US2692829A - Photographic emulsions sensitized with merocyanine dyes containing a 5(4)-thiazolone nucleus - Google Patents

Photographic emulsions sensitized with merocyanine dyes containing a 5(4)-thiazolone nucleus Download PDF

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US2692829A
US2692829A US211566A US21156651A US2692829A US 2692829 A US2692829 A US 2692829A US 211566 A US211566 A US 211566A US 21156651 A US21156651 A US 21156651A US 2692829 A US2692829 A US 2692829A
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dye
series
sensitized
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Aubert Per
Edward B Knott
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Eastman Kodak Co
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Eastman Kodak Co
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    • 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
    • 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

Definitions

  • This invention relates to photographic emulsions, methods for making,7 them, and to new nonmigratory dyes,
  • Photographic emulsions containing nondi1Tusing dyes have been previously described in Brooker U. S. Patent 2,282,116, dated May 5, 1942.
  • the disadvantages attending the use of such dyes resides primarily in their staining properties when the latent image is developed.
  • an object of our invention to provide new photographic silver halide emulu sions. Another object is to provide methods for obtaining these new photographic silver halide emulsions. Still another object is to provide photographic silver halide emulsions containing non-diffusing sensitizing dyes, which do not cause staining on development of the latent image. Still another object is to provide new merocyanine dyes which are useful in sensitizing the aforesaid photographic silver halide emulsions. Another object is to provide methods for making these new sensitizing dyes. Other ob jects will become apparent from a consideration of the following description and examples.
  • the merocyanine dyes containing a Z-alkylthio-5(4)thiazolone nucleus which can advantageously be used in our invention can be represented hy the following general formula:
  • R represents an alkyl group, such as methyl, ethyl, ete
  • n represents a positive inn tegel' from l to 2
  • d represents a positiv-e integer from l to 3
  • Z represents the non-uietallic atoms necessary to complete a heterooyelio nucleus containing from 5 to G atoms in the heterocyclic ring, such as heterocyclie nucleus selected from the group consisting of those of the thiazole series (e. g.
  • thiazole ll-methylthiazole, 4-phenylthiazole, -methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyDthiazole, ete), those of the benzothiazole series (e. g.
  • benzothiazole Llf-chlorooenzothiazole -chlorobenzothiazole, G-chlorobensothiazole, 7-chlorobenzothiazole, 4-inethylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole, 5pheny1- benzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6 dimethoxybenzothiazole, 5,6 dioxyrnethylenebenzothiazole, 5 hydroxybenzothiazole, 6 hydroxybenzothiazole, etc),
  • those of the naphthothiazole series e, g. a-naphthothiazole, -naphthothiazole, 5-methoXy-- naphthothiazole, 5-ethoXy-,B-naphthothiazole, 8- methoxy-u-naphthothiazole, 7methoxy-anaph thothiazole, etc.
  • those of the thionaphtheno- 7,6,4,5thiazole series e. g. 4methoxythionaphtheno-7,6,4,5thiazole, etc.
  • those of the oxazole series e. g.
  • benzoxazole 5 chlorobenzoxazole, 5 methylbenzoxazole, 5w phenylbenzoxazole, G-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,5-dimethylbenzoxazole, 5- methoxybenzoxazole, 5-ethoxybenzoxazole, 5- chlorobenzoxazole, 6-methoxybenzoxazole, 5hy droxybenzoxazole, S-hydroxybenzoxazole, ete), those of the naphthoxazole series (e. g. a-naphthoxazole, -naphthoxazole, etc), those of the selenazole series (e.
  • naphthoxazole series e. g. a-naphthoxazole, -naphthoxazole, etc
  • selenazole series e.
  • thiazoline, 4- methylthiazoline, eta) those of the 2-quinoline series (e. g. quinoline, S-methylquinoline, 5- methylquinoline, T-methylquinoline, S-methylquinoline, G-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, -ethoxyquinoline, 6-hydroxyquinoline, S-hydroxyquinoline, etc), those of the Ll-oiuinoline series (e. g. quinoline, 6- methoxyquinoline, 7-methylquinoline, 8methyl quinoline, etc.) those of the 1isoquinoline series (e. g.
  • Merocyanine dyes wherein R1 in the above formula represents an alkyl group of the formula CqH2q+1 wherein q .represents a positive integer from 6 to 20 have been found to be particularly useful in practicing our invention in that they are substantially non-dif ⁇ fusing when incorporated in a photographic silver halide emulsion and do not give rise to stain upon development of the latent image.
  • 'I'he dyes of Formula I above wherein d represents 1 can advantageously be prepared by condensing a compound selected from those represented by the following general formula:
  • Y represents an electronegative group, such as chlorine, bromine, alkoxyl (e. g. methoxyl, ethoxyl, etc), or a -S--Rz group wherein R2 represents an alkyl group, such as methyl, ethyl, etc., or an aryl group, such as phenyl, o, m, and p-tolyl, etc.
  • X represents an anion, such as chloride, bromide, iodide, perchlorate, thiocyanate, sulfonate, methylsulfate, ethylsulfate, benzenesulfonate, p-toluenesulfonate, acetate, etc.
  • the dyes of ⁇ Formula I above wherein ⁇ d represents 2 or 3 can advantageously be prepared by condensing a compound selected from those represented byv Formula II above Iwith a cyclammonium Quaternary salt selected from those represented by the following general formula:
  • R3 represents the vacyl group of a carboxylic acid, such as acetyl, propionyl, benzoyl, etc. (especially an acyl group of analiphatic carboXylic acid)
  • R4 represents a hydrogen atom lor an aryl group, such as phenyl, o, m, and p-tolyl, etc.
  • p represents va positive integer from 1 to 2
  • X1 represents an anion, suchas those set forth above for X, for example.
  • each of the above-mentioned condensations is advantageously carried out in the presence of an acid-binding agent, such as ythe trialkylamines v(e. g. triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-n-amylamine, etc.), N,Ndialkylanilines (e. g; N,N-dimethyl aniline, N,Ndiethylaniline, etc.) ⁇ N-alkylpiperidines (e. g. N-methylpiperidine, n-ethylpiperidine, etc.), heterocyclic amines (e. g. pyridine, quinoline, etc.) etc.
  • an acid-binding agent such as ythe trialkylamines v(e. g. triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-n-amy
  • Inert solvents can also be present during the condensations, if desired.
  • Typical solvents include the lower aliphatic alcohols, such as ethanol, n-propanol, isopropanol, n-butanol, etc., diethyl ether, acetone, 1,4-dioxane, n-pentane, n-heptane, benzene, toluene, chloroform, carbontetrachloride, etc.
  • the intermediates'represented by Formula II can advantageously be prepared by intermixing an aqueous alkali metal hydroxide solution, carbon disulfide, and glycine, ⁇ followed by addition of an alkyl halide to the alkali metal salt (M-s--NH-oHr--OM) formed, heating the mixture at a temperature of from about 40 to 100 C., and acidifying the reaction mixture to give the desired ester represented by Formula V above.
  • These steps can be illustrated by the following general equations:
  • the merocyanine dyes of Formula I above where drepresents 2 can advantageously be prepared by condensinga compound selected from those represented by the followingr general formula:
  • R1 has the values set forth above yand R5 represents a hydrogen atom or an alkyl group (e. g. methyl, ethyl, etc. groups), with a cyclam monium Quaternary salt selected from those represented by the following general formula:
  • condensations can advantageously be carried out in the presence of anv acidvdide, 2-ethylthio-5 (4) -thiazolone binding agent, such as the trialkyamines (e. g. triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-n-amylamine, etc), N,Ndialkylanilines (e. g. N,Ndimethylaniline, N,Ndiethylaniline, etc.) N-alkylpiperidines (e. g.
  • trialkyamines e. g. triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-n-amylamine, etc
  • N,Ndialkylanilines e. g. N,Ndimethylaniline, N,Ndiethylaniline, etc.
  • N-alkylpiperidines e. g.
  • N-methylpiperidines, N-ethylpiperidines, etc), heterocyclic amines (e. g. pyridine, quinoline, eta), etc. .an inert solvent can also be employed, if desired.
  • Typical solvents include the lower aliphatic alcohols (e. methanol, ethanol, npropanol, isopropanol, n-butanol, etc.), diethyl ether, 1,4-dioxane, n-pertane, n-hexane, benzene, toluene, chloroform, carbontetrachloride, etc. Heating accelerates Athe condensations, and temperatures varying from room temperature (about 25 C.) to the reux temperature of the reaction mixture can advantageously be used.
  • the intermediates represented by Formula VI above can advantageously be prepared by heating together a mixture o? one of the esters represented by Formula V above, acetic anhydride, and an ortho ethyl ester selected from those represented by the following general formula:
  • the dye was recrystallized lfrom ethanol as dat, steel-blue needles melting at It sensitized a gelatino silver chloride emulsion strongly with a maximum at 530 ma and a gelatine silver bromide emulsion with a maximum at 540 ma.
  • ethylthz'o 5(4) thiaeoZoneH dimethinemerocyam'ne 4.44 g. of 2--acetanilidovinylquinoline ethio- (obtained by heating 1.8 g. of N-dithiocarbethoxyglycine with acetic anhydride and driving oil the residual liquids), cc. of ethanol, and 2 cc. of triethylamine were refluxed for 5 minutes and the reaction mixture then chilled.
  • the desired dye was ⁇ obtained as soft, dark green needles melting at 163 C. on recrystallization from a benzene-ethanol mixture. It sensitized a gelatino silver chloride emulsion with a flat maximum lying between 530 and 590 ma.
  • Example 3.-[2 (3 ethylbenzoselenaeoleu [4- (2 ethylthio 5(4) thz'aeoloneH dimethinemerocyan'lne” This dye was prepared in the same manner as the dye of Example 1 by replacing the 2-methylbenzoxazole ethiodide used in that example by a molecularly equivalent amount of Z-methylbenzoselenazole ethiodide.
  • the desired dye was obtained as blue-grey prisms melting at 184 C. on recrystallizaton from benzene. It sensitized a gelatino silver bromide emulsion strongly.
  • This dye was prepared in the same manner as the dye of Example 1 by replacing the quaternary salt used in that example by a molecularly equivalent amount of Z-methylthiazoline methiodide.
  • the desired dye was obtained as maroon needles melting at 129 C. on recrystallization fr0-m ethanol. It sensitized a gelatine silver chloride emulsion with a maximum at 500 ma and a gelatine silver bromide emulsion with a maximum at 530 ma.
  • Example 6 -[4-(1-ethylquinolz'ne) l [4- (2l-ethylthz'o-5 (4) -thiaeolonw l dimethinemerocyanine
  • This dye was prepared in the same manner as the dye of Example 1 by replacing the 2-methylbenzoxazole ethiodlde used in that example by a molecularly equivalent amount of lepidinium ethiodide.
  • the desired dye was obtained as blue plates melting at 143 C. on recrystallization from ethanol. It sensitized a gelatine silver chloride emulsion with a maximum at 510 ma and a gelatino silver bromide emulsion with a ilat maximum lying between 560 and 640 ma.
  • This dye was prepared in the same manner as the dye of Example 2 by replacing the qua-ternary salt used in that example by a molecularly equivalent amount of 2-acetanilidovinylbenzothia zole ethodide.
  • the desired dye l was obtained as blue-grey prisms melting at 173 C. on recrystallization from benzene. It sensitized a gelatino silver chloride emulsion with a maximum at 550 ma and a gelatino silver bromide emulsion with a maximum at ⁇ 580 ma.
  • Example 11-[2-(3-ethylbeneothiazole)l [4-(21- eth1/limo 5(4) thiazoloneH methyldimethiaemerocyanine” This dye was obtained in the same manner as the dye of Example 10 by replacing the quaternary salt used in that example by a molecularly equivalent amount of Z-methylbenzothiazole ethiodide.
  • the desired dye was obtained as fine purple needles melting at C. on recrystal.- lization from benzene. It sensitized a gelatino silver chloride emulsion with a maximum at 550 mp. and a gelatino silver bromide emulsion with a maximum at 570 ma.
  • the desired dye was obtained as steelblue prisms melting at C. on recrystallization from benzene. It sensitized a gelatino silver chloride emulsion with a maximum at 560 ma and a gelatino silver bromide emulsion with a maximum at 570 ma.
  • Example 13 [2-(3-methylthiazoline)] [41(2- ethylthio 5 (4) thiaeoloneH methyldimethz'nemerocyamne
  • This dye was prepared in the same manner as the dye of Example 10 by replacing the quaternary salt used in that example by a molecularly equivalent amount of Z-methylthiazoline methiodide.
  • the desired dye was obtained as grey-red needles melting at 133 C. on reerystalvlization from a benzene-petroleum ether mixture. It sensitized a gelatino silver chloridev emulsion with a. maximum at 500 ma.
  • Example 14 -[2-(Lethylqainollne)l [4-(2-eth- @Ethic-(4) -thiazolonw lmethyldz'methznemerocyam'ne
  • This dye was prepared in the same manner as the dye of Example by replacing the quaternary salt used in that example by a molecularly equivalent amount of quinaldeinum ethiodide, The desired dye was obtained as fine green needles on recrystallization from benzene and had a melting point of 130 C. It sensitized a gelatino silver chloride emulsion with a maximum at 580 III/L.
  • Example 15.-[2-(3-ethyl--methylthiaaole) l [4- methlnemerocyamne This dye was prepared in the same manner as the dye of Example 10 by replacing the quaternary salt used in that example by a molecularly equivalent amount of 2,4-dimethylthiazole ethiodide.
  • the desired dye was obtained as glossy red needles melting at 154 C. on recrystallization from a benzene-petroleum ether mixture. It sensitized both a gelatino silver chloride emulsion and a gelatino silver bromide emulsion with a maximum at 530 my.
  • This dye was obtained in the same manner as the dye of Example 1 by replacing the quaternary salt used in that example by a molecularly equivalent amount of Z-methylbenzothiazole ethiodide and the 4-ethoxymethylene intermediate by a mo- 10 lecularly equivalent amount of 2-benzylthio-4- ethoxymethylene-5(4)-thiazolone
  • the desired dye was obtained as red needles melting at 179 C. on recrystallization from ethanol. It sensitized a gelatino silver chloride emulsion with a maximum at 550 m/l.
  • This dye was obtained in the same manner as Ithe dye of Example 1 by replacing the quaternary salt used in that example by a molecularly equivalent amount of 2methylbenzoselenazole ethiodide and the Il-ethoxymethylene intermediate by a molecularly equivalent amount (of 2-benzylthio l ethoxymethylene 5(4) thiazolone.
  • the desired dye was obtained as violet needles melting at C. or recrystallization. from ethanol. It sensitized a gelatine silver chloride emulsion with a maximum at 560 mit.
  • Example 19.-[2 (3 ethylbeneoxaaolwl ⁇ 4-(2- benzylthio-S (4) -thz'azolone) dimethnemerocyam'ne o o cs Oman-elke JJ-s-Cm-ctm ⁇ N N
  • This dye was prepared in the same manner as the dye of Example 1 by replacing the 4ethoxy methylene intermediate used in that example by a molecularly equivalent amount of 2-benzylthio- 4fethoxymethylene5(4) -thiazolone
  • the desired dye melted at 193 C. on recrystallization from ethanol and sensitized a gelatina silver chloride emulsion with a maximum at 510 ma.
  • Example 20 -[2(1-ethylpy1z'dine) M42-benzylthio- (4) -thiazolon l dimethinemerocyanine
  • Example 21 -[4-(I-ethylquinollne)] [4-(2-benaylthzo 5(4) thz'aeolone)] dimethinemerocyaulne lsalt used in'vthat [ex 'etlioxyiethylene ainterin'e dye yWals tob'tan'ed win the :same manner "as tie d'ye of yExanfipfle.,1 by replaei'rigthe Quaternary f ple byagmelcularly equivalent, mondiger iepidriiu' inname-'ane the .fi-
  • ythe oi x'ampleflby'replaeinggtheQuaternary salt used in that example b'yamoleulavrlyi equivalent "amount f 'zlixfrtnylthiazgiine methivod'dje and the Ll-etho:yinetldyl'ere intermediate by a molecularly equivalentarnount of 2-benzy1thio- 4ethoxymethy1ene5 (4) ethiazolone.
  • Thedesired dye was obtained as red-green prisms melting at 171 C. on recrystallization from a benzeneethanol mixture. It sensitized a gelatino ⁇ silver chloride emulsion Withv a maximum at 500I mp It sensitized a anda gelatino silver brmideemulsion with a f;
  • This dye was prepared in the same ⁇ manner as the dye of Example 1 by replacing the quaternary Ysalt used inthat example bya' molecularly equivalent vambunt of 'Zimethylthiazoline methiodide .1.
  • This dye was obtained in the same manner as the dye of Example 25 by replacing the quaternary salt used in that example by 1.95 g. of 5-chloro-Z-methylbenzothiazole etno-p-tolulenesulfonate. It formed purple needles melting at 156 C. on recrystallization from benzene. It sensitized a gelatno silver chloride emulsion with a maximum at 560 m/L and a gelatino silver bromiodide emulsion with a maximum at 580 mit.
  • Example 29 -[2 (3-ethylbeneothiaeole) l [4-(2- n-octylthz'o 5 (4) -thz'aeolone) ldzmethinemerocyamne
  • This dye was obtained in the same manner as the dye of Example 25 by replacing the quaternary salt used in that example by 1.55 g. of 2- methylbenzothiazole ethiodide. It was obtained as dark red needles melting at 81 C. from a benzene-methanol mixture. It sensitized a gelatine silver chloride emulsion with a maximum at 550 mit and a gelatino silver bromiodide emulsion with a maximum at 580 mit.
  • Example 30 -[2-(3-ethg/Zbeneoselenaeole)l [4- (2 n octylthzo-5 (4) thiaeolone l dimethinemerocyamne
  • This dye was obtained in the same manner as the dye of Example 25 by replacing the quaternary salt used in that example by 1.75 g. of 2methyl benzoselenazole ethiodide. It formed glossy, ilat, violet needles melting at 86 C. from a benzenemetha-nol mixture. It sensitized a gelatino silver chloride emulsion with a maximum at 570 my and a gelatine silver bromiodide emulsion with a maximum at 590 me.
  • Example 31 -[2- (S-ethylthiazoline) l [4- (Z-ethylthz'o-5 (4) -thiazolonel dimethinemerocyanine
  • This dye was prepared in the same manner as the dye of Example l by replacing the Quaternary salt used in that example by a molecularly equivalent amount of Z-methylthiazoline ethiodide.
  • the desired dye was obtained as yellow plates melting at 121 C. on recrystallization from ethanol. It sensitized a gelatine silver chloride emulsion with a maximum at 50i) ma and a gelatino silver bromide emulsion with a maximum at 525 mp.
  • Example 32 -[2-(S-ethylbeneoaeole) l [4-(2-11- dodecZythie-5 (4) -thzaeolone) l dimethz'nemerocyam'ne
  • This dye was prepared in the same manner as the dye of Example 1 by replacing the N-dithiocarbethoxyglycine used in that example by a molecularly equivalent amount of N -dithiocarbo-nhexoglycine.
  • the desired dye was obtained as glossy, rust-colored plates melting at 148 C. on recrystallization from ethanol, It sensitized a gelatine silver chloride emulsion with a maximum at 500 ma and a gelatine silver bromide emulsion with a maximum at 530 my.
  • This dye was prepared in the same manner as the dye of Example l by replacing.r the N-dithiocarbethoxyglycine used in that example by a molecularly equivalent amount of N-dithioearbo-n-heptoxyglycine.
  • the desired dye was obtained as glossy, rust-colored plates melting at 133 C. on recrystallization from ethanol. It sensitized a gelatine silver chloride emulsion with a maximum at 500 ma and a gelatine silver bromide emulsion with a maximum at 530 my.
  • This dye was prepared-'in thelfsarie"iriar1fnrfas the dye of Example 1 by replacing the N-dithiooarbe'tlioxyglyeine y used in v4that example by ⁇ a nolecularly; equivalent ⁇ Y anio'ut of'N-"dithi'oeaibon-decoxyglycine.
  • the desired dye was obtained as an orange powder melting at 106 C. on recrystallization from ethanol.
  • Example 38. -[2- (3-ethylbenzoaeole) 1.[4-(2-ndec'ylthio 5 (4) thiazolofnwl ,8 'methylcli- 1 methz'nemerocyw'me ⁇ O ⁇ Bo l"s S-*CH'2-(CHz)s ⁇ -GH3 ,N
  • ThisC dye was :prepared 1in thelsamerY manner as the '-dye @of 4.Example :1d-.by .replacing fthe ethyl orthoacetate used in that* example by a1m0leeularly eq-uivalentfamounti offethylorthopropionate and 7the :Nedi-thio'earb'ethoxyglycine :by f a molecularl'y equivalent amount noi -Nedi-thiocarbo-n-decoxyglycine.
  • the ,desired dye was f obtained -as orange needles melting at 96 C. on recrystallizationffrometlianol. It sensitize'd'a gelatino silver liloride "mulsion "with "'a 'maximum at 510 my and. a gelatino silver bromide emulsionwvith a maximum at 530 mit.
  • This dye waswprepared in-the-same ⁇ marmer as the dye of Example 2 by replacing the vquaternary salt used in that example by a molecularly equivalent amount-ot2-acetanilidoelAbutadienylbenzothiazoleethiodide.
  • the desiredl dye ' was obtained as a blue crystalline powder melting at 179 C. on recrystallization from ethanol. It strongly sensitized a gelatino silver 'bromide emulslon.
  • N-dithiocarbo-n-octoxyglycine employed in Example 25 above was prepared as follows:
  • Example 42 N dithiocarbo n ocloxyglycine l? i Ho-C-oHz-NH-o-s-cHr-(Cnm-CH@ 22.4 g. of potassium hydroxide were dissolved in 50 cc. of water and the solution chilled. There were then added 15.0 g. of glycine and 15.2 g. of carbondisulde, and the Whole shaken mechanically until a clear orange solution resulted. A solution of 38.6 g. of n-octylbromide in 50 cc. of ethanol was added, and the mixture heated for 30 minutes on a steam bath. To the resulting one-phase solution there were added 100 cc.
  • n-octylbromide used in the above example by molecularly equivalent amounts of n-hexyl, n-heptyl, n-decyl, n-dodecyl, and 'y-phenylpropyl halide, respectively.
  • Example 43 Ndithiocarbo-n-hezoyglycne Obtained as glistening, ⁇ waxy plates melting at 99 C. on recrystallization from petroleum ether.
  • Example 46 -N-dithiocarbo-n-dodecoyglycine (Il) Il l Ho-ccHf-NH-c-s-cnr-(om),l1-CH3 Obtained as glossy plates melting at 111 C. on recrystallization from ligroin.
  • concentration of the dye Will vary according to the type of lightsensitive material in the emulsion and according to the eiTect desired. The suitable and most economical concentration for any given emulsion will be apparent to those skilled in the art of emulsion making.
  • each ligure is a diagrammatic reproduction of a spectrogram showing the sensitivity of a gelatino silver bromide (speciiically a silver bromiodide) emulsion containing one of our alkylthio5(4)-thiazolone dyes.
  • the curve depicts the sensitivity of an ordinary gelatino silver bromiodide emulsion containing [2-(3-methylthiazoline) l [4-(2-ethy1thio-5 (4) thiazolone) ldimethinemerocyanine.
  • Fig. 1 the curve depicts the sensitivity of an ordinary gelatino silver bromiodide emulsion containing [2-(3-methylthiazoline) l [4-(2-ethy1thio-5 (4) thiazolone) ldimethinemerocyanine.
  • the curve depicts the sensitivity of an ordinary gelatine silver bromiodide emulsion containing [2- (S-ethylbenzothiazole) l [4- (2-ethylthio-5 (4) thiazolone) ldimethinemerocyanine.
  • the curve depicts the sensitivity of on ordinary gelatino silver bromiodide emulsion containing [2- (3-ethylbenzoxazole) l [4- (2ethylthio5(4) thiazolone) ldimethinemerocyanine.
  • R1 represents an alkyl group of the formula CqH2q+1 wherein q is a positive integer from 6 to 20 have lower solubility and diifusibility in photographic silver halide emulsions than many of the known 1sensitizing dyes and are especially valuable,
  • Expulsions sensitized according to: our inventioncanbe coated-T on thezusual': supports: of paper, cellulose acetate. lm glass' polyvinyl resin (acetate, acetal, etc.)l metal, etc., ⁇ in the usual manner.
  • a photographic silver halide emulsion sensitized with at least one merocyanine dye selected from those represented by the following general formula:
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, benzothiazole: series, naphthothiazole series, oxazole series, benzoxazole series, naphthoxazole series', selenazole series, benzoselenazole Series, naphthoselenazole series, thiazoline series, 2-quinoline series, 4-quinoline series, l-isoquinoline series, 3-isoquinoline series, pyridine series, and 3,3-dimethylindolenine series.
  • a photographic silver halidev emulsion sensitized with at least one merocyanine dye selected from; those represented byI the. following general formula.;
  • R represents, an alkyl group of the formula C'mI-I2m+1 wherein m represents a positive integer from 1 to 8
  • R1 represents an alkyl group of the formula CqH2q+1 wherein q represents a positive integer from 6 to 20
  • L represents a methine, group
  • n represents a positive integer from 1 to 2
  • d represents a positive integer from 1- to 3f
  • Z represents the'non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, benzothiazole series, naphthothiazole series, oxazole series, benzoxazole series, naphthoxazole series, selenazole series, benzoselenazole series, naphthoselenazole series, thiazoline series, Z-quinoline series, 4-quinoline series, l-isoquinoline series, -isoquinoline series, pyridine series, and 3,3-di
  • R1 represents an alkyl group of the formula CqHzqgi wherein q represents a positive integer from 6 to 20, L represents a methine group',y n lrepresents a positive integer from 1V to 2 d represents a positive integer from 1 to 3, and Z represents the non-metallic atoms necessary tol complete a heterocyclic nucleus selected from the group'y consisting of those of the thiazole series, benzothiazole series, naphthothiazole series, oxazole series, benzoxazole series,
  • R4 represents a. primary alkyl group of the. formula CmHzm-x-i wherein 'm ⁇ represents a positive integer from 1 to 8, R1 represents a priwherein R represents a primary alkyl group of the formula C'mHzmJfi wherein m represents a positive integer from 1 to 8, R1 represents a primary alkyl group of the formula CqH2q+1 wherein q represents a positive integer from 1 to 20, L represents a methine group, d represents a positive integer from 1 to 3, and Z represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the benzoxazoleseries.
  • R represents a primary alkyl group of the formula CmH2m+1 wherein m represents a positive integer from 1 to 8
  • R1 represents a primary alkyl group of the formula CqH2q+1 wherein q represents a positive integer from 1 to 20
  • L represents a methine group
  • d represents a positive integer from 1 to 3
  • Z represents the nonmetallic atoms necessary to complete a hetero- 25 cyclic nucleus of the benzoselenazole series.
  • R represents a primary alkyl group of the formula CmHzm+1 wherein m represents a positive integer from 1 to 8
  • R1 represents a primary alkyl group of the formula CqHzql-i wherein q represents a positive integer from 1 to 20
  • L represents a methine group
  • d represents a positive integer from 1 to 3
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the thiazoline series.
  • R represents a primary alkyl group of the formula CmHzmJri wherein m represents a positive integer from 1 to 8
  • R1 represents a primary alkyl group of the formula CqH2q+1 wherein 55 q represents a positive integer from 1 to 20, L represents a methine group, d represents a positive integer from l to 3, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the naphthothiazole series.
  • R represents a primary alkyl group of the formula CmH2m+1 wherein m represents a positive integer from 1 to 8
  • R1 represents a primary alkyl group of the formula CqHzq+1 wherein q represents a positive integer from 6 to 20
  • d represents a positive integer from 1 to 3
  • Z i represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series.
  • R represents a primary alkyl group of the formula CmHzm-f-i wherein m represents a positive integer from 1 to 8
  • R1 represents a primary alkyl group of the formula CqII2q+1 wherein Aq represents a positive integer from 6 to 20, d frepresents a positive integer from 1 to 3, and Z ,represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoselenazole series.
  • R represents a primary alkyl group of the formula CmII2m+1 wherein m represents a positive integer from 1 to 8
  • R1 represents a pri- 0 mary alkyl group of the formula CqHzq-ti wherein q represents a positive integer from 6 to 20, d represents a positive integer from 1 to 3
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the thiazoline series.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US211566A 1951-02-17 1951-02-17 Photographic emulsions sensitized with merocyanine dyes containing a 5(4)-thiazolone nucleus Expired - Lifetime US2692829A (en)

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BE509306D BE509306A (en(2012)) 1951-02-17
BE509307D BE509307A (en(2012)) 1951-02-17
US211566A US2692829A (en) 1951-02-17 1951-02-17 Photographic emulsions sensitized with merocyanine dyes containing a 5(4)-thiazolone nucleus
GB2229/52A GB703520A (en) 1951-02-17 1952-01-28 Improvements in and relating to processes of making merocyanine dyes and to photographic silver halide emulsions containing them
GB4041/52A GB700734A (en) 1951-02-17 1952-02-15 Improvements in sensitized photographic emulsions and in sensitizing dyes therefor
FR1099410D FR1099410A (fr) 1951-02-17 1952-02-15 Emulsions photographiques et colorants utilisables en particulier pour leur préparation
FR1101164D FR1101164A (fr) 1951-02-17 1952-02-15 Nouveaux colorants sensibilisateurs et leurs applications, notamment en photographie

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2743273A (en) * 1952-09-15 1956-04-24 Eastman Kodak Co Merocyanine dyes containing a chain substituent
US2839404A (en) * 1955-10-12 1958-06-17 Eastman Kodak Co Trinuclear optical sensitizing dyes and photographic emulsions containing them
US2882159A (en) * 1956-09-13 1959-04-14 Eastman Kodak Co Merocyanine sensitizing dyes and photographic emulsions containing them
US2886565A (en) * 1955-09-12 1959-05-12 Sperry Rand Corp Photographic sensitizing dyes derived from 2-alkyl-5, 6-dihydro-4-h-pyrano (3, 2d) thiazole
US2899430A (en) * 1959-08-11 Chxch
US3055952A (en) * 1957-10-09 1962-09-25 Du Pont Hydroxyl-terminated polymers
US3106466A (en) * 1961-06-14 1963-10-08 Horizons Inc Print-out photoprocess with merocyanine dyes
US3218204A (en) * 1962-07-13 1965-11-16 Monsanto Co Use of hydrogen halide as a carrier gas in forming ii-vi compound from a crude ii-vicompound
US3312570A (en) * 1961-05-29 1967-04-04 Monsanto Co Production of epitaxial films of semiconductor compound material
US3713828A (en) * 1969-09-05 1973-01-30 Fuji Photo Film Co Ltd Multi-layer color photographic silver halide light-sensitive materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2944901A (en) * 1957-01-18 1960-07-12 Eastman Kodak Co Multicontrast photographic emulsions

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2166736A (en) * 1937-04-23 1939-07-18 Eastman Kodak Co Photographic emulsion
US2177402A (en) * 1935-11-15 1939-10-24 Eastman Kodak Co Dye from thiazolones
US2263749A (en) * 1937-04-23 1941-11-25 Eastman Kodak Co Polymethine dyes and process for preparing the same
US2282116A (en) * 1939-04-14 1942-05-05 Eastman Kodak Co Photographic element
US2320654A (en) * 1940-08-08 1943-06-01 Riester Oskar Sensitization of photographic emulsions
US2322015A (en) * 1939-05-25 1943-06-15 Eastman Kodak Co Dye and photographic emulsion containing the same
US2338782A (en) * 1940-07-30 1944-01-11 Riester Oskar Cyanine dyestuff
US2340882A (en) * 1935-08-16 1944-02-08 Ilford Ltd Sensitized photographic material
US2353164A (en) * 1944-07-11 Dyestuffs and dyestuff
US2656353A (en) * 1950-12-29 1953-10-20 Eastman Kodak Co Sensitizing dyes containing a 2-thio-2, 5 (3, 4)-thiazoledione nucleus

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2353164A (en) * 1944-07-11 Dyestuffs and dyestuff
US2340882A (en) * 1935-08-16 1944-02-08 Ilford Ltd Sensitized photographic material
US2177402A (en) * 1935-11-15 1939-10-24 Eastman Kodak Co Dye from thiazolones
US2166736A (en) * 1937-04-23 1939-07-18 Eastman Kodak Co Photographic emulsion
US2263749A (en) * 1937-04-23 1941-11-25 Eastman Kodak Co Polymethine dyes and process for preparing the same
US2282116A (en) * 1939-04-14 1942-05-05 Eastman Kodak Co Photographic element
US2322015A (en) * 1939-05-25 1943-06-15 Eastman Kodak Co Dye and photographic emulsion containing the same
US2338782A (en) * 1940-07-30 1944-01-11 Riester Oskar Cyanine dyestuff
US2320654A (en) * 1940-08-08 1943-06-01 Riester Oskar Sensitization of photographic emulsions
US2656353A (en) * 1950-12-29 1953-10-20 Eastman Kodak Co Sensitizing dyes containing a 2-thio-2, 5 (3, 4)-thiazoledione nucleus

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2899430A (en) * 1959-08-11 Chxch
US2743273A (en) * 1952-09-15 1956-04-24 Eastman Kodak Co Merocyanine dyes containing a chain substituent
US2886565A (en) * 1955-09-12 1959-05-12 Sperry Rand Corp Photographic sensitizing dyes derived from 2-alkyl-5, 6-dihydro-4-h-pyrano (3, 2d) thiazole
US2839404A (en) * 1955-10-12 1958-06-17 Eastman Kodak Co Trinuclear optical sensitizing dyes and photographic emulsions containing them
US2882159A (en) * 1956-09-13 1959-04-14 Eastman Kodak Co Merocyanine sensitizing dyes and photographic emulsions containing them
US3055952A (en) * 1957-10-09 1962-09-25 Du Pont Hydroxyl-terminated polymers
US3312570A (en) * 1961-05-29 1967-04-04 Monsanto Co Production of epitaxial films of semiconductor compound material
US3106466A (en) * 1961-06-14 1963-10-08 Horizons Inc Print-out photoprocess with merocyanine dyes
US3218204A (en) * 1962-07-13 1965-11-16 Monsanto Co Use of hydrogen halide as a carrier gas in forming ii-vi compound from a crude ii-vicompound
US3713828A (en) * 1969-09-05 1973-01-30 Fuji Photo Film Co Ltd Multi-layer color photographic silver halide light-sensitive materials

Also Published As

Publication number Publication date
BE509307A (en(2012))
FR1101164A (fr) 1955-10-04
GB700734A (en) 1953-12-09
GB703520A (en) 1954-02-03
BE509306A (en(2012))
FR1099410A (fr) 1955-09-05

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