US2656351A - Trinuclear dyes containing a 5-thiazolidone nucleus - Google Patents

Trinuclear dyes containing a 5-thiazolidone nucleus Download PDF

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US2656351A
US2656351A US220332A US22033251A US2656351A US 2656351 A US2656351 A US 2656351A US 220332 A US220332 A US 220332A US 22033251 A US22033251 A US 22033251A US 2656351 A US2656351 A US 2656351A
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series
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emulsion
dyes
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Aubert Per
Roy A Jeffreys
Edward B Knott
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0075—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring
    • C09B23/0083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring the heteroring being rhodanine in the chain
    • 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
    • G03C1/26—Polymethine chain forming part of a heterocyclic ring

Definitions

  • This invention relates to trinuclear dyes concarbon atoms in the cycloalkyl ring), e and n taining a 5-thiazolidone nucleus and to methods each represents a positive integer from 1 to 2, for preparing them. More particularly, this in- (1 represents a positive integer from 1 to 3, X vention relates to trinuclear dyes useful in alter- H represents an anion, such as Cl, Br", I-, C104", ing the sensitivity of photographic silver halide p-CH3-C6H4--SO3, C6E5-SO3", CHSCOC", emulsions. SCN-.
  • L represents a methine group
  • Z and Trinuclear dyes obtained from merocyanine Z1 each represents the non-metallic atoms necesdyes containing a rhodanine nucleus have presary to complete a heterocyclic nucleus containviously been described.
  • Such dyes, h) ring such as those selected from the group conin certain cases, can advantageously be employed sisting of those of the thiazole series (e. g.
  • chlorobenzothiazole, 6-chlorobenzothiazole, '7- provide new trinuclear dyes.
  • a further object chlorobenzothiazole, 4-methylbenzothiazole, 5- is to provide methods for preparing these dyes.
  • Still another object is to provide photographic bromobenzothiazole, 6 -bromobenzothiazo1e, 4- silver halide emulsions containing these new dyes, phenylbenzothiazole, 5 phenylbenzothiazole, 4 and methods for preparing these emulsions.
  • R, R1, and R2 each represents an alkyl 4-methyloxazo1e, 5-methyloxazole, 4-pheny1oxgroup, such as methyl, et y sop y -propy azole, 4,5-diphenyloxazole, 4-ethyloxazo1e, 4,5-din-butyl, isobutyl, n-amyl, n-heptyl, n-octyl, ⁇ 3- methyloxazole, 5-phenyloxazole, etc.), those of hydroxyethm, p-acetoxyethyl, etc. groups (e. g.
  • benzoxazole series e. g. benzoxazole, 5-chloan alkyl group of the formula CmH2m+1 wherein 4-5 robenzoxazole, 5-methylbenzoxazole, S-phenylm represents a positive integer from 1 to 8
  • benzoxazole,'G-methylbenzoxazole, 5,6-dimethy1- and R1 can, in addition, represent alkyl groups, benzoxazole, 4,6 dimethylbenzoxazole, 5 methh as the cycloalkyl groups, e. g.
  • benzoselenazole series e. g. benzoselenazole, 5 chlorobenzoselenazole, 5 methoxybenzoselenazole, 5 hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.
  • naphthoselenazole series e. g. anaphthoselenazole, fl-naphthose
  • dine series e. g. pyridine, 5-methylpyridine, ctc.
  • Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from five to six atoms in the heterocyclic ring, such as those selected from the group consisting of a thiazolone nucleus, for example, a 2,4(3,5)-thiazoledione nucleus, such as 2,4(3,5) thiazoledione, 3-ethyl-2,4(-3,5)-thiazoledione, 3- phenyl-2,4(3,5) -thiazoledione or 3-naphthyl-2,-4 (3,5)-thiazoledione nuclei, a -2-thio-2-,4(3,5) -thiazoledione (a rhodanine) nucleus, such as 3-alkyl- 2-thio-2,4(3,5) -thiazoledione (3-alkylrhodanine) 3 phenyl-2-thio-2,4(3,5) thiazoledione (3 phenylrh
  • 3,4-dihydro-2 l) -quinclone nucleus such as 3,4-dihydro-2(1)-quinolone (dihydrocarbostyril) a 3,4 dihydro-2(1)- quinoxalone nucleus, such as 3,4-dihydro-2(1)- quinoxalone (oxydihydroquinoxaline) 3-phenomorpholone (l,4,2-benzoxazine-3(4)-one or benzo-fl-morpholone) nuclei; 1,4,2-benzothiazine-3 (4)-one (ketodihydrobenzoparathiazine) nuclei, and the like six-membered heterocyclic nuclei.
  • the dyes wherein Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five atoms in the heterocyclic ring, three of said atoms being carbon atoms, one of said atoms being a nitrogen atom, and the other of said atoms being a sulfur atom, a nitrogen atom, or an oxygen atom, have been found to be especially well adapted to the manufacture of photographic emulsions, we have found.
  • R, R1, L, n, d, and Z have the values set forth above
  • R3 represents an alkyl group, such as methyl, ethyl, n-hexyl, etc. groups
  • X1 represents an anion, such as those represented by X above, for example, with a compound selected from those represented by the following general formula:
  • R2, Z1, X, and e have the values set forth above.
  • the condensations can advantageously be carried out in the presence of a basic condensing agent, such as the trialkylamines, e. g. triethylamine, tri-n-propylamine, tri-n-butylamine etc., dialkylanilines, e. g. N,N-dimethylaniline, N,N- diethylaniline, etc., N-alkylpiperidines, e. g. N- methylpiperidine, N-ethylpiperidine, etc., heterocyclic amines. e. g. pyridine, quinoline, isoquinoline, etc., N-alkylpyrroles, e. g. N-methylpyrrole, etc.
  • a basic condensing agent such as the trialkylamines, e. g. triethylamine, tri-n-propylamine, tri-n-butylamine etc., dialkylanilines, e. g.
  • The-condensations can also be carried out in the presence of an inert solvent, such as the lower aliphatic alcohols, e. g. ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc. alcohols, diethyl ether, .1,4-dioxane,'benzene, n-hexane, etc. Heat accelcrates the condensations, and temperatures varying from about 25 C. to the reflux temperature of the reaction mixture can be used.
  • an inert solvent such as the lower aliphatic alcohols, e. g. ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc. alcohols, diethyl ether, .1,4-dioxane,'benzene, n-hexane, etc. Heat accelcrates the condensations, and temperatures varying from about 25
  • R, R1, n, d, L, and Z have the values given above, with an alkyl salt, such as those represented by the following general formula:
  • the reaction mixture set to a solid, and it was then ground to a powder and washed with dry benzene. It was recrystallized from an ethanol-diethyl ether mixture as red prisms with a blue reflex having a melting point of 222 C. It sensitized a gelatino silver chloride emulsion with a maximum at 510 ma and a gelatino silver bromide emulsion with a maximum at 530 ma.
  • Example 3 [2-(3-ethylbenzomazole) l [4-(2-eth ylthio 5(4) thiazoloneH dimethinemerocyanine ethiodide 2.0 g. of [2-(3-ethylbenzoxazole)][4-(2-ethylthio 5(4)-thiazolone)] dimethinemerocyanine and 10 cc. of ethyl iodide were fused together in a sealed tube at C. for 24 hours. The tube was then openedand the excess ethyl iodide driven off. The residue was recrystallized from ethanol as soft, rust-colored needles having a melting point of 136 C.
  • Example 5 [4-(1-ethylquinoline) [4 (Z-methylthzo 5(4) thiazolone) ldz'methinemerocya-
  • Example 6. [2 (B-ethylbenzoxazoleH [4 (2- methyZthio-S (4) -thiazolone) dimethinemerocyanine n-hepto-pt0luensalfonate zHl 1.0 g. of [2-(3-ethylbenzoxazole)l heptyl-2-thio-2,5 (3,4) -thiazoledione) [4- (3-ndimethinemerocyanine and 0.5 g. of methyl p-toluenel sulfonate were heated together at 120 C. for 30 minutes. The red solid obtained was ground to a powder, heated under reflux with benzene, and the benzene removed by decantation.
  • Example 1 0 .?--[2:-(S ethglbenzothiaaole)1: Lei-(.2; methyLthio-fifl)--thiazolone%l; dimetmnmem cyanine metho-p-toluenesulfanmte' 4.3 g. of EZ-(B-ethylbenzothiazolell [4-(3- methy1-2-thio-2,5(3,4) -thiazo1edione) dimethi-nemerocyanine and 2.9 g. of methyl p-toluene sulfonate wereheated together at 130 62..
  • This dye was prepared in the same manner as m nut
  • the Solid product w ground to a the dye of Example l-3 by replacing theZ-methylowder, washed.
  • the mixture, it was obtained asmaroomleaflets me fi desired product was: obtained as. maroon. needles ing at 182-? C. (6.2". g.)
  • the dye was recrystallized from a pyridine-diethyl ether mixture as small bluish needles melting at 310 C. It sensitized a gelatino silver chloride emulsion with maxima at 540 and 570 ml and a gelatino silver bromide emulsion with a maximum at 610 m
  • the reaction mixture was then chilled, and the precipitate collected on a filter. After recrystallization from aniline, the dye was obtained as a dark olive-green powder having a melting point of 234 C.
  • Example 20 [2- (1 -ethylquinoline) ] ⁇ 2- [4- (2- [3 ethylbenzoxazolinylidenel ethylidene) -3-n-heptyl-5 (4) -thiazolonel ⁇ methinecryanine iodide
  • Example 21 --[4-(1-ethylquinoline)] ⁇ 2-[4-(2- [3-ethylbenzoxazolinylidenel ethylidene)-3-nhepiyl 5(4) thiazolonel ⁇ methinecyanine iodide 0.5 g. of the quaternary salt obtained in Example 6 above, 0.26 g.
  • Example 2.3 [2-(3a6thZ/Zb3722011l20l3) 1 ⁇ 4- ⁇ 2- (5-omo-2-n-octg thzo 4 thiazolz'nylidene)-.3- .cyclohemyl-5-thz'azolidone] ⁇ dimethz'nemerocycame 01115 aHn ethylamine, and cc. of-ethanol, and the resulting solution was heated on a steam bath for 30 minutes and then chilled. The precipitate was collected on a filter and recrystallized from ligroin as yellow-green prisms melting at 150 C. It sensitized a gelatino silver chloride emulsion" with maxima at 400 and 590 m and a gelatino silver bromiodide emulsion with a maximum at 610 mu.
  • Example 24 [.2 .(3 a methylbenzothiazolefl ⁇ 2- [4 (.2 l3 ethylbeneomaaolinylidene] ethyl idene) -.3-.ethyl 5 .thz'azolidoneil ⁇ azamethinecyamne p-toluenesulfonate maxima at 400 and 560 m and a gelat-ino silver bromiodide emulsion with a maximum 9.17 530 me- 12 Example 2 5.
  • Example 28 ⁇ 4 (1 ethylquinoline) ⁇ 2 [4- (2-[ 3 ethylbenzoxazolinylidene]ethylidene)- 3 ethyl 5 thiazolidone] ⁇ methinecyanine iodide 0.488 g. of the quaternary salt obtained in Example 3 above, 0.299 g. of lepldine ethiodide, 0.2 cc. of triethylamine, and cc. of ethanol were refluxed for 30 minutes, and the solution then chilled.
  • the precipitate (0.4 g.) was collected on a filter and recrystallized from a methanol-diethyl ether mixture as glittering blue-black crystals melting at 272 C. It sensitized a gelatino silver chloride emulsion with a maximum at 6'70 m
  • Example 36 It sensitized a gelatino silver bromiodide emulsion with a maximum at 650 my"
  • Example 36 - ⁇ 2-(3-ethylbenzothiaeole) ⁇ 4-[2- (Z-n-heptylthz'o 5-oxo-4-thiazolinylidene)-3- methyl .5 thz'aolidonc] ⁇ dimethinemerocyanine 0.7 g. of N-(dithiocarbo-n-heptoxy) glycine and 7 cc. of acetic anhydride were heated for minutes on a steam bath, and the unreacted acetic anhydride and acetic acid formed during the reaction removed under a vacuum.
  • N-(dithiocarbo-n-octoxy)glycine used in Example 23 above was prepared as follows:
  • Example 37 --N-(.dithiocarbo-n-octowy)glycine 22.4 g. of potassium hydroxide were dissolved in cc. of water and the solution chilled. There were then added 15.0 g. of glycine and 15.2 g. of carbondisulfide, and the whole shaken mechanically until a clear orange solution resulted. A solution of 38.6 g. of n-octylamine 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. of water, and the cloudiness resulting removed by extraction with diethyl ether.
  • the aqueous layer was warmed gently under reduced pressure to expel any dissolved ether, the solution chilled, and acidified with concentrated hydrochloric acid.
  • the precipitate was collected on a filter. washed with water, air-dried, and. recrystallized from petroleum ether (13. P. -80" C.) as glistennsp'lates melting at 100 o.
  • Example 27 The ,N-Lthiocarbo-n-octoxy) glycine used in Example 27 above was prepared as follows:
  • d represents a positice
  • X represents an anion
  • Q represents the non-metallic atoms necessary solvent.
  • Methanol or acetone has proved satisto complete a heterocyclic nucleus containing 5 factory as a solvent for most of our new dyes. atoms in the heterocyclic ring, 3 of said atoms.
  • the dyes are quite insoluble in methyl being carbon atoms, 1 of said atoms being a alcohol, a mixture of acetone and pyridine is nitrogen atom, and the other of said atoms being advantageously employed as a solvent.
  • the dyes selected from the group consisting of an oxygen are advantageously incorporated in the finished, atom, a sulfur atom, and a nitrogen atom, and Zv washed emulsionsand should be uniformly disand Z1 each represents the non-metallic atoms tributed throughout the emulsions.
  • the parnecessary to complete a heterocyclic nucleus seticular solvent used Will, of course, depend on the lected from the group consisting of those of the solubility properties of the'particular dye.
  • the concentration of the dyes in the emulsions those of the naphthothiazole series, those of the can vary widely, e. g. from 5 to 100 mg. per liter oxazole series, those of the benzoxazole series, of flowable emulsion.
  • concentration of the those of the napththoxazole series, those of the dyes will vary according to the type of emulsion selenazole series, those of the benzoselenazole' and according to the effect desired.
  • the trinuclear dye represented by the m1- dispersed in the emulsion. lowmg formula! With most of our dyes, from 10 to 20 mg.
  • N N s A trinuclear dye selected from the group 6, 4111;
  • R-, R1, and E3 eachrepresents arr alkyl group ofthe formula; ,QmHzmerr wherein m-representsa positive-integer from 1 to 8; X1 represents" agranion; n represents a; positive integer-from If to 2; 11:- represents a positive integer-"from 1* to 3'; and" Z; represents the non-metallicatoms necessary to complete a heterocyolie nucleus selected from thegroup consisting of-those of the thiazole series, thoseof the benzothiazole series; those of the naphthothiazole series, those of theoxazoleseries; thoseof the 'benzoxazole series, those of' the naphthoxazoleseries,- those of?
  • m6 b wherein- Q- represents the non-metallic atoms necessary to completea heterocyoliolnucleus containing -atoms in the heterocyclic ring; 3of said atome-bein icarhoniatoms, 1* f; said; etomebein at nitrogeni atom. and the; otherofi said: atoms e ng; sel atedfrom; the group consistin of; an: oxy e atom a sulfun atom: andsanitmgsm atom; and cyolammoniumaquaternary salt; seleotedsimm, thoise: represented by. the; followinggeneral; 103- mu a;
  • R2 represent an alkyl group of the formula CmHZuH-l wherein m represents a positive integer from 1 to 8, X represents an anion, e represents, a; positi-te integerfrom; 1 to 21 and Z1, represents the: non-metallic, atoms necessary to, complete.- a heterocyolic nueleus selected from the. groupconsisting: of, those; of the thiazole; series, thoseeof the benzot-hiazole series, thoseoh the-naphthothiazole: series, thoseoi the oxazole:

Description

i atented Oct. 20, 195$ TRINUCLEAR DYES CONTAINING A S-THIAZOLIDONE NUCLEUS Per Aubert, Oslo, Norway, and Roy A. Jefireys and Edward B. Knott, Harrow, England, assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application March 2, 1951, Serial No. 220,332
8 Claims. (01. 260--240.1) 1 2 This invention relates to trinuclear dyes concarbon atoms in the cycloalkyl ring), e and n taining a 5-thiazolidone nucleus and to methods each represents a positive integer from 1 to 2, for preparing them. More particularly, this in- (1 represents a positive integer from 1 to 3, X vention relates to trinuclear dyes useful in alter- H represents an anion, such as Cl, Br", I-, C104", ing the sensitivity of photographic silver halide p-CH3-C6H4--SO3, C6E5-SO3", CHSCOC", emulsions. SCN-. etc., L represents a methine group, Z and Trinuclear dyes obtained from merocyanine Z1 each represents the non-metallic atoms necesdyes containing a rhodanine nucleus have presary to complete a heterocyclic nucleus containviously been described. Fry et al. U. S. Patent h ing from five to six atoms in the heterocyclic 2,388,963, dated November 13, 1945. Such dyes, h) ring, such as those selected from the group conin certain cases, can advantageously be employed sisting of those of the thiazole series (e. g. thiin altering the sensitivity of photographic silver azole, 4 methylthiazole, 4 phenylthiazole, 5- halide emulsions. methylthiazole, 5-phenylthiazo1e, 4,5 dimethyl- We have now found a new class of trinuclear thiazole, 4,5-dipheny1thiazole, 4 (2 thienyD- dyes which can also be used in altering the senthiazole, etc.), those of the benzothiazole series sivity of photographic silver halide emulsions. (e. g. benzothiazole, 4-chlorobenzothiazo1e, 5-
It is, therefore, an object of our invention to chlorobenzothiazole, 6-chlorobenzothiazole, '7- provide new trinuclear dyes. A further object chlorobenzothiazole, 4-methylbenzothiazole, 5- is to provide methods for preparing these dyes. methylbenzothiazole, 6-methy1benzothiazo1e, 5- Still another object is to provide photographic bromobenzothiazole, 6 -bromobenzothiazo1e, 4- silver halide emulsions containing these new dyes, phenylbenzothiazole, 5 phenylbenzothiazole, 4 and methods for preparing these emulsions. methoxybenzothiazole, 5 -methoxybenzothiazole, Other objects will become apparent from a conmet 0XybenZ0thiazo1e, fi-iodobenzothiazole, 6- sideration of the following description and exodobenzothiazole, 4 ethoxyb nzothi 5 amp1es ethoxybenzothiazole, tetrahydrobenzothiazole, 5,
According to our invention we provide tri- 6-dimeth0xybenzothiazole, 5,6 -dioxymethylenenuclear dyes selected from those represented by nzot iazole, 5 hydroxybenzothiazole, 6 hy the following two general formul droxybenzothiazole, etc.), those of the naphthothiazole series (e. g. a-naphthothiazole, p-naphwherein R, R1, and R2 each represents an alkyl 4-methyloxazo1e, 5-methyloxazole, 4-pheny1oxgroup, such as methyl, et y sop y -propy azole, 4,5-diphenyloxazole, 4-ethyloxazo1e, 4,5-din-butyl, isobutyl, n-amyl, n-heptyl, n-octyl, {3- methyloxazole, 5-phenyloxazole, etc.), those of hydroxyethm, p-acetoxyethyl, etc. groups (e. g. the benzoxazole series (e. g. benzoxazole, 5-chloan alkyl group of the formula CmH2m+1 wherein 4-5 robenzoxazole, 5-methylbenzoxazole, S-phenylm represents a positive integer from 1 to 8), benzoxazole,'G-methylbenzoxazole, 5,6-dimethy1- and R1 can, in addition, represent alkyl groups, benzoxazole, 4,6 dimethylbenzoxazole, 5 methh as the cycloalkyl groups, e. g. cyclopropyl, oxybenzoxazole, fi ethoxybenzoxazole, 5-ch1orocyclobutyly yclopentyl, cyclohexyl, etc. groups benzoxazole, 6-methoxybenzoxazole, S-hydroxy- (e. g. cycloalkyl groups containing from 3 to 6 5o benzoxazole, fi-hydroxybenzoxazole, etc.), those of the naphthoxazole series (e. g. a-naphthoxazole, p-naphthoxazole, etc), those of the selenazole series (e. g. 4-methylselenazole, 4-phenylselenazole, etc.), those of the benzoselenazole series (e. g. benzoselenazole, 5 chlorobenzoselenazole, 5 methoxybenzoselenazole, 5 hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.) those of the naphthoselenazole series (e. g. anaphthoselenazole, fl-naphthoselenazole, etc).
those of the naphthoselenazole series (e. g. a-
dine series (e. g. pyridine, 5-methylpyridine, ctc.),
etc., and Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from five to six atoms in the heterocyclic ring, such as those selected from the group consisting of a thiazolone nucleus, for example, a 2,4(3,5)-thiazoledione nucleus, such as 2,4(3,5) thiazoledione, 3-ethyl-2,4(-3,5)-thiazoledione, 3- phenyl-2,4(3,5) -thiazoledione or 3-naphthyl-2,-4 (3,5)-thiazoledione nuclei, a -2-thio-2-,4(3,5) -thiazoledione (a rhodanine) nucleus, such as 3-alkyl- 2-thio-2,4(3,5) -thiazoledione (3-alkylrhodanine) 3 phenyl-2-thio-2,4(3,5) thiazoledione (3 phenylrhodanine), 3 naphthyl-Z-thio-ZA(3.5) thiazoledione (3-naphthylrhodanine) nuclei or 3- (l-benzothiazyl) -2-thio 2,4(3.5)-thiazoledione (3-(1-benzothiazyl-) -rhodanine) nuclei, 9, 2-thio- 2,5(3,4) -thiazoledione nucleus, such as 3-methyl- 2-thio-2,5(3,4 thiazoledione, 3-ethyl-2-thio-2,5 (3,4) -thiazo1edione, 3-n-heptyl-2,5 (3,4) -thia'zoledione, 3-cyclohexyl-2,'5(3,4) -thiazoledione, etc., a 2-alkylmercapto-4(5)-thiazolone nucleus, such as 2-ethylmercapto-4(5)-thiazolone, a thiazolidone nucleus, such as 4-thiazolidone or its 3-alkyl-3-phenyl or 3-naphthyl derivatives, 2. 2-alkylphenylamino-4(5) -thiazolone nucleus, or a 2-diphenylamino-4(5) -thiazolone nucleus; an oxazolone nucleus, for example, a '2-thio-2,4(3,'5) oxazoledione nucleus, such as a 3-alkyl-2-thio-2A (3,5)-oxazoledione nucleus; an imidazolone nucleus, for example a 2,4(3,5)-imidazoledione nucleus, such as 2,4(3,5) -imidazoledione (hydantoin) or its 3-alkyl, 3-phenyl or 3-naphthyl derivatives as well as its 1,3-diallzyl, 1-alky1-3-phenyl, 1-alkyl-3-naphthyl, 1,3 diphenyl, etc., derivatives, a 2-thio-2,4(3,5)-imidazoledione nucleus, such as 2-thio-2,4(3,5)-imidazoledione (Z-thiohydantoin) or its 3-alkyl, 3-phenyl or 3-naphthyl derivatives as well as its 1,3-dialkyl, l-alkyl-B- phenyl, l-alkyl-B-naphthyl, 1,3-diphenyl, etc., derivatives, a 2-alkylmercapto-5(4) -imidazolone, such as 2-propylmercapto-5(4)-imidazolone; a thionaphthenone nucleus, such as 2-(1) thionaphthenone or 1(2) thionaphthenone, a pyrazolone nucleus, an oxindole nucleus, such as 2,3- dihydro-B-ketoindole, and like five-membered heterocyclic nuclei, a 2,4,6-triketohexahydropyrimidine nucleus, for example barbituric acid or 2-thiobarbituric acid, as well as their l-alkyl or 1,3-dialkyl derivatives; 9. 3,4-dihydro-2 l) -quinclone nucleus, such as 3,4-dihydro-2(1)-quinolone (dihydrocarbostyril) a 3,4 dihydro-2(1)- quinoxalone nucleus, such as 3,4-dihydro-2(1)- quinoxalone (oxydihydroquinoxaline) 3-phenomorpholone (l,4,2-benzoxazine-3(4)-one or benzo-fl-morpholone) nuclei; 1,4,2-benzothiazine-3 (4)-one (ketodihydrobenzoparathiazine) nuclei, and the like six-membered heterocyclic nuclei. The dyes wherein Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing five atoms in the heterocyclic ring, three of said atoms being carbon atoms, one of said atoms being a nitrogen atom, and the other of said atoms being a sulfur atom, a nitrogen atom, or an oxygen atom, have been found to be especially well adapted to the manufacture of photographic emulsions, we have found.
The new trinuclear dyes represented by Formula I above can advantageously be prepared by condensinga compound selected from those represented by the following general formula:
wherein R, R1, L, n, d, and Z have the values set forth above, and R3 represents an alkyl group, such as methyl, ethyl, n-hexyl, etc. groups, and X1 represents an anion, such as those represented by X above, for example, with a compound selected from those represented by the following general formula:
IV Q
wherein Q has the values set forth above.
The new trinuclear dyes represented by Formula II above can advantageously be prepared by condensing a compound selected from those represented by Formula HI above with a cyclammonium quaternary salt selected from those represented by the following general formula:
wherein R2, Z1, X, and e have the values set forth above.
The condensations can advantageously be carried out in the presence of a basic condensing agent, such as the trialkylamines, e. g. triethylamine, tri-n-propylamine, tri-n-butylamine etc., dialkylanilines, e. g. N,N-dimethylaniline, N,N- diethylaniline, etc., N-alkylpiperidines, e. g. N- methylpiperidine, N-ethylpiperidine, etc., heterocyclic amines. e. g. pyridine, quinoline, isoquinoline, etc., N-alkylpyrroles, e. g. N-methylpyrrole, etc.
The-condensations can also be carried out in the presence of an inert solvent, such as the lower aliphatic alcohols, e. g. ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc. alcohols, diethyl ether, .1,4-dioxane,'benzene, n-hexane, etc. Heat accelcrates the condensations, and temperatures varying from about 25 C. to the reflux temperature of the reaction mixture can be used.
The intermediates represented by Formula III above can advantageously be prepared by heating ayesdesi a compound selected from those represented by the following general formula:
wherein R, R1, n, d, L, and Z have the values given above, with an alkyl salt, such as those represented by the following general formula:
VII Rs-Xi wherein R1 and X1 have the values set forth above.
The intermediates represented by Formula VI above can be prepared as described in the copending application S. N. 203,526, filed on December 29, 1950, of R. A. Jeffreys and E. B. Knott. Intermediates of the type represented by Formula VIII above have been previously described by Cook e at al., Jour. Chem. Soc. (1949), DD. 1435-7.
The following examples describe more fully the manner whereby we prepare certain of the intermediates represented by Formula III above.
Example 1.-[2 (s ethyZbenzoxazoleHM-(Z- methylthio (4) thiazolone) ldimethinemerocyanine metho-p-toluenesulfonate 0=0--s C=CH CH=l t 2H5 CH: 0.32 g. of [2-(3-ethylbenzoxazole) [4 (3- methyl-2-thio-2,5(3,4) thiazoledione) ldimethinemerocyanine and 0.2 g. of methyl p-toluenesulfonate were heated together for minutes at 140 C. The reaction mixture set to a solid, and it was then ground to a powder and washed with dry benzene. It was recrystallized from an ethanol-diethyl ether mixture as red prisms with a blue reflex having a melting point of 222 C. It sensitized a gelatino silver chloride emulsion with a maximum at 510 ma and a gelatino silver bromide emulsion with a maximum at 530 ma.
Example 2.---[2-(3-ethylbenzoxazole) [4-,(2-ethylthz'o 5 (4) thiazoloneH dimethinemerocyam'ne metho-p-toluenesuljonate 1.0 g. of [2-(3-ethylbenzoxazole)] [4-(2-ethylthio 5(4) -thiazolone)l dimethinemerocyanine and 1.8 g. of'methyl p-toluene-sulfonate were heated together for one hour at 130 C. The resulting semi-solid was recrystallized from. an
ethanol-diethyl ether mixture as fiat red needles melting at 209 C.
Example 3.[2-(3-ethylbenzomazole) l [4-(2-eth ylthio 5(4) thiazoloneH dimethinemerocyanine ethiodide 2.0 g. of [2-(3-ethylbenzoxazole)][4-(2-ethylthio 5(4)-thiazolone)] dimethinemerocyanine and 10 cc. of ethyl iodide were fused together in a sealed tube at C. for 24 hours. The tube was then openedand the excess ethyl iodide driven off. The residue was recrystallized from ethanol as soft, rust-colored needles having a melting point of 136 C.
Example 4.-[2 (3 ethylb-enzoxazole) [4 (2- ethylthio 5(4) thiazolone) lolimethinemerocyanine methomethylsulfate 1.0 g. of [2-(3-ethylbenzoxazole)][4-(2-ethy1- thio-5 (4) -thiazolone) ldimethylmerocyanine and 0.7 cc. of methyl sulfate were fused at C. for
30 minutes. The crude product was then washed with diethyl ether.
Example 5.,[4-(1-ethylquinoline) [4 (Z-methylthzo 5(4) thiazolone) ldz'methinemerocya- Example 6.[2 (B-ethylbenzoxazoleH [4 (2- methyZthio-S (4) -thiazolone) dimethinemerocyanine n-hepto-pt0luensalfonate zHl 1.0 g. of [2-(3-ethylbenzoxazole)l heptyl-2-thio-2,5 (3,4) -thiazoledione) [4- (3-ndimethinemerocyanine and 0.5 g. of methyl p-toluenel sulfonate were heated together at 120 C. for 30 minutes. The red solid obtained was ground to a powder, heated under reflux with benzene, and the benzene removed by decantation.
i? EmmpZe; i i-E2 (3 ethyllei: 1 42% methyZthio-5 (4) -thzazolone) dimethinamz-em cyanine atho-p-toluenesuljonate.
4.1 g. of [2-(3-ethylbenzoxazole) l L4-(3-ethyl- 2-thio-2,5 (3,4) -thiazoledione) dimethinemerocyanine and 2.53 g. of methyl p-toluenesulfonate were heated at 120 C..for 30 minutes; The solid was ground. to a powder, washed, with diethyl ether,, and. then. recrystallized from an isopnopyl alcohol-diethyll ether mixture as an orange. microerystalline, powder melting, at 210 C. It, sensitized a gelatino silver chloride emulsion with a. maximum at 510. my. and a gelatino. silver. bromiodide emulsion with a.. maximum at 536 1119-.
Example 8.[2-(3-ethylbenzothiazole)] [4-(2- methylthz'o-fi'e)-thiazolone I dimethinemerm cyanine GZICZOIWBQKO-QHIYOZUETLCSEUMW 0.6 g. of [2-(3-ethylbenzothiazoleH [4-(3- cyclohexyl-2-thio-2,5(3,4) thiazoledione)l dimethi'nemeroeyanine and 0&3 g. of methyl p-toluenesul'fonate were heated together at: 120 C; for 30- minutes. The solid resulting was ground to a powder and washed diethyf ether. it was found to be deliquescent.
Example 9-.-E2.- (.i-ethylbenaowazolel 1* 54-42 methyZthz'o-5 (.4) -thiazolone) l dimethinememcyani'ne cyclohearo-p-toluenesulionate.
N 2H IHu 0.5 g. of [2-(3-ethylbenzoxazole)l [4-(3-cyclohexyl-2-thi0-2,5(3,4) -thiazoledione) l dimethinemerocyenine and 0 .28- g. of methyl p-toluenesulfonate were heated together for 30 minutes at 120 C: The" resulting solidi was ground to a powder, washed with diethyl ether, and'dried'. It was found to be deliquescent.
Example 1 0 .?--[2:-(S ethglbenzothiaaole)1: Lei-(.2; methyLthio-fifl)--thiazolone%l; dimetmnmem cyanine metho-p-toluenesulfanmte' 4.3 g. of EZ-(B-ethylbenzothiazolell [4-(3- methy1-2-thio-2,5(3,4) -thiazo1edione) dimethi-nemerocyanine and 2.9 g. of methyl p-toluene sulfonate wereheated together at 130 62.. for 30 Brmmpte tie-E2-tz-ethylbenzothiazolei:l 4962- ethylthz'o-5(4) thiazolonetl dimethinemerocyam'ne methomethylsulfate Example. 12.[2-(3-methylthiazoline)l [4-(2- ethyZthio-5C4) thiazolonelldimethinemerocyamne mefltomet'hyl'sulfate The tollowing. examples; illustrate the manner whereby certain of the intermediates represented by Formula. above can he prepared. Example. 13.[2'-fif-etkylbenzomazele)l 54-(2- anytime-5(4) fliz'dzolo'ne) 1 dimethinevmerocyanine iiHi 9.0 g. of N-(dithiocarbethoxy) glycine, 40. cc; of acetic anhydride, and 12 cc. of ethyl orthorformate were heated: together on' a steam bath for 30 minutes. The unreacted liquids were then distilledofi? and the. residual oil consisting of 2 ethylthio 4 ethoxymethylene 5(4') thiazolone was refluxed for five minutes: with 1&5 g. of Z-methylbenzoxazoleethiodide', 4'0 cc; of; ethane and 101 cc: of trietluyl'amiineand; the 1zeaction mixture then chilled. The resulting dye atter recrystallization; from ethanol formed fiat steel-blue: needles melting, at 156 0.. Example 14.-E2"(3'- methylthiazoZz'n-e) 1- [*efi- (-2- ethylth'i'o 5(4)I- tkzazolone) I dimethinemerocyanine:
This dye was prepared in the same manner as m nut The Solid product w ground to a the dye of Example l-3 by replacing theZ-methylowder, washed. diethyfi 61513811 911 benzoxazole ethiodidebyamolecularly equivalent cryst l z ti n fr an e -di t e r amount of Z-methylthiazoiine methiodide. The mixture, it was obtained asmaroomleaflets me fi desired product was: obtained as. maroon. needles ing at 182-? C. (6.2". g.) Itsensitized: bofli: a. gelatino silver chlorobromideemulsion and a gelatino silverbromide; emulsion with zit-maximum: at 570 my,
at 129 C1. from ethanol.
The followingv examples willserve to illustrate the manner whereby we: prepare: our new; tri nucleaedyes... V l V Example 15.--[2-(3-ethylbenzozazole)l [4 (5- oxo-2-phenyl-4-ozcazolinylidene) 3 methyl-5- (4) -thiazolidone) l dimethinemerocyanine 0.5 g. of the quaternary salt obtained in Example i above and 0.18 g. of 2-phenyl-5(4)-oxazolone were heated under reflux for four hours in the presence of 10 cc. of ethanol and 0.15 cc. of triethylamine. The reaction mixture was chilled and the solid filtered off. The dye was recrystallized from a pyridine-diethyl ether mixture as small bluish needles melting at 310 C. It sensitized a gelatino silver chloride emulsion with maxima at 540 and 570 ml and a gelatino silver bromide emulsion with a maximum at 610 m Example 16.-{2- (3-ethylbenzoxazole) {2-[-4- (2 [3 ethylbeneoxaeolinylidene] ethylidene) -3-methyl-5(4) -thiazolone]} methinecyam'ne 0.5 g. of the quaternary salt obtained in Example 1 above, 0.3 g. of 2-methylbenzoxazole ethiodide, 0.15 cc. of triethylamine, and 10 cc. of ethanol were heated under reflux for 4 hours. The reaction mixture was chilled and the precipitate filtered ofi. The dye, as recrystallized from methanol, melted at 300 C. and was obtained as rey prisms. It sensitized a gelatino silver chloride emulsion with maxima at 540 and 590 m and a gelatino silver bromide emulsion with a maximum at 590 m Example 17.-{2-(3-eihylbenzothiaeole)} {2[4- (2- [3-ethylbenzomazolinylidenel ethylidene) -3- methyl 5(4) thiazolonel} methinecyani'ne iodide 0.3 g. of the quaternary salt obtained in Example 1 above, 0.2 g. of 2-methylbenzothiazole ethiodide, 0.12 cc. of triethylamine, and 6 cc. of ethanol were refluxed together for one hour, chilled, and the reaction mixture filtered. The dye was recrystallized from pyridine as green needles melting at 286 C. It sensitized a gelatino silver chloride emulsion with maxima at 520 and 600 m and a gelatino silver bromide emulsion with a maximum at 630 m r.
Example .18.-{2-(3-methylthiazoline)} {2-[4- (2 [3 ethylbenzozrazolylidene]ethylidene) -3- 3H5 0.3 g. of the quaternary salt obtained in Ex 10 ample 1 above, 0.15 g. of 2-methylthiazoline methiodide, 0.12 cc. of triethylamine, and 6 cc. of ethanol were refluxed for one hour, chilled, and then filtered. The desired dye was recrystallized from methanol as red-bronze prisms melting at 298 C. It sensitized a gelatino silver chloride emulsion with maxima at 520 and 570 m and a. gelatino silver bromide emulsion with a maximum at 590 ma.
Example 19.--[4- (l-ethylquinoline) {2- [4- (4- [l-ethyl 1,4 dihydroquinolinylidene] ethylidene) 3-methyl 5 (4) thiazolonenmethinecyanine iodide I 0.51 g. of the quaternary salt obtained in Example 5 above, 0.3 g. of lepidine ethiodide, 0.2 cc. of triethylamine, and 10 cc. of ethanol were refluxed together for one hour on the steam bath.
The reaction mixture was then chilled, and the precipitate collected on a filter. After recrystallization from aniline, the dye was obtained as a dark olive-green powder having a melting point of 234 C.
Example 20.[2- (1 -ethylquinoline) ]{2- [4- (2- [3 ethylbenzoxazolinylidenel ethylidene) -3-n-heptyl-5 (4) -thiazolonel }methinecryanine iodide Example 21.--[4-(1-ethylquinoline)] {2-[4-(2- [3-ethylbenzoxazolinylidenel ethylidene)-3-nhepiyl 5(4) thiazolonel} methinecyanine iodide 0.5 g. of the quaternary salt obtained in Example 6 above, 0.26 g. of lepidine ethiodide, 0.2 cc. of triethylamine, and 5 cc. of ethanol were heated on a steam bath for 6 hours and the reaction mixture then chilled. The preeipitate was filtered off, and then recrystallized from a methanol-diethyl ether mixture as small moss-green needles melting at 184 C. -It sensitized a gela- 1 1 tino silver hromiodide emulsion with maxima at 640 and 700 m 0.9 g. of the quaternary salt obtained in Example 8 above, 0.25 g. of 3-ethylrhodanine, 0.2 cc. of triethylamine and 10 cc. of ethanol were re- Iluxed on a steam bath for one hour, and the mixture chilled. The precipitate was collected on a filter and recrystallized from a benzenepetroleum ether mixture as grass-green needles melting at 239 C. It sensitized a gelatino silver chloride emulsion with maxima at 470 and .650 m and a gelatino silver bromiodide emulsion with a flat maximum lying between 52.0 and 680 mu.
Example 2.3. [2-(3a6thZ/Zb3722011l20l3) 1 {4-{2- (5-omo-2-n-octg thzo 4 thiazolz'nylidene)-.3- .cyclohemyl-5-thz'azolidone]} dimethz'nemerocycame 01115 aHn ethylamine, and cc. of-ethanol, and the resulting solution was heated on a steam bath for 30 minutes and then chilled. The precipitate was collected on a filter and recrystallized from ligroin as yellow-green prisms melting at 150 C. It sensitized a gelatino silver chloride emulsion" with maxima at 400 and 590 m and a gelatino silver bromiodide emulsion with a maximum at 610 mu.
Example 24.[.2 .(3 a methylbenzothiazolefl {2- [4 (.2 l3 ethylbeneomaaolinylidene] ethyl idene) -.3-.ethyl 5 .thz'azolidoneil} azamethinecyamne p-toluenesulfonate maxima at 400 and 560 m and a gelat-ino silver bromiodide emulsion with a maximum 9.17 530 me- 12 Example 2 5. ---{2-( 3-ethylbenaothiazole) M442- (3 methyl 5 --o.ro 2 thio 4- thiazolidin ylidene) 3 methyl 5 thiazolindonefldi 1.04 .g. of the quaternary salt obtained in Example :10 above, 029 g. .of 3-methyl-2-thio-15-thiazolidone .(Cook etal, Jour. Chem. Soc. (1949'),
page 2340) 0.2 .cc. of triethylamine, and "10 cc. of
ethanol were heated on a steam bath for minrates. and then chilled. The precipitate was collected ona filter (0.8 g.) and recrystallized from a chloroform-petroleum ether mixture as a darkgreen microcrystalline powder melting at 274 C.
It sensitized both gelatino-silver chlorobromide and silver bromide emulsions with a maximum at 580 m Example 26. {2- (3-ethylbeneothiazole)}{4- [2- (3 ethyl 4 01:0 2 tha'o 5 thiazolidin ylidene) 3 methyl 5 thiazolidone]}dimethznemerocyanine 1.051: g. of the quaternary salt obtained in Example 10 above, 0.32 g. of '3-ethy'lrhodanine, 0.2 cc. of triethylamine, and 10 cc. of ethanol were heated on a steam bath for- 20 minutes and then chilled. The precipitate was collected on a filter (1.0 g.) and recrystallized from pyridine as long indigo needles, melting at 300 C. It sensitized a gelatino silver chloro'bromide emulsion with a maximum at 670 m Example 27. {2- (3-ethylbenzothiazole)}{4-[2- (5 ozco 2 n octory 4 thiazolinylidene) "3 -,methyl 5 .thzazolz'doncl}dimethinemero 5n cyanine 0.54 g. of N-(thiocarbo-n-octoxy) glycine and $0 .5 cc. of acetic anthydride were heated together on a steam bath for minutes. The unreacted acetic anhydride and acetic acid formed during the eraction were removed under .a vacuum. To the residual oil consisting of 2-n-octoxy-5(4)- thiazolone were added 1.04 g. of the quaternary salt .obtainedin Example 10 .above 0.3 c. of triethylamine and 10 cc. of ethanol, and. the mixture heated on a steam bath for 20 minutes and then chilled. The dye which separated weighed 0.9 g. and was recrystallized from a benzenepetroleum ether mixture as lustrous green leaflets meltin at C. It sensitized a gelatino silver chlorobromide emulsion with maxima at 7 5.80 and 640 mu.
13 Example 28.{4 (1 ethylquinoline)}{2 [4- (2-[ 3 ethylbenzoxazolinylidene]ethylidene)- 3 ethyl 5 thiazolidone]}methinecyanine iodide 0.488 g. of the quaternary salt obtained in Example 3 above, 0.299 g. of lepldine ethiodide, 0.2 cc. of triethylamine, and cc. of ethanol were refluxed for 30 minutes, and the solution then chilled. The precipitate (0.4 g.) was collected on a filter and recrystallized from a methanol-diethyl ether mixture as glittering blue-black crystals melting at 272 C. It sensitized a gelatino silver chloride emulsion with a maximum at 6'70 m Example 29.-{2 (3 ethylbeneothiazole)}{2- [4 (2 [3 ethylbenzomazolinylidenelethylz'dene) 3 methyl 5 thz'aeoli-done]}methine-cyamne iodide.
1.6 g. of the quaternary salt obtained in EX- ample 2 above, 0.9 g. of 2-methylbenzothiazole ethiodide, 0.5 cc. of triethylamine, and 10 cc. of ethanol were refluxed for 30 minutes and then chilled. The precipitate (0.9 g.) was collected on a filter and recrystallized from pyridine as fine green needles melting at 292 C. It sensitized a gelatino silver chloride emulsion with a maximum at 600 m and a gel-atino silver bromiodide emulsion with a maximum at 630 m Example 30.{2 (3 ethylbenzomazole)}{4- [2 (3 ethyl 4 oro 2 thio 5 thiazolidinylz'clene) 3 methyl 5 thiazolidonel} dimethine-merocyanine,
1.03 g. of the quaternary salt obtained in Example 2 above, 0.3 g. of 3-ethylrhodanine, 0.3 cc. of triethylamine and 10 cc. of ethanol were refluxed for 10 minutes, and then cooled. The precipitate was collected on a filter and recrystallized from pyridine as fine mauve needles melting above 310 C. It sensitized a gelatino silver chloride emulsion with a maximum at 600 m and a gelatino silver bromiodide emulsion with a maximum at 630 m Example 31.-{2 (3 ethylbenzothiazole) }{4- [2 (3 ethyl 4 omo 2 thio 5 thiaeolidinylidene) 3 ethyl 5 thiazolidonel} dimethine-merocyanine.
1.74 g. of [Z-(B-ethylbenzothiazole)l[4-(2- ethy1thio-5 -thiazol0ne) dimethinemerocya- Example 32.--{2 (3 ethylbeneomazole)}{4- [2- (3-ethyl-4-oro-2-thio-5 thiazolz'dinylidene) 3 ethyl 5 thiaeolidonel} dimethinemero-cyam'nc 1.0 g. of [2-(3-ethylbenzoxazole)l[4-(2-ethylthio 5(4) thiazolone)] dimethinemerocyanine and 0.5 g. of ethyl sulfate were fused at C. for 4 hours, and 0.45 g. of 3-ethylrhodanine, 0.5 cc. of triethylamine and 10 cc. of ethanol were added. The solution was refluxed for 10 minutes, and then chilled. The precipitate was collected on a filter and recrystallized from benzene as steel-blue needles melting at 278 C. It sensitized a gelatino silver chloride emulsion with a maximum at 600 m and a gelatino silver bromiodide emulsion with a maximum at 625 m Example 33.-{2 (3 ethylbeneomazole) }{*2- [4 (2 [3 ethylbenzothtazoltnylidenelethyltdene) 3 methyl 5 thiazoliclonal} methznecyamne iodide 1.2 g. of the quaternary salt obtained in Example 11 above, 0.7 g. of Z-methylbenzoxazole ethiodide, 0.5 cc. of triethylamine, and 10 cc. of ethanol were refluxed for 10 minutes, and then chilled. The precipitate was collected on a filter and on recrystallization was obtained as goldengreen needles melting at 280 C. It sensitized a gelatino silver chloride emulsion with a maximum at 610 m and a gelatino silver bromiodide emulsion with a maximum at 635 m Example 34.-{4-(i-ethylquinoline)} {2-[4-2- [3-ethylbenzothiazolinyltdene] ethylidene)-3 methyl- 5-thiazolidonel} methinecyanine io- 1.2 g. of the quaternary salt obtained in Example 11 above, 0.8 g. of lepidine ethiodide, 0.5 cc. of triethylamine, and 10 cc. of ethanol were refluxed for 10 minutes and then cooled. The precipitate was collectedon a filter and washed with ethanol until the washings were blue. The precipitate was then boiled out several times with i5 fresh portions or :methanol. needles melting at 292 C.
It formed ereen 1.2 g. of the quaternary salt obtained in EX- ample 11 above, 0.8 g. of 2-.methylbenzothiazole ethiodide, 0.5 cc. of triethy-lamine, and .1 cc. of ethanol were refluxed for .10 minutes and then cooled. The precipitate was collected on a filter, and washed with ethanol until the washings were blue. It was then boiled out several times with fresh portions of methanol. It formed green needles melting at 278 C. It sensitized a gelatino silver bromiodide emulsion with a maximum at 650 my" Example 36.-{2-(3-ethylbenzothiaeole)} 4-[2- (Z-n-heptylthz'o 5-oxo-4-thiazolinylidene)-3- methyl .5 thz'aaolidonc]}dimethinemerocyanine 0.7 g. of N-(dithiocarbo-n-heptoxy) glycine and 7 cc. of acetic anhydride were heated for minutes on a steam bath, and the unreacted acetic anhydride and acetic acid formed during the reaction removed under a vacuum. To the residue consisting of 2-n-heptylthio-5 (4) -thiazo.lone were added 1.2 g. of the quaternary salt obtained in Example 11 above, 0.5 cc. of triethylamine, and 10 cc. of ethanol, and the solution was refluxed for 5 minutes and chilled. The precipitate was collected on a filter and recrystallized from benzone as fine green needles melting at 200 C. It sensitized a gelatino silver bromide emulsion with a maximum at 645 C.
The N-(dithiocarbo-n-octoxy)glycine used in Example 23 above was prepared as follows:
Example 37.--N-(.dithiocarbo-n-octowy)glycine 22.4 g. of potassium hydroxide were dissolved in cc. of water and the solution chilled. There were then added 15.0 g. of glycine and 15.2 g. of carbondisulfide, and the whole shaken mechanically until a clear orange solution resulted. A solution of 38.6 g. of n-octylamine 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. of water, and the cloudiness resulting removed by extraction with diethyl ether. The aqueous layer was warmed gently under reduced pressure to expel any dissolved ether, the solution chilled, and acidified with concentrated hydrochloric acid. The precipitate was collected on a filter. washed with water, air-dried, and. recrystallized from petroleum ether (13. P. -80" C.) as glistennsp'lates melting at 100 o.
By replacing the .n-octylamine in Example .3?
.16 by :a moleoularly equivalent amount or .n-heptylamine, N tdithiocarboen-heptoxy) glycine was obtained as glistening, waxy plates melting at 99 C. on recrystallization from petroleum ether.
The ,N-Lthiocarbo-n-octoxy) glycine used in Example 27 above was prepared as follows:
Example 38r-N-tbiocarb0en-octoxy) glycine '1 41101. of n-octyl alcoholwas dissolved in.2.5.0 cc. of .carbondisulfide and 1 g. mol. of powdered potassium hydroxide was added. The whole was shaken mechanically until it had set to a solid, After chilling overnight, the salt was collected. washed with diethyl ether, .and airdried.
1 ;g. mol. of the potassium n-octoxydithio- Iormate (potassium n-octylzanthate) was added to 250 cc. of methanol, and 1 g. mol. of ethylbromide added. The mixture was warmed for several minutes, and water added. The oil which separated was taken up in diethyl ether, dried over sodium sulfate, and the ether removed by warming under a vacuum.
1 g. mol. of the ethyl n-octoxydithioformate (ethyl n-octylzanthate) thus obtained, 1 g. mol. of glycine, 1 g. mol. of potassium hydroxide were added to 200 cc. of a 50 per cent aqueous ethanol solution, and the whole refluxed on a steam bath for 18 hours. The solution was then concentrated to 00., 100 cc. of water was added, and the solution made acid with hydrochloric acid. The precipitate of the desired 2n-octoxy-5'(4)-thiazo'lone was recrystallized from petroleum other as fine'needles melting at 72 (3.
Operating in a similar manner to that illustrated in the above examples, other trinuelear dyes can be prepared according to our invention. For example, by replacing the quaternary salt used in Example 15 by a molecularly equivalent amount of [2-(B-methylbenzothiazole)] [4-(2- methylthio 5(4) thiazolone)l merocyanine metho-p-toluenesulfonate, [2 3 methylbenzothiazole)l [4 (5 oxo 2 phenyl 4 oxazolinylidene) -3-methyl-5 (4) -thiazolidone) merocyanine represented by the following formula:
din
can be obtained.
In like manner, by replacing the quaternary salt used in Example 18 above, by a molecularly equivalent amount of l2-(3-ethy1benzoxazole)l [4 .(2 .methylthio 5(4) thiazoloneH tetramethinemerocyanine metho-p-toluenesulfonate, {.2 (B-methvthiazoline {2-[4-(2-[3-ethy1benzoxazolylidene} 1,3-butadienylidene)-3-methylare) -thiazolonel} methinecyanine iodide represented bythe following formula;
can be obtained.
As shown above we have found thatour new consisting of those represented by the following dyes spectrally sensitive photographic silver general fgrmulas; halide emulsions when incorporated therein. z Q The dyes are especially useful for extending the M J: spectral sensitivity of the customarily employed B N("CH=CH)-1 73(=L L)d-l= gelatino silver-chloride, gelatino-silver-chlorobromide, gelatino-silver-bromide and gelatinosilver bromiodide developing-out emulsions. To d o=c-s prepare emulsions sensitized with one or more of wherein R, R1, and R2 each represents an alkyl our new dyes, it is only necessary to disperse the group of the formula C1nH2m+1 wherein m repredye or dyes in the emulsions. The methods of sents a positive integer of from 1 to 8, L repreincorporating dyes in emulsions are simple and sents a methine group, e and n each represents are known to those skilled in the art. In praca positive integer from 1 to 2, d represents a positice, it is convenient to add the dyes to the emultive integer from 1 to 3, X represents an anion, sions in the form of a solution in an appropriate Q represents the non-metallic atoms necessary solvent. Methanol or acetone has proved satisto complete a heterocyclic nucleus containing 5 factory as a solvent for most of our new dyes. atoms in the heterocyclic ring, 3 of said atoms.
Where the dyes are quite insoluble in methyl being carbon atoms, 1 of said atoms being a alcohol, a mixture of acetone and pyridine is nitrogen atom, and the other of said atoms being advantageously employed as a solvent. The dyes selected from the group consisting of an oxygen are advantageously incorporated in the finished, atom, a sulfur atom, and a nitrogen atom, and Zv washed emulsionsand should be uniformly disand Z1 each represents the non-metallic atoms tributed throughout the emulsions. The parnecessary to complete a heterocyclic nucleus seticular solvent used Will, of course, depend on the lected from the group consisting of those of the solubility properties of the'particular dye. thiazole series, those of the benzothiazole series,
The concentration of the dyes in the emulsions those of the naphthothiazole series, those of the can vary widely, e. g. from 5 to 100 mg. per liter oxazole series, those of the benzoxazole series, of flowable emulsion. The concentration of the those of the napththoxazole series, those of the dyes will vary according to the type of emulsion selenazole series, those of the benzoselenazole' and according to the effect desired. The suitseries, those of the naphthoselenazole series, able and most economical concentration for any those of the thiazoline series, those of the 2- given emulsion will be apparent to those skilled in quinoline series, those of the 4-quinoline series,
the art, upon making the ordinary tests and ob- 40 those of the l-isoquinoline series, those of the'3- servations customarily used in the art of emul isoquinoline series, those of the pyridine series, sion making. To prepare a gelatino-silverand those of the 3,3-dimethylindolenine series. halide emulsion sensitized with one or more of 2. The trinuclear dye represented by the folour new dyes, the following procedure is satislowing f rm 1a; factory:
A quantity of dye is dissolved in methyl alco- V hol or acetone (or a mixture of acetone and Q Q can pyridine) and a volume of this solution,- which morn =on n= may be diluted with water, containing from 5 to 100 mg. of dye, is slowly added to about 1000 cc. 6 I of gelatino-silver-halide emulsion, with stirring. Hi Stirring is continued until the dye is thoroughly The trinuclear dye represented by the m1- dispersed in the emulsion. lowmg formula! With most of our dyes, from 10 to 20 mg. of Q S\ dye per liter of gelatino-silver-bromide or 55 (5 bromiodide emulsion (containing about 40 g. of silver halide) sufiices to produce the maximum \N N sensitizing effect. With the finer grain emul- H sions, somewhat larger concentration of dye may I 01H; be needed to produce the maximum sensitizing 6o 4. The trinuclear dye represented by the folefiect. lowing formula:
The above statements are only illustrative, as it will be apparent that the dyes can be incorporated in photographic emulsions by any of the C=OHOH=( J t=cnc other methods customarily employed in the art, N
e. g. by bathing a plate or film upon which an 5 emulsion is coated in a solution of the dye in an 1H appropirate solvent. However, bathing methods 5. The trinuclear dye represented by the folare ordinarily not to be preferred. Emulsions lowing formula: sensitized with the dyes can be coated on suitable supports, such as glass, cellulose derivative film, resin film or paper in the usual manner. CY=CH CH=A 0: =8
What we claim as our invention and desire secured by Letters Patent of the United States is: N N s 1. A trinuclear dye selected from the group 6, 4111;
esteem 1Q me.- tainuoleazr dye: bx: the; fab lowing formula:
infant-)1.
wherein R-, R1, and E3 eachrepresents arr alkyl group ofthe formula; ,QmHzmerr wherein m-representsa positive-integer from 1 to 8; X1 represents" agranion; n represents a; positive integer-from If to 2; 11:- represents a positive integer-"from 1* to 3'; and" Z; represents the non-metallicatoms necessary to complete a heterocyolie nucleus selected from thegroup consisting of-those of the thiazole series, thoseof the benzothiazole series; those of the naphthothiazole series, those of theoxazoleseries; thoseof the 'benzoxazole series, those of' the naphthoxazoleseries,- those of? theselenazole series, those; of thebenzoselenazole series, those of, the, naphthoselenazqle series those of the thiazoline series, those of the 2- quinoline series, those of the: Q-qpinoline series; those of: the l-isoquinoline series-,- those" of-the- 3- isoquinoline series, those of the pyridine series; and'those of" the 3;3"-dimethylindolenine series; with acompoundrelected from the group, w n
sisting of a ketomethylene compound selected;
from those, represented by the following, neralj formula:
m6 b= wherein- Q- represents the non-metallic atoms necessary to completea heterocyoliolnucleus containing -atoms in the heterocyclic ring; 3of said atome-bein icarhoniatoms, 1* f; said; etomebein at nitrogeni atom. and the; otherofi said: atoms e ng; sel atedfrom; the group consistin of; an: oxy e atom a sulfun atom: andsanitmgsm atom; and cyolammoniumaquaternary salt; seleotedsimm, thoise: represented by. the; followinggeneral; 103- mu a;
wherein R2 represent an alkyl group of the formula CmHZuH-l wherein m represents a positive integer from 1 to 8, X represents an anion, e represents, a; positi-te integerfrom; 1 to 21 and Z1, represents the: non-metallic, atoms necessary to, complete.- a heterocyolic nueleus selected from the. groupconsisting: of, those; of the thiazole; series, thoseeof the benzot-hiazole series, thoseoh the-naphthothiazole: series, thoseoi the oxazole:
series those of the: henzoxazole; series, thOSB -.-QL. the-naphthoxazo1e series, those-0 theiselenazolei series, those of theabenzoselenazole seizies those; of, thefnaphthoselenazole-series, those Qfithethirazoline; series those: of. the 2-quinoline series, those of; the 4V-quin0line series those,-of the 1,- isoquinoline: series those--. of; thens isoguinoline. series, thosezof the pyridinerseries. and thosemt. the: 3,3-dimethylindoleninee series.
8,; A process, according to, olaimfl; whereimthe; condensationiisperformed in thenresenceottrie eths lamine.-.
BER RQY A.. JWEKSJ,
References Cited in the file of this patent, UNITED Sc'IIA'lIES PATENTS- Number; Name;- Date:
2;l70;80.4; Breaker-"many" Augzlfi; 19397' 223881962 Et'y n Noyes l3, 19.455
OTHER REFERENCES 00.9 J, Chem.. Soc,-, (1943), p.11. 1056:4057. Cools, L. Chem, Soc, (1943), li43'5$143?.-,, 2?$2e234fia

Claims (1)

1. A TRINUCLEAR DYE SELECTED FROM THE GROUP CONSISTING OF THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULAS:
US220332A 1951-03-02 1951-03-02 Trinuclear dyes containing a 5-thiazolidone nucleus Expired - Lifetime US2656351A (en)

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FR1086259D FR1086259A (en) 1951-03-02 1952-02-29 New trinclear compounds, process for their preparation and their applications in particular in photography

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2743272A (en) * 1952-03-28 1956-04-24 Eastman Kodak Co Sensitizing dyes containing a 4-aryl-5-aryloxy- or 5-arylthiothiazole nucleus
US3094418A (en) * 1960-03-10 1963-06-18 Eastman Kodak Co Silver halide meulsions containing cationic oxonol and benzylidene dyes
US3930869A (en) * 1973-01-12 1976-01-06 Mitsubishi Paper Mills, Ltd. Photographic silver halide photosensitive materials

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2170804A (en) * 1937-04-24 1939-08-29 Eastman Kodak Co Merocyanine dyes from benzoxazoles
US2388962A (en) * 1938-01-24 1945-11-13 Allied Chem & Dye Corp Dry cleaning composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2170804A (en) * 1937-04-24 1939-08-29 Eastman Kodak Co Merocyanine dyes from benzoxazoles
US2388962A (en) * 1938-01-24 1945-11-13 Allied Chem & Dye Corp Dry cleaning composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2743272A (en) * 1952-03-28 1956-04-24 Eastman Kodak Co Sensitizing dyes containing a 4-aryl-5-aryloxy- or 5-arylthiothiazole nucleus
US3094418A (en) * 1960-03-10 1963-06-18 Eastman Kodak Co Silver halide meulsions containing cationic oxonol and benzylidene dyes
US3930869A (en) * 1973-01-12 1976-01-06 Mitsubishi Paper Mills, Ltd. Photographic silver halide photosensitive materials

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FR1086259A (en) 1955-02-10

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