Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines

Definitions

• This invention relates to carbocyanine dyes containing a substituted benzimidazole nucleus and methods for making them.
• the new dyes of our invention have been found to be particularly useful in altering the sensitivity of photographic silver halide emulsions.
• the sensitizing bands of our new dyes are unusually sharp, hence they can be used expeditiously in sensitizing photographic silver halide emulsions where little or no sensitivity in a given region of the spectrum is desired. They are also quite useful in supersensitizing combinations with other optical sensitizing dyes. See the copending application of Jean E. Jones, Serial No. 451,500, filed on even date herewith now U. S. Patent 2,751,296, issued June 19, 1956.
• an object of our invention to provide a new class of carbocyanine dyes. Another object is to provide methods for making these new dyes. Still another object is to provide photographic silver halide emulsions sensitized with our new dyes. Other objects will become apparent from a consideration of the following description and examples.
• R represents an alkyl group, such as methyl, ethyl, n-propyl, n-butyl, allyl (vinylmethyl), carbethoxymethyl, etc. (e. g., an alkyl group containing from 1 to 4 carbon atoms), or an aryl group, such as phenyl, m-, or p-tolyl, etc. (e. g., a mononuclear aromatic group of the benzene series), R1 and R2 each represents an alkyl group, such as methyl, ethyl, n-propyl, n-butyl, allyl (vinylmethyl), carbethoxymethyl, etc. (e.
• R3 represents an acetyl group, a RNHCO group, wherein R is a group identical to the R defined above, or a bromine atom
• X represents an acid radical, such as chloride, bromide, iodide, perchlorate, thiocyanate, benzenesulfonate, p-toluenesulfonate, methylsulfate, ethylsulfate, etc.
• 12 represents a positive integer of from 1 to 2
• 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 of the thiazole series (e.
• thiazole 4-methylthiazole, 4-phenylthiazo1e, S-methylthiazole, S-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2 -thienyl)thiazo1e, etc.
• those of nited States Patent 0 2,778,823 Patented Jan. 22, 1957 the benzothiazole series e.
• benzothiazole 4-chlorobenzothiazole, S-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-rnethylbenzothiazole, 5- methylbenzothiazole, 6-methylbenzothiazole, S-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, 5- methoxybenzothiazole, 6-methoxybenzothiazole, S-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6- dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.
• a-naphthothiazole p-naphthothiazole, 5-methoxy-p-naphthiothia zole, 5-ethoXy-B-naphthothiazole, S-methoxy-a-naphthothiazole, 7-methoxy-wnaphthothiazole, etc.
• those of the thianaphtheno-7',6,4,5-thiazole series e. g., 4'-rnethoxythianaphtheno-7,6',4-5-thiazole, etc.
• those of the oxazole series e.
• benzoxazole S-chlorobenzoxazole, S-methylbenzoxazole, S-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, S-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5- hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), those of the naphthoxazole series (e. g., a-naphthoxazole, [3- naphthoxazole, etc.), those of the selenazole series (e.
• naphthoxazole series e. g., a-naphthoxazole, [3- naphthoxazole, etc.
• selenazole series e.
• 4-methylselenazole, 4-phenylselenazo1e, etc. those of the benzoselenazole series (e. g., benzoselenazole, 5- chlorobenzoselenazole, S-methoxybenzoselenazolti, S-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), those of the naphthoselenazole series (e. g., a-naphthoselenazole, B-naphthoselenazole, etc.), those of the thiazoline series (e.
• thiazoline 4-methylthiazoline, etc.
• Z-quinoline series e. g., quinoline, 3-methylquinoline, S-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8- hydroxyquinoline, etc.
• 4-quinoline series e. g., quinoline, 6-methoxyquinoline, 7-methylquinoline, S-methylquinoline, etc.
• l-isoquinoline series e.
• isoquinoline, 3,4-dihydroisoquinoline, etc. those of the 3-isoquinoline series (e. g., isoquinoline, etc.), those of the benzimidazole series (e. g., 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, 1,3-diethyl- 5-ethylcarbamylbenzimidazole, S-acetyl-1,3-diethylbenzimidazole, S-bromo-1,3-diethylbenzimidazole, S-chloro- 1,3-diethylbenzimidazole, etc.), those of the 3,3-dialkylindolenine series (e.
• pyridine series e. g., pyridine, S-methylpyridine, etc.
• the dyes of Formula I wherein R3 is an acetyl or ethylcarbamylgroup are particularly useful in practicing our invention.
• R, R1, R3, and X have the values given above, with chloral alcoholate.
• the condensations can advantageously be carried out in the presence of an inert diluent, such as the alcohol from which the alcoholate has been obtained.
• inert diluents such as ethanol, n-propanol, n-butanol, etc.
• the condensations are advantageously carried out in the presence of a strong base, such as an alkali metal alcoholate, e. g., sodium ethylate, potassium ethylate, etc. Heat accelerates the condensations, although temperatures varying from room temperature (ca. 20 C.) to the reflux temperature of the reaction mixture can be employed.
• the unsymmetrical carbocyanine dyes selected from those represented by Formula I can advantageously be prepared by condensing an'intermediate selected from those represented by Formula II with an intermediate selected from those represented by the following general formula:
• X1 represents an acid radical, such as those listed above for X
• R4 represents a carboxylic acyl group, such as acetyl, propionyl, butyryl, isobutyryl, benzoyl, etc. (e. g., a carboxylic acyl group containing from 2 to 7 carbon atoms)
• R5 represents an aryl group, such as phenyl, m-, or p-tolyl, etc. (e. g., a mononuclear aromatic group of the benzene series).
• the condensations can advantageously be effected in the presence of an inert diluent, such as the lower aliphatic alcohols (e. g., ethanol, n-propanol, isopropanol, n-butanol, etc.), pyridine, 1,4-dioxane, etc., and/or a basic condensing agent, such as the trialkylamines (e. g., triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, etc.), the N,N-dialkylanilines (e.
• an inert diluent such as the lower aliphatic alcohols (e. g., ethanol, n-propanol, isopropanol, n-butanol, etc.), pyridine, 1,4-dioxane, etc.
• a basic condensing agent such as the trialkylamines
• N,N-dimethylaniline, N,N-diethylaniline, etc. the N-alkylpiperidines (e. g., N-methylpiperidine, N-ethylpiperidine, etc.), etc.
• Heat accelerates the condensations although temperatures varying from room temperature (ca. 20 C.) to the reflux temperature of the reaction mixture can ad vantageously be employed.
• Example 1 5 -diacetyl-1 ,1 ',3,3'-tetraethylbenzimidazolocarbocyanine iodide CHnCO- COCES
• Example 3.5,5-dibr0m0-1,1',3,3tetraethylbenzimidazolocarbocyanine iodide To a solution of sodium ethylate, prepared from 0.6 g. (3 mols.) of sodium and 60 ml. of absolute ethyl alcohol,
• the reaction mixture was heated at the refluxing temperature for about one hour, chilled, filtered, and the residue was washed with a little ethyl alcohol and dried.
• the yield of dye was percent crude and 40 percent after two recrystallizations from ethyl alcohol.
• the minute red crystals melted at 230232 C. with decomposition.
• Example 5.1,3,3'triethyl-5-etlzylcarbamylbenzimidazolooxacarbocyanine iodide This dye was obtained in the same manner as that of Example 4, by using 1.9 g. (1 mol.) of 1,3-diethyl-5-ethylcarbamyl-2-methy1benzimidazolium iodide instead of 5- acetyl-l,3-diethyl-2-methylbenzimidazolium iodide.
• the desired product was obtained in 37 percent yield after two recrystallizations from 50 percent aqueous alcohol, and the minute orange crystals melted at 94-96 C.
• Example 6.5-bromo-l,3,3'-triethylbenzimidazolooxacarbocyanine iodide This dye was obtained in the same manner as that of Example 4, by using 2.0 g. (1 mol.) of 5bromo-1,3- diethyl-2-methylbenzimidazolium iodide, instead of 5- acetyl-l,3-diethyl-Z-methylbenzimidazolium iodide.
• the desired dye was obtained in 18 percent yield after two recrystallizations from ethyl alcohol, and the orange needles melted at 188-189 C. with decomposition.
• Example 7.1 S-diethyZ-S-ethylcarbamyl-I ',3,3'-trimelh ylbenzimidazoloindocarbocyanine perchlorate
• This dye was prepared in the same manner as that of Example 7, by using 1.8 g. (1 mol.) of 5-acetyl-1,3-dir ethyl-2-methylbenzimidazolium iodide, instead of 1,3-diethyl 5-ethylcarbamyl-2-methylbenzimidazolium iodide.
• the desired dye was obtained in 17 percent yield after two recrystallizations from absolute ethyl alcohol, and the red crystals with a golden reflex melted at 219-221 C. with decomposition.
• the desired dye was obtained in 19 percent yield after two recrystallizations from ethyl alcohol and the orange crystals melted at 231-233" C. with decomposition.
• an intermediate selected from those represented by Formula III can be used wherein R4 represents a hydrogen atom, instead of an acyl group, provided a carboxylic anhydride, such as acetic anhydride, is present together with a basic condensing agent, such as triethylamine.
• Example 11 5- (5-acetyl-1,3-diethyl-2 (3H) -benzimidazolylidene) ethylidene] -3-ethylrhodanine
• This dye was prepared in the same manner as that of Example 10, by using 1.8 g. (1 mol.) of 5-acetyl-1,3-diethyl-Z-methylbenzimidazolium iodide, instead of 5- bromo1,3-diethyl-2-methylbenzimidazolium iodide.
• the desired dye was obtained in 35 percent yield after two recrystallizations from ethyl alcohol, and the scarlet crystals melted at 231-233 C. with decomposition.
• Example 12 (1,S-diethyl-5-ethylcarbamyl2(3H) benzimidazolylidene) ethylidene] -3-ethylrhodanine
• This dye was prepared in the same manner as that of Example 10, by using 1.9 g. (1 mol.) of 1,3-diethyl-5- ethylcarbamyl-Z-methylbenzimidazolium iodide, instead of S-bromo 1,3diethyl-Z-methylbenzirnidazolium iodide.
• the desired dye was obtained in 14 percent yield after two recrystallizations from methyl alcohol, and the minute orange crystals melted at 247-249" C. with decomposition.
• Example J3.-5-acetyl-1,3-zlietlzyl-2-methylbenzimidazolium iodide CgHg A mixture of 47 g. (1 mol.) of S-acctyl-l-ethyl-Z- methylbenzimidazole and 72.5 g. (1 mol. plus 50 percent excess) of ethyl iodide was heated at the refluxing temperature for 4 hours. The cake of crystals was broken up, ground to a line crystalline mass under acetone, filtered, and the residue was Washed with acetone. The yield was 47 percent. The colorless crystals from ethyl alcohol melted at 159-162 C. and decomposed at 202 C.
• Example 16 -1-ethyl-5-ethylcarbamyl-2-methylbenzimidazole A solution of 106 g. (1 mol.) of N-ethyl-4-ethylamino-B-nitrobenzamide in 1 liter of glacial acetic acid and 195 g. (2 mols. plus 100 percent excess) of acetic anhydride was heated to C. and 185 g. (3 mols. plus percent excess) of zinc dust was added, with stirring, in small portions over a period of 15-20 minutes. During the addition of the zinc dust the temperature of the reaction mixture increased to the boiling point. Stirring and heating were continued at the refluxing temperature for 3 hours. The reaction mixture was filtered hot and the residue was washed with 500 ml.
• 70 percent aqueous solution of ethylamine was added, in small portions with shaking, 107 g. (1 mol.) of methyl 4- chloro-3-nitrobenzoate.
• the reaction mixture was cooled from time to time in a cold water bath. After the reaction mixture had stood 1 /2 hours at room temperature, it was heated at 40- 50 C. for 4 hours, then cooled, filtered, and the residue was Washed with water and dried. The yield was 95 percent. The pale-yellow crystals from ethyl alcohol melted at 131-134 C.
• All of 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 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.
• our new dyes can be incorporated by other methods in many of the photographic silver halide emulsions customarily employed in the art.
• the dyes can be incorporated by bathing a plate or film 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.
• Photographic silver halide emulsions which can advantageously be sensitized by means of the new dyes of our invention comprise the customarily employed gelatinosilver-halide, gelatino-silver-chlorobromide, gelatino-silyer-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 addenda as chemical sensitizers, e. g.,sulfur sensitizers (e. g., allyl thiocarbamide, thiourea, 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. 8'.
• chemical sensitizers e. g.,sulfur sensitizers (e. g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.)
• gold compounds e.
• anti-foggants such as ammonium chloroplatinate (U. S. 2,566,245), ammonium chloroplatinite (U. S. 2,566,263), benzotriazole, nitrobenzimidazole, 5-nitroindazole, benzidine, mercaptans, etc. (see MeesThe Theory of the Photographic Process, Macmillan Pub., 1942, page 460), or mixtures thereof; hardners, such as formaldehyde (U. S. 1,763,533), chrome alum (U. S. 1,763,533), glyoxal (U. S.
• a carbocyanine dye selected from those represented by the following general formula:
• R represents a member selected from the group consisting of an alkyl group containing from 1 to 4 carbon atoms and a mononuclear aromatic group of the benzene series containing from 6 to 7 carbon atoms
• R1 and R2 each represents an alkyl group containing from 1 to 4 carbon atoms
• R3 represents a member selected from the group consisting of an acetyl group and a --NHCO group
• R represents an alkyl group containing from 1 to 4 carbon atoms
• X represents an acid radical
• n represents a positive integer of from 1 to 2
• Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the naphthothiazole series, those of the thianaphtheno-7,6,4,5-thiazole series, those of the oxazole series, those of the benzoxazole series, those of the nap
• a carbocyanine dye selected from those represented by the following general formula:
• R and R1 each represents an alkyl group containing from 1 to 4 carbon atoms and X represents an acid radical.
• a carbocyanine dye selected from those represented by the following general formula:
• R and R1 each represents an alkyl group containing from 1 to 4 carbon atoms and X represents an acid radical.
• a carbocyanine dye selected from those represented by the following general formula:
• R, R1 and R2 each represents an 'alkyl group containing from 1 to 4 carbon atoms and X represents an acid radical.
• a carbocyanine dye selected from those represented by the following general formula:
• R, R1 and R2 each represents an alkyl group containing from 1 to 4 carbon atoms and X represents an acid radical.
• a carbocyanine dye selected from those represented by the following general formula:
• R, R1 and R2 each represents an alkyl group containing from 1 to 4 carbon atoms and X represents an acid radical.
• the carbocyanine dye having the following formula:
• the carbocyanine dye having the following formula:
• R represents a member selected from the group consisting of an alkyl group containing from 1 to 4 carbon atoms and a mononuclear aromatic group of the henzene series containing from 6 to 7 carbon atoms
• R1 represents an alkyl group containing from 1 to 4 carbon atoms
• R3 represents a member selected from the group consisting of an acetyl group and an R'NHCO- group wherein R represents an alkyl group containing from 1 to 4 carbon atoms
• X represents an acid radical, together with a compound selected from those represented by the following general formula:
• R2 represents an alkyl group containing from 1 to 4 carbon atoms
• Re represents a carboxylic acyl group containing from 2 to 7 carbon atoms
• R5 represents a mononuclear aromatic group of the benzene series containing from 6 to 7 carbon atoms
• X1 represents an acid radical
• n represents a positive integer of from 1 to 2
• Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring selected from.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Plural Heterocyclic Compounds (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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Cited By (8)

Citations (4)

• 0
  • BE BE540705D patent/BE540705A/xx unknown
• 1954
  • 1954-08-23 US US451696A patent/US2778823A/en not_active Expired - Lifetime
• 1955
  • 1955-08-17 GB GB23658/55A patent/GB776050A/en not_active Expired
  • 1955-08-23 FR FR1148444D patent/FR1148444A/fr not_active Expired

Patent Citations (4)

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