US2520358A - Heterocyclic bis acetones, thioacetones, and selenoacetones - Google Patents

Description

Patented Aug. 29,

UNITED STATES PATENT OFFICE HETERUCYCLKC BIS ACETONES, THIOACE- TONES, AND SELENOACETONES Leslie G. S. Brooker and Frank L. White, Rochester, N. 25., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application September 4, 1948, Serial No. 47,948

20 Claims.

wherein R and R1 each represents an alkyl group (i. e., an alcohol radical), e. g., methyl, ethyl, n-propyl, n-butyl, isobutyl, n-amyl, isoamyl, shydroxyethyl, 'y-hydroxypropyl, ,B-methoxyethyl, (B-ethoxyethyl, 'allyl, Z-methallyl, benzyl (phenylmethyl), ,e-phenylethyl, fi-carboxyethyl, carboxymethyl, a-carboxyethyl, /-carboxypropyl, {3-- acetoxyethyl, 'y-acetoxypropyl, carbomethoxymethyl, carbethoxymethyl, B-carbomethoxyethyl, e-carhethoxyethyl, phenoxymethyl, B- phenoxyethyl, fi-phenylmeroaptoethyl, phenylmercaptomethyl, etc., d and n each represents a positive integer of from 1 to 2, R2 and R3 each represents a hydrogen atom or an alkyl group (i. e., an alcohol radical), e. g., methyl, ethyl, etc., Q represents an atom selected from the group consisting of an oxygen atom, a sulfur atom and a selenium atom, Z and Z1 represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, R, in addition represents an aryl group when Z represents the non-metallic atoms necessary to complete a hetero-cyclic nucleus of the thiazole series, the benzothiazole series, the thiazoline series or the 3,3- dialkylindolenine series, and R1 in addition represents an aryl group when Z1 represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the thiazole series, the hemethiazole series, the thiazoline series or the 3,3- dialkylindolenine series. More specifically, Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the oxazole series (e. g., methyl, l-phenyloxazole, 4- ethyloxazole, 4,5-diphenyloxazole, 5-pheny1oxazole), the benzoxazole series (e. g., henzoxazcle, 5-ch1orobenzoxazole, .B-phenylbenzoxazole, 5- methylbenzoxazcle, 5-hydroxybenzoxazole, 5- methoxybenzoxazole, etc.), the naphthoxazole series (e. g., a-n'aphthoxazole, fi-naphthoxazole, etc.) the thiazole series (e. g., thiazole, -methyh thiazole, -phenylthiazole, 4,5-dipheny1thiazo1e, E-phenylthiazole, 4,5-dimethylthiazole, l-(2-thieny1)thiazole, etc.), the benzothiazole series (e. g., benzothiazole, 4-phenylbenz0thiazole, 5- phenylbenzothiazole, l-methylbenzothiazole, 5- methylbenzothiazole, 5-methoxybenzothiazole, 5-

ethoxybenzothiazole, G-methylbenzothiazole, 6- methoxybenzothiazole, 6-ethoxybenzothiazole, 5- chlorobenzothiazole, 6-chlorobenzothiazole, 5,6- dimethoxybenzothiazole, 5,6 dioxymethylenebenzothiazole, tetrahydrobenzothiazole, 5-bromobenzothiazole, 5-iodobenzothiazole, 4-ethoxybenzothiazole, etc.), the naphthothiazole series (e. g., a-naphthothiazole, ,B-naphthothiazole, etc.), the selenazole series (ei-methylselenazole, l-phenylselen'azole, etc.), the benzoselenazole series (benzoselenazole, fi-chlorobenzoselenazole, tetrahydrobenzoselenazole, etc.), the thiazoline series (e. g., thiazoline), the 3,3-dialky1indolenine series (e. g., 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7 trimethylindolenine, etc.), the quinoline series (e. g., quinoline, 6- methylquinoline, 7-methylquinoline, B-methyl quinoline, fi-chloroquinoline, 8-chloroquinoline,

' l-chloroquinoline, 5-ethoxyquinoline, G-ethoxyquinoline, '7-ethoxyquinoline, B-methoxyquinoline, etc.), the pyridine series (e. g., pyridine, 51 methylpyridine, etc.), etc.

The bis acetones formulated above can be prepared, in accordance with our invention, by reacting a metal oxide, a metal hydroxide, a metal sulfide, a metal hydrosulfide, a metal selenide, or a metal hydroselenide, with a carbocyanine selected from those represented by the following general formula:

wherein R, R1, R2, R3, Z, Z1, d and n have the values set forth above, Q1 represents a sulfur atom or a selenium atom, R4 represents an alkyl group, e. g. methyl, ethyl, n-propyl, isobutyl, nbutyl, n-hexyl, lauryl, cetyl, etc. (e. g. an alkyl group, especially a primary alkyl group, containing 1 to 20 carbon atoms, and X represents an anion.

If a metal sulfide or hydrosulfide is employed, the resulting compound is a his thioacetone, regardless of the value of Q1 in the starting carbocyanine dye (Formula II). If a metal selern'de or hydroselenide is used, the resulting compound is a his selenoacetone regardless of the value of Q1 in the starting carbocyanine dye. If a metal oxide or hydroxide is used, the resulting compound is bis acetone regardless of the value of Q1 in the starting material.

The reactions are advantageously effected in a diluent. Alcohols, such as methyl, ethyl, npropyl, isopropyl, n-butyl and tort. butyl are advantageously employed. Heat accelerates the reaction and temperatures between 50 and 150 C. are advantageously employed, although higher or lower temperatures can be used.

As metal oxides and hydroxides, sulfides and hydrosulfides, selenides and hydroselenides, the alkali metal compounds, especially sodium and potassium, are advantageously employed. A1- kaline earth compounds, e. g. calcium, strontium and barium compounds can also be used.

The following examples will serve to illustrate further the manner of obtaining our new bis acetones, bis thioacetones and bis selenoacetones.

Example 1.-Bzs(3-ethyl-2 (3) -ben2othiazolylidene) thioacetone A solution of 1.16 g. (l mol.+l%) of sodium sulfide in cc. of water was added to a suspension of 4.00 g. (1 mol.) of 3,3-diethyl-9-methylmercaptothiacarbocyanine iodide in 75 cc. of ethyl alcohol, and the reaction mixture was heated at the refluxing temperature for minutes. After chilling at 0 C., the product was collected on a filter and washed with methyl alcohol. The yield of product was 75% crude and 68% after purification (the crude product was dissolved in hot pyridine and 5 volumes of methyl alcohol was added to the hot filtrate). The reddish crystals with blue reflex had a melting point of 29l-j292 C. with decomposition, and they sensitized a photographic gelatino-silverbromoiodide emulsion to about 610 nm with maxima sensitivity at about 525 and 560 m Example 2.--Bis (3-ethyZ-2 (3) -benzothiazo- Zifllidene) selemoacetone A solution of 3.75 g. (1 mol.+200% excess) of sodium selenide in cc. of water was added to a suspension of 5.38 g. (1 mol.) of 3,3'-diethyl-9- methylmercaptothiacarbocyanine iodide in 50 cc. of ethyl alcohol, and the reaction mixture was heated at the refluxing temperature for 5 minutes. After chilling at 0 C., the solids were col lected on a filter and washed with methyl alcohol. The mixed solids were extracted with 70 cc. of hot oyclopentanone and the suspension was filtered. To the hot filtrate was added 280 cc. of ethyl alcohol and the mixture was chilled at 0 C. After another similar purification, the yield was 50%. The green crystals had a melting point of 269-271 C. with decomposition, and they sen sitized a photographic gelatino-silver-bromoiodide emulsion to about 630 m with maximum sensitivity from about 540 m to about 590 m Bis(3-ethyl-2 (3) -benzothiazolylidene) acetone, represented by the following formula:

N 412115 zHs was prepared in a manner similar to that described in Example 2 by adding a solution of 3.95

g. (1 mol.+200% excess) of potassium hydroxide in 5 cc. of water to a suspension of 5.38 g. (1 mol.) of 3,3-diethyl9-methylmercaptothiacarbocyanine iodide in cc. of ethyl alcohol, and heating the reaction mixture at the refluxing temperature for 15 minutes.

Example 3.1 [1 ethyl-2 (1) fi-naphthothiazolylz'denel -3 [1 -ethy'l-2 (1) -qainolylidenel thicacetone To a suspension of 2.77 g. (1 mol.) of 1,3-diethyl-9-methylmercapto-4,5-benzothia2-carbocyanine perchlorate in 25 cc. of ethyl alcohol was added 0.78 g. (1 mol.+100%) of sodium sulfide dissolved in 10 cc. of water, and the reaction mixture was heated at the refluxing temperature for 10 minutes. After chilling, the product was collected on a filter and washed with methyl alcohol. It was purified by being dissolved in hot pyridine, and adding methyl alcohol to the hot filtrate. The yield of product was crude and 36% after two such purifications. The dark green needles had a melting point of 242243 C. with decomposition, and they sensitized a photographic gelatino-silver-bromiodide emulsion from about 530 m to about 680 m with maxima sensitivity at about 570 rm. and 640 m Example 4.1-[3-ethyl 2(3) benzothiaeolylidene] -3- [l-ethyZ-G-methoxy 2(1) qaz'nonlylz denel thz'oacetone CzHs To a suspension of 1.07 g. of l,3-diethyl-6'- methoxy-Q-methylmercaptothia-Z"-carbocyanine perchlorate in 25 cc. of ethyl alcohol was added 0.30 g. of sodium sulfide in 5 cc. of water, and the reaction mixture was heated at the refluxing temperature for 10 minutes. After chilling, the product was collected on a filter and washed with methyl alcohol. It was purified by being dissolved in hot pyridine, and adding methyl alcohol to the hot filtrate. The yield of product was 54% crude, and 36% after two such purifications. The green needles with a bronze reflex had a melting point of 23l-233 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion from about 530 m to about 670 m, with maxima sensitivity at about 555 mi and about 640 m Example 5 .-Bis 3-ethyl-2 3) -a-naphthothiazolylidene) thzoacetone acetate it a sus'finsion of 6.16 g. &1 mar. tr sla -db ethyI-Q-methylmercapto 6,7,6)? dibeniothia atbocyanine iodide in 20 co. or ethyl alcohol was added 0,65 g. (1 'I'nol;|-l50% excess) of sodium sulfide dissolved in 2 cc. of water, and the reaction mixture heated at the refluxing temperature for 10 minutes. After chilling, the product was eolle' ted on a filter and washed with methyl alcohol, It was purified by being dissolved in hot pyridine, and adding methyl alcohol to the hot filtrate. The yield of product was 84% crude, and 25% after we such Durifications. The orange crystals had a melting point above 300 C., and they sensitized a photographic gelatino-silverbromoiodide emulsion from about 530 m to about 610 m Example 6.1-[3-ethyl 2(3) -benzose le1'zazolylz'clenel-3-[3-ethyl 2(3)-benzcthiazolylidenelthz'oaceione To a sup'en'sion of Tl-.59 g. (1 mol.) of 3,3-diethyl-9 methylmercaptoselenathiacarbocyanine iodide-m to cc. of ethyl alcohol was added 0.16 g. (rmoi.+r uc% exeess) or sodium Sulfide dissolved in cc. of water, and the reaction mixture was heated at the refluxing temperature for 10 minates; After chilling, the product was collected on afilter and washed with methyl alcohol, It was purified by being dissolved in hot pyridine, and adding methyl alcohol to the hot filtrate. The yield o f product was crude, and 38% after two such purifications, The reddish crystals had a "melting point of 274-275 C. with decompositi'on, and they sensitized a photographic gelatinos'ilver-bromoiodide emulsion to about 630 mp with maximal. sensitivity about 530 m and about 580 m To a suspension of 0.54 g. (1 mol.) of 5-chloro- 3-ethyl- 3-methyl 9 methylmercapto-oxathiacarbocyanine iodide in 35 cc. of ethyl alcohol was added 0.16 g. (1 mol.+l00% excess) of sodium sulfide dissolved in 2 cc. of water, and the reaction 'mixture was heated at the refluxing temperature for 10 minutes. After chilling, the prod-- not was collected on a filter and washed with ethyl alcohol. The yield of product was 25% crude, and 12% after two recrystallizations from absolute ethyl alcohol. The brownish needles had a melting point of 22l-222 C. with decomposition, and they sensitized a photographic gelatino=silver-broinoiodide emulsion to about aeolg Zidene] -3-methyl 3- [3-methyZ-2fi3) 17811,- zothiazolylidenelthioacetone A mixture of 4.? g. (1 mol.) of 5-chloro-2-(2- methyl mercaptobutenyl)benzothiazole etho-ptoluenesulfonate and 3&67 g. (1 mol.) of 2-methylmercaptobenzothiazole metho-p-toluenesulfonate in 25 cc; of pyridine were heated together at the refluxing temperature for 30 minutes. The cool reaction mixture was stirred with ether and the whole chilled. The ether-pyridine layer was decanted, the sticky residue was dissolved in hot methyl alcohol and the dye converted to the perchlorate by adding a hot aqueous solution of sodium perchlorate. After chilling, the aqueousalcohol layer was decanted and the residue was treated with several successive portions: of ethyl alcohol. The small residue remained sticky; it was dissolved in hot ethyl alcohol and treated with an aqueous solution of sodium sulfide at the refluxing temperature, for 10 minutes. After chilling, the product was collected on a filter and washed with ethyl alcohol. It was purified by dissolving in hot pyridine, and adding methyl alcohol to the hot filtrate. The yield of product was 5% crude, and 3% after two such purifications. The red needles had a melting point of 290 -291 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoicdide emulsion to about 630 mp with maxima sensitivity at about 520 m and about 575 m Example 9.-Bis[3 ethyl 2(3) benzothiazolylidencl thioacetone To a suspension of 0.30 g. (1 mol.) of 3,3'-diethyl-'9#ethylselenylthiacarbocyanine iodide in 20 cc. of ethyl alcohol, 0.08 g. (l mol.+100%) of sodium sulfide dissolved in 3 cc. of water was added, and the reaction mixture was heated at the refluxing temperature for 15 minutes. After chilling to 0 C., the product was collected on a filter and washed with methyl alcohol. The yield of the product was 100% crude, and after two purifications (the crude product was dissolved in hot pyridine and 5 volumes of methyl alcohol was added to the hot filtrate). The reddish crystals had a blue reflex and melted at 29l-292 C. A mixedmelting point of the dye of the above example and that of Example 1 was run, and the mixture melted at 29l-292 C.

In a similar manner, other bis acetones can be prepared by replacing the alkylmercapto or alkylselenyl dy'es used in the above examples with an equivalent amount of one of the dyes represented by Formula 11 above. For example, by replacing the 9-methylmercapto dyes of Examples 1 to 7 by a molecularly equivalent amount of 3,3-diethy1 9 ethylselenylthiacarbocyanine perchlorate and the sodium sulfide or sodium selenide by a molecularly equivalent amount of sodium hydroxide, bis(3-ethyl-2(3) -benzothia'zo-.-

lylidene)acetone represented by the following can be obtained. Similarly, by replacing the sodium sulfide or sodium selenide in Examples 1 to 9 by a molecularly equivalent amount of sodium oxide (NazO) the corresponding bis acetones can be obtained, e. g., heating 1 mol. of -chloro-3-ethyl-3-methyl-Q-methylmercaptooxathiacarbocyanine iodide with 1 mol. plus 100% excess of sodium oxide in the manner described in Example 7 gives 1-[5-chloro-3-ethyl-2(3) -benzothiazolylidene] 3-[3-methyl-2(3)-benzoxazolylidenelacetone represented by the formula:

If the 3,3-diethyl-Q-methylmercaptothiacarbocyanine iodide of Example 1 is replaced by a molecularly equivalent amount of 3-ethyl-9- methylmercapto-3',4-trimethylenethiacarbocyanine perchlorate, 1- [3-ethyl-2(3) -benzothiazolylidene] 3 [3,4 trimethylene-2(3) -benzothiazolylidene]selenoacetone represented by the formula:

can be obtained. When a molecularly equivalent amount of sodium hydrosulfide replaces the sodium selenide in Example 2, bis (3-ethyl-2(3)- benzothiazolylidene)thioacetone can be obtained. Other metal sulfides, hydrosulfides, oxides, hy-

droxides, selenides and hydroselenides can likewise be advantageously used to produce our new bis-acetone compounds.

Our new bis acetone, bis thioaoetone and bis selenoacetone compounds are useful as starting materials for the preparation of carbocyanine dyes containing at the central position of the trimethine chain (the meso position) an oxy (-OR5), mercapto (SR5) or selenomercapto (--SeR5) substituent. Various compounds of the formula:

wherein X represents an anion and R5 represents an organic radical can be added to the his acetone, bis thioacetone and bis selenoacetone compounds, e, g., methyl iodide, ethyl iodide, n-propyl bromide, n-buty1 chloride, n-butyl iodide, isobutyl bromide, n-decyl bromide, lauryl bromide, cetylbromide, B-hydroxyethyl bromide, 'y-hYdIOX- ypropyl bromide, [S-rnethoxyethyl bromide, ,B-ethoxyethyl bromide, bromoacetic acid, ii-bromopropionic acid, a-bromopropionic acid, ethyl bromoacetate, ethyl B-iodopropionate, 2-chloroquinoline, 2-ch1orobenzothiazole, -ohloroquinoline, 2- chloropyridine, methyl p-toluenesulfonate, ethyl p-toluenesulionate, methyl benzenesulfonate, di-.

8 methyl sulfate, diethyl sulfate, 2,4-dinitrochloi'obenzene, etc.

The additions are advantageously efiected by heating the bis acetone, bis thioacetone or bis selenoacetone with the m5 compound at to C. Higher or lower temperatures can be used.

The following examples will serve to illustrate further the manner of obtaining meso-substh tuted carbocyanine dyes in accordance with our invention.

Example 10.3,3-diethyl-Q-ethylselenylthiacarbocyanine iodide 0.89 g. (1 mol.) of bis (3-ethyl-2(3) -benzothiazolylidene)selenoacetone and 2.00 g. (1 mol.+ 400% excess) of ethyl p-toluenesulfonate were heated together in an oil-bath at 120 C. for 6 minutes. The excess of ethyl p-toluenesulfonate was removed with ether. The crude dye was dissolved in methyl alcohol and the hot alcoholic solution was treated with a hot solution of potassium iodide (3 g.) in water (30 00.). After chilling at 0 0., the dye iodide was collected on a filter and washed with water. The dye was transferred to a beaker and stirred with hot acetone. After chilling at 0 C., the dye Was collected on a filter and washed with acetone. The yield of dye was 83% crude, and 58% after two recrystallizations from methyl alcohol (45 cc. per gram of dye), The blue and green crystals had a melting point of l78-179 C. with decomposition, and they sensitized a photographic gelatino-silverbromoiodide emulsion to about 680 m with maximum sensitivity at about 640 m n.

In like manner, 3,3-diethyl-9-methy1selenylthiacarbocyanine iodide was prepared by using 1.86 g. (1 mol.+400% excess) of methyl p-toluenesulfonate in place of the ethyl p-toluenesulfonate. The yield of dye iodide was 80% crude and 64% after two recrystallizations from methyl alcohol (55 cc. per gram of dye). The beautiful green crystals had a melting point of 162 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 665 m Example 1 1 .-9-Carbethorymethylmercapto- 3,3-diethylthiacarbocyanine iodide s s SCHzCOOCzHs o=0H- t=oH-o N N 62115 Gi H5 \I r 0.99 g. (1 mol.) of bis (3-ethyl-2(3)-benzothiazolylidine)thioacetone and 1.67 g. (1 mol.+ 300% excess) of ethyl bromoacetate were heated together at the temperature of the steam bath for about 2 hours. The cake of crystals was broken up, ground under acetone, filtered and washed with acetone. The dye was dissolved in methyl alcohol and the hot alcoholic solution was treated with a hot solution of aqueous potassium iodide. After chilling at 0 C., the dye was collected on a filter and washed with water. The dye was transferred to a beaker and stirred with hot acetone. After chilling at 0 0., the dye was collected on a filter and washed with acetone. The yield of dye was 85% crude and 52% after two recrystallizations from methyl alcohol (50 cc. per gram of dye). The green needles had a melting point of 1729-173 0. with decomposition, and they sensitized a photographic gelatinosilver-bromoiodide emulsion to about 640 m In like manner, 9-c-carboxyethylmercapto- 3,3-diethylthiacarbocyanine iodide was prepared by heating 0.79 g. (1 mol.) of his (3ethyl-2(3)- benzothiazolylidene)thioacetone and 2.00 g. (1 mo1.+400% excess) of c-iodopropionic acid together in an oil bath at 120 C. for 4 minutes. The yield ofdye was 96% crude and 71% after two recrystallizations from methyl alcohol (160 cc. per gram of dye). The blue-green needles had a melting point of 246-247 C. with decomposition, and they sensitized a photographic gelatinosilVer-bromoiodide emulsion to about 650 m 0.99 g. (1 mol.) of bis(3-ethyl-2(3) -benzothiazolylidene)thioacetone and 1.70 g. (1 mol.+ 300% excess) of z-chlorobenzothiazole were heated together at the temperature of the steam bath for 4 hours. The cool reaction mixture was stirred with acetone, and the dye was collected on a filter and washed with acetone. The yield of twice-recrystallized dye (from methyl alcohol, 125 cc. per gram of dye) was 11%. The dull purplish crystals had a melting point of 252-254 C. with decomposition, and they sensitized a. photographic gelatino silver-bromoiodide emulsion to about 615 In with maxima sensitivity at about 520 and 590 m The new bis acetone dyes (including the his thioacetone and his selenoacetone dyes) and the carbocyanine dyes obtained therefrom sensitize photographic silver halide emulsions when incorporated therein.

In the preparation of photographic emulsions containing our new bis acetone dyes or carbocyanine dyes made therefrom, it is only necessary to disperse the dyes in the emulsions. The methods of incorporating dyes in emulsions are simple well known to those skilled in the art It is convenient to add the dyes from solutions in appropriate solvents. Methanol has proved satisfactory as a solvent for some of our new bis acetone dyes and for carbocyanine dyes made therefrom. A mixture of pyridine and acetone can be used Where the solubility of the new bis acetone dyes in methanol is lower thandesired.

Sensitization by means of our new bis acetone dyes and carbocyanine dyes made therefrom is, of course, directed primarily to the ordinarily employed gelatino-silver-halide developing-out emulsions. The dyes are advantageously incorporated in the washed, finished emulsions and should, of course, be uniformly distributed throughout the emulsions.

The concentration of our new bis acetone dyes and carbocyanine dyes made therefrom in the emulsion can vary widely, i. e., from about 5 to about mgs. per liter of flowable emulsion. The concentration of the dye will vary according to the type of light-sensitive material in the emulsion and according to the eiiects desired. The suitable and most economical concentration for any given emulsion will be apparent to those skilled in the art upon making the ordinary tests and observations customarily used in the art of emulsion making.

To prepare a gelatino-silver-halide emulsion sensitized with one of our new bis acetone dyes or a carbccyanine dye made therefrom, the following procedure is satisfactory: A quantity of the dye is dissolved in methyl alcohol or other suitable solvent and a volume of this solution (which may be diluted with water) containing from 5 to 100 mgs. of dye is slowly added to about 1000 cc. of a gelatino-silver-halide emulsion, with stirring. stirring is continued until the dye is uniormly distributed throughout the emulsion. With most of our new bis acetone dyes, 10 to '20 mgs. of dye per liter of emulsion suffices to produce the maximum sensitizing efiect with the ordinary gelatino-silver-bromide (including bromiodide) emulsions. With fine-grain emulsions, which include most of the ordinarily employed gelatino-silver-chloride emulsions, somewhat larger concentrations of dye may be necessary to secure the optimum sensitizing effect.

The above statements are only illustrative and are not to be understood as limiting our invention in any sense, as it will be apparent that our new bis acetone dyes and carbocyanine dyes made therefrom can be incorporated by other methods in many of the photographic silver halide emulsions customarily employed in the art. For instance, the dyes may be incorporated by bathing a plate or film upon which an emulsion has been coated, in the solution of the dye, in an appropriate solvent. Bathing methods, however, are not to be preferred ordinarily.

One method of preparing the alkylmercapto carbocyanine dyes, from which our new bis acetones can be prepared, comprises condensing, in the presence of a basic condensing agent, a cyclammonium quaternary salt represented by the following general formula:

n-Nlfon-on)., 1R:o=i -om1u wherein R, R2, R3, R4, Z, X and d have the definitions set forth above, with a cyclammonium alkyl quaternary salt represented by the following general formula:

Rl1 f= on-oH ,.I=os-m wherein R1, Z1, Z and n have the values set forth above, and R6 represents an alkyl group, e. g. methyl, ethyl, n-butyl, benzyl, etc. groups, or an aryl group, e, g. phenyl, p-chlorophenyl, ,B-naphthyl, etc. groups. Such a process is described in the copending application of H. W. J. Cressman, Ser. No. 624,91,fi16d Oct. 26, 1945'; As basic condensing agents we can use a tertiar amine (e. g. pyridine, triethylamine, dimethylaniline, tri-n-butylamine, etc.), alkali metal carbonates (e; g. sodium or potassium carbonate, etc.), etc. Heating accelerates the condensations. While the copending application of Cressman relates to 11 condensations wherein R2 and R3 in the above formula represent hydrogen atoms, it is to be understood that our invention contemplates condensations wherein R2 and R3 each represents either a hydrogen atom or an alkyl group. Intermediates wherein R2 of Formula Ia represents an alkyl group can be prepared by methods disclosed in U. S. Patents 2,369,646 and 2,369,657, dated Feb. 29, 1945. Intermediates wherein R2 and R3 of Formula Ia each represents an alkyl group, and intermediates wherein R2 represents an alkyl group and R3 represents a hydrogen atom are described in the copending application of G. H. Keyes, Serial No. 620,161, filed Oct. 3, 1945, now U. S. Patent 2,500,126, dated March 7, 1950. The intermediates of Formula Ia are, in general, prepared by treating the thioketones described in U. S. Patents 2,369,646 and 2,369,657, with an alkyl salt (e. g. methyl p-toluenesulfonate, ethyl benzenesulfonate, etc.) e. g.

III

R-rf-Z6H=o1. 3;1%=o o112-R3 R X s z SR4 R-1 T=(oH-oH)d:=T1-o= :omm

wherein R, R2, R3, R4, Z, X and d have the values set forth above. The intermediates represented by Formula III above can be prepared by reacting a compound selected from those represented by the following general formula:

IV X1 RITI =ZCHCH)a-1 CC=(BCHQR n-rf-(omomdlbzo-o-om-na wherein R, R2, R3, Z and d hav the values defined above, with a phosphorus oxyhalide, e. g. phosphorus oxychloride as described in U. S. Patent 2,231,659, dated Feb. 11, 1941. The compounds represented by Formula V can be prepared by reacting cyclammonium quaternary salts represented by the following general formula:

wherein R, R2, Z, X and d have the values defined above, with an acyl chlorid selected from those represented by the formula:

wherein R2 has the above designated value, in the presence of an acid binding agent (e. g. pyridine, dimethylaniline, etc.) as described in U. S. Patent 2,112,139, dated Mar. 22, 1938. Many of the cyclammonium quaternary salts represented by Formula VI above are known. The heterocyclic bases themselves, from which the w ernary salts of Formula VI can be prepared are also known for the most part. Several of the 2- methylbenzothiazole bases can be prepared by the method of Fries et al., Ann. 4-07, 208 (1915), in which the appropriate thioacetylaniline is oxidized with alkalin potassium ferricyanide. Thus p-chlorothioacetanilide can be prepared by treating the corresponding acetylaniline with phosphorus pentasulfide. The acetylanilines can be prepar d by the action Of acetic anhydride or acetyl chloride on the corresponding aniline compound. Several of the 2-methylbenzothiazole bases can also be prepared by reducing bis (0- nitrophenyDdisulfides with zinc dust and acetic acid, acetylating the reduction mixture with acetic anhydride, and closing the ring by heating the resulting mixture. The bis (o-nitrophenyl) disulfides can be prepared from the corresponding o-bromonitrobenzenes by heating the o-bromonitrobenzene with sodium disulfide in methyl alcohol. Thus Z-bromo 4 chloronitrobenzene give bis(5-chloro2-nitrophenyl) disulfide which, on reduction and acetylation of the reduction product and closing the ring by heating the re sulting mixture, gives 2-methyl-6-chlorobenzothiazole. 2-methyl-5-phenylbenzothiazole can be prepared by reducing bis(3-nitro-4-biphenyl)- disulfide with zinc and acetic acid, acetylating the reduction product and closing the ring by heating the resulting mixture. (See the copending application of Gertrude Van Zandt and L. G. S. Brooker, Serial No. 711,816, filed November 22, 1946, now Patent 2,515,913, July 18, 1950.) 2-methyl-4-phenylbenzothiazole can be prepared by oxidizing o-thioacetamidobiphenyl with an alkali metal ferricyanide. (See the copending application of Gertrude Van Zandt and L, G. S. Brooker, Serial No. 709,414, filed November 13, 1946, now U. S. Patent 2,405,679, dated October 25, 1949.) Z-methylbenzoselenazole bases can be prepared by reducing bis(o-nitrophenyl) diselenides with zinc dust and acetic acid, acetylating the reduction mixture with acetic anhydride, and closing the ring by heating the resulting mixture. The bis(o-nitrophenyl) diselenides can be prepared from the corresponding o-bromonitrobenzenes by heating the 0-bromonitrobenzenes with sodium diselenide in methyl alcohol. See also Clark, J. Chem. Soc. (London) 1928, 2313. Other 2-alkylcyclammonium bases can be prepared in a similar manner by substituting other acylating agents for the corresponding acetyl derivatives used above. For example, Z-ethylbenzothiazol can be prepared by heating 2-aminothiopheno1 with propionyl chloride (Hofmann, Berichte, vol. 13, 21).

Another method for making the alkylmer -apto carbocyanine dyes, from which our new bis acetones can be prepared, comprises condensing, in the presence of a basic condensing agent (e. g. pyridine, dimethylaniline, quinoline, etc.), a cyclammonium quaternary salt selected from those represented by Formula VI with a trithiocarbonate selected from those represented by the following general formula:

wherein R4 has the definition designated above. Heat accelerates the reaction. This method yields symmetrical dyes, i. e. dyes wherein Z and Z1 in the above general formulas represent the atoms necessary to complete the same heterocyclic nucleus.

Still another method for preparing the alkylmercapto carbocyanine dyes from which our new bis acetones can be. prepared,.comprises condensing a cyclammonium quaternary salt selected from those represented by the following general formula:

VII SR4 wherein R1, R3, R4,.Z1, X and n have the values set forth above, with a cyclammonium quaternary salt selected from those represented by Formula VI above. The condensations are advantageously, effected in. the presence of a basic condensing agent (0. g. pyridine, triethylamine, quinoline, dimethylam'line, etc.). Heat accelerates the reaction. The intermediates represented by Formula VII above can be prepared by condensing the corresponding dithioacetic acid with an alkyl salt (e. g. RiX) in the presence of an alcohol.

One method for preparing the alkylselenyl dyes, from which our bis acetones can be prepared, comprises condensing in the presence of a basic condensing agent (e, g. pyridine, triethylamine, quinoline, dimethylaniline, etc.), a cyclammonium quaternary salt selected from those represented by the following eneral formula:

wherein R, R2, R3, R4, Z, X and d have the values set forth above with. a cyclammonium quaternary salt selected from those represented by the following general formula:

iii-640E011 "Lira,

wherein R1, Z, X and n have the values set forth above, and R7 represents a halogen atom (e. g. chlorine) ora group, wherein R6 and Q1 have the values set forth above. Heat accelerates the condensations. The intermediates represented by Formula VIII above can be prepared in a manner similar to that illustrated by Formula Ia, except that the corresponding selenium compounds are employed for the sulfur compounds illustrated.

Some of the bis acetones of this invention exhibit interesting behavior toward solutions of silver nitrate. For example, th his thioacetone of Example 1 is turned. a bright bluish red upon the addition of a silver nitrate solution. Similar behavior is exhibited by the bias selenoacetone of Example 2, provided methyl alcohol. is added to prevent precipitation of the product. The bis acetone prepared in Example 2, i. e.

which is yellow in acetone, is not changed much by the addition of dilute aqueous silver nitrate solution. The deeper colored products formed .upon addition of a silver nitrate solution are probably silver complexes, e. g. that formed by the addition of a silver nitrate solutionto the his selenoacetone of Example 1, has the probable constitution of the type:

Xa S

\ N N 12115 l zHs and XI) S S In this typ of resonance, Xa andb will clearly be more favored the greater the basieity of the heterocyclic ring. The greater the resonance between the dipolar structures. of the type of Xa Xb, the more the color of the compound will approach that of a 9-substituted1 mercapto carbocyanine.

What we claim as our invention and desire to be secured by Letters. Patent of the United States is:

1. A bis acetone compound selected from those which are represented by the following general formula:

wherein R and R1 each represents an alkyl group containing from 1 to 4 carbon atoms, R2 and R3 each represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms, d and n each represents a positive integer .of from 1 to 2, Q represents a member selected from the group consisting of an oxygen atom, a sulfur atom and a selenium atom, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring.

2. A bis thioacetone compound selected from those represented by the following general formula:

o=on-oon=o wherein R, represents a primary alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from 1. to 4 and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series,

15 3. A bis thioacetone compound selected from those represented by the following general formula:

wherein R. represents a primary alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from 1 to 4.

4. The bis thioacetone compound which is represented by the following formula:

5. A bis selenoacetone compound selected from those represented by the following general formula:

wherein R represents a primary alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from 1 to 4 and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series.

6. A bis selenoacetone compound selected from the group consisting of those represented by the following general formula:

wherein R represents a primary alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from 1 to 4.

7. The bis selenoacetone compound which is represented by the following formula:

8. A bis acetone compound selected from those represented by the following general formula:

/Z\ ,2 l R-N o=oH-corr=o N-R wherein R represents a primary alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from 1 to 4 and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series. 9. A bis acetone compound selected from those represented by the following general formula:

wherein R represents a primary alkyl group of the formula CmHZm-l-l wherein m represents a positive integer of from 1 to 4.

10. The bis acetone compound which is represented by the following formula:

(52115 JzHs wherein R and R1 each represents an alkyl group of the formula CmH2m+l wherein m represents a positive integer of from 1 to 4.

13. The bis thioacetone compound which is represented by the following formula:

14. The bis thioacetone compound which is represented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula CmH2m+1 wherein m represents a positive interger of from 1 to 4, R3 represents an alkyl group containing from 1 to 2 carbon atoms, Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series, and Z1 represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series.

15. The bis thioacetone compound which is represented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from 1 to 4.

16. The bis thioacetone compound which is represented by the following formula:

17. A process for preparing bis acetone compounds comprising heating a compound selected from those represented by the following general formula:

wherein R and R1 each represents a primary alkyl group of the formula CmH2m+1 wherein m is a positive integer from 1 to R2 and R3 each represents a member selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group, R4 represents a primary alkyl group of the formula CqH2q+1 wherein q represents a positive integer from 1 to 20, X represents naphthothiazole series, the selenazole series, the

benzoselenazole series, the thlazoline series, the 3,3-dialkylindolenine series, the quinoline series and the pyridine series, with an aqueous solution of a member selected from the group consisting of metal oxides, metal hydroxides, metal sulfides, 4

metal hydrosulfides, metal selenides and metal hydroselenides.

18. A process for preparing his acetones com,- prising heating a compound selected from those represented by the following general formula:

wherein R and R1 each represents a primary alkyl group of the formula CmH2m+1 wherein m represents a positive integer of from 1 to 4, R4

wherein R and R1 each represents a primary alkyl group of the formula C'mHzm rl wherein m represents a positive integer of from 1 to 4, R4 represents a primary alkyl group of the formula CqH2q+1 wherein q represents a positive integer of from 1 to 20, X represents an anion, and. Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, with a metal selem'de.

20. A process for preparing his acetones comprising heating a compound selected from those represented by the following general formula:

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Reister June 1 1940 Number

Claims (1)

1. A BIS ACETONE COMPOUND SELECTED FROM THOSE WHICH ARE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: