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Publication numberUS3836370 A
Publication typeGrant
Publication dateSep 17, 1974
Filing dateMar 8, 1972
Priority dateMar 9, 1971
Also published asDE2211200A1
Publication numberUS 3836370 A, US 3836370A, US-A-3836370, US3836370 A, US3836370A
InventorsP Beretta, L Magnani
Original AssigneeMinnesota Mining & Mfg
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Merocyaninic dyes and their use in silver halides photographic emulsions containing the same
US 3836370 A
Abstract
Merocyanine dyes comprising a heterocyclic nitrogenous nucleus and a heterocyclic ketomethylene nucleus, and silver halide emulsions containing such dyes.
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Sores karenr [191 Berewn et a1.

[ Sept. 17, 1974 1 1 MEROCYANINIC DYES AND THEIR USE IN SlILVIER ll-IALIDES IPHOTOGRAPHIC EMULSlONS CONTAINING THE SAME [75] Inventors: Paolo Beretta, Ferrania; Luigi Magnani, Carcare, both of Italy [73] Assignee: Minnesota Mining and Manufacturing Company, St. Paul, Minn.

22 Filed: Mar.8,1972

211 Appl.No.:232,724

[30] Foreign Application Priority Data Mar. 9, 1971 Italy 48919/71 [52] US. Cl 96/127, 96/139, 96/141, 260/2401, 260/240.4

[51] on. C1 G03C 11/11) Primary Examiner-J. Travis Brown Attorney, Agent, or Firm-Alexander, Sell, Steldt & DeLaHunt [57] ABSTRACT Merocyanine dyes comprising a heterocyclic nitrogenous nucleus and a heterocyclic ketomethylene nucleus, and silver halide emulsions containing such dyes.

5 Claims, 8 Drawing Figures PATENIEU 3. 836.3 70

SHEEI 1 nr 3 MEROCYANINIC DYES AND THEIR USE IN SILVER HALIDES PHOTOGRAPHIC EMULSIONS CONTAINING THE SAME The present invention relates to merocyaninic dyes and to silver halides emulsions containing the same and to photographic elements containing such dyes.

Silver halides, by themselves, are substantially insensitive to the visible radiations with the exception of those having a lower wave length. The sensitivity of the silver halides emulsions has been extended to higher wave lengths by the introduction into them of various dyeing sensitizers such as those of the merocyaninic class. These dyes are now of common use in the black and white photographic emulsions and in the colored photographic emulsions. For example, a useful photographic element for colored photography may contain layers of silver halides emulsion which have been sensitized to the red, green and blue light. The dyeing sensitizers used in the above photography must exhibit, according to what hereinabove said, the sensitization characteristics required and moreover they must be completely removable from the photographic elements during the processing so as to impart the least residual coloration possible to the final colored image.

A summary of the technology of the dyeing sensitizers and examples of various dyeing sensitizers may be found in Mees and James, The Theory of the Photographic Process, Third Edition, The McMillan Company, New York, 1966, Chapter 1 1. For the desensitizers re same Chapter 11 and 8 and e.g. British Patent l,186,713.

In brief the present invention relates to merocyaninic dyes comprising on one side a heterocyclic, nitrogeneous nucleus and on the other one of a heterocyclic ketomethylenic nucleus.

These merocyaninic dyes are characterized by the ketomethylenic group containing at least a nitrogen atom, carrying, as a substituent, a furfurylor a tetrahydrofurfuryl group. The invention relates moreover to photographic silver halides emulsions containing such dyes, as sensitizers and desensitizers, and to photographic elements prepared with them.

In its preferred realization, the presentinvention refers to merocyaninic dyes representatable by the following formula:

In the hereinabove formula,

R represents a substituted and a non substituted alkyl having from one to eight carbon atoms such as for ex- LII ample methyl, ethyl, hydroxyethyl, sulphoethyl, car- Z represents the non metallic atoms required to complete a heterocyclic nucleus.

Q represents the non metallic atoms necessary to completea heterocyclic nucleus comprising at least a nitrogen atom carrying, as a substituent, a furfuryl or a tetrahydrofurfuryl group.

nis l or2anddis 1,2or3.

Examples of heterocyclic rings which are completed by the non metallic atoms represented by Z in the hereinabove formula (1) are those of the thiazole series (thiazole, 4-methyl-thiazole, 4-phenylthiazole, 5- methyl-thiazole, S-phenyl-thiazole, 4,5-dimethylthiazole, 4,5-diphenyl-thiazole); those of the benzothiazole series (benzothiazole, 4-chlorobenzothiazole, 5- chloro-benzothiazole, 6-chloro-benzothiazole, 7- chloro-benzothiazole, 4-nitro-benzothiazole, S-nitrobenzothiazole, 6-nitro-benzothiazole, 5-chloro-6-nitrobenzothiazole, 5-bromo-o-nitrobenzothiazole, 4-methyl-benzothiazole, S-methyl-benzothiazole, 6- methylbenzothiazole, S-bromo-lbenzothiazole, 6- bromo-benzothiazole, 4-phenylbenzothiazole, S-phenyl-benzothiazole, 4-methoxy-benzothiazole, 5- methoxybenzothiazole, 6-methoxy-benzothiazole, 5-

methyl-6-methoxy-benzothiazole, 5-iodobenzothiazole, 6-iodo-benzothiazole, 4-ethoxybenzothiazole, 5 -ethoxy-benzothiazole, 4,5 ,6, 7-

tetrahydro-benzothiazole, 5,'6-hydroxymethylenbenzothiazole, S-hydroxy-benzothiazole, o-hydroxybenzothiazole, 5,6-dimethyl-benzothiazole, 5,6-dimethoxy-benzothiazole); those of the naphthothiazole series l,2-d]-naphthothiazole, [2, l -d]- naphthothiazole, 5-methoxy-[ l ,2-d]-naphthothiazole, 5-ethoxy-[ 1 ,2-d]-naphthothiazole, 8-methoxy-[2, l -d]- naphthothiazole, 7-methoxy-[2,1-d]-naphthothiazole); those of the oxazole series (4 -methyl-oxazole, 5- methyl'oxazole, 4-phenyl-oxazole, 4,5-diphenyloxazole, 4-ethyl-oxazole, 4,5-dimethyloxazole, 5- phenyl-oxazole; those of the benzoxazole series (5- chloro-benzoxazole, 5-methyl-benzoxazole, S-phenylbenzoxazole, 6-methyl-benzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethyl-benzoxazole, S-metoxybenzoxazole, S-hydroxy-benzoxazole, o-hydroxybenzoxazole, 4-nitro-benzoxazole, S-nitrobenzoxazole, 6-nitro-benzoxazole, 5-chloro-6-nitrobenzoxazole, 5-bromo-6-nitro-benzoxazole; those of the naphthoxazole series ([2,l-d]-naphthoxazole, [1,2- dl-naphthoxazole); those of the selenazole series (4- methyl-selenazole, 4-phenyl-selenazole); those of the benzoselenazole series (benzoselenazole, S-chlorobenzoselenazole, 5-metoxy-henzoselenazole, 5- hydroxy-benzoselenazole, fi-metoxy-benzoselenazole, 5,6-dimetoxy-benzoselenazole, 4-nitrobenzoselenazole, S-nitro-benzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitro-benzoselenazole, 5- bromo-6-nitro-benzoselenazole; those of the naphthoselenazole l ,2-d]-naphthoselenazole, [2, l -d]- naphthoselenazole); those of the thiazoline series (thiazoline, 4-methyl-thiazoline, 4-hydroxymethylthiazoline, 4,4-bis-hydroxymethyl-thiazoline, 4- acetoxymethyl-4-methyl-thiazoline, 4,4-bis-acetoxymethyl-thiazoline); those of the oxazoline series (oxazoline, 4-hydroxymethyl-4-methyl-oxazoline, 4,4-bisacetoxymethyl-oxazoline); those of the selenazoline series, those of the Z-quinoline series (quinoline, 3- methyl-quinoline, Smethyl-quinoIine, 7-methylquinoline, 3-methyl-quinoline, 6-chloro-quinoline, 8- chloro-quinoline, o-methoxy-quinoline, 6-etoxyquinoline, 6-hydroxy-quinoline, 8-hydroxy-quinoline); those of 4-quinoline series (quinoline, 6-methoxyquinoline, 7-metoxy-quinoline, 8-methyl-quinoline); those of the l-isoquinoline series (isoquinoline, 3,4- diisoquinoline); those of the 3-isoquinoline series; those of the 3,3-dialkyl-indolenine series (3,3- dimethyl-indolenine, 3,3,S-trimethyl-indolenine, 3,3,7- trimethyl-indolenine); those of the 2-pyridine series (such as for example 2-pyridine, S-methyl-Z-pyridine, etc); those of the 4-pyridine series (4-pyridine, 3-methyl-4-pyridine, etc. those of the imidazole series (for example imidazole, l-alkyl-imidazole, 1-alkyl-4- phenyl-imidazole, l-alkyl-4,5-dimethyl-imidazole, ctc.); those of the henzimidazole series (for example bcnzimidazolc, l-alkyl-bcnzimidazolc, l-alkyl-5,6- dichloro-benzimidazole, l-phenyl-benzimidazole, lhydroxyethyl,5,6-dichloro-benzimidazole, l-ethyl-S- chloro-benzimidazole, l-acetoxyethyl-S ,6-dichlorobenzimidazole, l-ethyl-5-chloro-6-aminobenzimidazole, l-ethyl-5-chloro-6-bromobenzimidazole, l-ethyl-5-acetyl-benzimidazole, etc.

Examples of nuclei which are completed by atoms represented by Q in the hereinabove formula (1) are the nucleus of the thiazole, for example 2,4-thiazoledione, 4-thiazolidone, 2-thio-2,4-thiazole-dione (roda' nine); nuclei of the oxazolone type, for example 2-thio- 2,4-oxazole-dione and 2-imino-2,4 oxazole-dione (pseudo-hydantoin); nuclei of the imidazolone type, such as the 2,4-imidazole-dione (hydantoin, for example 2-thio-2,4-imidazolo-dione (2-thio-hydantoin); nuclei of the pyrazolone type, oxindole (2,3- dihydroketoindole), 2,4,6-triketohexahydropyrimidine (barbituric or thiobarbituric acid); nuclei of the 3,4-dihydro-quinoline, 3,4-dihydroquinoxazolone, l,4-rnorpholine-3-one and 2H-l,4-benzothiazine-3-one.

The merocyaninic dyes of the present invention represented by the general formula l wherein d is equal to I, can be prepared by reacting an ammonium salt chosen among those known to the skilled in the art, represented by the formula:

wherein R and Z have the hereinabove reported values;

R represents an alkyl group (such as for example methyl, ethyl, etc.) or an aryl group (such as for example phenyl, o-, m-, p-tolyl, etc.);

X represents an acid anion such as chloride, bromide, iodide, thiocyanate, sulfamate, methylsulfate, ethylsulfate, perchlorate, benzensulfonate, p-toluenesulfonate, etc. with a compound chosen among those represented by the following formula:

ma -(i=0 where Q has the hereinabove reported meaning.

The compounds (3) not known before the present invention, as they contain the furfurylor the tetrahydrofurfuryl substituent, can be prepared in a way known to the skilled in the art, as it results from the hereinafter following description and examples.

The dyes according to the invention represented by the general formula l where d 2, 3 can be prepared by condensing a compound of the general formula (3) with a compound chosen among those known to the skilled in the art, represented by the general formula:

wherein R, Z and n have the meanings hereinabove reported.

Another process usefully employed in the synthesis of the merocyaninic dyes of the general formula (1) with d 2 and L equal to substituted methinic group as hereinabove reported, consists of the condensation of a compound of the general formula (3) with a compound chosen among the class known to the skilled in the art, represented by the formula:

where R, R,, X, Z and n have the meaning hereinabove reported and R is equivalent to monovalent alkyl group such as methyl, ethyl, etc.

Another method to prepare the merocyaninic dyes of the general formula (1), where d 2 and L is equal to non substituted methinic group consists of reacting a quaternary salt belonging to the class of the compounds known to the skilled in the art, represented by the following formula:

where R, X, Z, n have the hereinabove cited meanings, with a compound belonging to the class represented by the following formula:

where Q, R R have the hereinabove cited meanings.

The compounds of the formula (8), not know before the present invention, as they contain the furfurylor the tetrahydrofurfuryl substituent, can be prepared in a way known to the skilled in the art, from compound of formula (3), as it results also from the examples following hereinafter.

The condensations of which hereinabove, can be ad vantageously performed by heating the reacting mixture at temperatures ranging between room tempera-' where R, L, Z, n and d have the meanings hereinabove reported and where at least one among the substituents R and R is a furfurylor tetrahydrofurfuryl group, while the other one is an alkyl group (for example methyl, ethyl, n-propyl, n-butyl, n-amyl, n-hexyl, nheptyl, benzyl (phenylmethylene), allyl, cyclo-penty], cyclo-hexyl, etc.; a substituted alkyl group such as car- 'boxyethyl, carboxymethyl, sulfo-propyl, dialkylaminoalkyl, etc.; an aryl group such as phenyl, 0-, m-, ptolyl.

The compounds (9) are prepared according to the above indicated general methods, from compounds not known before the present invention, having the formula:

where R and R have the hereinabove reported mean- 6 ings, obtained in a known way, for example according to Wheeler and Al, J.A.C.S. (1911), 45, 456-474, and from compounds not known before the present invention, having the formula obtained in a way known to the skilled in the art from compounds having the formula (10) as it results from the following examples.

Among the compounds represented by formula (1), particularly useful are also the merocyanines represented by the following formula:

Ike

where R, L, Z, n, d, have the hereinabove said meanings W is equal to S and O and R represents a furfuryl or tetrahydrofurfuryl radical.

The compounds (12) are prepared according to the most general methods hereinabove reported, from compounds not known before the present invention,

having the formula:

(12) bis CH;W

where W and R have the hereinabove reported meanings, obtained in a way known to the skilled in the art, for example according to Holberg and Al in K. Prakt, Chemie, 81 (1910) 451 and Andreasch and Zizsser in monatschr. fur Chemie 24 (1903) 504 and 25 (1904) 167 and according to A. Ahlquist in Journ. Prakt. Chemie [2], 84 (1911), 662-675, and from compounds, not known before the present invention, having the formula:

obtained in a way known to the skilled in the art from compound having the formula 12 bis) as it results also from the following examples.

The sensitizers of the present invention introduced into the silver halides photographic emulsions have the advantage of imparting to them and to the photographic element containing them a more extended spectral sensitization (and therefore a greater sensitivity) and of not presenting any residual coloring.

The present invention will be more easily understood, by referring to the following illustrative examples.

Example 1 Tetrahydrofurfuryl-isothiocyanate CH;-CH:

H2 I'L-GHPN C S o 24 g of NaOH drops were dissolved in 120 cc of water and to this solution 52.5 g of tetrahydrofurfurylamine were added. The stirred mixture was brought by cooling to +4C and then 60.3 g of carbon sulfide were added in small portions. The temperature was maintained below 10C during the whole period of the addition. The mixture was left under stirring for 7 hours and then allowed to stand at rest overnight. A solution of 228 g of lead acetate in 240 cc of water was poured into the reaction mixture under stirring at room temperature and the semisolid black mass obtained was diluted with 200 cc of water and furtherly stirred for 2 hours. The mixture was steam distilled until 3 liters of distillate were obtained; the distillate was then'extracted with ethyl ether. The ethereal solution was dried with Na SO and evaporated to dryness. A dark dense oil (34 g) was obtained, which was distilled under vacuum. The fraction distilled at ll-ll5C/27 mm Hg was collected.

The yield was 16 g.

Example 2 furfuryl-senfol This compound has been prepared similarly to the preceeding one by using 50 g of furfurylamine, 22.8 g of NaOH in l 14 cc of water, 60.3 g of CS and a solu tion of 240 g of lead acetate in 600 cc of water. At the end a dark dense oil was obtained which was immediately used without further purification, since it decomposed very easily (even if stored under vacuum).

Example 3 l-methyl-3-tetrahydro-furfuryl-Z-thio-hydantoin Centesimal analysis Found: C% 50.78; H% 6.82; N% 12.87

14.75 Calculated: C% 50.51; H% 6.59; N% 13.09

Example 4 l-carboxymethyl-3-tetrahydrofurfuryl-2- thiohydantoin 37.6 g of the iminoacetic acid diethyl ester were introduced in a flask supplied with reflux and dropper. From the latter 28.5 g of tetrahydrofurfuryl-senfol (example 1) were allowed to drop in and then the mixture was boiled for 10 minutes. The reaction mixture was poured in a vessel containing 200 cc of cold water; an oil was separated which was extracted with ethyl ether. The ethereal solution was treated with bone black, dried with Na SO and evaporated ultil dryness.

The yield was 55.4 g and thus it was obtained the lcarboxyethoxymethyl-3-(tetrahydrofurfuryl)-2- thiohydantoin. This product was treated with 186 cc of a 10 percent sodium hydroxide solution, heating to boiling for 10 and thus obtaining a complete solution. After acidification with HCl and cooling, the mixture was extracted with ethyl ether. The solution was dried with Na SO and evaporated.

A dark oil (9.5 g) was obtained, which was used immediately for the synthesis of the dyes without further purification.

Example 5 N-tetrahydrofurfuryl-rodanine 18 g of tetrahydrofurfuryl-senfol, 32 g of absolute alcohol and 16 g of thioglycolic acid were introduced into a 250 cc flask and placed on an oil bath at l 10C. After 1 hour, 2 cc of acetic anhydride were added and the heating was continued for 24 hours. A yellow solution was obtained which was concentrated under vacuum until the formation of a solid which was filtered on a buckner.

The yield was 10.7 g of dried product. The raw product was crystallized from 425 cc of ligroin and 9.4 g of pure product having a M.P. 88-89C was obtained.

Centesimal analysis Found: Cal cu lated:

Example 6 Acetamidofurfurylamine hydrochloride g of furfurylamine, 486.4 g of chloroacetamide and 1600 cc of absolute alcohol, were heated at 5050C on a steam bath for 2 hours and then at reflux for 4 hours. The mixture was cooled and allowed to stand. A brown solid was separated and was filtered on a buckner. The solid was mashed with acetone several times until it became white; it was collected on a buckner and washed with ethyl ether. The flaky white product obtained was dried and gave a yield of 186 g M.P. l80.5 l8l.5C.

Example 7 1-furfuryl-3-(y-dimethylaminopropyl )-2- thiohydantoin In a refluxing flask placed in an oil bath at 100C, 52.5 g of acetamido-furfurylamine hydrochloride, 100 cc of methyl alcohol and 39 g of -di-methylaminopropyl-senfol were introduced. A vivacious reaction occurred which was quenched by immerging the flask into a bath of water and ice. 200 cc more of methyl alcohol were added and to the dark re sulting mixture 16.6 g of potassium hydroxide dissolved in 110 cc of water were added and the mixture was boiled for 3 hours, making sure once in a while that the pH remained alkaline. When the heat was terrnined, to the likewarm solution 137 cc of concentrated HCl were added in small portions. When the addition was terminated, the mixture was brought to ebullition again for 3 hours making sure that the pH remained acid; then it was allowed to stand overnight. A solid was separated and was eliminated by gravity filtering. The mixture was evaporated under vacuum until a solid remained. It was diluted with water, alkalized to pH 9 with percent sodium carbonate, extracted with ethyl ether and finally the ethereal soluion was dried. The mixture was heated with bone black and was evaporated. A dark oil remained, the yield of which was 59.5 g. The product, which was difficult to purify was immediately used for the dye synthesis.

Example 8 N-furfuryl-rodanine The reaction was performed similarly to that one of Example 5. The amounts used were 40 g of furfurylsenfol, 73 cc of ethyl alcohol, 4.5 cc of acetic anhydride and 36 g of thioglycolic acid. The obtained yield was 7.2 g of oil which was distilled under reduced pres sure. B.P. ll6l20C/l mm Hg.

Example 9 l-furfuryl-3-propyl-thiohydantoin 52.5 g of acetamido-furfurylamine hydrochloride, 300 cc of methyl alcohol, 27.8 g of propyl-senfol and 16.6 g of KOH dissolved in 110 cc of water, were mixed in a l l flask. The mixture was boiled for 3 hours then I37 cc of concentrated HCl were added after cooling the flask with water and ice. The mixture was then boiled for half an hour and then 200 cc of solvent were distilled off. The mixture was diluted with 200 cc of water and was extracted with ethyl ether, drying the ethereal solution with Na SO After evaporation of the ether, 53 g of a dark yellow oil remained which was distilled under vacuum collecting the fraction distilled at 168l70C/l mm Hg. The yield was 45.5 g ofa slightly yellow oil.

Centesimal analysis Calculated: Found:

Example 10 N-furfurylglycine ethyl ester 30 g of furfurylamine, together with cc of absolute ethyl alcohol, were introduced in a flask and from a reflux 54 g of ethyl bromo-acetate were added. A dark solution was obtained and 32 g of triethylamina were added to it. A white solid separated. The mixture was brought to ebullition and was allowed to react for 15 hours while the solid went completely into solution. By cooling and standing a solid tri-ethylamine hydrobromide separated, which was separated from the solution by filtration on a buckner. To the: solution was added more ethyl ether to complete the triethylamine hydrobromide precipitation. The ethereal solution was concentrated under reduced pressure and the remained dark oil was diluted under vacuum collecting the fraction having a HP. l60l 70C/2 mm Hg. The obtained yield was 33.6 g.

Example 1 l l-furfuryl-3-carboxymethyl-2-thiohydantoin oH,--N-orn-o of this product were boiled for minutes with 82 cc of a 10 percent sodium hydroxide. The dark yellow solution obtained was cooled and acidified with HCI. Then it was extracted with ether, the ethereal solution was dried with anhydrous sodium sulfate and then was evaporated under vacuum. The residual yellow oil by standing a few days in the dessiccator, solidified and was crystallized from ethyl alcohol. Yield 23 g M.P. l25126C.

Centesimal analysis Calculated: Found:

C% 47.24; H% 3.94; N C% 47.36; H% 4.09; N

Example 12 l-tetrahydrofurfuryl-3-ethyl-2thiohydantoin JaHr 9.8 g of N-tetrahydrofurfuryl-glycine-ethyl ether (Example 11) and 4.45 g of ethylsenfol were heated at 150C for 36 hours. The obtained dense liquid was distilled under vacuum and a yellow oil having a B.P. 168l 72C/ 1 2 mm Hg was obtained. The yield was 7.1

Example 13 l-carboxymethyl-3-tetrahydrofurfuryl-2- thiohydantoin N am H CH: O

- were dissolved in 186 cc of 10 percent sodium hydroxide by boiling for 5 minutes. The solution'was poured into a beaker containing 200 cc of water and while cooling in a bath of water and ice was acidified with concentrated HCl and was extracted with ethyl ether. The ethereal solution dried with anhydrous sodium sulfate was evaporated obtaining an oil which solidified after some days. The product was used as such for the synthesis of the dyes.

Example 14 N-furfuryl-2-thio-oxazolidone 26.1 g of furfuryl-amine and a solution consisting of 21.19 g of potassium hydroxyde dissolved in 81.8 cc of water were mixed in a keller. Under fast stirring 57 g of acetamido-carbodithioloneglycolic acid (prepared according to what has been reported in J. Prakt. Chem./2/99 (1919) p. 45 and following), were added in small portions. The mixture was allowed to stand overnight, was diluted with 271 cc of water and was stirred again for 2 hours then was acidified with HCl. A separated oil was extracted with ethyl and the ethereal solution was dried with anhydrous sodium sulfate. The solution was filtered by gravity and the solvent was evaporated. A yellow oil remained giving a yield of 63 g. It was distilled under reduced pressure and the fraction distilled at 168170C llmm Hg was collected; its weight totaled 38.6 g. after a little while it solidified in a crystalline mass which was crystallized from ethyl alcohol. 26.5 g of shining white scales were obtained, having M.P. 68.569C. The compound was found to comply with the formula:

l... 1 C O Centesimal analysis Calculated: 7.1 1 Found: 7.12

Example 15: N-tetrahydrofurfuryl-2-thio-oxazolidone.

CH2O

N (EH2 It was prepared analogously to Example 14, by using 27.1 g of tetrahydrofurfuryl-amine, 21.19 g of potassium hydroxide, 81.8 cc of water and 37.5 g of acetamido-carbodithiolone-glycolic acid. By evaporation of the ethereal solution 37 g of reddish oil were obtained; the oil was distilled under vacuum and the fraction distilled at ll82C/ 1 mm Hg was collected. The yield was 20.15 g.

Centesimal analysis Calculated: Found:

Example 16 -acetanilido methylene-3-furfuryl-2-thiooxazolidone.

9.85 g of N-furfuryl-2-thio-oxazolidone, 9.80 g of diphenyl-formamidine and 3 cc of kerosene were reacted for 2 and a half hours at 120C. An oil separated and solidified after standing overnight. The yield of the pure product, having MP. 165-l67C was 5.7 g. 4.7 g of this product (5-anilino-methylene-3-furfuryl-2- thio-oxazolidone) were refluxed with cc of acetic anhydride and 3 cc of trimethylamine for an hour. The solution was poured into a beaker containing 250 cc of water. The obtained solidified oil was crystallized from ethyl alcohol. A yield of 4 g of yellow needless having M.P. l37138C was obtained.

Example 17 5-acetanilido-methylene-3-tetrahydrofurfuryl-2-thiooxazolidone It was prepared analogously to the intermediate 16, using the N-tetrahydrofurfuryl-Z-thio-oxazolidone instead of the N-furfuryl-2-thio-oxazolidone. At the end of the operation, 3,5 g of crystallized product having MP. l74 -175C were obtained.

Example 18 5 -acetanilido methylene-1-furfuryl-3 -propyl-2-thiohydantoin The reaction was analogous to that of Example 16.15 g of l-furfuryl-3-propyl-2-thiohydantoin, 12.3 g of diphenyl-formamidine and 45 cc of kerosene were used. The 5-anilino-methylene-l-furfuryl-3-propyl-2- thiohydantoin obtained (8.5 g M.P. l24-5C) was boiled with acetic anydride and triethylamine. The yield of the crystallized product was 3.5 g, MP. l67-9C.

Example 19 5-( 3 -ethyl-thioazolidine-Z-ylidene-ethylidene )-3- tetrahydroiu rfuryl'rodanine 1,39 g of tetrahydro-furfuryl-rodanine, 2 g of 2-(wacetanilido-vinyl)thioazoline-iodo-ethylate, 15 cc of ethyl alcohol and 1 cc of triethylamine, were boiled for 20 minutes obtaining an orange solution. The solution was cooled and precipitated with water. A fluid pitch separated and it hardened after standing. It was boiled twice with water and crystallized from ethyl alcohol. Shining violaceous scales were obtained having M.P. 148C.

()t max of absorption is ethanol: 485 nm) Centesimal analysis Calculated 5 Found:

Example 20 5-( 3-methylbenzoxaline-2-ylidene-ethylene-)-3- tetrahydrofurfuryl-rodanine as t. 5H3 EH2 2.78 g of N-tetrahydrofurfuryl-rodanine, 4.2 g of 2-(wacetanilidovinyl)benzoxazole-iodo-methylate, cc of ethylic alcohol and 3 cc of triethylamine, were boiled for 20 minutes, obtaining an orange solution. By cooling it separated the dye which was crystallized from a mixture of pyridine and ethyl alcohol in the ratio 2:1.

Red shining crystals having M.P. 212-215C were obtained. (kmax of absorption in ethanol: 41-93 nm) Centesimal analysis Calculated: C%=57.30; H%=4.85; N=7.49; S=l7.l5 Found: C%=57.76; H%=5.03; N%=7.38; S%=l7.l0

Example 21 CH: \N/ (in.

(A max of absorption in ethanol: 456 nm) 15 Example 22 5-( l :2-dihydro-l-methyl-6-metoxiquinoline-2- ylidene )-3-tetrahydro-furfuryl-2-thio-oxazolidone N (EH2 Hr Hz 2 g of N-tetrahydrofurfuryl-Z-thio-oxazolidone, 3.28 g of 2-ethylmercapto-6-methoxyquinoline-bromoethylate, 25 cc of ethyl alcohol, 0.5 cc of triethylamine, were boiled for 15 minutes. The orange dye separated out in the hot and was filtered and washed with ethyl alcohol and ethyl ether. The product was boiled with water and crystallized from ethyl alcohol and needlelike crystals having golden reflexes were obtained. The yield was 1.7 g, the M.P. 1945C.

()t max of absorption in ethanol: 458-486 nm):

Centesimal analysis Calculated: Found:

Example 23 5-( 1-,8-acetoxyethyl-3-carboxyethyl-5.6-dichlorobenzimidazoline-Z-ylidene-ethylidene )-3- tetrahydrofurfuryl-2-thio-oxazolidone pmcmo O CH3 N 01 C=CHCH=:;- Z 01 N Hz-CHz-OQOH 5 Hz-( H2 0.86 g of 5-acetanilido-methylene-3- tetrahydrofurfuryl-2-thioxazolidone, 1.1 g of l-B- acetoxy-ethyl-Z-methyl-S.6-dichlorobenzimidazole-3- carboxyethyl bromide, 30 cc of butyl alcohol and 3 cc of triethylamine were boiled for 2 hours. The mixture was concentrated under vacuum and was boiled in water; finally it was crystallized from ethyl alcohol. Red microcrystals having M.P. 209-2l0C were obtained.

(A max of absorption in ethanol 498 nm) Example 24 5-( l-B-acctoxycthyl-3-ethyl-5.6-dichlorobenzimidazoline-Z-ylideneethyldene )-3- tetrahydrofurfuryl-2-thio-oxazolidone tetrahydrofurfuryl-2-thiooxazolidone, 1.1 g of l-B- acetoxyethyl-Z-methyl-S.6-dichlorobenzimidazoleiodo-ethylate, 30 cc of butyl alcohol and 3 cc of trimethylamine were boiled for 2 hours. The mixture was concentrated under vacuum. The solid product separated was boiled with water, crystallized from ethyl alcohol and allowed to stand at room temperature. Violet crystals M.P. -181C were obtained.

(A max of absorption in ethanol: 497 nm).

Example 25 5-[-,8-acetoxyethyl-3-carboxyethyl-5 .6dichlorobenzimidazoline-2-ylidene]-3-furfuryl-2-thiooxazolidone ICHQCHQOOOCH: N 01 C=CHCH=C-E Cl N e N HQCHZCOOH 5 0.8 g of 5-acetanilido-methylene-3-furfuryl-2-thiooxazolidone, 1.1 g of 1-(B-acetoxyethyl)2-methyl-5.6- dichloro-benzimidazole-3-carboxyethyl bromide, 15 cc of butyl alcohol, 1.5 ccof triethylamine were boiled for 20 minutes. The mixture was poured into water and the precipitate formed was filtered and crystallized from ethyl alcohol. An orange amorphus product having M.P. 284-5C was obtained.

(A max of absorption in ethanol: 498 nm) Example 26 5-[( 1-B-acetoxyethyl)-3-ethyl-5 .6-dich1orobenzimidazoline-Z-yIidene-ethylene]-3-furfuryl-2-thiooxazolidone.

Example 27 l-2-dihydro-1 -methyl-pyridin-2-ylidene )-3-furfuryl- 2-thiooxazolidone 1.97 g of N-furfuryl-2-thio-oxazolidone, 2.67 g of 2- methylmercapto-pyridine-iodoethylate, 25 cc of ethyl alcohol 2.5 cc of triethylamine were boiled for min utes. By cooling the orange solution thus obtained, the raw dye separated out; the dye was crystallized from ethyl alcohol. Yellow needles were obtained.

(A max of absorption in ethanol: 430 nm).

Example 28 5-( 3-methyl-benzothiazoline-2-ylidene)-3-furfuryl-2- thiooxazoliclone 0.98 g of N-furfuryl-2-thio-oxazolidone, 1.61 g of 2- methylmercapto-benzothiazole-iodo-methylate, cc of ethyl alcohol, 2 cc of triethylamine were boiled for 5 minutes. The dye separated immediately and was crystallized from N,N-dimethyl-formamide. Yellow needles having a M.P. 280-1C were obtained.

(A max of absorption: 405 nm).

Example 29 5 3'ethyl-5 ,6-dimethyl-benzoxazoline-2-ylideneethylene)-2-thio-3-furfuryl oxazolidone 0.98 g of 3-furfuryl-2-thio-oxazolidone, 2.23 g of 2-(wacetanilidoviny1)-5,6-dimethyl-benzothiazole-iodoethylate, 10 cc of ethyl alcohol and 1 cc of triethylamine were boiled for 30 minutes. The mixture was filtered and the product was crystallized from pyridine. An orange amorphous product having M.P. 276-7C was obtained.

(A max of absorption in ethanol: 472 nm).

Example 30 5 3 -ethyl-benzothiazoline-2-ylidene-isobutilidene- 3 tetrahydrofurfuryl-2-thio-oxazolidone H Cz O 0.4 g of N-tetrahydrofurfuryl-2-thio-oxazolidone, 0.8 g of 2-( 2 -ethylmercapto-3-butenyl )-benzothiazole-iodoethylate, 8 cc of ethyl alcohol, 0.8 cc of triethylamine were boiled for 10 minutes. The mixture was cooled and diluted with acidified water. A dark pitchy material with violaceus reflexes separated out. It was crystallized from ethyl alcohol and red violaceus crystals having MP. l34135C were obtained.

(A max of absorption in ethanol: 502 nm).

Example 31 5-(3-ethylbenzothiazoline-Z-yIidene-isopropylidene 3-furfuryl-2-thio-oxazolidone 0.4 g of N-furfuryl-2-thio-oxazolidone, 0.87 g of 2-(2- ethylmercapto-propenyl)-benzothiazole-ethylparatoluenesulfonate, 8 cc of ethyl alcohol, 0.8 cc of triethylamine were boiled for 5 minutes. The dye separated out and was crystallized from pyridine. Red violet crystals 5 having M.P. 224-5C were obtained.

(A max of absorption in ethanol: 497 nm).

0.8 g of N-tetrahydrofurfuryl-2-thio-oxazolidone, 0.94 g of 2-(2-ethyl-mercapto-propenyl)-benzothiazole ethyl-p-toluensulfonate, 8 cc of ethyl alcohol, 0.8 cc of triethylamine, were boiled for 10 minutes. the dye separated out and was crystallized from a mixture of pyridine and ethyl alcohol 1:1. Red mycrocrystals of the dye having M.P. l979C were obtained. (A max of absorption in ethanol: 499 nm).

Example 33 5-(3-ethyl-benzothiazoline-2-ylidene-isobutylidene)-3- furfuryl-2-thio-oxazolidone 0.4 g of N-furfuryl-2-thio-oxazolidone, 0.8 g of 2-(2- ethylmercapto-butenyl)-benzothiazole-iodoethylate, 8 cc of ethyl alcohol and 0.8 cc of triethylamine, were boiled for 5 minutes. By standing the dye separated out and was crystallized from ethyl alcohol. Purplish pink crystals of the dye, having M.P. l67-9C were obmined.

(A max of absorption in ethanol: 500 nm) Example 34 5-( 3-ethyl-5-methyl-benzoselenazoline-Z-ylideneisobutylidene )-3-furfuryl-2 -thio-oxazolidone 0.59 g of N-furfuryl-2-thio-oxazolidone, 0.93 g of 2- (2-ethylmercapto-3-butenyl)-5-methylbenzoselenazole ethyl p. toluensulfonate, 8 cc of ethyl alcohol and 0.8 cc of triethylamine were boiled for 15 minutes. By cooling the dye separated out and was crystallized from a large amount of ethyl alcohol. An orange amorphous product was obtained having M.P. l83.5-184.5C

(A max of absorption in ethanol: 507 nm) Example 35 5-( 3-ethyl-5-methyl-benzoselenazoline-2-ylideneisobutylidene )-3 -tetrahydrofurfuryl-2-thio-oxazolidone 0.6 g of N-tetrahydrofurfuryl-2-thio-oxazolidone, 1.5 g of 2-(2'-ethylmercapto-3-butenyl)-5- methylbenzoselenazole ethyl p-toluenesulfonate, 8 cc of ethyl alcohol, 0.8 cc of triethylamine, were boiled for 10 minutes. The mixture was precipitated with water. The dye was separated and crystallized from ethyl alcohol. Orange crystals having M.P. 2l5-7C were obtained.

(A max of absorption in ethanol: 506 nm).

Example 36 5-( 3-ethyl-naphthol ,2-4,5-oxazoline-2-ylideneethylidene )-3-furfuryl-2-thiooxazolidone o s N N i JJ'HS din Zll 1.97 g of N-furfuryl-2-thio-oxazolidone, 4.84 g of 2-(wacetanilidovinyl)-B-naphthooxazole-iodo-ethylate, 40 cc of ethyl alcohol and 4 cc of triethylamine, were boiled for 10 minutes. The orange dye separated in the hot. It was filtered and crystallized from pyridine. Red orange crystals having MP. 285-6C;

(A max of absorption in ethanol: 486 nm) Example 37 5-( l-,8-acetoxyethyl-3-ethyl-5 ,6-dichlorobenzimidazoline-2-ylidene-ethylidene l -furfuryl-3- propyl-Z-thio-hydantoin thiodantoin, 4.42 g of l-B-acetoxyethyl-2-methyl-5,6- dichloro-benzimidazoleiodo-ethylate, 30 cc of N,N-dimethylformamide and 3 cc of triethylamine were reacted for 30 minutes at 150C. The hot mixture was poured into hot water then decanted and the washing was repeated several times. The product was dissolved in boiling ethyl alcohol and was allowed to stand. The obtained dye weighed 2.3 g and had a M.P. l73-5C (Purplish pink crystals).

(A max of absorption in ethanol: 522 nm) Centesimal analysis Example 38 5-( 3-ethyl-5-methoxy-benzoselenazoline-2-ylideneethylidene)- l-furfuryl-3-('y-dimethylaminopropyl)-2- thiohydantoin G=CH-CH=C-NCHa-C 6 N 0=b\ s 011-- H 2H5 N CH3 (iHicmcmN 5.62 g of l-(furfuryl)-3(y-dimethylaminopropyl)- 2thiohydant0in, 5.06 g of 2 (w-aldehydomethylene)-3- ethyl--methoxy-benzoselenazolidene, cc of pyridine, 2 cc of acetic anhydride were boiled for 15 minutes. By standing overnight the dye separated out; it was filtered and crystallized from pyridine. Purplish red crystal of dye having M.P. 194-5C were obtained. (A max of absorption in ethanol: 528 nm) Centesimal analysis Example 39 5-( 3-methyl-5-bromo-benzoxazoline-Z-ylideneethylidene l -furfuryl-3-propyl-2-thio-hydantoin 2.39 g of l-furfuryl-3-propyl-2-tiohydantoin, 4.83 g of 2-(w-acetanilidevinyl)-5-bromo-benzoxazole-iodomethylate, 30 cc of ethyl alcohol and 3 cc of triethylamine were boiled for 10 minutes. The dye separated by cooling and was crystallized from pyridine. Red orange crystals having M.P. 254-5C were obtained. (A max of absorption in ethanol: 479 nm) Example 40 5-( 3-ethyl-5-acetylamino-benzoxazoline-Z-ylideneethylidene l -furfuryl-3-propyl-2-thiohydantoin 2.39 g of 1-furfuryl-3-propyl-2-thiohydantoin, 4.1 g of Z-(w-acetanilidovinyl)-3-ethyl-5-acetylamino-benzoxazole-iodo-ethylate, 20 cc of butyl alcohol and 4 cc of piperidine were boiled 20 minutes. The dye separated by standing was filtered and crystallized from ethyl alcohol.

()t max of absorption in ethanol: 488 nm) Example 41 5-( 3,5-dimethyl-benzoxazoline-2-ylidene-ethylidene)- 1 -furfuryl-3-propyl-2-thyo-hydantoin 2.39 g of l-furfuryl-3-propyl-2-thiohydantoin, 4.3 of 2-(w-acetanilidovinyl)-benzoxazole-iodo-ethylate, 60 25 cc of butyl alcohol, 5 cc of piperidine, were boiled for minutes. The dye separated by standing was crystallized from pyridine. Ocre crystals having M.P. l86.5l87C were obtained.

(A max of absorption in ethanol: 481 nm).

Example 43 5 3 -methyl-5-phenyl-benzoxazoline-2-ylideneethylidene)-1-furfuryl-3-propyl-2-thiohydantoin 5 /c=oH cH=Z--1I crno Q \N 0 s OH H N CH3 (I:

ZCI' QCHS 45 2.39 g of l-furfuryl-3-propyl-2-thiohydantoin, 4.96 g of Z-(w-acetanilidovinyl)-5-phenyl-benzoxazole-iodomethylate, 80 cc of butyl alcohol, 8 cc of piperidine were boiled for 1 hour. The dye separated by cooling and was crystallized from piperidine. A light brown amorphous product having M.P. 2624 C was obtained. (A max absorption in ethanol: 485 nm) Example 44 5 3-ethyl-5 ,7-dimethyl-benzoxazoline-Z-ylideneethylidene)- l -furfuryl-3-propyl-2-thiohydantoin O /OCH CH3 c=oH-orr=o N om o l \N/ CH 1H 24 2.39 g of l-furfuryl-3-propyl-2-thiohydantoin, 4.62 g of Z-(A-acetanilidovinyl)-5,7-dimethylbenzoxazole-iodoethylate, 20 cc of butyl alcohol and 4 cc of piperidine were boiled for 20 minutes. The dye separated by cooling and was crystallized from pyridine. Red orange crystals of the dye having M.P. 197-9C were obtained. (A max of absorption in ethanol: 492 nm) Example 45 5-( 3-ethyl-benzoxazoline-Z-yIidene-ethylidene l furfuryl-3-carboxymethyl-2-thiohydantoin C=CHCH=CNOHz-C \N o: s 011- H on N 0.508 g of 1-furfuryl-3-carboxymethyl-2- thiohydantoin, 0.868 g of 2-(w-acetanilidovinyl)- benzoxazole-iodo-ethylate, 7 cc of pyridine and 1 cc of triethylamine were boiled for 10 minutes. After cooling water was added and the mixture was acidified with acetic acid. The dye separated out and was crystallized from pyridine acidified with acetic acid. Dark orange crystals having M.P. 2634C were obtained.

(A max of absorption in ethanol: 479 nm).

Example 46 5 3-ethyl-5,6-dimethyl-benzoxazoline-Z-ylideneethylidene)-1-furfuryl-3-carboxymethyl-2- thiohydantoin thiohydantoin, 0.892 g of Z-(A-acetanilidovinyl)-5,6- dimethyl-benzoxazole-iodo-ethylate, 7 cc of pyridine and 1 cc of trimethylamine were boiled for 10 minutes. After cooling water was added and the mixture was slightly acidified with acetic acid. Purple pink crystals of the dye having M.P. 258260C. were obtained (A max of absorption in ethanol: 490 nm).

Example 47 5-( 3-ethyl-5-phenyl-benzoxazoline-2-ylideneethylidene-1-furfuryl-3(y-dimethylamino-propyl)-2- thiohydantoin 1.4 g of 1-furfuryl-3-('y-dimethylaminopropyl)-2- thiohydantoin, 2.55 g of 2-(w-acetanilidovinyl)-5- phenyl-benzoxazole-iodoethylate, cc of ethyl alcohol and 1.5 cc of piperidine were boiled for minutes. The dye separated out and was crystallized from pyri- 5 dine. Red orange crystals of dye having M.P. 2257C were obtained. (A max of absorption in ethanol: 490 nm) Example 48 5-( 3-ethyl-5-chloro-benzoxazoline-2-ylideneethylidene)-1-furfuryl-3(y-dimethylaminopropyl)-2- thiohydantoin 1.4 g of l-furfuryl-3-('y-dimethylaminopropyl)-2- thiohydantoin, 2.34 g of 2-(w-acetanilidovinyl)-5- chloro-benzoxazole-iodoethylate, 4 cc of pyridine and 0.5 cc of triethylamine were boiled by 10 minutes. The dye separated by cooling and was crystallized from pyridine. An orange amorphous product having M.P. 2l02C was obtained.

(A max of absorption in ethanol: 480 nm).

The compound was prepared analogously to Example 48 using the S-methyl derivative of the benzoxazole instead of the 5-chloro derivative. Red orange crystals. M.P. 192-4C.

(A max of absorption in ethanol: 488 nm) Example 50 5 5 5-( 3-ethyl-5-acetylamino-benzoxazoline-Z-ylideneethylidene)-1-furfuryl-S-(y-dimethylaminopropyl)-2- thiohydantoin 011.10 ONIlmn- -N (Illa The compound was prepared analogously to Example 48 using the 5-acetylamino derivative of the benzoxazole instead of the 5-chloro derivative. Violet crystals. M.P. l5l-2C. (A max of absorption in ethanol: 494 nm) Example 5 1 5-( 3-ethyl 5-metoxy-benzoxazoline-2-ylideneethylidene l -furfuryl-3-(y-dimethylaminopropyl )-2- thiohydantoin The compound was prepared analogously to Example 48, using the 5-methoxy derivative of the benzoxazole instead of the 5-chloro derivative. Orange amorphous product. M.P. 227-8C.

(y max of absorption in ethanol: 491 nm) Example 52 5-( 3-ethyl-5,6-dimethyl-benzoxazoline-2-ylideneethylidene l -furfuryl-3-(-y-dimethylaminopropyl)-2- thioydantoin The compound was prepared analogously to Example 48, using the 5,6-dimethyl derivative instead of the 5- chloro derivative.

(A max of absorption in ethanol: 493 nm) Example 53 5-( 3-ethyl-5 ,7-dimethyl-benzoxazoline-2-ylideneethylidene)-1-furfuryl-3-(-y-dimethylaminopropyl)-2- thioydantoin The compound was prepared according to what reported for Example 48, using the 5,7-dimethyl derivative of the benzoxazole instead of the -chloro derivative. M.P. 22l-3C. Red brick amorphous product. (A max of absorption in ethanol: 489 nm) Example 54 5-( 3-ethyl-benzoxazoline-2-ylidene-ethylidene l methyl-3-tetrahydrofurfuryl-2-thiohydantoin thiohydantoin, 1.02 g of 2-(w-acetanilidovinyl-benzoxazole-iodo-ethylate, 7 cc of ethyl alcohol and 1 cc of triethylamine were boiled for minutes. The dye separated by cooling and was crystallized from pyridine. Red orange crystals of dye, having M.P. 215-7C were obtained.

(A max of absorption in ethanol: 480 nm) Example 55 5-( 3-ethyl-5-phenyl-benzoxazoline-Z-ylideneethylidene l -m ethyl-3-tetrahydrofurfuryl-2- thiohydantoin The compound was obtained analogously to Example 54, using the S-phenyl derivative of the benzoxazole. M.P. 218-9C. Purple pink crystals.

()t max of absorption in ethanol: 486 nm) Example 5 6 5( 3-ethyl-5-methyl-benzoxazoline-2-ylideneethylidene l -methyl-3-tetrahydrofurfuryl-2- thiohydantoin The compound was obtained analogously to Example 54, using the S-methyl derivative of the benzoxazole. The product was orange and amorphous with M.P. 240-lC.

(A max of absorption in ethanol: 484 nm) Example 57 5-( 3-ethyl-5-chloro-benzoxazoline-Z-ylideneethylidene)-1-methyl-3-tetrahydrofurfuryl-2- thiohydantoin din-mi,

The compound was obtained analogously to Example 54 using the 5-chloro derivative of the benzoxazole. The product was orange and amorphous, with M.P. 250.5251.5C.

(A max of absorption in ethanol: 478 nm) Example 58 5-(3-ethyl-5 ,7-dimethyl-benzoxazoline-2-ylideneethylidene l -methyl-3-tetrahydrofurfuryl-2- thiohydantoin The compound was prepared analogously to Example 54 using the 5,7-dimethyl derivative of the benzoxazole; the product was in orange crystals with M.P. 239.5-240C.

(A max of absorption in ethanol: 492 nm) Example 59 5-( 3-ethyl-5-acetylamino-benzoxazoline-Z-ylideneethylidene )-l -methyl-3-tetrahydrofurfuryl-2- thiohydantoin HaCC ONH 1r 2 \O JEEP-dim The compound was prepared analogously to Example 54, using the S-acetylamino derivative of the benzoxazole, in red orange microcrystals having M.P. 280-lC.

()t max of absorption in ethanol: 487 nm).

Example 60 5-(3-ethyl-5 ,6-dimethyl-benzoxazoline-2-ylideneethylidene)-1-methyl-3tetrahydrofurfuryl-2- thiohydantoin 926 l C was obtained. (A max of absorption in ethanol: 495 nm).

Example 61 5-(3-ethyl-naphtho-2',l -4,S-oxazoline-2-ylideneethylidene l -methyl-3-tetrahydrofurfuryl-2- thiohydantoin \N O: S

( lgHa 1? The compound was prepared analogously to Example 54, using the naphto-2.l '-4,5-oxazole derivative. M.P. 270"-7"272(. Dark red crystals.

(A max of absorption in ethanol: 496 nm).

Example 62 5-(3-ethyl-naphtho-2'. l '-4.5-oxazoline-2-ylideneethylidene l -furluryl-3-('y-dimethylaminopropyl )-2- thiohydantoin Ulla 1.4 g of 1-furfuryl-3-(y-dimethylaminopropyl)-2- thiohydantoin, 2.42 g of 2-(w-acetanilidovinyl)- napththo-2',l '-4,5-oxazole-iodo-ethylate, 8 cc of ethyl alcohol, 2 cc of piperidine were boiled for 20 minutes. Water was added to the reaction mixture and the latter was allowed to stand. The dye separated out was filtcred and crystallized from pyridine. Red crystals of the dye having a MP. l7C were obtained. (A max of absorption in ethanol: 505 nm).

Example 63 5-( 3-ethyl-naphtho-l ,2-4,5 oxazoline-Z-ylideneethylidene l -furfuryl-3-propyl2-thiohydantoin I at.

0.239 g of l-furfuryl-3-propyl-2-thiohydantoin, 0.48 g of 2-(w-acetanilidovinyl)-naphtho-1,2'-4,5-oxazoleiodo-ethylate, 4 cc of ethyl alcohol, 0.4 cc of triethylamine were boiled for 1 minute. The dye separated immediately and was crystallized from pyridine. An orange amorphous product having MP. 2424C was obtained.

(A max of absorption in ethanol: 504 nm).

Example 64 5 3-ethyl-naphtho.-l ,2 -4,5-oxazoline-2-ylideneethylidene l -methyl-3-tetrahydrofurfuryl-2- thiohydantoin l lltl llr The compound was prepared analogously to Example 54 using the naphtho-l ',2-4,5-oxazole. (A max of absorption in ethanol: 502 nm).

Example 65 -(3-ethyl-naphtho-l ,2-4,5-oxazoline-2-ylideneethylidene l -furfuryl-3-('y-dimethylaminopropyl )-2- thiohydantoin naphtho-l,2-4,5-oxazoleiodo-ethylate, 5 cc of pyridine, 1 cc of triethylamine were boiled 20 minutes. A crystalline solid separated out and was crystallized from pyridine.

(A max of absorption in ethanol: 504 nm) Example 66 5-( B-methyI-naphtho-l ,2-4,5-oxazoline-2-ylideneethylidene)- 1-furfuryl-3-carboxymethyl-2- thiohydantoin thiohydantoin, 0.968 g of 2-(w-acetanilidovinyl)- naphtho-l,2-4,S-oxazole-iodoethylate, 7 cc of pyridine and 1 cc of triethylamine were boiled for 10 minutes. By addition of water and of acetic acid the dye separated out and was purified by hot-dissolving in pyridine and acidification with acetic acid. The dye obtained presented a M.P. 25961C.

(A max of absorption in ethanol: 500 nm).

. Example 67 5-(3-methylnaphtho-l ,2'-4,5-oxazoline-2-ylidene- 1.14 g of l-(tetrahydrofurfuryl)-3-ethyl-2- thiohydantoin, 2.35 g of 2-(w-aldehydomethylene)- naphtho-l',2-4,5-oxazoleiodo-ethylate. 5 cc of ethyl alcohol and 0.5 cc of triethylamine were boiled for 10 minutes.

The separated dye was crystallized from ethyl alcohol. ()t max of absorption in ethanol: 504 nm).

Example 68 5-( 3-methyl-naphtho-4,5-oxazoline-2-ylideneethylidene l furfuryl )-3-propyl-2-thiohydantoin 0.239 g of l-(furfuryl)-3-propyl-2-thiohydantoin, 0.47 g of 2-(w-acetanilidovinyl)'-naphtho-4,5-oxazole-i0doethylate, 3,5 cc of butyl alcohol, 0.5 cc of piperidine were boiled for 15 minutes. The dye separated out and was crystallized from pyridine. The dye dried in the oven has M.P. 2535C. Dark red crystals.

(A max of absorption in ethanol: 486 nm) Example 69 5-( 3-ethyl-naphtho-4,5-oxazoline-2-ylideneethylidene l -methyl-3-tetrahydrofurfuryl-2- thiohydantoin (I: N 2H5 CH: 5 014. 1H1 CH7 0. 5 3 g of 1-methyl-3 -tetrahydrofurfuryl-2- thiohydantoin, 1.17 g of Z-(w-acetanilidovinyD- naphtho-4,5-oxazole-iodo-ethylate, 7 cc of ethyl alcohol and 1 cc of triethylamine were boiled for 4 minutes. The separated dye, cristallized from pyridine in pink microcrystals. M.P. 2768C.

(A max of absorption in ethanol: 487 nm) Example 70 5-( 3-methylnaphtho-4,5-oxazoline-2-ylideneethylidene )-l -furfuryl-3-(y-dimethylaminopropyl)-2- thiohydantoin CH II ills

Patent Citations
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US3384486 *May 4, 1964May 21, 1968Eastman Kodak CoMerocyanine dyes for photographic elements containing an extracyclic tertiary amino group
US3632349 *Apr 9, 1970Jan 4, 1972Fuji Photo Film Co LtdSilver halide supersensitized photographic emulsion
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3976640 *Feb 18, 1975Aug 24, 1976Polaroid CorporationBis-type quaternary salts including benzothiazole and benzimidazole rings and process for preparing dye therewith
US5418126 *Jan 19, 1994May 23, 1995Eastman Kodak CompanyFuran or pyrrole substituted dye compounds and silver halide photographic elements containing such dyes
US6066443 *Jul 16, 1996May 23, 2000Eastman Kodak CompanyBlue sensitizing dyes with heterocyclic substituents
Classifications
U.S. Classification430/578, 430/593, 548/121, 548/217, 548/146, 548/226, 548/183, 548/180, 548/181, 430/591
International ClassificationC07D307/52, C09B23/10, C07D307/14, C09B23/01, G03C1/22
Cooperative ClassificationC09B23/10, G03C1/22, C07D307/14, C09B23/0033, C07D307/52, C09B23/107, C09B23/105, C09B23/0025
European ClassificationC09B23/00B4, C09B23/10B, G03C1/22, C09B23/00B6, C07D307/14, C09B23/10D, C09B23/10, C07D307/52