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Ârofïon H. Keyes ¿Ès//È 6 5 Jan.. 2„ 1940. A G. H. KEYES E1- AL 2,185,343 POLYMETHINE DYÉS AND PROCESS FOR PREPARING THEM Filed Sept. 14, 1937 .320 36 40 44 48 .52 .5 6 60 64007,!! 320 .i6 40 44 4a 52 56 60 E40/fp `320 36 40 44’ v48 .52 56 60 640030 ârofïon H. Keyes ¿ès//è 6 5. ßmokef‘ l N VEN TOR Patented Jan. 2, 1940 2,185,343 UNITED STATES PATENT oFFIcE 2,185,343 POLYMIETHINE D‘YES ANDl PROCESS FOR l PREPARING THEM Grafton H. Keyes and Leslie G. S. Brooker, ­ a. Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application ‘September 14, 1937, Serial No. 163,782 In Great Britain September 15, 1936 10 Claims. (Cl. 260-240) This invention relates to new dyes and to Our new dyes are probably resonance hybrids photographic emulsions sensitized therewith. between two forms which can be illustrated for We have found that new dyes can be prepared the dyes of Formula IIa.` as follows: by reacting a monoacylated aminoacetic acid with a formylmethylene compound of one of the following formulas: wherein D represents the non-metallic atoms necessary to complete a heterocyclic nucleus, such 15 as a pyridine or a quinoline nucleus for example, Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus, such as a The dyes of Formula IIb can similarly be ex pressed as resonance hybrids between two forms. 20 live-membered or siX-membered heterocyclic nucleus for example, and R represents an ali In the instant application, we shall formulate our phatic radical, i. e. an alkyl group. We have new dyes in accordance with but one of the forms, further found that our new dyes sensitize photo namely, that set forth by Formulas IIa and lIb. More specifically, in Formulas IIa and IIb, D graphic emulsions in a new and useful manner. represents the non-metallic atoms to complete 25 Accordingly, it is among the objects of our in Vention to provide new dyes and a process for a pyridine nucleus which may carry substituents 25 preparing the same. A further object is to pro such as alkyl, alkoxy, amino or the like or D vide photographic emulsions sensitized with our represents the non-metallic atoms necessary to new dyes and a process for preparing such emul complete a quinoline nucleus which may carry sions. A still further object is to provide a substituents such as alkyl, alkoxy, amino or the 30 like. Z represents the non-metallic atoms neces photographic element comprising an emulsion 30 sensitized with our new dyes. Other objects will sary to complete a ñve-membered or six-mem appear hereinafter. bered heterocyclic nucleus, for example a quino Our new dyes can be represented by the follow line nucleus, such as a 5­alkyl­ or a 5­alkoxy­ ing general formulas: quinoline nucleus, for example, a pyridine nu 35 cleus, a thiazole nucleus, such as 4-methyl thiazole, 4~phenylthiazole, 4,5-dìphenylthiazole, 35 benzothìazole, 4-chlorobenzothiazole, a-naphtho thiazole or ß-naphthothiazole for example, an oxazole nucleus, suchV as 4-methyloxazole, 4 40 phenyloxazole, benzoxazole, œ-naphthoxazole or ß-naphthoxazole for‘example, a selenazole nu 40 cleus, such as ll-methylselenazole or benzoselen azole for example or a thiazoline nucleus, such as 4-methylthiazoline or Ll-phenylthiazoline. R 45 represents an aliphatic radical, such as methyl, ethyl, isoamyl, allyl, n-decyl or cyclohexyl for 45 example. R’ represents an aliphatic radical, such as methyl, ethyl or the'like, or an aryl group, wherein D represents the non-metallic atoms such as an aryl radical containing one benzene necessary to complete a heterocyclic nucleus, such ring or an aryl radical containing two benzene 50 as pyridine or a quinoline nucleus for example, Z rings which may be fused together for example. represents the noni-metallic atoms necessary to In preparing our new dye, we react a formyl complete a heterocyclic nucleus, Rirepresents an methylene compound of Formula Ia or Ib with a alkyl group and R’ represents an alkyl group or monoacylated aminoacetic acid, such as aceturic 55 an aryl radical. acid, hippuric acid or naphthoylaminoacetic 2 2,185,343 acids for example, i. e. acids of the following EXAMPLE 3.-4­[ (3-methyZ-2 (3) -thiazolínylz'dene) formula: ethylz‘dene] -Z-phenyZ-ä-oœazolone HaCIì-COOH 0.48 g. (1 mol.) of 2-formylmethylene­3­meth­ NEI-COR ylthiazolidine and 0.60 g. (1 mol.) of hippuric wherein R represents an alkyl or an aryl group acid were heated together in about 10 cc. of acetic for example. The reactions are advantageously anhydride for about seven minutes at about 100° conducted in the presence of a water-binding C. The dye was isolated as in Example 1. agent. Anhydrides of lower aliphatic acids, par After two recrystallizations from methyl alcohol, 10 ticularly aliphatic acids containing from two to it was obtained as orange needles, melting at 210° 10 four carbon atoms, are advantageously employed to 212° C. with decomposition. The formula as Water-binding agents. Diluents can be added of the dye can be expressed as follows: to the reaction mixtures. Heat accelerates the formation of our dyes. 15 While the process of preparing our new dyes 15 is subject to Variation, particularly as respects the nature and quantity of formylmethylene com pound employed, the nature and quantity of the monoacylated aminoacetic acid employed, the 20 nature and quantity of the water-binding agent 20 employed, the temperatures employed, the order of proceduresand methods of isolation and puri fication of the dyes, the following examples will EXAMPLE 4.-4-l (3-ethyZ-4-methyl-2 ( 3) -thz'azol serve to illustrate the mode of practicing the ylidene) ethz/Zidane] -Z-phenyZ-5-oœazolcme 25 process of our invention. These examples are 25 not intended to `limit our invention. 0.85 g. (1 mol.) of 3-ethyl-‘l-methyl-2-formyl methylene-A‘î-thiazoline and 0.90 g. (1 mol.) of hippuric acid were heated in 1_5 cc. of acetic anhy dride for about seven minutes at 100° C. The dye 30 was isolated as in Example 1. After two recrystal 30 1.28 g. (1 mol.) of 1-ethyl-2-formylmethylene lizations from glacial acetic acid, the dye was ß-naphthothiazoline and 0.90 g. (1 mol.) of hip obtained as dark red needles melting at 209° to puric acid were stirred in about 15 cc. of acetic 211° C. with decomposition. The dye has the anhydride for about seven minutes at about 100° following formula: C. The cooled reaction mixtures was stirred with 85 85 100 cc. of diethyl ether and the whole chilled to 0° C. The dye separated and was ñltered off. The dye was boiled with about 10 cc. of methyl alcohol. The alcoholic mixture was chilled at 0° C. for several hours. The dye separated and was recrystallized from glacial acetic acid. It was obtained as dull purple crystals melting at 242° to 243° C. with decomposition. The formula of the dye can be represented as follows: 45 1.00 g. (1 mol.) of 2-formylmethylene-1,6­di­ methyl­1(2)­dihydroquinoline and 0.90 g. (1 ' mol.) of hippuric acid were heated in 30 cc. of 50 acetic anhydride for about seven minutes at about 50 100° C. The dye was isolated as in Example 1. After two recrystallizations from glacial acetic acid, the dye was obtained as very dark blue crys tals melting at 247° to 248° C. with decomposi 55 tion. The formula of the dye can be expressed 55 as follows: 1.03 g. (1 mol.) of 2­ethyl­l-formylmethylene benzothiazoline and 0.90 g. (1 mol), of hippuric 60 acid were stirred in about 10 cc. of acetic anhy 60 dride at about 100° C. for about ten minutes. The dye was isolated as in Example 1. After two re crystallizations from acetic acid, the dye was ob l tained as minute reddish crystals melting at 211° CH3 65 to 212° C. with decomposition. The dye can be 65 represented by the following formula: EXAMPLE 6.-4­[ (1 -methyZ-4 (1) -quinolylidene) ethylidenel -2-phenyl-5-omazolone 05H5 è 0.93 g. (1 mol.) of 4-formylmethylene-l-meth yl-1(4)dihydroquino1ine and 0.90 g. (1 mol.) of 70 70 hippuric acid were heated in about 30 cc. of acetic 4 anhydride for about seven minutes at about 100° 3 2 C. The dye was isolated as in Example 1. After N two recrystallizations from acetic acid, the dye 75 was obtained as purple crystals melting at 262° 2,185,343 3 to 263° C. with decomposition. The dye has the acid and 0.20 g. (l mol.) of anhydrous sodium following formula: acetate were heated in about 10 cc. of acetic an hydride at the refiuxing temperature for about fifteen minutes. The reaction mixture was chilled 7 ß C s 5 /2 for several hours at 0° C. The dye which separat ed was filtered off and washed with water. After oHG-_N12 34c=oH­cH=ogc=o\ rf )fr two recrystallizations from methyl alcohol, the \:/ dye was obtained as reddish crystals melting at EXAMPLE 7.-4- [ (1 -etltyZ-Z (1) -ß-naphthothiaeyl 218° to 220° C. with decomposition. 'I'he dye has 10 diene) -ethylidenel -2-methyZ-5-orcazolone 10 1.28 g. (l mol.) of 1-ethyl-2-formylmethylene ß-naphthothiazoline and 0.59 g. (1 mol.) of aceturic acid were heated in acetic anhydride for 15 about ñve minutes at 100° C.
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