Jan.. 2„ 1940. A G. H. KEYES E1- AL 2,185,343 POLYMETHINE DYÉS AND PROCESS FOR PREPARING THEM Filed Sept. 14, 1937

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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. The dye was iso lated as in Example 1. After two recrystalliza 15 tions from glacial acetic acid, the dye was ob tained as a mat of minute orange crystals melt ing at 258° to 259° C. with decomposition. The dye has the following formula: 20 20

2.2 g. (1 m01.) of l-(ß-acetanilidovinyl) -benz 25 oxazole ethiodide, 0.9 g. (l mol.) of hippuric acid and 0.4 g. (1 mol.) of anhydrous sodium acetate 25 were heated for about ten minutes in about 15 cc. of acetic anhydride at about 100° C. The dye was isolated as in Example 8. After two recrys tallizations from glacial acetic acid, the dye was 30 \/l l 30 Cur new dyes can also be prepared, we have obtained as minute dull reddish crystals melt found, by reacting the monoacylated aminoacetic ing at 233° to 235° C. with decomposition. The acid with a cyclammonium Quaternary salt con dye has the following formula: - taining a ß-arylaminovinyl group in the alpha or 35 gamma position, i. e. one of the so-called reactive 35 positions. The ß-arylaminovinyl group is ad vantageously acylated, e. g. acetylated, propi onylated or butyrylated. The reactions are ad vantageously effected in the presence of an acid binding agent an-d a water-binding agent. As 40 acid-binding agents, we have foimd salts of lower aliphatic acids, such as acetic, propionic and butyric, to be particularly useful. However, other EXAMPLE 10.-4-[(3 - methyl ­ 2(3) ­ thz‘azolinyl acid-binding agents can be employed. For exam idene) -ethylz'dene‘l -Z-pherLyZ-ô-oxazolone ple, strong organic bases, i. e. organic bases hav 45 ing a dissociation constant substantially greater 1.7 g. (l mol.) of 2-(ß-ani1inovinyl)-thiazoline than that of pyridine, such as triethylamine and methiodide, 0.9 g. (1 mol.) of hippuric acid and piperidine, can be used. Likewise, sodium car 0.4 g. (l mol.) of anhydrous sodium acetate were bonate, sodium hydroxide, potassium carbonate heated in about 15 cc. of acetic anhydride at the 50 or sodium ethylate can be employed. As water refluxing temperature for about 15 minutes. The bin-ding, we have found fatty acid anhydrides, dye was isolated as in Example B. After two re 50 particularly anhydrides of lower fatty acids such crystallizations from methyl alcohol, the dye was as acetic, propionic or butyric acids, to be par obtained as orange needles melting at 210° to 212° ticularly suitable. Dilucnts can be added to the C. with decomposition. The dye has the following reaction mixtures. Heat accelerates the forma formula: 55 55 tion of our new dyes. While this process of preparing our new dyes is subject to variation, particularly as respects the nature and quantity of ß-arylaminovinyl 60 Quaternary salt employed, the nature and quanti 60 ty of the monoacylated aminoacetic acid em ployed, the nature and quantity of the acid-bind 1T ing agent employed, the nature and quantity of CH3 the water-binding agent employed, the tempera tures employed and the order of procedures and EXAMPLE 11.-4 ­ [(1-ethyl ­ 2(1) - quinolylidcne) 65 65 methods of isolation and purification of dyes, the ethylidene] -Z-phenyZ-S-orasolone following examples will serve to illustrate the mode of practicing the process of our invention. 2.0 g. (l mol.) of 2-(ß-anilinoviny1)-quinoline l`í'hese examples are not intended to limit our in ethiodide, 0.9 g. (1 mol.) of hippuric acid and 70 vention. 0.4 g. (1 mol.) of anhydrous sodium acetate 70 were heated in about l5 cc. of acetic anhydride EXAMPLE 8.--4- [(2 - ethyl-1 (2) -bensosclenaeolyl ideate) -ei?Lg/Zz'denel -2-phenyl-5-oxazolone at the refluxing temperature for about fifteen minutes. The dye was isolated as in. Example 1.25 g. (l mol.) of l-(ß-acetanilidovinyl)-ben 8. After two recrystallízatíons from methyl zoselenazole ethiodide, 0.45 g. (1 mol.) of hippuric alcohol, the dye was obtained as dark greenish 75 4 2,185,843 plates melting at 224° to 226° C. with decom glycine and 0.4 g. (1 mol.) of anhydrous sodium position. The dye has the following formula: acetate were heated at the reñuxing temperature in about 15 cc. of acetic anhydride for about ten minutes. The dye was isolated as in Example 8. After two recrystallizations from methyl alcohol, the dye was obtained as brownish crystals melt ing at 251° to 253° C. with decomposition. The dye has the following formula: as. l -10 10 EXAMPLE 12.-4 ­ [(1­ethyl-4(1)-quinolylidene) ethylidene] -2 _phenyl-5-oxazolone 2.0 g. (1 mol.) of 4-(ß-anilinovinyl) -quinoline ethiodide, 0.9 g. (1 mol.) of hippuric acid and 15 0.4 g. (l mol.) of anhydrous sodium acetate 15 were heated for about fifteen minutes in about 15 cc. of acetic anhydride at about 100° C. The In the above examples, we have found it ad dye was isolated as in Example 8. After vantageous to employ about one molecular pro two recrystallizations from methyl alcohol, portion of formylmethylene compound or 20 20 the 4dye­ was obtained as greenish needles melting cyclammonium quaternary salt for each mole of at 205° to 208° C. with decomposition. The dye acylated aminoacetic acid. However, an excess has the following formula: of either can be employed. The monoacylated aminoacetic acids are well known compounds o and can be prepared by acylated glycine, i. e. 25 25 87 65 aminoacetic acid. The following examples are illustrative of such acylations: EXAMPLE 16.-Aceturic acid 7.5 g. (1 mol.) of glycine were heated at about 30 100° C. in 11 g. (1.1 mol.)` of acetic anhydride 30 2.25 g. (1 mol.) of l-(ß-acetanilidovinyD for about five minutes. The reaction mixture benzothiazole ethiodide, 0.6 g. (1 mol.) of aceturic was chilled, the crystals which separated col acid and 0.4 g. (1 mol.) of anhydrous sodium lected on a ñlter and washed with diethyl ether. acetate were heated at the refluxing tempera The washed product was recryïstallized from 35 ture in about 15 cc. of acetic anhydride for about water and obtained as colorless crystals melting 35 ten minutes. The dye was isolated as in Ex at 204° to 206° C. with decomposition. ample 8. After two recrystallizations from EXAMPLE 17.-Propio'nylglycine methyl alcohol, the dye was obtained as brown ish crystals melting at 256° to 258° C. with de 7.5 g. (1 mol.) of glycine were heated at about 40 composition. The dye has the following 100° C. in 15 g. (1.1 mol.) of propionic anhydride 40 formula: for about ten minutes. The reaction mixture was chilled, the crystals which separated collected on im a filter and washed with diethyl ether. The washed product was recrystallized from methyl 45 Ns/ 10 alcohol and obtained as colorless crystals melting 45 at 130° to 133° C. with decomposition. 2 The cyclammonium quaternary salts contain N ing a ß-arylaminovinyl group in a reactive posi C zHlS tion can be prepared by condensing a clyclam 50 EXAMPLE 14.-4-[(2­ethyl - 1(2) - benzoœaeolyl monium Quaternary salt containing a reactive 50 idc/ne) ethylz'dene] -2-methyl-5-oœazolone methyl group in a reactive position with a diaryl formamidine. If the condensation is carried out 2.2 g. (l mol.) of l-(ß-acetanilidovinyl)-benz in the presence of an organic acid anhydride, the oxazole ethiodide, 0.6 g. (1 mol.) of aceturic acid resulting condensation product is ordinarily acyl 55 and 0.4 g. (1 mol.) 0f anhydrous sodium acetate ated. The process of making the ß-arylamino 55 were heated in about 15 cc. of acetic anhydride vinyl compounds is well known and the following for about t‘en minutes at about 100° C. The few examples will serve to illustrate the prepara dye was isolated as in Example 8. After two tion: recrystallizations from methyl alcohol, the dye EXAMPLE 18.-1- (ß-Acetcmilidovinyl) -benzoœazole 60 was obtained as brownish crystals melting at 60 213° to 215° C. with decomposition. The dye ethiodide has the following formula: ' 58 g. (1 mol.) of l-methylbenzoxazole ethiodide and 40 g. (1 mol.) of diphenylformamidine were heated in about 250 cc. of acetic anhydride for 65 about twenty minutes at the reñuxing tempera 65 ture. The product separated from the chilled reaction mixture. It can be employed without further puriñcation. EXAMPLE 19,-1- (ls-Acetam'lz‘dovinyl) -benzothz‘a 70 gole ethiodide 70 EXAMPLE 15.-2­ethyl­4­ [ (2-ethyZ-1- (2) -benzo 6'? g. (1 mol.) of l-methylbenzothiazole ethio thz'azolylidene) ethylidenel-5-oœazolone dide and 40 g. (1 mol.) of diphenylformamidine 2.25 g. (1 mol.) of l-ß-acetanilidovinyl) -benzo were heated in about 250 cc. of acetic anhydride thiazole ethiodide, 0.65 g. (1 mol.) of propionyl for about twenty minutes at the refluxing tem 75 75 2,185,343 5 perature. The product separated from the chilled 100 mg. per liter of iiowable emulsion. The con reaction mixture. It can be employed without centration of the dye will vary according to the further purification. type of light-sensitive material in the emulsion fr and according to the effects desired. The suitable EXAMPLE 20.-4-(ß-Am'linooz‘nyl) -quz'noline ethz' and most economical concentration for any given odide emulsion will be apparent to those skilled in the art, upon making the ordinary tests and observa 29.9 g. (1 mol.) of lepidine ethiodide and 19.6 g. tions customarily used in the art of emulsion (1 mol.) of diphenylformamidine were heated at making. To prepare a gelatino-silver-halide from 150° to 160° C. for about ten minutes with emulsion, the following procedure is satisfactory: stirring. The reaction mixture was cooled and A quantity of the dye is dissolved in methyl alco 10 ground with acetone. The acetone-treated prod hol or acetoney and a volume of this solution uct was recrystallized from methyl alcohol and (which may be diluted with water) containing obtained as red crystals melting at 248° to 250° C. with decomposition. from 5 to 100 mg. of dye is slowly added to about 1000 cc. of a flowable gelatino-siiver-halide emul The formylmethylene compounds employed in sion with stirring. Stirring is continued until the above examples are prepared by hydrolyzing the dye is uniformly and practically homogene the ß-arylamino compounds. The method of ously dispersed. Ordinarily 10 to 20 mg. of dye preparation is fully described in British Patent No. 465,268. rIlhe following example is illustrative per 1000 cc. of flowable emulsion will suiiìce to of the preparation: produce the maximum sensitizing eiiect with the ordinary gelatino-silver-halide emulsions. The 20 above statements are only illustrative and not to EXAMPLE 21.-3-etltyl-4-methyZ-2-formylmethyl be understood as limiting our invention in any ene-A4-thz'aeolz‘nc sense, as it will be apparent that our dyes can be 25 incorporated by other methods in many of the 7.44 g. (l mol.) of 2-(ß-anilinovinyD-4-meth 25 ylthiazole ethiodide and 1.45 g. (1.1 mol.) of 85% photographic emulsions customarily employed in powdered potassium hydroxide were heated in the art, such, for instance, as by bathing the about 20 cc. of 95% ethyl alcohol at the reflux plate or film, upon which the emulsion has been ing temperature for about six hours. The reac coated, in a solution or the dye in an appropriate 30 solvent, although such a method is ordinarily not tion mixture was poured into about 100 cc. of 30 cold water and the resulting mixture chilled for to be preferred. The claims are intended to cover about twelve hours at 0° C. The crude product any combination of these new dyes with a photo which separated was ñltered off and washed with graphic silver halide emulsion whereby the dye exerts a sensitizing effect upon the emulsions, as 35 water. After two recrystallizations from ligroin (boiling point 90° C. to 120° C.) the formylmeth well as a photographic element comprising a sup 35 ylene compound was obtained as brownish-yellow port, ordinarily transparent, upon which the crystals melting at 120° to 123° C. with decompo light-sensitive emulsion is coated or spread and sition. allowed to dry. n Our new dyes give rise to photographic emul The accompanying drawing is by way of illus tration and depicts the sensitivity of emulsions sions possessing novel sensitivity when incorpo 40 rated in the emulsions. Our invention is partic containing four of our new dyes. Each ligure in ularly directed to the customarily employed gela the drawing is a diagrammatic reproduction of tino-silver-halide emulsions. However, our new a spectrogram showing the sensitivity of a silver dyes can be employed in emulsions in which the bromide emulsion containing one of our new dyes. 45 In Fig. 1, the sensitivity of an ordinary gelat carrier is other than gelatin, for example, a resin 45 ous substance or cellulosic derivative which has ino-silver-bromide emulsion containing 4­[(2 substantially no deleterious effect on the light ethyl-1(2) -benzoselenazolylidene) ethylidenel -2 sensitive materials. As silver halide emulsions, phenyl-5-oxazolone is depicted. we include such emulsions as are commonly em In Fig. 2, the sensitivity of an ordinary gelat ployed in the art, for example, silver chloride or ino-silver-bromide emulsion containing 4-[(2­ 50 silver bromide emulsions which can contain other ethyl- 1(2) ­ benzothiazolylidene) ethylidene] ­ 2 salts which may be light-sensitive. By way of phenyl-â-oxazolone is depicted. illustration, the herein-described sensitized In Fig. 3, the sensitivity of an ordinary gelat-v 55 photographic emulsions were prepared by em ino-silver-bromide emulsion containing 4­[(1­ ploying ordinary gelatino-silver-bromide emul ethyl-2 (1) -ß ­ naphthothiazylidene) ethylidene] - sions. ` 2-phenyl-5-oxazolone is depicted. In the preparation of photographic emulsions In Fig. 4, the sensitivity of an ordinary gelat containing our new dyes, it is only necessary to ino-silver-bromide emulsion containing 4-[(1,6­ disperse the dyes in the emulsions. The methods dimethyl - 2(1) ­ quinolylidene) ethylidene] ­ 2 of incorporating dyes in emulsions are simple and phenyl-ö-oxazolone is depicted. well known to those skilled in the art. In prac We have found that these of our new dyes ticing our invention, it is convenient to add the containing a 1,2-dihydrothiazole nucleus, such as dyes from their solutions in appropriate solvents. a 1,2-dlhydrobenzothiazole or a 1,2-dihydronaph 65 The solvent must, of course, be compatible with thothiazole nucleus, are particularly useful in the emulsion, substantially free from any dele preparing sensitized gelatino-silver-chloride or 65 terious effect on the light-sensitive materials and bromide emulsions. As shown in the drawing, capable of dissolving the dyes. Methanol or such dyes produce emulsions strongly sensitized acetone have proven satisfactory as a solvent for in the region of 520 mu and the sensitivity ex 70 our new dyes. The dyes are advantageously in tends far out, at least to 640 mu. corporated in the finished, washed emulsion and Still further examples illustrating our inven 70 should be uniformly distributed throughout to tion could be cited, but the foregoing will be suf secure the best results. ñcient to teach those skilled in the art the man The concentration of our new dyes in the emul ner in which our invention is carried out. 75 sions can vary widely, e. g. from about 5 to about What we claim as our invention and desire to 75 6 2,185,343 be secured by Letters Patent of the United States wherein R represents an alkyl group, R’ repre sents an organic group selected from the group is:v » l 1. A dye characterized by one of the following consisting of alkyl groups and aryl groups con taining from one to two benzene rings and Z rep formulas: l Y resents the non-metallic atoms necessary to com plete a naphthothiazole nucleus. , 5. A dye characterized by the following for mula: 10 10

15 I wherein R represents an alkyl group, R’ repre R-N’ sents an organic group selected from the group consisting of alkyl groups and aryl groups con wherein D represents the non-metallic atoms nec taining from one to two benzene rings and Z rep essary to complete a heterocyclic nucleus selected resents the non-metallic atoms necessary to com 20 20 from the group consisting of pyridine nuclei and plete a benzothiazole nucleus. quinoline nuclei, R represents an alkyl group, R' 6. A dye characterized by the following for represents an organic group selected from the mula: group consisting of alkyl groups and aryl groups R, containing from one to twol benzene rings and l 25 Z represents the non-metallic atoms necessary to /C\ complete a heterocyclic nucleus selected from the ,z. N/ o group consisting of ñve-membered and six-mem bered heterocyclic organic nuclei. 2. A dye characterized by the following for wherein R represents an alkyl group, R’ repre 30 30 mula: Y sents an organic group selected from the group consisting of alkyl groups and aryl groups con taining from one to two benzene rings and Z rep resents the non-metallic atoms necessary to com 'fzs` Y 1T' (l) plete a benzoselenazole nucleus. 35 85 R-N-o‘=oH-cH=o•-•o=o 7. A process for preparing a dye comprising wherein R represents an alkyl group, R’ repre reacting, in the presence of an acid-binding agent sents an organic group selected from the group and a water-binding agent, a monoacylated consisting of alkyl groups and aryl groups con aminoacetic acid with a cyclammonium quater taining from one to two ybenzene rings and Z nary salt containing a ß-arylaminovinyl group in represents the non-metallic atoms necessary' to a reactive position. 40 complete a ñve-mernbered heterocyclic organic 8. A process for preparing a dye comprising re acting, in the presence of a lower fatty acid an nucleus. 3. A dye characterized by the following for hydride and an alkali salt of a lower fatty acid, a monoacylated aminoacetic acid with a cyclam mula: monium quaternary salt containing a ß-aryl 45 45 Rl l aminovinyl group in a reactive position. 9. A process for preparing a dye comprising re acting, in the presence of a lower fatty acid anhydride and an alkali salt of a lower fatty acid, 50 híppuric acid with a cyclammonium Quaternary 50 lwherein R represents an alkyl group, R’ repre salt containing a ß-anilinovinyl group in a reactive sents an organic group selected from the group i position. consisting oi alkyl groups and aryl groups con 10. A process for preparing a dye comprising taining from one to two benzenerings and Z rep reacting, in the presence of a lower fatty acid 55 resents the non-metallic atoms necessary to com anhydride and an alkali salt of a lower fatty acid, 55 plete a heterocyclic nucleus of the azole series. hippuric acid with a cyclammonium alkiodide 4. A dye characterized by the following for containing a ß-anilinovinyl group in a reactive mula: position. Rl GRAFTON H. KEYES. è LESLIE G. S. BROOKER.