US2856404A - Merocyanine dyes and intermediates - Google Patents

Merocyanine dyes and intermediates Download PDF

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US2856404A
US2856404A US592507A US59250756A US2856404A US 2856404 A US2856404 A US 2856404A US 592507 A US592507 A US 592507A US 59250756 A US59250756 A US 59250756A US 2856404 A US2856404 A US 2856404A
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Leslie G S Brooker
Donald W Heseltine
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C07D231/26—1-Phenyl-3-methyl-5- pyrazolones, unsubstituted or substituted on the phenyl ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/12—Oxygen 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
    • C07D277/32—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/36—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D421/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D421/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing two hetero rings
    • C07D421/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • 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
    • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
    • 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
    • C09B23/102—The polymethine chain containing an even number of >CH- groups two heterocyclic rings linked carbon-to-carbon

Definitions

  • This invention relates to an improved method of making merocyanine dyes, some of which are new compositions of matter, and new intermediates for making these merocyanine dyes.
  • the merocyanine dyes produced according to our invention can be employed in optically sensitizing photographic silver halide emulsions.
  • an object of our invention to provide an improved method for making merocyanine dyes. Another object is to provide certain new merocyanine dyes. Still another object is to provide new intermediates for making these merocyanine dyes. A further object is to provide photographic silver halide emulsions sensitized with these merocyanine dyes. Other objects will become apparent from a consideration of the following description and examples.
  • D represents the atoms necessary to complete a cyclohexene ring and Q represents the non-metallic atoms necessary to complete a nucleus of the indandione series (e. g., 1,3-diketohydrindene, etc.) or a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, such as those of the pyrazolone series (.e. g.,- 3-methyl-l-phenyl-S-pyrazolone, l-phenylS-pyrazolone, 1-(2-benzothiazolyl)-3-methy1r5pyrazolone, etc.), those of the isoxazolone series (e.
  • l-n heptyl etc.
  • 1,3-dialkyl e. g., 1,3-dimethyl, 1,3- diethyl, 1,3-di-n-propyl, 1,3-diisopropyl, 1,3-dicyclohexyl, LB-diQS-methoxyethyl), etc.
  • 1,3-diaryl e. g., 1,3- diphenyl, 1,3-di(p-chlor0phenyl), 1,3-di(p-ethoxycarbonylphenyl), etc.
  • l-aryl e.
  • rhodanine series i. e., 2-thio- 2,4-thiazolidinedione series
  • 3-alkylrhodanines e. g., 3-ethylrhodanine, 3-allylrhodanine, etc.
  • 3-arylrhodanines e.
  • (3H,4H)-thiazoledione series) (e. g., 3-ethyl-2-thio-2,5- thiazolidinedione, etc.), those of the 2,4-thiazolidinedione series (e. g., 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, Sax-naphthyl-2,4-thiazolidinedione, etc.), those of the thiazolidinone series (e.
  • 4-thiazolidinone 3-ethyl-4-thiazolidinone, 3-phenyl-4-thiazolidinone, 3-a-naphthyl-4-thiazolidinone, etc.
  • 4-thiazolinone series e. g., 2- ethylr'nercapto-4-thiazolinone, 2-alkylphenylamino-4-thiazolinones, 2-diphenylamino-4-thiazolinone, etc.
  • 2-imino-2,4-oxazolinone i. e., pseudohydantoin
  • 2,4-imidazolinedione hydantoin
  • R represents an alkyl group (e. g., methyl ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, p-methoxyethyl, ⁇ 3-ethoxyethyl, allyl (i. e., methylvinyl), benzyl (phenylmethyl), p-phenylethyl, carboxymethyl, etc.) (especially alkyl groups containing from 1 to 4 carbon atoms), n represents a positive integer of from 1 to 2, X represents an acid radical (e.
  • alkyl group e. g., methyl ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, p-methoxyethyl, ⁇ 3-ethoxyethyl, allyl (i. e., methylvinyl), benz
  • D represents an electronegative radical, such as alkyhnercapto (e. g., methylmercapto, ethylmercaptq; etc.), arylmercapto (e. g., phenylmercapto, tolylmercapto, etc.), a B-acylanilidovinyl group (e.
  • fl-acetanilidovinyl, fl-benzoylanilidovinyl, etc. a B-acylanilido-1,3-butadienyl group (e. g., fi-acetanilido- 1,3-butadienyl, a-benzoylanilido-1,3-butadienyl, etc.), etc.
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 (n is 1) to 6 (n is 2) atoms in the heterocyclic ring, such as those selected from the group consisting of those of the thiazole series (e.
  • thiazole 4-methylthiazole, 4- phenylthiazole, S-methylthiazole, S-phenylthiazole, 4,5- dimethylthiazole, 4,5-diphenylthiazole, 4(2-thienyl)thiazole, etc.
  • benzothiazole series those of the benzothiazole series (e.
  • benzothiazole 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazo1e, -bromobenzothiazole, 4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, ti-methoxybenzothiazole, S-iodobenzothiazole, 6-iodobenzothiazole, 4- ethoxybenzothiazole, S-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,G-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole, 6-hy droxybenzo
  • R, Z, n, d, R R R and Q each have the values given above.
  • N-alkylthoxazole series e. g., naphtho[1,2]oxazole, naphthopiperidines (e. g., N-methylpiperidine, N-ethylpiperidine, [2,l]oxazole, etc.), those of the selenazole series (e. g., etc.), etc.
  • the condensations can be carried out in the 4-methylselenazole, 4-phenylselenazole, etc.), those of the presence of an inert diluent, such as the lower alcohols benzoselenazole series (e. g., benzoselenazole, S-chloro- (e. g., ethanol, n-propanol, isopropanol, n-butanol, etc.), benzoselenazole, S-methoxybenzoselenazole, S-hydroxypyridine, quinoline, 1,4-dioxane, etc.
  • an inert diluent such as the lower alcohols benzoselenazole series (e. g., benzoselenazole, S-chloro- (e. g., ethanol, n-propanol, isopropanol, n-butanol, etc.), benzoselenazole, S-methoxy
  • az-oline series (e. g., thiazoline, 4-methylthiazoline, etc.),
  • 2-quinoline series-(e. g., quinoline, 3-methyldiates represented by Formula I above by condensing a quinoline, S-methylquinoline, 7-methylquinoline, 8- ketone selected from those represented by the following methylquinoline, 6-chloroquino1ine, 8-chloroquinoline, general formula:
  • those of the 4-quinoline X series e. g., quinoline, 6-methoxyquinoline, 7-methyl- H5O C ⁇ quinoline, S-methylquinoline, etc.
  • those of the l-isoquinoline series e. g., isoquinoline, 3,4-dihydroisoquinoline, etc.
  • those of the 3-isoquinoline series e. g., iso- I quinoline, etc.
  • those of the benzimidazole series e.
  • 3,3-dialkylindolenine series e. g., 3,3- VI ,Q ⁇ dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-tri- X methylindolenine, etc.
  • those of the 2-pyridine series H2O 0:0 'e.
  • Typical ketone compounds selected from those repre group such as 'carbomethoxyl, carbethoxyl, etc. include isophorone, a carbalkoxyl group containing from 2 to 3 carbon 3,5-dimethyl-2'cyclohexen-l-one, S-methyI-Z-cyclohexenatoms), R and R each represents a hydrogen atom or a l-one, 4 carbethoxy-3-methyl-Z-cyblohexeh-l-one, etc.
  • condensations of the compounds of Formula VI has the values given above. with those of Formulas V or VII can be accelerated by The dyes produced by condensing an intermediate 86- strong basic condensing agents, such as piperidine, dilected from those represented by Formula I above with ethylamine, etc., or by a mixture of ammonium acetate.
  • those of Formula II can be represented by the following and acetic acid.
  • These condensations can be convenientgeneral formula: 1y carried out in an inert diluent, such as chloroform,
  • Example 1.3-ethyl-5-(3,5,S-tfimethyl-Z-cyclohexen-J- ylidene)-rhodanine tion was concentrated to 50 ml. and chilled overnight.
  • Example 3 .1 ,3-diethyl-5 3,5 ,5 -trimethyl-2-cyclohexen- 1 -ylidene) -2-thi0barb iturl'c acid 1,3-diethyl-2-thiobarbituric acid (40 g., 1 mol.) and isophorone (30.3 g., 1 mol.+%) were dissolved in chloroform (100 ml.), and ammonium, acetate (2.5 g.) and acetic acid (4 ml.) were added. The mixture was heated under reflux for an hour in a system fitted for continuous removal of water. The reaction mixture was then Washed with two 100 ml. portions of water and the chloroform removed by distillation. The residue was recrystallized from methyl alcohol and the yield of purified material was 35.2 g. (55%), M. P. 108-9 C.
  • the crude dye was purified by boiling with three 100 ml. portions of methyl alcohol and filtering hot each time. After two recrystallizations from pyridine and methyl alcohol, the yield of purified dye was 0.73 g. (31% M. P. 25l-2 C. dec.
  • All the dyes of our invention are particularly useful in manufacturing photographic, silver halide emulsions, serving to alter the sensitivity thereof. Sensitization by means of our new dyes is, of course, directed primarily to the ordinarily employed, gelatino-silver-halide, developing-out emulsions.
  • the dyes are advantageously incorporated in the washed, finished emulsion and should, of course, be uniformly distributed throughout the emulsion. In the preparation of photographic emulsions containing our new dyes, it is only necessary to disperse the dyes in the emulsions.
  • the methods of incorporating dyes in emulsion are simple and well known to those skilled in the art of emulsion making.
  • concentration of our new dyes in the emulsion can vary widely, i. e., from about 5 to about 100 mgs. per liter of flowable emulsion.
  • concentration of the dye will vary according to the type of light-sensitive material in the emulsion and according to the effects desired.
  • 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.
  • Photographic silver halide emulsions which. can advantageously be sensitized by means of the new dyes of our invention comprise the customarily employed gelatinosilver-chloride, gelatino-silver chlorobromide, gelatinosilver-bromide, and gelatino-silver-bromiodide developingout emulsions.
  • Photographic silver halide emulsions such as those listed above, containing the sensitizing dyes of our invention can also contain such addendaas chemical sensitizers, e. g., sulfur sensitizers (e. g., allyl thiocarbamide, thio urea, allylisothiocyanate, cystine, etc.), various gold compounds (e. g., potassium chloroaurate, auric trichloride, etc.) (see U. S. Patents 2,540,085; 2,597,856 and 2,597,915, various palladium compounds, such as palladium chloride (U. S. 2,540,086), potassium chloropalladate (U. S.
  • chemical sensitizers e. g., sulfur sensitizers (e. g., allyl thiocarbamide, thio urea, allylisothiocyanate, cystine, etc.)
  • gold compounds e. g.,
  • anti-foggants such as ammonium chloroplatinate (U. S. 2,566,245), ammonium chloroplatinite (U. S. 2,566,263), benzotriazole, nitrobenzimidazole, S-nitroindazole, benzidine, mercaptans, etc. (see Mees-- The Theory of the Photographic Process, MacMillan Pub, 1942, page 460), or mixtures thereof; hardeners ⁇ such as formaldehyde (U. S. 1,763,533), chrome alum (U. S. 1,763,533), glyoxal (U. S.
  • R represents a member selected from the group consisting of a hydrogen atom. and a carbalkoxyl group containing from 2v to 3 carbon atoms
  • R2 and R3 each represents a member selected from the group consisting of a hydrogen atom and. a. lower alkyl group
  • Q represents the non-metallic atoms necessary to complete a nucleus selected from the group consisting of anindan':
  • nucleus an oxindole nucleus, at 2,4,6-triketohexahydropyrimidine nucleus, a 2-thio-2,4,6-triketohexahydropyrimidine nucleus, a rhodanine nucleus, a 2(3H')-imidazo- [1,2-alpyridone nucleus, a 5,7-dioXo-6,7-dihydro-5-thia Z010 [3,2-alpyrimidine nucleus, a 2-thio-2,4-oxazolidine1-- dione nucleus, a thianaphthenone nucleus, a- 2-.thio?2,5- thiazolidinedione nucleus, a 2,4-thiazolidinedionenucleus, a thiazolidinone nucleus, a 4-thiazolinone nucleus, a 2- imino-2,4-oxazolinone nucleus, a 2,4
  • R represents an alkyl group containing from 1 to 8 carbon atoms
  • 11 represents a positive integer of from 1 to 2
  • X represents an acid radical
  • D represents a member selected from the group consisting of an alkylmercapto group containing from 1 to 2 carbon atoms, anaryl':
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected fromthe groupconsisting of a thiazole nucleus, 21 benzothiazole nucleus, a naphthothiazole nucleus, at thianaph theno-7',6',4,5-thiazole nucleus, an oXazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, at naphthoselenazole nucleus, a thiazoline nucleus, a 2-quinoline
  • 4-quinoline nucleus a l-isoquinoline nucleus, a henzimidazolc nucleus, a 3,3-clialkylindolenine nucleus,.a 2ipyridine nucleus, and a 4-pyridine nucleus.
  • R represents a member selected from the group consisting of a hydrogen atom and a carbalkoxyl group containing from 2 to 3 carbon atoms
  • R and R each represents a member selected from the group consisting of a hydrogen atom and a lower alkyl group
  • Q represents the non-metallic atoms necessary to complete a nucleus selected from the group consisting of an indandione nucleus, a pyrazolone nucleus, an isoxazolone nucleus, an oxindole nucleus, a 2,4,6-triketohexahydropyrimidine nucleus, 21 2-thio-2,4,6-triketohexahydropyrimidine nucleus, 'a rhodanine nucleus, a 2(3H)-imidazo[l, Z-allpyridone nucleus, a 5,7-dioxo-6,7-dihydro-5-thiazolo ['3,2-a]pyrimidine nucleus
  • thiazolidinone nucleus a 4-thiazolinone nucleus, a 2- imino-2,4-oxazolinone nucleus, a 2,4-imidazolinedi0ne nucleus, a 2-thio-2,4-imidazolinedione nucleus", anda. 5'.- i'midazoli'nonenucleus.

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Description

United States Patent 2,856,404 MEROCYANINE DYES AND INTERMEDIATES Leslie G. S. Brooker and Donald W. Heseltine, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey 1 No Drawing. Application June 20, 1956 Serial No. 592,507
8 Claims. (Cl. 260-240) This invention relates to an improved method of making merocyanine dyes, some of which are new compositions of matter, and new intermediates for making these merocyanine dyes. The merocyanine dyes produced according to our invention can be employed in optically sensitizing photographic silver halide emulsions.
It is, therefore, an object of our invention to provide an improved method for making merocyanine dyes. Another object is to provide certain new merocyanine dyes. Still another object is to provide new intermediates for making these merocyanine dyes. A further object is to provide photographic silver halide emulsions sensitized with these merocyanine dyes. Other objects will become apparent from a consideration of the following description and examples.
According to our invention, we provide an improved method for making merocyanine dyes by condensing an intermediate selected from those represented by the following general formula:
HaC-
H wherein D represents the atoms necessary to complete a cyclohexene ring and Q represents the non-metallic atoms necessary to complete a nucleus of the indandione series (e. g., 1,3-diketohydrindene, etc.) or a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, such as those of the pyrazolone series (.e. g.,- 3-methyl-l-phenyl-S-pyrazolone, l-phenylS-pyrazolone, 1-(2-benzothiazolyl)-3-methy1r5pyrazolone, etc.), those of the isoxazolone series (e. g., 3-phenyl-5(4H)-isoxazolone, 3-methyl-5(4H)-isoxazolone, etc.), those of the oxindole' series, (e. g., 1-alkyl-2,3-dihydro-2-oxindoles, etc.), those of the 2,4,6-triketodhexahydropyrimidiue series (e. g., barbituric acid or 2-thiobarbituric acid as well as their l-alkyl (e. g., l-methyl, l-ethyl, l-n-propyl,
l-n heptyl, etc.), or 1,3-dialkyl (e. g., 1,3-dimethyl, 1,3- diethyl, 1,3-di-n-propyl, 1,3-diisopropyl, 1,3-dicyclohexyl, LB-diQS-methoxyethyl), etc.), or 1,3-diaryl (e. g., 1,3- diphenyl, 1,3-di(p-chlor0phenyl), 1,3-di(p-ethoxycarbonylphenyl), etc.), or l-aryl (e. g., 1-pheny1, l-p-chlorophenyl, 1-p-ethoxycarbonylphenyl), etc.) or l-alkyl-S- aryl (e. g., 1-ethyl-3-phenyl, l-n-heptyl-S-phenyl, etc.) derivatives), those of the rhodanine series (i. e., 2-thio- 2,4-thiazolidinedione series), such as rhodanine, 3-alkylrhodanines (e. g., 3-ethylrhodanine, 3-allylrhodanine, etc.) or 3-arylrhodanines (e. g., 3-phenylrhodanine, etc.), etc., those of the 2(3H)-imidazo[l,2-a]-pyridone series, those of the 5,7-dioxo-6,7-dihydro-5-thiazolo-[3,2-a]- pyrimidine. series (e. g., 5,7-dioxo-3-phenyl-6,7-dihydro- 5-thiazolo[3,2-u]pyrimidine, etc.), those of the 2-thio-2,4- oxazolidinedione series (i. e., those of the 2-thio-2,4- (3H,5H)-oxazoledione series) (e. g., 3-ethyl-2-thio-,2,4- oxazolidinedione, etc.), those of the thianaphthenone series (e. g., 3(2H)-thianaphthenone, etc.), those of the Z-thio-2,5-thiazolidinedione series (i. e., the 2-thio-2,5-
(3H,4H)-thiazoledione series) (e. g., 3-ethyl-2-thio-2,5- thiazolidinedione, etc.), those of the 2,4-thiazolidinedione series (e. g., 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, Sax-naphthyl-2,4-thiazolidinedione, etc.), those of the thiazolidinone series (e. g., 4-thiazolidinone, 3-ethyl-4-thiazolidinone, 3-phenyl-4-thiazolidinone, 3-a-naphthyl-4-thiazolidinone, etc.), those of the 4-thiazolinone series (e. g., 2- ethylr'nercapto-4-thiazolinone, 2-alkylphenylamino-4-thiazolinones, 2-diphenylamino-4-thiazolinone, etc.), those of the 2-imino-2,4-oxazolinone (i. e., pseudohydantoin) series, those of the 2,4-imidazolinedione (hydantoin) series (e. g., 2,4-imidazolinedione, 3-ethyl-2,'4-imidazolinedione, 3-phenyl-2,4-imidazolinedione, 3-u-naphthyl- 2,4-imidazolinedione, 1,3-diethyl-2,4-imidazolinedione, 1- ethyl-3-a-naphthyl 2,4 imidazolinedione, 1,3 diphenyl- 2,4-imidazolinedione, etc.), those of the 2-thio-2,4-imidazolinedione (i. e., 2-thiohydantoin) series (e. g., 2-thio- 2,4-imidazoliuedione, 3-ethyl-2-thio-2,4-imidaz0linedione, 3-phenyl-2-thio-2,4-imidazolinedione, 3-a-naphthyl-2-thio- 2,4-imidaz0linedione, 1,3 diethyl-2-thio-2,4-imidazolinedione, 1-ethyl-3-phenyl-2-thio-2,4-imidazolinedione, 1- ethyl-3-a-naphthyl-2-thio 2,4 imidazolinedione, 1,3-diphenyl-2-thio-2,4-imidazolinedione, etc.), those of the 5- imidazolinone series (e. g., 2-n-propylmercapto-5-imidazolinone, etc.), etc. (especially a heterocyclic nucleus containing 5 atoms in the heterocyclic ring, 3 of said atoms being carbon atoms, 1 of said atoms being a nitrogen atom, and 1 of said atoms being selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom), with a compound selected from those represented by the following general formula:
wherein R represents an alkyl group (e. g., methyl ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, p-methoxyethyl, {3-ethoxyethyl, allyl (i. e., methylvinyl), benzyl (phenylmethyl), p-phenylethyl, carboxymethyl, etc.) (especially alkyl groups containing from 1 to 4 carbon atoms), n represents a positive integer of from 1 to 2, X represents an acid radical (e. g., chloride, bromide, iodide, p-toluenesulfonate, benzenesulfonate, ethylsulfate, methylsulfate, etc.), D represents an electronegative radical, such as alkyhnercapto (e. g., methylmercapto, ethylmercaptq; etc.), arylmercapto (e. g., phenylmercapto, tolylmercapto, etc.), a B-acylanilidovinyl group (e. g., fl-acetanilidovinyl, fl-benzoylanilidovinyl, etc.), a B-acylanilido-1,3-butadienyl group (e. g., fi-acetanilido- 1,3-butadienyl, a-benzoylanilido-1,3-butadienyl, etc.), etc., and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 (n is 1) to 6 (n is 2) atoms in the heterocyclic ring, such as those selected from the group consisting of those of the thiazole series (e. g., thiazole, 4-methylthiazole, 4- phenylthiazole, S-methylthiazole, S-phenylthiazole, 4,5- dimethylthiazole, 4,5-diphenylthiazole, 4(2-thienyl)thiazole, etc.), those of the benzothiazole series (e. g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazo1e, -bromobenzothiazole, 4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, ti-methoxybenzothiazole, S-iodobenzothiazole, 6-iodobenzothiazole, 4- ethoxybenzothiazole, S-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,G-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole, 6-hy droxybenzothiazole, etc.), those of the naphthothiazole series (e. g., naphtho[l,2-]thiazole, naphtho[2,1]thiaz0le 5 -methoxynaphtho[2,1]thiazole, 5 -ethoxynaphtho[2,1] wherein R, Z, n, D and Q each have the values given thiazole, 8-meth0xynaphthoI1,2]thiazole, 7-methoxynaphabove and d represents a positive integer of from 1 to 3. tho[1,2]thiazole, etc.), those of the thianaphtheno- The dyes produced by condensing an intermediate se- 7',6,4,5-thiazole series (e. g., 4-methoxythianaphthenolected from those represented by Formula III with those 7,6',4.,5-thiazole, etc.), those of the oxazole series (e. g., 5 of Formula II can be represented by the following gen- 4-methyloxazole, S-methyloxazole, 4-phenyloxaz-o1e, 4,5- eral formula:
wherein R, Z, n, d, R R R and Q each have the values given above.
diphenyloxazole, 4-ethy1o'xazole, 4,5-dimethyloxazo1e, 5- phenyloxazole, etc.), those of the benzoxazole series I (e. g., benzoxazole, S-chlor-obenzoxazole, S-methylben- The condensations of the intermediates of Formulas zoxazole, 5 phenylbenzoxazole, 6 methylbenzoxazole, I or III with the compounds of Formula II can be acceler- 5,6-dimethylbenzoxazole, 4, 6- dimethylbeuzoxazole, 5- 2 ated by basic condensing agents, such as the trialkylmethoxybenzoxazole, ethoxybenzoxazole, S-chloroamines, (triethylamine, tri-n-propylamine, triisopropylbenzoxazole, '6-methoxybenzoxazole, S-hydroxyb'enzoxamine, trim-butylamine, etc.), N,N-dialkylanilines (e. g., azole, 6-hydroxybenzoxazole, etc.), those of the naph- N,N-dimethylaniline, N,N-diethylaniline, etc.), N-alkylthoxazole series (e. g., naphtho[1,2]oxazole, naphthopiperidines (e. g., N-methylpiperidine, N-ethylpiperidine, [2,l]oxazole, etc.), those of the selenazole series (e. g., etc.), etc. The condensations can be carried out in the 4-methylselenazole, 4-phenylselenazole, etc.), those of the presence of an inert diluent, such as the lower alcohols benzoselenazole series (e. g., benzoselenazole, S-chloro- (e. g., ethanol, n-propanol, isopropanol, n-butanol, etc.), benzoselenazole, S-methoxybenzoselenazole, S-hydroxypyridine, quinoline, 1,4-dioxane, etc. Heat accelerates benzoselenazole, tetrahydrobenzoselenazole, etc.), those the condensations, although temperatures varying from of the naphthoselenazole series (e. g., naphtho[1,2]selenambient (ca. 25 C.) to the reflux temperature of the reazole, naphtho[2,1]selenazole, etc.), those of the thiaction mixture can be employed.
az-oline series (e. g., thiazoline, 4-methylthiazoline, etc.), According to our invention, we provide the intermethose of the 2-quinoline series-(e. g., quinoline, 3-methyldiates represented by Formula I above by condensing a quinoline, S-methylquinoline, 7-methylquinoline, 8- ketone selected from those represented by the following methylquinoline, 6-chloroquino1ine, 8-chloroquinoline, general formula:
G-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinov line, S-hydroxyquinoline, etc.), those of the 4-quinoline X series (e. g., quinoline, 6-methoxyquinoline, 7-methyl- H5O C\ quinoline, S-methylquinoline, etc.), those of the l-isoquinoline series (e. g., isoquinoline, 3,4-dihydroisoquinoline, etc.), those of the 3-isoquinoline series (e. g., iso- I quinoline, etc.), those of the benzimidazole series (e. g., one compound selected from those represented by the 1,3-diethylbenzimidazole, -1-ethyl-3-phenylbenzimidazole, following general formula: etc.), those of the 3,3-dialkylindolenine series (e. g., 3,3- VI ,Q\ dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-tri- X methylindolenine, etc.), those of the 2-pyridine series H2O 0:0 ('e. g., pyridine, S-methylpyridine, etc.), those of the 4 wherein Q-has the values given above. Particularlyu'sepyridine series idin m), t ful ketones selected from those represented by Formula Particularly useful intermediates selected from those V above'include those represented y the57f0110wing "8 represented by Formula I above include those reprefll formula:
wherein D has the values given above with a ketomethylsented by the following general formula: R2 Rs 111 R2 /Rz H C/ \CH 11-0 21:: o HaO- b=0 Hie-o o=6- -b=o Q H H wherein R R and R each have'the values given above.
wherein R -represents a hydrogen atom or a carbalkoxyl Typical ketone compounds selected from those repre group such as 'carbomethoxyl, carbethoxyl, etc. (e. g., sented by Formulas V and VII above include isophorone, a carbalkoxyl group containing from 2 to 3 carbon 3,5-dimethyl-2'cyclohexen-l-one, S-methyI-Z-cyclohexenatoms), R and R each represents a hydrogen atom or a l-one, 4 carbethoxy-3-methyl-Z-cyblohexeh-l-one, etc. lower alkyl group, such as methyl, ethyl, etc., and Q The condensations of the compounds of Formula VI has the values given above. with those of Formulas V or VII can be accelerated by The dyes produced by condensing an intermediate 86- strong basic condensing agents, such as piperidine, dilected from those represented by Formula I above with ethylamine, etc., or by a mixture of ammonium acetate. those of Formula II can be represented by the following and acetic acid. These condensations can be convenientgeneral formula: 1y carried out in an inert diluent, such as chloroform,
diethyl ether, etc.. Heating accelerates. these condensations, temperatures varying from ambient (ca. 25' C.) to the reflux temperature of the reaction mixture being particularly useful.
The following examples will serve to illustrate more fully the manner whereby we practice our invention.
Example 1.3-ethyl-5-(3,5,S-tfimethyl-Z-cyclohexen-J- ylidene)-rhodanine tion was concentrated to 50 ml. and chilled overnight.
The crude crystalline product was filtered off and recrystallized from methyl alcohol. The yield of purified product was 8.5 g. (15%), M. P. 122-3 C.
Example 2.3-methyl-1-phenyl-4-(3,5,5-trimethyl-2-cyclohexen-I -ylidene)-5-pyrazol0ne CH3 CH;
HaC- N 3-methyl-l-phenyl-S-pyrazolone 17.4 g., 1 mol.), isophorone (15 g., 1 mol.+l0%) and two drops of piperidine were mixed and heated in an oil bath at ISO-135 C. for four hours. The reaction mixture was then extracted with 400 ml. of 90l20 C. ligroin. The ligroin solution was allowed to cool to room temperature and was then decanted from separated resinous material. After chilling and stirring the desired product separated from the ligroin solution. The crude product was filtered off and recrystallized from ligroin. The yield of purified product was 14.2 g. (48%), M. P. 115-117 C.
Example 3 .1 ,3-diethyl-5 3,5 ,5 -trimethyl-2-cyclohexen- 1 -ylidene) -2-thi0barb iturl'c acid 1,3-diethyl-2-thiobarbituric acid (40 g., 1 mol.) and isophorone (30.3 g., 1 mol.+%) were dissolved in chloroform (100 ml.), and ammonium, acetate (2.5 g.) and acetic acid (4 ml.) were added. The mixture was heated under reflux for an hour in a system fitted for continuous removal of water. The reaction mixture was then Washed with two 100 ml. portions of water and the chloroform removed by distillation. The residue was recrystallized from methyl alcohol and the yield of purified material was 35.2 g. (55%), M. P. 108-9 C.
6 Example 4.,-3-phenyl-4 (3,5,5-trimethyl-Z-cyclohexen-I- ylidene-5-(4H) -isoxaz0lone OH; CH
Back
| CH: /N
Example 5 .1 2 -benzothiazolyl) -3-mgthyl-4- (3,5 ,5 -trimethyl-Z-cyclohexen-I -ylidene) -5-pyrazalone i CH:
1 (2 benzothiazolyl) 3 methyl 5 pyrazolone (7.7 g., 1 mol.) and isophorone (5.1 g., l mol.+10%) were dissolved in chloroform (40 ml.), and ammonium acetate (2 g.) and acetic acid (4 ml.) were added. The mixture was heated under reflux for twenty-four hours in an apparatus designed for the continuous removal of water. The chloroform solution was washed with two 20 ml. portions of water and the solvent removed under reduced pressure. The residue was stirred with methyl alcohol (50 ml.) and filtered, the solid being discarded. The methyl alcoholic solution was treated with water (200 ml.) and the precipitated product filtered off. After recrystallization from methyl alcohol, the yield of purified material was 2.8 g. (24%), M. P. 204-5 C. dec.
Example 6.--3-ethyl- -[4 (3-methyl-2(3H)-benz0xazolylidene)-1-3-ne0pentylene-Z-butenylidene]rhodanine chilling overnight, the crude dye was filtered ofi, washed with water and methyl alcohol and dried. The yield of purified dye after two recrystallizations from pyridine and methyl alcohol was 0.42 g. 41%), M. P. 21mg? C.dec. -f
2-methylmercapto-wnaphthoxazole (2.15 g.,. 1 mol.-l-.-
100%) andmethyl p-toluenesulfonate (2.05. g., 1 moll l- 120%) were mixed and heatedovernight in. anoil' bath at IOU-105 C. The crude quaternary salt and 3-ethyl-5- (3,5,5 trimethyl 2 cyclohexen 1 ylidene)rhodanine (1.40 g., 1 mol.) were dissolved in pyridine and triethylamine (1.4 ml., 1 mol.+100%) was added. After heating under reflux for a half-hour, the reaction mixture was poured with stirring into methyl alcohol (150 ml.) and chilled overnight. The crude dye was filtered off, washed with methyl alcohol and dried. The crude dye was purified by boiling with three 100 ml. portions of methyl alcohol and filtering hot each time. After two recrystallizations from pyridine and methyl alcohol, the yield of purified dye was 0.73 g. (31% M. P. 25l-2 C. dec.
Example 8.--3 ethyl 5 [4 (1 methyl 2(1H)- naphth[1,2]oxazo lylidene) 1,3 neopentylene 2- butenylidene] rhodanz'ne.
2-methylmercapto-B-naphthoxazole (2.15 g., 1 mol.+ 100%) and methyl p-toluenesulfonate (2.05 g., 1 mol.+ 120%) were mixed and heated on the oilbath at 100- 105 C. overnight. The crude quaternary salt and 3- ethyl 5 (3,5,5 trimethyl 2 -cyclohexen 1 ylidene) rhodanine (1.40 g.,.1 mol.)-were dissolved in pyridine ml.) and triethylarnine (1.4 ml., 1. mol.+100%) was added. After the reaction mixture was heated under reflux for a half-hour, it was poured into methyl alcohol (150 ml.) with stirring. After chilling overnight, the crude dye"was'filtered oflf', boiled with three 100 ml. portions of methyl alcohol, filtered and dried. After two recrystallizations from pyridine and methyl alcohol, the yield of purified dye was'0.37 g. (16%), M. P. 2645 C. dec. Example 9.--3-ethyl-5-[4-(l-methyl 2(1H)-ntrptho[1,2]
selenazolylidene) 1,3 neopentylene Z-butenylidene] rhodanine 3-e'thyl'5-(3,5,5-trimethyl -'2 cyclohexen 1 ylidene) rhodanine (0.70 g., 1 mol.) and l-methyl-Z-methyl'rnercaptonaphtho 1,2] selenazolium p-toluenesulfonate (1.20" gt, 1 moll+10%)' were dissolved in pyridine" (151111.), and triethylam'ine (0.7 ml., 1 mo1.+100%-) was added.
. 8 The reaction mixture was heated under reflux for a half-hour and was; then poured into methyl alcohol (150 11111). After chilling" overnight, the crude dye was filtered off, washed with methyl alcohol and dried. After two recrystallizations from pyridine and methyl alcohol the yield" of purified dye was 0.65 g. (49%), M. P. 234-5" C. dec.
Exam p le 1 0: 3 methyl 4-[4 (3 methyl-2 (3H)-benz0xazolylidene) 1,3 neopentylene 2 butenylidene] 1- phenyl-S-pyrwzolone N H I,
l CH3 CH2 3-methyl -l-phenyl4 (3,5,5 trimethyl 2 cyclohexe'n- 1-ylidene)'- 5 -pyra'zolon'e (1.47 g., 1 mol.), 3-methyl-2- methylmercaptobenzoxazolium p-toluenesulfonate (5.26 g., 1 mol.+200% and triethylaniine (2.1 ml., 1 H10l2+ 200%) were dissolved in pyridine ('15 ml.) and the mix CH CH2 1, 3' 'diethy1-5-(3 ,5 ,S-trimethyl-2-cyclohexen-1-y1idenei)- Z-thiobarbiturio acid (1.54 g., 1 mol.) and 3-methyl-2- methylmercaptobenzothiazolium p-toluene'sulfo'nate (3.67" g.,. 1 m'ol.+1'00%) were dissolved in pyridine (15 ml.) and triethyla'mine (1.4 ml., 1 mol.+-100%) was added.
The reaction mixture was heated under reflux for. ten:
minutes and the crude dye was then precipitated by the addition of methylalcohol (100 ml.). overnight, the dye was filtered off, washed with methyl alcohol and dried. After two recrystallizations from pyridine and methyl alcohol, the yield of purified dye was 1.82 g. M. P. 237-8 C.
Example 12.-4-[4-(3-ethyl-2(3H)-benzothiazolylidene)- 1,3-ne0pentylene-2+butenylidene] 3 phenyl 5(4H)- isoxazalone CH| CH 3-phenyl-4-(3,5,S-trimethyl-Z-cyclohexen 1 ylidene)- 5 ('4H)-isoxazolone (1.41 g., 1 mol.), 3-ethyl-2-ethylmercaptobenzothiazolium ethylsulfate (3.32 g., 1 mol.+- and triethylamine (1.4 ml., 1 mol.+1.00%) were dissolved in. pyridine (.10 ml.) and heated under reflux for ten minutes; The crude dye was then precip-- After chilling Example 13.-4 [6 (3 ethyl 2 (3H) benzothiazolylidene) 1,3 neopentylene 2,4 hexadienylidenel-3- phenyl-5 (4H) -isoxazolone 3-phenyl-4-(3,5,5-trimethyl-2-cyclohexen 1 ylidene)- 5(4H)-isoxazolone (1.41 g., 1 mol.), Z-ti-acetanilidovinyl-3-ethylbenzothiazolium iodide (2.25 g., 1 mol.) and triethylamine (1.4 ml., 1 mol.+l%) were dissolved in pyridine (10 ml.) and heated under reflux for ten minutes. The reaction mixture was poured into a beaker,
100 ml. of methyl alcohol added with stirring and the mixture chilled overnight. The crude dye was then filtered off, washed with methyl alcohol and dried. After two recrystallizations from pyridine and methyl alcohol, the yield of purified dye was 1.59 g. (68%), M. P. 232-3 C. dec.
Example 14.4-[8-3-ethyl-2(3H) benzothiazolylidene)- 1,3-ne0pentylene2,4,6 oczatrienylidene] 3 phenyl- (4H) -is0xazolone Example 15.1-(2 benzothiazolyl) 3-methyl 4-[4-(3- methyl-2 (3H) -benzoxazolylidene) 1,3 neopentylene- Z-butenylidene] -5-pyrazol0ne CH3 CH3 He CH5 Z-methylmercaptobenzoxazole (1.65 g., 1 mol.+400%) and methyl p-toluenesulfonate (1.86 g., 1 mol.+400%) were mixed and heated to reflux over a free flame and then allowed to cool slowly to room temperature. 1 (2 benzothiazolyl) 3 methyl 4 (3,5,5 trimethyl- 2-cyclohexen-1-ylidene)-5-pyrazolone (0.71 g., 1 mol.), triethylamine (1.4 ml., 1 mol.+400%) and pyridine ml.) were then added and the reaction mixture heated '10 under reflux for ten minutes. The crude dye was precip itated by the addition of methyl alcohol ml.), filtered from the reaction mixture, washed with methyl alcohol and dried. After two recrystallizations from pyridine and methyl alcohol, the yield of purified. dye was 0.24 g. (25%), M. P. 310-11 C. dec.
In a manner similar to that illustrated in the above examples, other new intermediates and merocyanine dyes can be prepared. For example, the intermediate represented by the following formula:
can be prepared by condensing l-methyl-Z-thiobarbituric acid with 4-carbethoxy-3-methyl-2-cyclo hexen-l-one.
All the dyes of our invention are particularly useful in manufacturing photographic, silver halide emulsions, serving to alter the sensitivity thereof. Sensitization by means of our new dyes is, of course, directed primarily to the ordinarily employed, gelatino-silver-halide, developing-out emulsions. The dyes are advantageously incorporated in the washed, finished emulsion and should, of course, be uniformly distributed throughout the emulsion. In the preparation of photographic emulsions containing our new dyes, it is only necessary to disperse the dyes in the emulsions. The methods of incorporating dyes in emulsion are simple and well known to those skilled in the art of emulsion making. It is convenient to add the dyes from solutions in appropriate solvents. The solvent must, of course, be compatible with the emulsion and substantially free from any deleterious effect on the light-sensitive materials. Pyridine has proven satisfactory as a solvent for the majority of our new dyes.
The concentration of our new dyes in the emulsion can vary widely, i. e., from about 5 to about 100 mgs. per liter of flowable emulsion. The concentration of the dye will vary according to the type of light-sensitive material in the emulsion and according to the effects 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.
To prepare a gelatino-silver-halide emulsion sensitized with one of our new dyes, the following procedure is satisfactory: A quantity of the dye is dissolved in pyridine or other suitable solvent and a volume of this solution (which may be diluted with methanol) containing from 5 to 100 mgs. of dye is slowly added to about 1000 cc. of a gelatino-silver-halideemulsion, with stirring. Stirring is continued until the dye is uniformly distributed throughout the emulsion. With most of our new dyes, 10 to 20 mgs. of dye per liter of emulsion suflices to produce the maximum sensitizing effect with the ordinary gelatino-silver-bromide (including bromiodide) emulsions. With fine-grain emulsions, which include most of the ordinarily employed. gelatino-silverchloride emulsions, somewhat larger concentrations of dye may be necessary to secure the optimum sensitizing effect.
The above statements, are only illustrative and are not to be understood as limiting our invention in any sense, as it will be apparent that our new dyes can be incorporated by other methods in many of the photographic silver halide emulsions customarily employed in the art. For instance, the dyes can be incorporated by bathing a plate or fihn upon which an emulsion has been coated, in the solution of the dye, in an appropriate solvent. Bathing methods, however, are not to be preferred ordinarily.
11 Photographic silver halide emulsions which. can advantageously be sensitized by means of the new dyes of our invention comprise the customarily employed gelatinosilver-chloride, gelatino-silver chlorobromide, gelatinosilver-bromide, and gelatino-silver-bromiodide developingout emulsions.
Photographic silver halide emulsions, such as those listed above, containing the sensitizing dyes of our invention can also contain such addendaas chemical sensitizers, e. g., sulfur sensitizers (e. g., allyl thiocarbamide, thio urea, allylisothiocyanate, cystine, etc.), various gold compounds (e. g., potassium chloroaurate, auric trichloride, etc.) (see U. S. Patents 2,540,085; 2,597,856 and 2,597,915, various palladium compounds, such as palladium chloride (U. S. 2,540,086), potassium chloropalladate (U. S. 2,598,079), etc., or mixtures of such sensitizers; anti-foggants, such as ammonium chloroplatinate (U. S. 2,566,245), ammonium chloroplatinite (U. S. 2,566,263), benzotriazole, nitrobenzimidazole, S-nitroindazole, benzidine, mercaptans, etc. (see Mees-- The Theory of the Photographic Process, MacMillan Pub, 1942, page 460), or mixtures thereof; hardeners} such as formaldehyde (U. S. 1,763,533), chrome alum (U. S. 1,763,533), glyoxal (U. S. 1,870,354), dibromacrolein (Br. 406,750), etc.; color couplers, such as those described in U. S. Patent 2,423,730, Spence and Carroll U. S. Patent 2,640,776, etc; or mixtures of such addenda. Dispersing agents for color couplers, such as those set forth in U. S; Patents 2,322,027 and 2,304,940, can also be employed in the above-described emulsions.
In the manner described above, a number of the dyes of our invention represented by Formulas IV or IVa above were separately incorporated in an ordinary gelatino-silver-bromiodide emulsion, the dyes being thoroughly incorporated in the emulsions by stirring. After a short digestion, the-emulsions were coated onto ordinary cellulose acetate film supports and the coatings exposed in a spectrograph and sensitometer and then developed in the usual way. The sensitizing range and maximum absorption for each of the dyes are indicated in the following table.
What we claim as our invention and desire secured by Letters Patent of the United States is:
l. A process for makingpolymethine dyes comprising condensing in the presence of a basic condensing agent an intermediate selected from those represented by the following general formula:
wherein R represents a member selected from the group consisting of a hydrogen atom. and a carbalkoxyl group containing from 2v to 3 carbon atoms, R2 and R3 each represents a member selected from the group consisting of a hydrogen atom and. a. lower alkyl group, and Q represents the non-metallic atoms necessary to complete a nucleus selected from the group consisting of anindan':
dione nucleus, a pyrazolone nucleus, an isoxazolone:
nucleus, an oxindole nucleus, at 2,4,6-triketohexahydropyrimidine nucleus, a 2-thio-2,4,6-triketohexahydropyrimidine nucleus, a rhodanine nucleus, a 2(3H')-imidazo- [1,2-alpyridone nucleus, a 5,7-dioXo-6,7-dihydro-5-thia Z010 [3,2-alpyrimidine nucleus, a 2-thio-2,4-oxazolidine1-- dione nucleus, a thianaphthenone nucleus, a- 2-.thio?2,5- thiazolidinedione nucleus, a 2,4-thiazolidinedionenucleus, a thiazolidinone nucleus, a 4-thiazolinone nucleus, a 2- imino-2,4-oxazolinone nucleus, a 2,4-imidazolinedione nucleus, a 2-thio-2,4-imidazolinedione nucleus, and a 5- imidazolinone nucleus, with a compound selected from those represented by the following general formula:
wherein R represents an alkyl group containing from 1 to 8 carbon atoms, 11 represents a positive integer of from 1 to 2, X represents an acid radical, D represents a member selected from the group consisting of an alkylmercapto group containing from 1 to 2 carbon atoms, anaryl':
mercapto group containing from 6 to 7 carbon atoms, a- B-acylanilidovinyl group wherein the acyl radical contains from 2 to 7 carbon atoms, and a B-acylanilido-LS- butadienyl group wherein the acyl radical contains from 2 to 7 atoms, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected fromthe groupconsisting of a thiazole nucleus, 21 benzothiazole nucleus, a naphthothiazole nucleus, at thianaph theno-7',6',4,5-thiazole nucleus, an oXazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, at naphthoselenazole nucleus, a thiazoline nucleus, a 2-quinoline nucleus, 8. 4-quinoline nucleus, a l-isoquinoline nucleus, a henzimidazolc nucleus, a 3,3-clialkylindolenine nucleus,.a 2ipyridine nucleus, and a 4-pyridine nucleus.
2. A process as defined in claim 1 wherein the basic condensing agent is a trialkylamine.
3. A process as defined in claim 2 wherein the tri alkylamine is triethylamine.
4. An intermediate useful in the preparation of polyfollowing general formula:
wherein R represents a member selected from the group consisting of a hydrogen atom and a carbalkoxyl group containing from 2 to 3 carbon atoms, R and R each represents a member selected from the group consisting of a hydrogen atom and a lower alkyl group, and Q represents the non-metallic atoms necessary to complete a nucleus selected from the group consisting of an indandione nucleus, a pyrazolone nucleus, an isoxazolone nucleus, an oxindole nucleus, a 2,4,6-triketohexahydropyrimidine nucleus, 21 2-thio-2,4,6-triketohexahydropyrimidine nucleus, 'a rhodanine nucleus, a 2(3H)-imidazo[l, Z-allpyridone nucleus, a 5,7-dioxo-6,7-dihydro-5-thiazolo ['3,2-a]pyrimidine nucleus, a 2-thio-2,4-oxazolidinedi-one nucleus, a thianaphthenone nucleus, a 2-thio-2,5-thiazolidinedione nucleus, a 2,4-thiazolidinedione nucleus, 8. thiazolidinone nucleus, a 4-thiazolinone nucleus, a 2- imino-2,4-oxazolinone nucleus, a 2,4-imidazolinedi0ne nucleus, a 2-thio-2,4-imidazolinedione nucleus", anda. 5'.- i'midazoli'nonenucleus.
13 14 5. The compound represented by the following formula: O
CH3 CH3 HzC OHQ I l--1| -CzH A R W s H2? (3H1 -N\ s 8. The compound represented by the following foro C--N mnla: H g g H 01%; CH;
2 a /Q( (I) 11,0 cm d--N-om 6. A compound represented by the following formula: H1041} l;
CH3 011 I \O/ 0 CH3 References Cited in the file of this patent E UNITED STATES PATENTS K 2,465,883 Kendall et a1 Mar.29, 1949 g 0 2,505,497 Kendall et a1 Apr. 25, 1950 (5,11, 2,734,900 Heseltine Feb. 14, 1956 FOREIGN PATENTS 7. The compound represented by the following for- 595,784 Great Britain Dec. 16, 1947 mula: 595,785 Great Britain Dec. 16, 1947

Claims (1)

1. A PROCESS FOR MAKING POLYMETHINE DYES COMPRISING CONDENSING IN THE PRESENCE OF A BASIC CONDENSING AGENT AN INTERMEDIATE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA:
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3013015A (en) * 1959-09-29 1961-12-12 Gen Aniline & Film Corp 1-substituted-2-pyrazoline-3-carbox-aldehyde dye intermediates
US3194805A (en) * 1960-09-02 1965-07-13 Eastman Kodak Co Merocyanine and holopolar dyes containing arylene-chain substitution
US3357833A (en) * 1962-11-23 1967-12-12 Agfa Ag Photographic emulsions sensitized with cyanine dyestuffs
US5453505A (en) * 1994-06-30 1995-09-26 Biometric Imaging, Inc. N-heteroaromatic ion and iminium ion substituted cyanine dyes for use as fluorescence labels

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB595785A (en) * 1945-07-03 1947-12-16 John David Kendall Improvements in or relating to dyestuff intermediates
GB595784A (en) * 1945-07-03 1947-12-16 John David Kendall Improvements in or relating to cyanine dyestuffs
US2465883A (en) * 1949-03-29 Production of dyestuff
US2505497A (en) * 1945-07-03 1950-04-25 Ilford Ltd Production of photographic sensitizing dyestuffs
US2734900A (en) * 1953-12-28 1956-02-14 Chxgh

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2465883A (en) * 1949-03-29 Production of dyestuff
GB595785A (en) * 1945-07-03 1947-12-16 John David Kendall Improvements in or relating to dyestuff intermediates
GB595784A (en) * 1945-07-03 1947-12-16 John David Kendall Improvements in or relating to cyanine dyestuffs
US2505497A (en) * 1945-07-03 1950-04-25 Ilford Ltd Production of photographic sensitizing dyestuffs
US2734900A (en) * 1953-12-28 1956-02-14 Chxgh

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3013015A (en) * 1959-09-29 1961-12-12 Gen Aniline & Film Corp 1-substituted-2-pyrazoline-3-carbox-aldehyde dye intermediates
US3194805A (en) * 1960-09-02 1965-07-13 Eastman Kodak Co Merocyanine and holopolar dyes containing arylene-chain substitution
US3357833A (en) * 1962-11-23 1967-12-12 Agfa Ag Photographic emulsions sensitized with cyanine dyestuffs
US3379727A (en) * 1962-11-23 1968-04-23 Agfa Ag Cyanine dyestuffs
US5453505A (en) * 1994-06-30 1995-09-26 Biometric Imaging, Inc. N-heteroaromatic ion and iminium ion substituted cyanine dyes for use as fluorescence labels

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