * 1970-10-23 1973-02-27 Eastman Kodak Co Silver halide element containing merocyanine dyes with a 3-pyrrolinylalkyl group

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976640A (en) * 1975-02-18 1976-08-24 Polaroid Corporation Bis-type quaternary salts including benzothiazole and benzimidazole rings and process for preparing dye therewith
US5418126A (en) * 1992-11-19 1995-05-23 Eastman Kodak Company Furan or pyrrole substituted dye compounds and silver halide photographic elements containing such dyes
US6066443A (en) * 1994-05-18 2000-05-23 Eastman Kodak Company Blue sensitizing dyes with heterocyclic substituents

Also Published As

Publication number Publication date
FR2128737B1 (enrdf_load_stackoverflow) 1978-03-03
BE780443A (fr) 1972-09-11
FR2128737A1 (enrdf_load_stackoverflow) 1972-10-20
DE2211200A1 (de) 1973-03-22
GB1385030A (en) 1975-02-26

Similar Documents

Publication Publication Date Title
US2688545A (en) Supersensitization of photographic emulsions with benzimidazolocarbocyanine dyes
US2493748A (en) Merocyanine dyes
US2078233A (en) Photographic emulsion
US3282933A (en) Methine dyes
US4515888A (en) Cyanine dyes for sensitizing silver halide emulsions to infrared radiation and photographic elements including them
US2519001A (en) Merocyanine dyes containing a carboxyalkyl group or a sulfoalkyl group
US4025347A (en) Fogged direct-positive silver halide emulsion containing a cyanine dye having an indole or indolenine nucleus substituted with a benzoyl or a phenylsulfonyl group
US3384486A (en) Merocyanine dyes for photographic elements containing an extracyclic tertiary amino group
US2430558A (en) Photographic emulsion sensitized with combination of merocyanine dye and a monomethinecyanine, a trimethinecyanine, a dimethinehemicyanine, or a styryl dye
US2443136A (en) Photographic elements containing 1, 3, 4-triazaindolizine cyanine dyes
US3385707A (en) Optically sensitized photographic materials containing neutrocyanine dyes
US3836370A (en) Merocyaninic dyes and their use in silver halides photographic emulsions containing the same
US2495260A (en) 3-arylbenzothiazolium quaternary salts and process for preparing the same
US3288610A (en) Optically sensitized photographic silver halide emulsions
DE966046C (de) Verfahren zur Herstellung von Sensibilisatoren
US2541400A (en) N, n'-alkylenecyanine dyes
US3469985A (en) Light-absorbing dyes derived from barbituric and 2 - thiobarbituric acid compounds useful for photography and their preparation
US3408195A (en) Silver halide emulsions containing n, alpha-alkylene bridged indocarbocyanine sensitizing dyes
US3440052A (en) Sensitized silver halide emulsions with holopolar dyes containing a dilactone ring
US3044875A (en) Cyanine dyes derived from thienylbenzoxazoles and silver halide emulsions sensitized therewith
US3725398A (en) Process for preparing 9-aryloxycarbocyanine compounds
US2895959A (en) Process for manufacture of oxazole quaternary salts
US2496899A (en) Azamerocyanine dyes and a process for the preparation thereof
US2537880A (en) Process for preparing polymethine dyes
US2691652A (en) Acyloxy polymethine dyes