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3-amido-7-disubstituted amino-10-carbonylphenothiazines - Patent # 4652643 - PatentGenius
3-amido-7-disubstituted amino-10-carbonylphenothiazines
4652643 3-amido-7-disubstituted amino-10-carbonylphenothiazines
Application: 06/847,985
Inventors: Gunn; Michael B. (Cincinnati, OH)
Hung; William M. (Cincinnati, OH)
Assignee: The Hilton-Davis Chemical Company (Cincinnati, OH)
Attorney Or Agent: Miesle; Terrence E.Johnson; Thomas L.Dupont; Paul E.
U.S. Class: 544/103; 544/37
Field Of Search: 544/37
U.S Patent Documents: 2909520; 4309255
Foreign Patent Documents: 48-052778; 55-040798
Other References: Mariga & Oda, "Color Reaction of Some Derivatives of Aminophthalide and Acylleucomethylene Blue Derivatives"-Kogyo Kagaku Zasshi 67 (7)1050-4, (1964), (C.A. 62 2852b)..
Smets & Simionescu, "Polymer Induced Aggregation of Dye Molecules", Makromolecular Chemistry, 1977, 198(9), 2719-23 (C.A. 87 186052t)..
Abstract: 3-(N--R.sup.2 --N-Acylamino)-7-(N--R.sup.3 --N--R.sup.4 -amino)-10-acylphenothiazines and phenoxazines useful as color formers, particularly in electrochromic recording systems, are prepared by the interaction of the corresponding 3-(N--R.sup.2 -amino)-7-(N--R.sup.3 --N--R.sup.4 -amino)phenothiazinium or phenoxazinium halide with a reducing agent to obtain the corresponding leuco compound and subsequently interacting the leuco compound with at least two molecular proportions of an acylating agent.
1. A compound having the structural formula ##STR13## wherein: R and R.sup.5 independently represent hydrogen, non-tertiary C.sub.1 to C.sub.4 alkyl, non-tertiary C.sub.1 toC.sub.4 alkoxy, halogen or nitro;
R.sup.1 represents hydrogen; C.sub.1 to C.sub.12 alkyl; C.sub.4 to C.sub.8 cycloalkyl; C.sub.1 to C.sub.12 alkyl substituted with halogen, non-tertiary C.sub.1 to C.sub.4 alkoxy, phenyl, phenoxy or non-tertiary C.sub.1 to C.sub.4alkoxycarbonyl; phenyl; naphthyl; or phenyl substituted by one to three of non-tertiary C.sub.1 to C.sub.4 alkyl, non-tertiary C.sub.1 to C.sub.4 alkoxy, nitro, halo, phenyl, cyano, or trihalomethyl;
R.sup.2 represents hydrogen; non-tertiary C.sub.1 to C.sub.4 alkyl; phenyl; phenyl substituted by one or two of halo, nitro, non-tertiary C.sub.1 to C.sub.4 alkyl or non-tertiary C.sub.1 to C.sub.4 alkoxy; benzyl; or benzyl substituted inthe benzene ring by one or two of halo, nitro, non-tertiary C.sub.1 to C.sub.4 alkyl or non-tertiary C.sub.1 to C.sub.4 alkoxy; and
R.sup.3 and R.sup.4 independently represent non-tertiary C.sub.1 to C.sub.4 alkyl; phenyl; phenyl substituted by one or two of halo, nitro, non-tertiary C.sub.1 to C.sub.4 alkyl or non-tertiary C.sub.1 to C.sub.4 alkoxy; benzyl; or benzylsubstituted in the benzene ring by one or two of halo, nitro, non-tertiary C.sub.1 to C.sub.4 alkyl or non-tertiary C.sub.1 to C.sub.4 alkoxy.
2. 3-(N-Acetyl-N-methylamino)-7-(dimethylamino)-10-acetylphenothiazine according to claim 1.
3. 3-[N-(4-Methoxyphen ylcarbonyl)-N-methylamino]-7-(dimethylamino)-10-(4-methoxyphenylcarbonyl)ph enothiazine according to claim 1.
4. 3-(N-Propylcarbonyl-N-methylam ino)-7-(dimethylamino)-10-propylcarbonylphenothiazine according to claim 1.
5. 3-[N-(4-Methylphenylcarbonyl)-N-methylamino]-7-(dimethylamino)-10-(4-met hylphenylcarbonyl)phenothiazine according to claim 1.
6. 2-Methyl-3-(N-acetyl-N-methylamino)-7-(dimethylami no)-10-acetylphenothiazine according to claim 1.
This invention relates to novel compounds classified in the field of organic chemistry as phenothiazines and phenoxazines, useful as color-forming substances; particularly in the art of electrochromic recording; to electrochromic recordingsystems containing said compounds; and to processes for preparing said compounds.
Several classes of organic compounds of widely diverse structural types are known to be useful as colorless precursors for electrochromic recording. Among the more important classes, there may be named leuco-type dyestuffs such as: phthalides,for example, crystal violet lactone, Malachite green lactone; fluorans, for example, 3-diethylamino-5,7-dimethylfluoran; and indolinobenzospirorans, for example, 1,3,3-trimethyl-6'-chloro-8'-methoxyindolinobenzospiropyrans. Also utilized as colorlessprecursors for electrochromic recording, either alone or in admixture with the leuco compounds indicated above, are substances known as redox indicators. The redox indicator which becomes colored in situ in the electrochromic recording process also isgenerally a leuco compound. Among the types of compounds which are applicable as redox indicators are phenothiazines, for example, leuco methylene blue and benzoyl leuco methylene blue. Other specific indicators are Leucoethyl Nile Blue, LeucomethylCapryl Blue and Leucosafranine T. Typical of the many such electrochromic recording systems taught in the prior art are those described in U.S. Pat. Nos. 3,726,769, 3,871,972, 3,864,684, 4,017,366, 4,133,933, and Reissue U.S. Pat. No. Re. 29,427which issued Apr. 10, 1973, Mar. 18, 1975, Feb. 4, 1975, Apr. 12, 1977, Jan. 9, 1979, and Oct. 4, 1977, respectively. The methods for electrochromic recording taught in the prior art have many variations. Basically, a sheet of paper is coated ortreated on one or both sides with a coating formulation containing at least one colorless color-forming (leuco) compound. Electrical current is then selectively applied to the coated side of the paper by some means, for example, a stylus or a printinghead to which an electrical potential can be applied. The application of the current causes an electrochromic reaction involving the leuco compound to produce a visible image corresponding to the design traced by the stylus or that of the printing head.
U.S. Pat. No. 2,909,520, issued Oct. 20, 1959, discloses compounds having the formula ##STR1## in which R is a phenyl or naphthyl moiety substituted with one or more of the following moieties: alkyl, alkoxy, halo, nitro, haloalkyl,alkoxycarbonyl, phenyl, and phenylalkoxy. These compounds are disclosed as being useful as blue color formers in carbonless carbon papers, i.e., carbonless duplicating systems.
Japanese Patent Publication No. 80,040,798, published Mar. 22, 1980, discloses thionines having the structural formula ##STR5## in which R.sub.1 and R.sub.2 represent hydrogen or methyl; R and X represent halogen; Z represents (CH.sub.2).sub.3to 12 ; n represents zero to one; m represents one or two; and m+n equals two. The compounds are disclosed as being monomers for reaction with polyethyleneimine to obtain a green-blue solid which is swellable by water and N,N-dimethylformamide.
Japanese Patent Publication No. 48,052,778, published July 24, 1973, discloses phenoxazines having the structural formula ##STR6## wherein there may be a tertiary amino group such as dimethylamino, diethylamino, ethylbenzylamino,methylphenylamino, methylcyclohexylamino, di(.beta.-cyanoethyl)amino, di(.beta.-chloroethyl)amino, morpholino, piperidino, pyrrolidino, etc., at position 7, ring A and ring B may be substituted by a lower alkyl having no more than 4 carbon atoms,allyl-substituted methyl such as bis(p-dimethylaminophenyl)methyl, etc., halogen, hydroxyl, alkoxy such as methoxy, benzyloxy, phenoxy, .beta.-chloroethyloxy, etc., acyloxy such as acetoxy, benzoyloxy, etc., primary amino, secondary amino such asmethylamino, ethylamino, benzylamino, cyclohexylamino, etc., acylamino such as acetamino, benzoylamino, N-benzyl-benzoylamino, etc., carboxyl, carbamoyl, alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, etc., or acyl such as acetyl, benzoyl, etc.,groups, or ring B may have groups that form rings bonded at positions 1 and 2, positions 2 and 3, or positions 3 and 4, e.g., --CH.dbd.CH--CH.dbd.CH-- or --O--CH.sub.2 --C--, etc., and R represents an alkyl having no more than 17 carbon atoms, asubstituted or unsubstituted vinyl such as vinyl, propenyl, styryl, etc., substituted methyl such as chloromethyl, cyanomethyl, benzyl, aryl, etc., aryl such as phenyl, tolylanisyl, xylyl, chlorophenyl, nitrophenyl, naphthyl, etc., or a nitrogen-,oxygen-, or sulfur-containing five-membered or six-membered heterocycle such as pyridyl, furyl, thienyl, etc. The compounds are disclosed as being useful as a color former in pressure-sensitive carbonless duplicating paper.
In its composition of matter aspect, the invention relates to certain 3-(N--R.sup.2 --N-acylamino)-7-(N--R.sup.3 --N--R.sup.4 -amino)-10-acylphenothiazines and phenoxazines useful as colorless precursors in electrochromic recording systems.
The present invention provides in its article of manufacture aspect, a substrate for use in electrochromic recording systems comprising a support sheet containing as a color-forming substance 3-(N--R.sup.2 --N-acylamino)-7-(N--R.sup.3--N--R.sup.4 -amino)-10-acyl-phenothiazines and phenoxazines.
In its process aspect, the invention relates to a process for producing 3-(N--R.sup.2 --N-acylamino)-7-(N--R.sup.3 --N--R.sup.4 -amino)-10-acyl-phenothiazines and phenoxazines which comprises interacting the corresponding 3-(N--R.sup.2-amino)-7-(N--R.sup.3 --N--R.sup.4 -amino)phenothiazinium or phenoxazinium halide with a reducing agent to obtain the corresponding leuco compound and subsequently interacting the leuco compound with at least two molecular proportions of an acylatingagent.
More specifically, this invention in its composition of matter aspect resides in the novel compounds having the structural formula ##STR7## wherein R and R.sup.5 independently represent non-tertiary C.sub.1 to C.sub.4 alkyl, non-tertiary C.sub.1to C.sub.4 alkoxy, halogen or nitro; R.sup.1 represents hydrogen; C.sub.1 to C.sub.12 alkyl; C.sub.4 to C.sub.8 cycloalkyl; C.sub.1 to C.sub.12 alkyl substituted by halogen, non-tertiary C.sub.1 to C.sub.4 alkoxy, phenyl, phenoxy, or non-tertiary C.sub.1to C.sub.4 alkoxycarbonyl; phenyl; naphthyl; or phenyl substituted by one to three of non-tertiary C.sub.1 to C.sub.4 alkyl, non-tertiary C.sub.1 to C.sub.4 alkoxy, nitro, halo, phenyl, cyano or trihalomethyl; R.sup.2 represents hydrogen; non-tertiaryC.sub.1 to C.sub.4 alkyl; phenyl; phenyl substituted by one or two of halo, nitro, non-tertiary C.sub.1 to C.sub.4 alkyl or non-tertiary C.sub.1 to C.sub.4 alkoxy; benzyl; or benzyl substituted in the benzene ring by one or two of halo, nitro,non-tertiary C.sub.1 to C.sub.4 alkyl or non-tertiary C.sub.1 to C.sub.4 alkoxy; R.sup.3 and R.sup. 4 represent hydrogen; non-tertiary C.sub.1 to C.sub.4 alkyl; phenyl; phenyl substituted by one or two of halo, nitro, non-tertiary C.sub.1 to C.sub.4alkyl or non-tertiary C.sub.1 to C.sub.4 alkoxy; benzyl; or benzyl substituted in the benzene ring by one or two of halo, nitro, non-tertiary C.sub.1 to C.sub.4 alkyl or non-tertiary C.sub.1 to C.sub.4 alkoxy; and X represents S or O.
Particular embodiments within the ambit of the composition of matter aspect are the novel 1/2-R-3-[N(R.sup.1 --CO)--N--R.sup.2 -amino]-7-(N--R.sup.3 --N--R.sup.4 -amino)-8/9-R.sup.5 -10-(R.sup.1 --CO)-phenothiazines of Formula I wherein X is Shaving the formula ##STR8## in which R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the same respective meanings given in Formula I.
Other particular embodiments with the ambit of the composition of matter aspect are the novel 1/2-R-3-[N--(R.sup.1 --CO)--N--R.sup.2 -amino]-7-(N--R.sup.3 --N--R.sup.4 -amino)-8/9--R.sup.5 --10-(R.sup.1 --CO)-phenoxazines of Formula I wherein Xis O having the structural formula ##STR9## in which R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the same respective meanings given in Formula I.
In its process aspect, the invention sought to be patented resides in the process for preparing a compound according to Formula I having the structural formula ##STR10## which comprises in the first step interacting a compound having thestructural formula ##STR11## with a reducing agent to obtain the corresponding leuco compound having the structural formula ##STR12## and in a second step, interacting the leuco compound with at least two molecular proportions of an acylating agenthaving the structural formula
In its article of manufacture aspect, the invention sought to be patented resides in a substrate for use in electrochromic recording comprising a support sheet containing as a color-forming substance a phenothiazine or phenoxazine having thestructure of Formula I.
A particular embodiment within the ambit of the article of manufacture aspect is the substrate for use in electrochromic recording comprising a support sheet containing as a color-forming substance a 1/2-R-3-[N--(R.sup.1 --CO)--N--R.sup.2-amino]-7-(N--R.sup.3 --N--R.sup.4 -amino)-8/9-R.sup.5 -10-(R.sup.1 --CO)-phenothiazine of Formula II wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the same respective meanings given in Formula II.
In a second particular embodiment within the ambit of its article of manufacture aspect is the substrate for use in electrochromic recording comprising a support sheet containing as a color-forming substance a 1/2-R-3-[N--(R.sup.1--CO)--N--R.sup.2 -amino]-7-(N--R.sup.3 --N--R.sup.4 -amino)-8/9-R.sup.5 -10-(R.sup.1 --CO)-phenoxazine of Formula III wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the same respective meanings given in Formula III.
As used herein the terms "non-tertiary C.sub.1 to C.sub.4 alkyl" and "non-tertiary C.sub.1 to C.sub.12 alkyl" denote saturated monovalent straight or branched aliphatic hydrocarbon radicals including methyl, ethyl, propyl, isopropyl, butyl,isobutyl, amyl, 1-methylbutyl, 3-methylbutyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, 3-ethylheptyl, n-decyl, n-undecyl, n-dodecyl and the like.
As used herein the terms "halo" and "halogen" include chloro, fluoro, bromo and iodo. Chloro is the preferred halo substituent because of the relatively low cost and ease of preparation of the required chloro-substituted intermediates andbecause the other halogens offer no particular advantages over chloro. However, the other above-named halo substituents are also satisfactory.
The phenothiazinium and phenoxazinium dyes which are used as intermediates or starting materials for the compounds of Formula I are generally known dyestuffs readily prepared by procedures well known in the dyestuff art. Four references to thepreparation of the phenothiazine and phenoxazine dyestuffs are: (a) Journal of the Society of Dyers and Colourists 4, 39 (1888); (b) Liebig's Annalen der Chemie 251, 1 (1889); (c) Chemische Berichte 25, 3128 (1892); (d) FIAT Final Report No. 1313 and PBReport 85172, vol. II, p. 372.
The acylating agents of Formula VI may be either aliphatic acid anhydrides (Z=R.sup.1 COO) or acid halides (Z=halo, preferably chloro), both of which constitute well known classes of compounds many of which are commercially available or arereadily obtained by conventional synthesis well known in the art. The following list exemplifies aliphatic acid anhydrides and acid halides useful in carrying out the processes of this invention. Acetic anhydride, chloroacetic anhydride, dichloroaceticanhydride, trifluoroacetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, hexanoic anhydride, hepanoic anhydride, acetyl bromide, acetyl chloride, acetyl fluoride, bromoacetyl bromide, bromoacetyl chloride,chloroacetyl chloride, methoxyacetyl chloride, propionyl chloride, 2-bromopropionyl chloride, 3-bromopropionyl chloride, 2-chloropropionyl chloride, 3-chloropropionyl chloride, butyryl chloride, 4-chlorobutyryl chloride, 2-ethylbutyryl chloride,isobutyryl chloride, valeryl chloride, 5-chlorovaleryl chloride, isovaleryl chloride, 4-methylvaleryl chloride, hexanoyl chloride, 6-bromohexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, decanoyl chloride, 10-undecanoylchloride, palmitoyl chloride, myristoyl chloride, lauroyl chloride, cyclopropyl carboxylic acid chloride, cyclobutane carboxylic acid chloride, cyclohexyl carboxylic acid chloride, m-anisoyl chloride, p-anisoyl chloride, benzoyl bromide, benzoylchloride, benzoyl fluoride, 4-biphenylcarbonyl chloride, 2-bromobenzoyl chloride, 4-bromobenzoyl chloride, 4-butoxybenzoyl chloride, 4-butylbenzoyl chloride, 2-chlorobenzoyl chloride, 3-chlorobenzoyl chloride, 4-chlorobenzoyl chloride, 4-cyanobenzoylchloride, 2,4-dichlorobenzoyl chloride, 2,6-dichlorobenzoyl chloride, 3,4-dichlorobenzoyl chloride, 3,5-dimethoxybenzoyl chloride, 3,4-dimethoxybenzoyl chloride, 3,5-dinitrobenzoyl chloride, 2-fluorobenzoyl chloride, 3-fluorobenzoyl chloride,4-fluorobenzoyl chloride, 3-nitrobenzoyl chloride, 4-nitrobenzoyl chloride, 2-methoxybenzoyl chloride, 3-methylbenzoyl chloride, 4-methylbenzoyl chloride, 2-iodobenzoyl chloride, 4-iodobenzoyl chloride and 4-trifluoromethylbenzoyl chloride.
The compounds of Formula I hereinabove are essentially colorless in the depicted form. When contacted with an electric current from an applied voltage stylus of the type ordinarily employed in electrochromic recording systems, the compounds ofFormula I develop green, green-black, black and blue-black-colored images. These developed images are very insensitive to light, that is, once the color is developed, it remains unchanged when subjected to light exposure. The developed images alsopossess excellent xerographic reproducibility.
The compounds of this invention may be incorporated in any of the commercially-accepted systems known in the electrochromic recording art. Typical techniques for the application of the color formers to paper are well known and are described innumerous patents, for example, U.S. Pat. Nos. Re. 29,427; 3,726,769; 3,864,684; 3,871,972; 3,951,757; 4,017,366; and 4,133,933. The usual paper coatings consist of the color-forming component, an organic metal salt, a binder and some type ofconductor, either an inorganic salt or a conductive polymer. This mixture is milled together optionally in the presence of a non-ionic surface active agent until the desired particle size is obtained and then the mixture is coated on paper and dried. Optionally, the color-forming substance can be milled in the presence of a binder and the remaining components milled also in the presence of a binder and the two mixtures combined together prior to coating on paper. Normally the surface of the coatedpaper is wet with a conductive solution containing an inorganic alkaline metal or alkaline earth metal salt, for example, potassium chloride, calcium chloride, sodium chloride, sodium bromide, potassium bromide, potassium nitrate or sodium sulfateimmediately prior to the printing with the applied voltage stylus. For a quick qualitative test, it has been determined that the color-forming component can be dissolved in a suitable volatile organic solvent, coated on paper and the coated paper driedto obtain a paper sheet coated with the color-forming component. This coated sheet can then be wet with a conductive salt solution and an image traced with an applied voltage stylus to develop the colored image.
The compounds of Formula I can be used alone as color-forming components in electrochromic recording paper or can be used in admixture with one or more other color-forming compounds from the classes consisting of phthalides, for example, CrystalViolet Lactone; fluorans, for example, 3-diethylamino-5,7-dimethylfluoran; redox indicators, for example, phenothiazines such as benzoyl leuco methylene blue and various other types of color-forming components currently employed in commercially-acceptedelectrochromic recording systems.
In accordance with the aforementioned process aspects of this invention, the compounds of Formula I are obtained by reacting one molecular proportion of a leuco compound of Formula V with at least two molecular proportions of an acylating agentof Formula VI. When using an anhydride as the acylating agent, the reaction is conveniently carried out in an excess of the acylating agent which is utilized as both the reaction medium and as the reactant. Optionally a small amount of an organic base,for example, pyridine may be used as a catalyst. The reaction is conveniently carried out at a temperature in the range of 90.degree. C. to reflux of the mixture for periods of approximately thirty minutes to approximately four hours. The compounds ofFormula I thus obtained are isolated by pouring the reaction mixture into ice water and extracting the desired products into a suitable water immiscible organic liquid, for example, toluene. The organic liquid layer containing the product issubsequently washed with water to remove inorganic salts and water-soluble organics and then treated with decolorizing charcoal, if desired. The resulting organic liquid solution of the product is then concentrated by conventional means such asevaporation or distillation.
Alternatively, the compounds of Formula I can be obtained also by reacting approximately one molecular proportion of a leuco compound of Formula V with about two molecular proportions of an acyl halide of Formula VI (Z=halo). A solution of theleuco compound dissolved in an organic liquid is cooled to a temperature in the range of 60.degree. to 80.degree. C. and disodium phosphate and acyl halide, dissolved in the same organic liquid, is added. The reaction is conveniently carried out atthe reflux temperature of the mixture for periods of approximately fifteen minutes to approximately nineteen hours. Water and additional disodium phosphate are added to the reaction mixture and the resulting mixture is heated at reflux temperature for aperiod of approximately thirty minutes to approximately one hour. The organic liquid solution containing the desired product is separated from the water layer, washed with water and concentrated by conventional means such as evaporation or distillation. The isolated product can be purified by conventional means such as recrystallization or reslurrying with a suitable organic liquid and then collected by filtration. Purification can also be effected by column chromatography. The material to be purifiedis dissolved in a suitable organic liquid and the solution is passed through a chromatography column which has been packed with a suitable substrate, for example, silica gel, cellulose, alumina and the like. Numerous fractions are collected and analyzedto determine fraction(s) containing the desired product. The fraction(s) which contain the desired product are then combined (if more than one) and concentrated to obtain the product. The leuco compound of Formula V is conveniently prepared by reducingthe corresponding phenothiazinium or phenoxazinium halide dyestuff of Formula IV with a reducing agent, for example, zinc dust. This reaction is conveniently carried out in an excess of the alkanoic anhydride acylating agent thus resulting in no needfor an inert organic liquid reaction medium. Alternatively, the leuco compound of Formula V is conveniently prepared by reducing the corresponding phenothiazinium halide or phenoxazinium halide of Formula IV with a reducing agent, for example, analkaline hydrosulfite. The reaction in which the leuco compound is prepared is conveniently carried out in a mixture of water and a suitable water immiscible organic liquid, for example, toluene or xylene in an inert atmosphere, for example, nitrogen. The reaction is carried out in the presence of an alkaline substance, for example, sodium carbonate or disodium phosphate using, as the reducing agent, an alkali hydrosulfite, for example, sodium hydrosulfite. The reaction is conveniently carried out atambient temperature for a period of approximately fifteen minutes to approximately two hours. The organic liquid solution which contains the leuco compound is separated from the water layer. Additional alkali hydrosulfite is added to the organic liquidsolution and the resulting mixture is azeotroped to remove the remaining traces of water. The resulting solution can be used directly in the acylating step of the process.
A mixture of 10.0 g of Azure B (Aldrich) 7-(dimethylamino)-3-(methylamino)phenothiazin-5-ium chloride, 75.0 ml of 90 percent formic acid, 5.0 g of zinc dust and 5.0 ml of pyridine was maintained at approximately 90.degree. C. for approximatelythree hours. The reaction mixture was cooled to room temperature and filtered, saving the filtrate. The filter cake was washed twice, each time with 50.0 ml of acetone, and the washes combined with the filtrate. The combined filtrate and washes waspoured into ice water with stirring. The resulting solution was extracted with toluene. The toluene solution was separated, treated with decolorizing carbon, filtered and the resulting solution was evaporated under reduced pressure to obtain a gummyresidue. The gummy residue was titurated with a 1:1 (V:V) mixture of isopropyl alcohol and hexane. The solid which formed was collected by filtration and dried to obtain 0.14 g of 7-(dimethylamino)-3-(N-formyl-N-methylamino)-10-formylphenothiazine(Formula II: R.dbd.R.sup.1 .dbd.R.sup.5 .dbd.H; R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3), an off-white-colored powder which melted at 139.degree. to 143.degree. C. A significant infrared maximum appeared at 1685 cm.sup.-1 (C.dbd.O; s). A papertreated with an ink formulation of the product produced a black-colored image when traced with an applied voltage stylus.
A mixture of 9.0 g of 7-(dimethylamino)-3-methylamino-2-methyl-phenothiazin-5-ium chloride, 150.0 ml of acetic anhydride and 10.0 g of zinc dust was maintained at reflux temperature for approximately four hours. After the reaction mixture wascooled to ambient temperature, it was poured into ice water with stirring and toluene was added. After stirring for approximately one-half hour, the toluene layer was separated and washed twice, once with tap water and once with saturated aqueous sodiumchloride solution. The toluene was then removed at reduced pressure. The residue which remained was dissolved in ethyl acetate and separated into various components by subjecting the solution to column chromatography using silica gel as the substrate. The fourth and fifth fractions were combined and the ethyl acetate evaporated to obtain 3.79 g of 7-(dimethylamino)-3-(N-acetyl-N-methylamino)-2-methyl-10-acetylphenothiazi ne (Formula II: R.dbd.2--CH.sub.3 ; R.sup.1 .dbd.R.sup.2 .dbd.R.sup.3.dbd.R.sup.4 .dbd.CH.sub.3 ; R.sup.5 .dbd.H), a white-colored solid which melted over the range of 148.degree. to 161.degree. C. A significant infrared maximum appeared at 1665 cm.sup.-1 (C.dbd.O; s). A significant maxima appeared in the mass spectrumat 369 (M.sup.+) and 326 (M.sup.+ --CH.sub.3 CO). Paper treated with an ink formulation of the product produced a black-colored image when traced with an applied voltage stylus.
The reaction vessel was purged of residual air with nitrogen and, while maintaining a nitrogen atomsphere, there was placed in the vessel, 10.0 g of Azure B (Aldrich) 7-(dimethylamino)-3-(methylamino)-phenothiazin-5-ium chloride, 500.0 ml ofwater and 500.0 ml of toluene. With stirring, there was added to the resulting mixture, 10.0 g of sodium carbonate and 15.0 g of sodium hydrosulfite. The resultant mixture was stirred for approximately fifteen minutes at ambient temperature and thewater layer was separated and discarded. To the toluene layer, 10.0 g of sodium hydrosulfite was added and the resulting mixture was heated at reflux temperature until all of the water was azeotroped from it. After the mixture dried, it was cooled toapproximately 70.degree. C. and 15.0 g of disodium phosphate was added. To this mixture, there was added a solution of 20.0 ml of 4-methylbenzoyl chloride dissolved in 30.0 ml of toluene. The reaction mixture was heated at reflux temperature forapproximately two and one-half hours. After cooling the resulting mixture to ambient temperature, 500.0 ml of water and 15.0 g of disodium phosphate was added. This mixture was then refluxed for approximately one-half hour and then cooled to roomtemperature. The toluene layer was separated and saved and the water layer discarded. The toluene layer was washed twice, each time with 400.0 ml of water, once with 400.0 ml of aqueous saturated sodium carbonate solution, then with 400.0 ml of waterand finally with 400.0 ml of aqueous saturated sodium chloride solution. All of the aqueous washes were discarded. The toluene layer was then evaporated to dryness under reduced pressure. The residue was reslurried in a mixture of 200.0 ml ofisopropyl alcohol, 100.0 ml of water and 20.0 g of disodium phosphate at approximately 80.degree. C. for approximately ten minutes. After cooling, the solid was collected by filtration and dried to obtain 8.24 g of7-(dimethylamino)-3-[N-(4-methylphenylcarbonyl)-N-methylamino]-10-(4-methy lphenylcarbonyl)-phenothiazine (Formula II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd.4--CH.sub.3 C.sub.6 H.sub.4 ; R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3), a white powder whichmelted at 220.degree. to 224.degree. C. Significant infrared maxima were observed at 1670 cm.sup.-1 (C.dbd.O; s) and 1660 cm.sup.-1 (C.dbd.O; s). The nuclear magnetic resonance spectrum was in accord with the assigned structure. Paper treated with anink formulation of the product produced a black-colored image when traced with an applied voltage stylus.
Proceeding in a manner similar to that described in Example 2 above, the appropriate phenothiazinium or phenoxazinium halide described in the second column of Part 1 of Table A hereinbelow was reduced in the reaction medium indicated in the thirdcolumn of Part 1 with the reducing agent listed in column 4 and subsequently acylated with the acylating agent given in the fifth column of Part 1 at the temperature indicated in column 6 for the period of time specified in the seventh column of Part 1. The product obtained is given in the second column of Part 2 of Table A having the structural formula referred to in the third column of Part 2 with its physical appearance described in the fourth column of Part 2. Its melting point is shown in thefifth column of Part 2, significant infrared is shown in the sixth column of Part 2, and nuclear magnetic resonance spectral analysis is shown in the seventh column of Part 2. The color produced when a paper sheet treated with an ink formulationcontaining the product was treated with an applied voltage stylus is described in the eighth column of Part 2.
TABLE A __________________________________________________________________________ Exam- ple Temper- Reaction No. Starting Material Reaction Medium Reducing Agent Acylating Agent ature Time __________________________________________________________________________ 4 8.0 g 7-(Dimethylamino)-3- 100.0 ml Acetic 10.0 g Zinc 100.0 ml Acetic Reflux 0.5 Hour (methylamino)phenothi- anhydride dust anhydride azin-5-ium bromide 10.0 ml Pyridine 5 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 27.6 ml 2-Naph- Reflux 2 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- thoic acid azin-5-ium chloride sulfite chloride 6 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 20.0 ml Benzoyl Reflux 2 Hours (methylamino)-2-bromo- 500.0 ml Toluene hydro- chloride phenothiazin-5-ium sulfite chloride 7 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 20.0 g Diphenyl- Reflux 2.5 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- acetyl azin-5-ium chloride sulfite chloride 8 9.0 g 7-(Dibutylamino)-3- 75.0 ml Acetic 5.0 g Zinc 75.0 ml Acetic Reflux 1.5 Hours (methylamino)phenothi- anhydride dustanhydride azin-5-ium chloride 5.0 ml Pyridine 9 6.0 g 7-(Dimethylamino)-3- 80.0 ml Acetic 4.0 g Zinc 80.0 ml Acetic Reflux 0.5 Hour (ethylamino)phenothi- anhydride dust anhydride azin-5-ium chloride zinc chloride double salt 10 8.0 g 7-(Diethylamino)-3- 80.0 ml Acetic 4.0 g Zinc 80.0 ml Acetic Reflux 0.5 Hour (methylamino)phenothi- anhydride dust anhydride azin-5-ium chloride zinc chloride double salt 11 8.0 g 7-(Diethylamino)-3- 400.0 ml Water 25.0 g Sodium 30.0 ml Benzoyl Reflux 18 Hours (methylamino)phenothi- 400.0 ml Toluene hydro- chloride azin-5-ium chloride sulfite zinc chloride double salt 12 8.0 g 7-(Dimethylamino)-3- 400.0 ml Water 25.0 g Sodium 30.0 ml Benzoyl Reflux 19 Hours (methylamino)phenothi- 400.0 ml Toluene hydro- chloride azin-5-ium chloride sulfite zinc chloride double salt 13 5.0 g 7-(Dimethylamino)-3- 250.0 ml Water 15.0 g Sodium 10.0 g Methoxy- Reflux 2.5 Hours (methylamino)phenothi- 250.0 ml Toluene hydro- acetyl azin-5-ium chloride sulfite chloride 14 6.43 g 7-(N--Benzyl-N--ethyl- 65.0 ml Acetic 6.5 g Zinc 65.0 ml Acetic Reflux 0.5 Hour amino)-3-(methylamino)- anhydride dust anhydride phenothiazin-5-ium chloride 15 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 25.0 g 2,6-Di- Reflux 2.5 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- fluoro- azin-5-ium chloride sulfite benzoyl chloride __________________________________________________________________________ Exam- ple Physical Melting Significant Produced No. Product Name Product Formula Appearance Point Infrared NMR Image __________________________________________________________________________ Color 4 1.85 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. White 147- 1690 cm.sup.-1 Consistent Black acetyl-N--methylamino)- R.sup.2 .dbd.R.sup.3.dbd.R.sup.4 .dbd.CH.sub.3 Powder 155.degree. C. (C.dbd.O;s) 10-acetylphenothiazine 5 0.16 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Tan 117- 1650 cm.sup.-1 Black
2-naphthylcarbonyl-N-- 2-C.sub.10 H.sub.7 ; R.sup.2 .dbd.R.sup.3 .dbd. Powder 122.degree. C. (C.dbd.O;s) methylamino)-10-(2- R.sup.4 .dbd.CH.sub.3 naphthylcarbonylpheno- thiazine 6 1.39 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5.dbd.H; R.sup.1 .dbd. Pale 79- 1655 cm.sup.-1 Blue- benzoyl-N--methylamino)- C.sub.6 H.sub.5 ; Green- 84.degree. C. (C.dbd.O;s) black 10-benzoylphenothiazine R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 yellow Powder 7 1.3 g7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Tan 78- 1660 cm.sup.-1 Consistent Black diphenylacetyl-N--methyl- 4-C.sub.6 H.sub.5 C.sub.6 H.sub.4 ; R.sup.2 Powder 86.degree. C. (C.dbd.O;s) amino)-10-diphenylacetyl- R.sup.3.dbd.R.sup.4 .dbd.CH.sub.3 phenothiazine 8 0.86 g 7-(Dibutylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Brown -- 1670 cm.sup.-1 Black acetyl-N--methylamino)- R.sup.2 .dbd.CH.sub.3 ; R.sup.3 .dbd.R.sup.4 Gumd. (C.dbd.O;s) 10-acetylphenothiazine C.sub.4 H.sub.9 9 0.52 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Yellow 107- 1675 cm.sup.-1 Green- acetyl-N--ethylamino)- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 ; R.sup.2 Powder 110.degree. C. (C.dbd.O;s) black 10-acetylphenothiazine C.sub.2 H.sub.5 10 1.0 g 7-(Diethylamino)-3-(N-- II: R.dbd. R.sup.5 .dbd.H; R.sup.1 .dbd. Tan 92.5- 1665 cm.sup.-1 Consistent Green- acetyl-N--methylamino)- R.sup.2 .dbd.CH.sub.3 ; R.sup.3 .dbd.R.sup.4 Powder 97.degree. C. (C.dbd.O;s) black 10-acetylphenothiazine C.sub.2 H.sub.5 11 1.04 g 7-(Diethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Brown -- 1660 cm.sup.-1 Black benzoyl-N--methylamino)- C.sub.6 H.sub.5 ; R.sup.2.dbd.CH.sub.3 ; Gum (C.dbd.O;s) 10-benzoylphenothiazine R.sup.3 .dbd.R.sup.4 .dbd.C.sub.2 H.sub.5 12 1.0 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Brown 100- 1650 cm.sup.-1 Black benzoyl-N--ethylamino)- C.sub.6 H.sub.5; R.sup.2 .dbd.C.sub.2 H.sub.5 Powder 130.degree. C. (C.dbd.O;s) 10-benzoylphenothiazine R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 13 3.54 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Brown -- 1667 cm.sup.-1 Consistent Black methoxyacetyl-N--methyl- CH.sub.3 OCH.sub.2 ; Gum (C.dbd.O;s) amino)-10-methoxyacetyl- R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 phenothiazine 14 0.52 g 7-(N--Benzyl-N--ethyl- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Brown 65- 1670cm.sup.-1 Black amino)-3-(N--acetyl-N-- R.sup.2 .dbd.CH.sub.3 ; R.sup.3 .dbd. Powder 69.degree. C. (C.dbd.O;s) methylamino)-10-ace- C.sub.6 H.sub.5 CH.sub.2 ; R.sup.4 .dbd. tylphenothiazine C.sub.2 H.sub.5 15 3.60 g 7-(Dimethylamino)-3- II:R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Pale 106- 1670 cm.sup.-1 Black [N--(2,6-difluoroben- 2,6-F.sub.2 C.sub.6 H.sub.3 ; R.sup.2 .dbd. Brown 112.degree. C. (C.dbd.O;s) zoyl)-N--methylamino]-10- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Powder (2,6-difluorobenzoyl)- phenothiazine __________________________________________________________________________
Proceeding in a manner similar to that described in Example 3 above, the appropriate phenothiazinium halide described in the second column of Part 1 of Table B hereinbelow was reduced in the reaction medium indicated in the third column of Part 1with the reducing agent listed in column 4 and subsequently acylated with the acylating agent given in the fifth column of Part 1 at the temperature indicated in column 6 for the period of time specified in the seventh column of Part 1. The productobtained is given in the second column of Part 2 of Table B having the structural formula referred to in the third column of Part 2 with its physical appearance described in the fourth column of Part 2. Its melting point is shown in the fifth column ofPart 2, significant infrared in the sixth column of Part 2, and nuclear magnetic resonance spectral analysis is shown in the seventh column of Part 2. The color produced when a paper sheet treated with an ink formulation containing the product wastraced with an applied voltage stylus is described in the eighth column of Part 2.
TABLE B __________________________________________________________________________ Exam- ple Temper- Reaction No. Starting Material Reaction Medium Reducing Agent Acylating Agent ature Time __________________________________________________________________________ 16 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 20.0 ml 4-Methyl- Reflux 2.5 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- benzoyl azin-5-iumchloride sulfite chloride 17 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 20.0 ml 3-Nitro- Reflux 2 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- benzoyl azin-5-ium chloride sulfite chloride 18 10.0 g7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 20.0 ml Phenoxy- Reflux 2 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- acetyl azin-5-ium chloride sulfite chloride 19 6.0 g 7-(Dimethylamino)-3- 300.0 ml Water 12.0 g Sodium 10.0 g 4-Bromo- Reflux 19 Hours (methylamino)phenothi- 300.0 ml Toluene hydro- benzoyl azin-5-ium chloride sulfite chloride 20 6.0 g 7-(Dimethylamino)-3- 300.0 ml Water 12.0 g Sodium 10.0 g 4-Phenyl- Reflux 19 Hours (methylamino)phenothi- 300.0 ml Toluene hydro- benzoyl azin-5-ium chloride sulfite chloride 21 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 25.0 g Cyclohex- Reflux 2 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- anecarbox- azin-5-ium chloride sulfite ylic acid chloride 22 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 20.0 ml 2-Methyl- Reflux 2 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- benzoyl azin-5-ium chloride sulfitechloride 23 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 20.0 ml 2-Chloro- Reflux 2 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- benzoyl azin-5-ium chloride sulfite chloride 24 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 25.0 g 3,4,5-Tri- Reflux 2 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- methoxy- azin-5-ium chloride sulfite benzoyl chloride 25 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 20.0 ml 3-Carbo- Reflux 2 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- methoxy- azin-5-ium chloride sulfite propanyl chloride 26 5.0 g 7-(Dimethylamino)-3- 250.0 ml Water 5.0 g Sodium 5.0 g 4-Cyano- Reflux 2 Hours (methylamino)phenothi- 250.0 ml Toluene hydro- benzoyl azin-5-ium chloride sulfite chloride 27 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 10.0 g Sodium 25.0 ml Decanoyl Reflux 2 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- chloride azin-5-ium chloridesulfite 28 13.0 g 7-(Dimethylamino)-3- 400.0 ml Water 25.0 g Sodium 30.0 ml Benzoyl Reflux 4 Hours (methylamino)phenothi- 400.0 ml Toluene hydro- chloride azin-5-ium chloride sulfite 29 30.0 g 7-(Dimethylamino)-3- 1500.0 ml Water 30.0 g Sodium 50.0 ml 4-Anisoyl Reflux 2 Hours (methylamino)phenothi- 1500.0 ml Toluene hydro- chloride azin-5-ium chloride sulfite
30 5.0 g 7-(Dimethylamino)-3- 250.0 ml Water 7.5 g Sodium 15.0 g 3,4-Di- Reflux 2 Hours (methylamino)phenothi- 300.0 ml Toluene hydro- chloro- azin-5-ium chloride sulfite benzoyl chloride 31 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 15.0 g Sodium 20.0 g 2,4,6-Tri- Reflux 2.5 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- methyl- azin-5-ium chloride sulfite benzoyl chloride 32 10.0 g 7-(Dimethylamino)-3- 500.0 ml Water 15.0 g Sodium 20.0 g 2-Tri- Reflux 2.5 Hours (methylamino)phenothi- 500.0 ml Toluene hydro- fluorometh- azin-5-ium chloride sulfite ylbenzoyl chloride __________________________________________________________________________ Ex- am- ple Physical Melting SignificantProduced No. Product Name Product Formula Appearance Point Infrared NMR Image __________________________________________________________________________ Color 16 8.24 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. White220- 1670 cm.sup.-1 Consistent Black (4-methylphenylcarbon- 4-CH.sub.3 C.sub.6 H.sub.4 ; R.sup.2 .dbd. Powder 224.degree. C. (C.dbd.O;s) yl)-N--methylamino]-10- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 1660 cm.sup.-1 (4-methylphenylcarbon-(C.dbd.O;s) yl)phenothiazine 17 9.7 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Pale 85- 1665 cm.sup.-1 Black (3-nitrophenylcarbon- 3-NO.sub.2 C.sub.6 H.sub.4 ; R.sup.2 .dbd. Brown 100.degree. C. (C.dbd.O;s) yl)-N--methylamino]-10- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Powder (dec.) 1650 cm.sup.-1 (3-nitrophenylcarbon- (C.dbd.O;s) yl)phenothiazine 18 5.5 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 50 White 110.degree. C. 1690cm.sup.-1 Consistent Gray phenoxyacetyl-N--methyl- C.sub.6 H.sub.5 OCH.sub.2 ; R.sup.2 .dbd. Powder (dec.) (C.dbd.O;s) amino)-10-phenoxyace- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 1676 cm.sup.-1 tylphenothiazine (C.dbd.O;s) 19 8.5 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 50 Pale 178- 1650 cm.sup.-1 Black (4-bromophenylcarbonyl)- 4-BrC.sub.6 H.sub.4 ; R.sup.2 .dbd. Green 180.degree. C. (C.dbd.O;s) N--methylamino]-10-(4- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Powder 1665 cm.sup.-1 bromophenylcarbonyl)- (C.dbd.O;s) phenothiazine 20 3.1 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 50 Pale 165- 1662 cm.sup.-1 Consistent Black (4-phenylphenylcarbon- 4-C.sub.6 H.sub.5 C.sub.6 H.sub.5 ; Green.2 .dbd. 170.degree. C. (C.dbd.O;s) yl)-N--methylamino]-10- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Powder (dec.) 1645 cm.sup.-1 (4-phenylphenylcarbon- (C.dbd.O;s) yl)phenothiazine 21 7.7 g 7-(Dimethylamino)-3-N-- II: R.dbd.R.sup.5 .dbd.H;R.sup.1 .dbd. Pale -- 1662 cm.sup.-1 Black cyclohexylcarbonyl-N-- C.sub.6 H.sub.11 ; Yellow (C.dbd.O;s) methylamino)-10-cylco R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Gum hexylcarbonylphenothi- azine 22 12.1 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. White 211- 1667 cm.sup.-1 Black (2-methylphenylcarbon- 2-CH.sub.3 C.sub.6 H.sub.4 ; R.sup.2 .dbd. Powder 214.degree. C. (C.dbd.O;s) yl)-N--methylamino]-10- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 1650 cm.sup.-1 (2-methylphenylcarbon- (C.dbd.O;s) yl)phenothiazine 23 12.1 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. White 236- 1670 cm.sup.-1 Black (2-chlorophenylcarbon- 2-ClC.sub.6 H.sub.9 ; R.sup. 2 .dbd. Powder 243.degree. C. (C.dbd.O;s) yl)-N--methylamino]-10- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 1652 cm.sup.-1 (2-chlorophenylcarbon- (C.dbd.O;s) yl)phenothiazine 24 14.2 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Pale Tarry 1663 cm.sup.-1 Black (3,4,5-trimethoxyphen- 3,4,5-(CH.sub.3 O).sub.3 C.sub.6 H.sub.2 ; Brown (C.dbd.O;s) ylcarbonyl)-N--methyl- R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Powder 1650 cm.sup.-1 amino]-10-(3,4,5-tri- (C.dbd.O;s) methylphenylcarbonyl)- phenothiazine 25 14.2 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; Pale -- 1740 cm.sup.-1 Black (3-carbomethoxypropyl- R.sup.1 .dbd.3- Yellow (C.dbd.O;s) carbonyl)-N--methyl- CH.sub.3 OCOC.sub.3 H.sub.6 ; R.sup.2 .dbd. Gum 1665cm.sup.-1 amino]-10-(3-carbometh- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 (C.dbd.O;s) oxypropylcarbonyl)pheno- thiazine 26 6.0 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Pale 139- 1648 cm.sup.-1 Black (4-cyanophenylcarbon- 4-CNC.sub.6 H.sub.4 ; Yellow 155.degree. C. (C.dbd.O;s) yl)-N--methylamino]-10- R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 (dec.) 1655 cm.sup.-1 (4-cyanophenylcarbon- (C.dbd.O;m) yl)phenothiazine 27 2.4 g 7-(Dimethylamino)-3-(N-- II:R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Pale -- 1670 cm.sup.-1 Black decanylcarbonyl-N--meth- C.sub.10 H.sub.21 ; Green (C.dbd.O;s) ylamino)-10-decanyl- R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Tar carbonylphenothiazine 28 1.84 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. White 235.degree. C. 1670 cm.sup.-1 Consistent Black phenylcarbonyl-N--meth- C.sub.6 H.sub.5 ;
Powder (C.dbd.O;s) ylamino)-10-phenyl- R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 1655 cm.sup.-1 carbonylphenothiazine (C.dbd.O;s) 29 26.9 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. White 228.5- (Mass Spectra Black (4-methoxyphenylcarbon- 4-CH.sub.3 OC.sub.6 H.sub.4 ; R.sup.2 .dbd. Powder 230.degree. C. and Elemental yl)-N--methylamino]-10- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Analysis Both (4-methoxyphenylcarbon- Consistent) yl)phenothiazine 30 4.5 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Yellow 223.5- 1670 cm.sup.-1 Consistent Black 3,4-dichlorophenylcarbon- 3,4-ClC.sub.6 H.sub.3 ; R.sup.2 .dbd. Powder 225.degree. C. (C.dbd.O;s) yl)-N--methylamino]-10- R.sup.3.dbd.R.sup.4 .dbd.CH.sub.3 1645 cm.sup.-1 (3,4-dichlorophenyl- (C.dbd.O;s) carbonyl)phenothazine 31 4.48 g 7-(Dimethylamino)-3-[N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Pale 192- 1635 cm.sup.-1 Consistent Black (2,4,6-trimethylphenyl- 2,4,6-(CH.sub.3).sub.3 C.sub.6 H.sub.2 ; Green 194.degree. C. (C.dbd.O;s) carbonyl)-N--methylamino] R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Powder 10-(2,4,6-trimethylphen- ylcarbonyl)phenothiazine 32 1.02 g 7-(Dimethylamino)-3-[N-- II:R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Pale 198- 1675 cm.sup.-1 Black (2-trifluoromethylphen- F.sub.3 CC.sub.6 H.sub.4 ; R.sup.2 .dbd.R.sup.3 Grey. 210.degree. C. (C.dbd.O;s) ylcarbonyl)-N--methyl- R.sup.4 .dbd.CH.sub.3 1663 cm.sup.-1 amino]-10-(2-trifluoro- (C.dbd.O;s) methylphenylcarbonyl)- phenothiazine __________________________________________________________________________
Proceeding in a manner similar to that described in Example 3 above, the appropriate phenothiazinium halide described in the second column of Part 1 of Table C hereinbelow was reduced in the reaction medium indicated in the third column of Part 1with the reducing agent listed in column 4 and subsequently acylated with the acylating agent given in the fifth column of Part 1 at the temperature indicated in column 6 for the period of time specified in the seventh column of Part 1. The productobtained is given in the second column of Part 2 of Table C having the structural formula referred to in the third column of Part 2 with its physical appearance described in the fourth column of Part 2. Its melting point is shown in the fifth column ofPart 2, significant infrared in the sixth column of Part 2, and nuclear magnetic resonance spectral analysis is shown in the seventh column of Part 2. The color produced when a paper sheet treated with an ink formulation containing the product wastraced with an applied voltage stylus is described in the eighth column of Part 2.
TABLE C __________________________________________________________________________ Example Temper- Reaction No. Starting Material Reaction Medium Reducing Agent Acylating Agent ature Time __________________________________________________________________________ 33 10.0 g 7-(Dimethylamino)-3- 5.0 ml Pyridine 5.0 g Zinc 50.0 ml Hexanoic 100- 2 Hours methylamino)pheno- 50.0 ml Hexanoic dust anhydride 110.degree. C. thiazin-5-ium anhydride chloride 34 10.0 g 7-(Dimethylamino)-3- 5.0 ml Pyridine 5.0 g Zinc 50.0 ml Butyric 100- 2 Hours methylamino)pheno- 50.0 ml Butyric dust anhydride 110.degree. C. thiazin-5-ium anhydride chloride 35 10.0 g7-(Dimethylamino)-3- 5.0 ml Pyridine 5.0 g Zinc 50.0 ml Trimethyl- 100- 3 Hours methylamino)pheno- 50.0 ml Trimethyl- dust acetic 105.degree. C. thiazin-5-ium acetic anhydride chloride anhydride 36 10.0 g 7-(Dimethylamino)-3- 5.0 ml Pyridine 5.0 g Zinc 25.0 g Trichloro- Reflux 3 Hours methylamino)pheno- 100.0 ml Acetone dust acetic thiazin-5-ium 25.0 g Trichloro- anhydride chloride acetic anhydride 37 10.0 g 2-Methyl-3-amino-7- 50.0 ml Acetic 10.0 g Zinc 50.0 ml Acetic 85-90.degree. 1. Hour dimethylaminopheno- Anhydride dust Anhydride thiazin-5-ium 10.0 ml Pyridine chloride 38 15.0 g 2-Methyl-3-amino-7- 400.0 ml Water 40.0 g Sodium 20.0 ml Benzoyl 60-65.degree. 1. Hour dimethylaminopheno- 400.0 ml Toluene Hydro- Chloride thiazin-5-ium sulfite chloride 39 10.0 g 2-Methyl-3-amino-7- 400.0 ml Water 30.0 g Sodium 25.0 ml Anisoyl Reflux 2.5 Hours dimethylaminopheno- 400.0 ml Toluene Hydro- Chloride thiazin-5-ium sulfite chloride 40 10.0 g 2-Methyl-3-amino-7- 75.0 ml Butyric 6.0 g Zinc 75.0 ml Butyric 70.degree. C. 4 Hours dimethylaminopheno- Anhydride Dust Anhydride thiazin-5-ium 10.0 ml Pyridine chloride __________________________________________________________________________ Example Physical Melting Significant Produced No. Product Name Product Formula Appearance Point Infrared NMR Image __________________________________________________________________________ Color 33 31.57 CH.sub.3 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Brown -- 1670 cm.sup.1 Consistent Black hexanoyl-N--methylamino)- C.sub.6 H.sub.13; Gummy (C.dbd.O;s) 10-hexanoylphenothiazine R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Solid 34 24.4 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Orange- -- 1660 cm.sup.-1 Consistent Black butyryl-N--methylamino)- C.sub.4 H.sub.9 ; brown (C.dbd.O;s) 10-butyrylphenothiazine R.sup.2 .dbd.R.sup.3 .dbd.R.sup.4 *50 Gummyb.3 Solid 35 5.49 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Dark 174- 1620 cm.sup.-1 trimethylacetyl-N--meth- (CH.sub.3).sub.3 C; R.sup.2 .dbd.R.sup.3 Green 180.degree. C. (C.dbd.O;s) ylamino)-10-trimethyl- R.sup.4 .dbd.CH.sub.3 Powder acetylphenothiazine 36 5.9 g 7-(Dimethylamino)-3-(N-- II: R.dbd.R.sup.5 .dbd.H; R.sup.1 .dbd. Blue 280- 1675 cm.sup.-1 trichloroacetyl-N--meth- Cl.sub.3 C; R.sup.2 .dbd.R.sup.3 .dbd. Powder 285.degree. C. (C.dbd.O;s) ylamino)-10-trichloro- R.sup.4 .dbd.CH.sub.3 acetylphenothiazine 37 0.95 g 2-Methyl-3-acetamido-7- II: R.dbd.2-CH.sub.3 ; R.sup.1 .dbd. Tan 157-1668 cm.sup.-1 Consistant Gray dimethylamino-10-acetyl- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 ; Powder 159.degree. C. (C.dbd.O;s) (Mass Spec. phenothiazine R.sup.2 .dbd.H Consistent) 38 1.8 g 2-Methyl-3-benzamido-7- II: R.dbd.2-CH.sub.3 ;R.sup.1 .dbd. Yellow 167- 1650 cm.sup.-1 Gray dimethylamino-10-ben- C.sub.6 H.sub.5 ; R.sup.2 .dbd.H; Powder3 .dbd. 175.degree. C. (C.dbd.O;s) zoylphenothiazine R.sup.4 .dbd.CH.sub.3 39 2.65 g 2-Methyl-3-(4-methyl- II: R.dbd.2-CH.sub.3 ;R.sup.1 .dbd. Pale 238- 1650 cm.sup.-1 Blue- phenylamido)-7-dimeth-
4-CH.sub.3 C.sub.6 H.sub.4 ; R.sup.2 .dbd.H; Yellow 242.degree. C. (C.dbd.O;s) gray ylamino-10-(4-methyl- R.sup.3 .dbd.R.sup.4 .dbd.CH.sub.3 Powder phenylcarbonyl)pheno- thiazine 40 1.46 g 2-Methyl-3-butyryl- II: R.dbd.2-CH.sub.3 ;R.sup.1 .dbd. White 208- 1665 cm.sup.-1 Consistent Blue- amido-7-dimethylamino- C.sub.3 H.sub.7 ; R.sup.2 .dbd.H; Powder3 .dbd. 210.degree. C. (C.dbd.O;s) gray 10-butyrylcarbonylpheno- R.sup.4 .dbd.CH.sub.3 thiazine __________________________________________________________________________
It is contemplated that by following the procedure described in the foregoing examples, but employing the appropriate 1/2-R-3-(N--R.sup.2 -amino)-7-(N--R.sup.3 --N--R.sup.4 -amino)phenothiazinium halide or phenoxazinium halide of Formula IV witha reducing agent and the appropriate acid halide of Formula VII or alkanoic acid anhydride of Formula VI, there will be obtained 1/2-R-3-(N--R.sup.2 --N--COR.sup.1 -amino)-7-(N--R.sup.3 --N--R.sup.4 -amino)-10-(R.sup.1 --CO)phenothiazine or phenoxazineof Formula I, presented in Examples 41 to 59 in Table D hereinbelow.
TABLE D __________________________________________________________________________ Example No. R R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 __________________________________________________________________________ 41 C.sub.2 H.sub.5 O ClCH.sub.2 CH.sub.3 C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2 H 42 Cl CH.sub.3 OCH.sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 43 C.sub.2 H.sub.5 C.sub.3 H.sub.5 C.sub.4 H.sub.9 C.sub.6 H.sub.5 CH.sub.3 CH.sub.3 O 44 BrCl.sub.2 CH CH.sub.3 C.sub.4 H.sub.9 C.sub.4 H.sub.9 H 45 NO.sub.2 C.sub.5 H.sub.11 C.sub.3 H.sub.7 4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2 4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2 Br 46 C.sub.4 H.sub.9 O BrCH.sub.2 CH.sub.3 4-NO.sub.2 C.sub.6H.sub.4 CH.sub.2 CH.sub.3 NO.sub.2 47 H 3-BrC.sub.2 H.sub.4 C.sub.6 H.sub.4 CH.sub.2 CH.sub.3 C.sub.6 H.sub.5 C.sub.4 H.sub.9 48 CH.sub.3 2-BrC.sub.2 H.sub.4 CH.sub.3 3-ClC.sub.6 H.sub.4 CH.sub.2 C.sub.2 H.sub. 5 CH.sub.3 49 CH.sub.3 O 4-ClC.sub.3 H.sub.7 C.sub.4 H.sub.9 C.sub.4 H.sub.9 C.sub.4 H.sub.9 C.sub.2 H.sub.5 O 50 F 2-(C.sub.2 H.sub.5)C.sub.3 H.sub.7 CH.sub.3 C.sub.2 H.sub.5 3-BrC.sub.6 H.sub.4 CH.sub.2 C.sub.3 H.sub.7 51 NO.sub.2 6-BrC.sub.5 H.sub.11 C.sub.2H.sub.5 2,4-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2 CH.sub.3 F 52 C.sub.3 H.sub.7 C.sub.11 H.sub.23 CH.sub.3 C.sub.2 H.sub.5 2,3-(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2 NO.sub.2 53 C.sub.2 H.sub.5 O C.sub.3 H.sub.5 C.sub.3 H.sub.7 2,5-(CH.sub.3).sub.2 C.sub.6 H.sub.3 CH.sub.2 C.sub.2 H.sub.5 CH.sub.3 54 I 4-C.sub.4 H.sub.9 OC.sub.6 H.sub.4 CH.sub.3 2,6-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.2 CH.sub.3 H 55 H 4-C.sub.4 H.sub.9 C.sub.6 H.sub.4 C.sub.6 H.sub.5 2-FC.sub.6 H.sub.4CH.sub.2 C.sub.4 H.sub.9 C.sub.4 H.sub.9 O 56 CH.sub.3 2,4-Cl.sub.2 C.sub.6 H.sub.3 CH.sub.3 2-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2 2-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2 H 57 CH.sub.3 O 3,5-(CH.sub.3 O).sub.2 C.sub.6 H.sub.3 4-CH.sub.3 C.sub.6H.sub.4 CH.sub.2 4-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2 C.sub.2 H.sub.5 Br 58 Cl 3,5-(NO.sub.2).sub.2 C.sub.6 H.sub.3 4-ClC.sub.6 H.sub.4 CH.sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 59 NO.sub.2 2-IC.sub.6 H.sub.4 3-NO.sub.2 C.sub.6H.sub.4 CH.sub.2 CH.sub.3 CH.sub.3 C.sub.4 H.sub.9 __________________________________________________________________________
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