Patent Publication Number: US-4652643-A

Title: 3-amido-7-disubstituted amino-10-carbonylphenothiazines

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation-in-part of our copending application Ser. No. 772,111, filed Sept. 3, 1985, now abandoned, which in turn is a divisional application of our prior copending application Ser. No. 636,460, filed July 31, 1984, now U.S. Pat. No. 4,561,001. 
    
    
     BACKGROUND OF THE INVENTION 
     (a) Field of the Invention 
     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 recording systems containing said compounds; and to processes for preparing said compounds. 
     (b) Information Disclosure Statement 
     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&#39;-chloro-8&#39;-methoxyindolinobenzospiropyrans. Also utilized as colorless precursors 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 is generally 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, Leucomethyl Capryl 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. 29,427 which 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 or treated 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 printing head 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. 
     The following items to date appear to constitute the most relevant prior art with regard to the instant invention. 
     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. 
     Mariga and Oda in Kogyo Kagaku Zasshi 67 (7), 1050-4 (1964) (C.A. 62 2852b) describe the preparation and properties of acylated methylene blue having the structural formula ##STR2## in which R represents an alkyl or a substituted phenyl moiety. The compounds are disclosed as being useful in pressure-sensitive carbonless duplicating systems. 
     U.S. Pat. No. 4,309,255, issued Jan. 5, 1982, discloses and claims a phenothiazine having the structural formula ##STR3## which is disclosed as being useful as a blue color former in electrochromic recording paper. 
     Smets and Simionescu in Makromolecular Chemistry 1977 178(9), 2719-23 (C.A. 87 186052t) disclose as a monomer for a color polymer N-acryloyl-N,N&#39;,N&#39;-trimethylthionine having the formula ##STR4## 
     Japanese Patent Publication No. 80,040,798, published Mar. 22, 1980, discloses thionines having the structural formula ##STR5## in which R 1  and R 2  represent hydrogen or methyl; R and X represent halogen; Z represents (CH 2 ) 3  to 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(β-cyanoethyl)amino, di(β-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, β-chloroethyloxy, etc., acyloxy such as acetoxy, benzoyloxy, etc., primary amino, secondary amino such as methylamino, 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═CH--CH═CH-- or --O--CH 2  --C--, etc., and R represents an alkyl having no more than 17 carbon atoms, a substituted 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. 
     SUMMARY OF THE INVENTION 
     In its composition of matter aspect, the invention relates to certain 3-(N--R 2  --N-acylamino)-7-(N--R 3  --N--R 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 2  --N-acylamino)-7-(N--R 3  --N--R 4  -amino)-10-acyl-phenothiazines and phenoxazines. 
     In its process aspect, the invention relates to a process for producing 3-(N--R 2  --N-acylamino)-7-(N--R 3  --N--R 4  -amino)-10-acyl-phenothiazines and phenoxazines which comprises interacting the corresponding 3-(N--R 2  -amino)-7-(N--R 3  --N--R 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. 
     DETAILED DESCRIPTION INCLUSIVE OF THE PREFERRED EMBODIMENTS 
     More specifically, this invention in its composition of matter aspect resides in the novel compounds having the structural formula ##STR7## wherein R and R 5  independently represent non-tertiary C 1  to C 4  alkyl, non-tertiary C 1  to C 4  alkoxy, halogen or nitro; R 1  represents hydrogen; C 1  to C 12  alkyl; C 4  to C 8  cycloalkyl; C 1  to C 12  alkyl substituted by halogen, non-tertiary C 1  to C 4  alkoxy, phenyl, phenoxy, or non-tertiary C 1  to C 4  alkoxycarbonyl; phenyl; naphthyl; or phenyl substituted by one to three of non-tertiary C 1  to C 4  alkyl, non-tertiary C 1  to C 4  alkoxy, nitro, halo, phenyl, cyano or trihalomethyl; R 2  represents hydrogen; non-tertiary C 1  to C 4  alkyl; phenyl; phenyl substituted by one or two of halo, nitro, non-tertiary C 1  to C 4  alkyl or non-tertiary C 1  to C 4  alkoxy; benzyl; or benzyl substituted in the benzene ring by one or two of halo, nitro, non-tertiary C 1  to C 4  alkyl or non-tertiary C 1  to C 4  alkoxy; R 3  and R.sup. 4 represent hydrogen; non-tertiary C 1  to C 4  alkyl; phenyl; phenyl substituted by one or two of halo, nitro, non-tertiary C 1  to C 4  alkyl or non-tertiary C 1  to C 4  alkoxy; benzyl; or benzyl substituted in the benzene ring by one or two of halo, nitro, non-tertiary C 1  to C 4  alkyl or non-tertiary C 1  to C 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 1  --CO)--N--R 2  -amino]-7-(N--R 3  --N--R 4  -amino)-8/9-R 5  -10-(R 1  --CO)-phenothiazines of Formula I wherein X is S having the formula ##STR8## in which R, R 1 , R 2 , R 3 , R 4  and R 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 1  --CO)--N--R 2  -amino]-7-(N--R 3  --N--R 4  -amino)-8/9--R 5  --10-(R 1  --CO)-phenoxazines of Formula I wherein X is O having the structural formula ##STR9## in which R, R 1 , R 2 , R 3 , R 4  and R 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 the structural 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 agent having the structural formula 
     
         R.sup.1 --CO--Z 
    
     
         Formula VI 
    
     in which Z represents halo or R 1  COO and R, R 1 , R 2 , R 3 , R 4  and R 5  have the same respective meanings given in Formula I. 
     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 the structure 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 1  --CO)--N--R 2  -amino]-7-(N--R 3  --N--R 4  -amino)-8/9-R 5  -10-(R 1  --CO)-phenothiazine of Formula II wherein R, R 1 , R 2 , R 3 , R 4  and R 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 1  --CO)--N--R 2  -amino]-7-(N--R 3  --N--R 4  -amino)-8/9-R 5  -10-(R 1  --CO)-phenoxazine of Formula III wherein R, R 1 , R 2 , R 3 , R 4  and R 5  have the same respective meanings given in Formula III. 
     As used herein the terms &#34;non-tertiary C 1  to C 4  alkyl&#34; and &#34;non-tertiary C 1  to C 12  alkyl&#34; 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. 
     The term &#34;non-tertiary C 1  to C 4  alkoxy&#34; includes saturated acyclic, straight or branched-chained groups such as methoxy, ethoxy, propoxy, isopropoxy, sec-butoxy and isobutoxy. 
     As used herein the terms &#34;halo&#34; and &#34;halogen&#34; 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 and because the other halogens offer no particular advantages over chloro. However, the other above-named halo substituents are also satisfactory. 
     As used herein the term &#34;C 4  to C 8  cycloalkyl&#34; denotes saturated monovalent cyclic aliphatic hydrocarbon radicals including cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. 
     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 the preparation of the phenothiazine and phenoxazine dyestuffs are: (a) Journal of the Society of Dyers and Colourists 4, 39 (1888); (b) Liebig&#39;s Annalen der Chemie 251, 1 (1889); (c) Chemische Berichte 25, 3128 (1892); (d) FIAT Final Report No. 1313 and PB Report 85172, vol. II, p. 372. 
     The acylating agents of Formula VI may be either aliphatic acid anhydrides (Z=R 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 are readily 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, dichloroacetic anhydride, 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-undecanoyl chloride, 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, benzoyl chloride, 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-cyanobenzoyl chloride, 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 of Formula 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 also possess 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 in numerous 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 of conductor, 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 coated paper 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 sulfate immediately 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 dried to 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, Crystal Violet 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-accepted electrochromic recording systems. 
     The best mode contemplated by the inventors of carrying out this invention will now be described so as to enable any person skilled in the art to which it pertains to make and use the same. 
     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 agent of 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° C. to reflux of the mixture for periods of approximately thirty minutes to approximately four hours. The compounds of Formula 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 is subsequently 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 as evaporation 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 the leuco compound dissolved in an organic liquid is cooled to a temperature in the range of 60° to 80° C. and disodium phosphate and acyl halide, dissolved in the same organic liquid, is added. The reaction is conveniently carried out at the 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 a period 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 purified is 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 analyzed to 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 reducing the 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 need for 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, an alkaline 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 at ambient 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 liquid solution 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. 
     The molecular structures of the compounds were assigned on the basis of the modes of synthesis and a study of their infrared, nuclear magnetic resonance and mass spectra. 
     The following examples will further illustrate the invention without, however, limiting it thereto. 
    
    
     EXAMPLE 1 
     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° C. for approximately three 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 was poured 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 gummy residue. 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═R 1  ═R 5  ═H; R 2  ═R 3  ═R 4  ═CH 3 ), an off-white-colored powder which melted at 139° to 143° C. A significant infrared maximum appeared at 1685 cm -1  (C═O; s). A paper treated with an ink formulation of the product produced a black-colored image when traced with an applied voltage stylus. 
     EXAMPLE 2 
     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 was cooled 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 sodium chloride 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-acetylphenothiazine (Formula II: R═2--CH 3  ; R 1  ═R 2  ═R 3  ═R 4  ═CH 3  ; R 5  ═H), a white-colored solid which melted over the range of 148° to 161° C. A significant infrared maximum appeared at 1665 cm -1  (C═O; s). A significant maxima appeared in the mass spectrum at 369 (M + ) and 326 (M +  --CH 3  CO). Paper treated with an ink formulation of the product produced a black-colored image when traced with an applied voltage stylus. 
     EXAMPLE 3 
     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 of water 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 the water 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 to approximately 70° 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 for approximately 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 room temperature. 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 water and 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 of isopropyl alcohol, 100.0 ml of water and 20.0 g of disodium phosphate at approximately 80° C. for approximately ten minutes. After cooling, the solid was collected by filtration and dried to obtain 8.24 g of 7-(dimethylamino)-3-[N-(4-methylphenylcarbonyl)-N-methylamino]-10-(4-methylphenylcarbonyl)-phenothiazine (Formula II: R═R 5  ═H; R 1  ═4--CH 3  C 6  H 4  ; R 2  ═R 3  ═R 4  ═CH 3 ), a white powder which melted at 220° to 224° C. Significant infrared maxima were observed at 1670 cm -1  (C═O; s) and 1660 cm -1  (C═O; s). The nuclear magnetic resonance spectrum was in accord with the assigned structure. Paper treated with an ink 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 third column 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 the fifth 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 formulation containing 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  dust     anhydride                   
         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═R.sup.5 ═H; R.sup.1 ═             
                                White  147- 1690 cm.sup.-1                
                                                  Consistent              
                                                        Black             
         acetyl-N--methylamino)-                                          
                      R.sup.2 ═R.sup.3 ═R.sup.4 ═CH.sub.3     
                                Powder 155° C.                     
                                            (C═O;s)                   
         10-acetylphenothiazine                                           
 5  0.16                                                                  
       g 7-(Dimethylamino)-3-(N--                                         
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Tan    117- 1650 cm.sup.-1                
                                                        Black             
         2-naphthylcarbonyl-N--                                           
                      2-C.sub.10 H.sub.7 ; R.sup.2 ═R.sup.3 ═     
                                Powder 122° C.                     
                                            (C═O;s)                   
         methylamino)-10-(2-                                              
                      R.sup.4 ═CH.sub.3                               
         naphthylcarbonylpheno-                                           
         thiazine                                                         
 6  1.39                                                                  
       g 7-(Dimethylamino)-3-(N--                                         
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Pale   79-  1655 cm.sup.-1                
                                                        Blue-             
         benzoyl-N--methylamino)-                                         
                      C.sub.6 H.sub.5 ;                                   
                                Green- 84° C.                      
                                            (C═O;s) black             
         10-benzoylphenothiazine                                          
                      R.sup.2 ═R.sup.3 ═R.sup.4 ═CH.sub.3     
                                yellow                                    
                                Powder                                    
 7  1.3                                                                   
       g 7-(Dimethylamino)-3-(N--                                         
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                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° C.                      
                                            (C═O;s)                   
         amino)-10-diphenylacetyl-                                        
                      R.sup.3 ═R.sup.4 ═CH.sub.3                  
         phenothiazine                                                    
 8  0.86                                                                  
       g 7-(Dibutylamino)-3-(N--                                          
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Brown  --   1670 cm.sup.-1                
                                                        Black             
         acetyl-N--methylamino)-                                          
                      R.sup.2 ═CH.sub.3 ; R.sup.3 ═R.sup.4        
                                Gumd.       (C═O;s)                   
         10-acetylphenothiazine                                           
                      C.sub.4 H.sub.9                                     
 9  0.52                                                                  
       g 7-(Dimethylamino)-3-(N--                                         
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Yellow 107- 1675 cm.sup.-1                
                                                        Green-            
         acetyl-N--ethylamino)-                                           
                      R.sup.3 ═R.sup.4 ═CH.sub.3 ; R.sup.2        
                                Powder 110° C.                     
                                            (C═O;s) black             
         10-acetylphenothiazine                                           
                      C.sub.2 H.sub.5                                     
10  1.0                                                                   
       g 7-(Diethylamino)-3-(N--                                          
                      II: R═ R.sup.5 ═H; R.sup.1 ═            
                                Tan    92.5-                              
                                            1665 cm.sup.-1                
                                                  Consistent              
                                                        Green-            
         acetyl-N--methylamino)-                                          
                      R.sup.2 ═CH.sub.3 ; R.sup.3 ═R.sup.4        
                                Powder 97° C.                      
                                            (C═O;s) black             
         10-acetylphenothiazine                                           
                      C.sub.2 H.sub.5                                     
11  1.04                                                                  
       g 7-(Diethylamino)-3-(N--                                          
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Brown  --   1660 cm.sup.-1                
                                                        Black             
         benzoyl-N--methylamino)-                                         
                      C.sub.6 H.sub.5 ; R.sup.2 ═CH.sub.3 ;           
                                Gum         (C═O;s)                   
         10-benzoylphenothiazine                                          
                      R.sup.3 ═R.sup.4 ═C.sub.2 H.sub.5           
12  1.0                                                                   
       g 7-(Dimethylamino)-3-(N--                                         
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Brown  100- 1650 cm.sup.-1                
                                                        Black             
         benzoyl-N--ethylamino)-                                          
                      C.sub.6 H.sub.5 ; R.sup.2 ═C.sub.2 H.sub.5      
                                Powder 130° C.                     
                                            (C═O;s)                   
         10-benzoylphenothiazine                                          
                      R.sup.3 ═R.sup.4 ═CH.sub.3                  
13  3.54                                                                  
       g 7-(Dimethylamino)-3-(N--                                         
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Brown  --   1667 cm.sup.-1                
                                                  Consistent              
                                                        Black             
         methoxyacetyl-N--methyl-                                         
                      CH.sub.3 OCH.sub.2 ;                                
                                Gum         (C═O;s)                   
         amino)-10-methoxyacetyl-                                         
                      R.sup.2 ═R.sup.3 ═R.sup.4 ═CH.sub.3     
         phenothiazine                                                    
14  0.52                                                                  
       g 7-(N--Benzyl-N--ethyl-                                           
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Brown  65-  1670 cm.sup.-1                
                                                        Black             
         amino)-3-(N--acetyl-N--                                          
                      R.sup.2 ═CH.sub.3 ; R.sup.3 ═               
                                Powder 69° C.                      
                                            (C═O;s)                   
         methylamino)-10-ace-                                             
                      C.sub.6 H.sub.5 CH.sub.2 ; R.sup.4 ═            
         tylphenothiazine                                                 
                      C.sub.2 H.sub.5                                     
15  3.60                                                                  
       g 7-(Dimethylamino)-3-                                             
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                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 ═         
                                Brown  112° C.                     
                                            (C═O;s)                   
         zoyl)-N--methylamino]-10-                                        
                      R.sup.3 ═R.sup.4 ═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 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 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 of Part 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 was traced 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-ium chloride         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                                                                  
       g 7-(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-   ane carbox-                 
         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         sulfite  chloride                    
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 chloride         sulfite                              
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                              
                                          Significant   Produced          
No.                                                                       
   Product Name     Product Formula                                       
                              Appearance                                  
                                     Point                                
                                          Infrared                        
                                                NMR     Image             
__________________________________________________________________________
                                                        Color             
16 8.24 g                                                                 
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              White  220- 1670 cm.sup.-1                  
                                                Consistent                
                                                        Black             
       (4-methylphenylcarbon-                                             
                    4-CH.sub.3 C.sub.6 H.sub.4 ; R.sup.2 ═            
                              Powder 224° C.                       
                                          (C═O;s)                     
       yl)-N--methylamino]-10-                                            
                    R.sup.3 ═R.sup.4 ═CH.sub.3                    
                                          1660 cm.sup.-1                  
       (4-methylphenylcarbon-             (C═O;s)                     
       yl)phenothiazine                                                   
17 9.7 g                                                                  
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              Pale   85-  1665 cm.sup.-1                  
                                                        Black             
       (3-nitrophenylcarbon-                                              
                    3-NO.sub.2 C.sub.6 H.sub.4 ; R.sup.2 ═            
                              Brown  100° C.                       
                                          (C═O;s)                     
       yl)-N--methylamino]-10-                                            
                    R.sup.3 ═R.sup.4 ═CH.sub.3                    
                              Powder (dec.)                               
                                          1650 cm.sup.-1                  
       (3-nitrophenylcarbon-              (C═O;s)                     
       yl)phenothiazine                                                   
18 5.5 g                                                                  
       7-(Dimethylamino)-3-(N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 50                  
                              White  110° C.                       
                                          1690 cm.sup.-1                  
                                                Consistent                
                                                        Gray              
       phenoxyacetyl-N--methyl-                                           
                    C.sub.6 H.sub.5 OCH.sub.2 ; R.sup.2 ═             
                              Powder (dec.)                               
                                          (C═O;s)                     
       amino)-10-phenoxyace-                                              
                    R.sup.3 ═R.sup.4 ═CH.sub.3                    
                                          1676 cm.sup.-1                  
       tylphenothiazine                   (C═O;s)                     
19 8.5 g                                                                  
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 50                  
                              Pale   178- 1650 cm.sup.-1                  
                                                        Black             
       (4-bromophenylcarbonyl)-                                           
                    4-BrC.sub.6 H.sub.4 ; R.sup.2 ═                   
                              Green  180° C.                       
                                          (C═O;s)                     
       N--methylamino]-10-(4-                                             
                    R.sup.3 ═R.sup.4 ═CH.sub.3                    
                              Powder      1665 cm.sup.-1                  
       bromophenylcarbonyl)-              (C═O;s)                     
       phenothiazine                                                      
20 3.1 g                                                                  
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═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 ═                               
                                     170° C.                       
                                          (C═O;s)                     
       yl)-N--methylamino]-10-                                            
                    R.sup.3 ═R.sup.4 ═CH.sub.3                    
                              Powder (dec.)                               
                                          1645 cm.sup.-1                  
       (4-phenylphenylcarbon-             (C═O;s)                     
       yl)phenothiazine                                                   
21 7.7 g                                                                  
       7-(Dimethylamino)-3-N--                                            
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              Pale   --   1662 cm.sup.-1                  
                                                        Black             
       cyclohexylcarbonyl-N--                                             
                    C.sub.6 H.sub.11 ;                                    
                              Yellow      (C═O;s)                     
       methylamino)-10-cylco                                              
                    R.sup.2 ═R.sup.3 ═R.sup.4 ═CH.sub.3       
                              Gum                                         
       hexylcarbonylphenothi-                                             
       azine                                                              
22 12.1 g                                                                 
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              White  211- 1667 cm.sup.-1                  
                                                        Black             
       (2-methylphenylcarbon-                                             
                    2-CH.sub.3 C.sub.6 H.sub.4 ; R.sup.2 ═            
                              Powder 214° C.                       
                                          (C═O;s)                     
       yl)-N--methylamino]-10-                                            
                    R.sup.3 ═R.sup.4 ═CH.sub.3                    
                                          1650 cm.sup.-1                  
       (2-methylphenylcarbon-             (C═O;s)                     
       yl)phenothiazine                                                   
23 12.1 g                                                                 
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              White  236- 1670 cm.sup.-1                  
                                                        Black             
       (2-chlorophenylcarbon-                                             
                    2-ClC.sub.6 H.sub.9 ; R.sup. 2 ═                  
                              Powder 243° C.                       
                                          (C═O;s)                     
       yl)-N--methylamino]-10-                                            
                    R.sup.3 ═R.sup.4 ═CH.sub.3                    
                                          1652 cm.sup.-1                  
       (2-chlorophenylcarbon-             (C═O;s)                     
       yl)phenothiazine                                                   
24 14.2 g                                                                 
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              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═O;s)                     
       ylcarbonyl)-N--methyl-                                             
                    R.sup.2 ═R.sup.3 ═R.sup.4 ═CH.sub.3       
                              Powder      1650 cm.sup.-1                  
       amino]-10-(3,4,5-tri-              (C═O;s)                     
       methylphenylcarbonyl)-                                             
       phenothiazine                                                      
25 14.2 g                                                                 
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H;                             
                              Pale   --   1740 cm.sup.-1                  
                                                        Black             
       (3-carbomethoxypropyl-                                             
                    R.sup.1 ═3-                                       
                              Yellow      (C═O;s)                     
       carbonyl)-N--methyl-                                               
                    CH.sub.3 OCOC.sub.3 H.sub.6 ; R.sup.2 ═           
                              Gum         1665 cm.sup.-1                  
       amino]-10-(3-carbometh-                                            
                    R.sup.3 ═R.sup.4 ═CH.sub.3                    
                                          (C═O;s)                     
       oxypropylcarbonyl)pheno-                                           
       thiazine                                                           
26 6.0 g                                                                  
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              Pale   139- 1648 cm.sup.-1                  
                                                        Black             
       (4-cyanophenylcarbon-                                              
                    4-CNC.sub.6 H.sub.4 ;                                 
                              Yellow 155° C.                       
                                          (C═O;s)                     
       yl)-N--methylamino]-10-                                            
                    R.sup.2 ═R.sup.3 ═R.sup.4 ═CH.sub.3       
                                     (dec.)                               
                                          1655 cm.sup.-1                  
       (4-cyanophenylcarbon-              (C═O;m)                     
       yl)phenothiazine                                                   
27 2.4 g                                                                  
       7-(Dimethylamino)-3-(N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              Pale   --   1670 cm.sup.-1                  
                                                        Black             
       decanylcarbonyl-N--meth-                                           
                    C.sub.10 H.sub.21 ;                                   
                              Green       (C═O;s)                     
       ylamino)-10-decanyl-                                               
                    R.sup.2 ═R.sup.3 ═R.sup.4 ═CH.sub.3       
                              Tar                                         
       carbonylphenothiazine                                              
28 1.84 g                                                                 
       7-(Dimethylamino)-3-(N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              White  235° C.                       
                                          1670 cm.sup.-1                  
                                                Consistent                
                                                        Black             
       phenylcarbonyl-N--meth-                                            
                    C.sub.6 H.sub.5 ;                                     
                              Powder      (C═O;s)                     
       ylamino)-10-phenyl-                                                
                    R.sup.2 ═R.sup.3 ═R.sup.4 ═CH.sub.3       
                                          1655 cm.sup.-1                  
       carbonylphenothiazine              (C═O;s)                     
29 26.9 g                                                                 
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              White  228.5-     (Mass Spectra             
                                                        Black             
       (4-methoxyphenylcarbon-                                            
                    4-CH.sub.3 OC.sub.6 H.sub.4 ; R.sup.2 ═           
                              Powder 230° C.                       
                                                and Elemental             
       yl)-N--methylamino]-10-                                            
                    R.sup.3 ═R.sup.4 ═CH.sub.3                    
                                                Analysis Both             
       (4-methoxyphenylcarbon-                  Consistent)               
       yl)phenothiazine                                                   
30 4.5 g                                                                  
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              Yellow 223.5-                               
                                          1670 cm.sup.-1                  
                                                Consistent                
                                                        Black             
       3,4-dichlorophenylcarbon-                                          
                    3,4-ClC.sub.6 H.sub.3 ; R.sup.2 ═                 
                              Powder 225° C.                       
                                          (C═O;s)                     
       yl)-N--methylamino]-10-                                            
                    R.sup.3 ═R.sup.4 ═CH.sub.3                    
                                          1645 cm.sup.-1                  
       (3,4-dichlorophenyl-               (C═O;s)                     
       carbonyl)phenothazine                                              
31 4.48 g                                                                 
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              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° C.                       
                                          (C═O;s)                     
       carbonyl)-N--methylamino]                                          
                    R.sup.2 ═R.sup.3 ═R.sup.4 ═CH.sub.3       
                              Powder                                      
       10-(2,4,6-trimethylphen-                                           
       ylcarbonyl)phenothiazine                                           
32 1.02 g                                                                 
       7-(Dimethylamino)-3-[N--                                           
                    II: R═R.sup.5 ═H; R.sup.1 ═               
                              Pale   198- 1675 cm.sup.-1                  
                                                        Black             
       (2-trifluoromethylphen-                                            
                    F.sub.3 CC.sub.6 H.sub.4 ; R.sup.2 ═R.sup.3       
                              Grey.  210° C.                       
                                          (C═O;s)                     
       ylcarbonyl)-N--methyl-                                             
                    R.sup.4 ═CH.sub.3 1663 cm.sup.-1                  
       amino]-10-(2-trifluoro-            (C═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 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 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 of Part 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 was traced 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° 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° C.        
          thiazin-5-ium   anhydride                                       
          chloride                                                        
35   10.0                                                                 
        g 7-(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° 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°         
                                                         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°         
                                                         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° 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═R.sup.5 ═H; R.sup.1 ═             
                                Brown  --   1670 cm.sup.1                 
                                                  Consistent              
                                                        Black             
         hexanoyl-N--methylamino)-                                        
                      C.sub.6 H.sub.13 ;                                  
                                Gummy       (C═O;s)                   
         10-hexanoylphenothiazine                                         
                      R.sup.2 ═R.sup.3 ═R.sup.4 ═CH.sub.3     
                                Solid                                     
34   24.4 g                                                               
         7-(Dimethylamino)-3-(N--                                         
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Orange-                                   
                                       --   1660 cm.sup.-1                
                                                  Consistent              
                                                        Black             
         butyryl-N--methylamino)-                                         
                      C.sub.4 H.sub.9 ;                                   
                                brown       (C═O;s)                   
         10-butyrylphenothiazine                                          
                      R.sup.2 ═R.sup.3 ═R.sup.4 *50               
                                Gummyb.3                                  
                                Solid                                     
35   5.49 g                                                               
         7-(Dimethylamino)-3-(N--                                         
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Dark   174- 1620 cm.sup.-1                
         trimethylacetyl-N--meth-                                         
                      (CH.sub.3).sub.3 C; R.sup.2 ═R.sup.3            
                                Green  180° C.                     
                                            (C═O;s)                   
         ylamino)-10-trimethyl-                                           
                      R.sup.4 ═CH.sub.3                               
                                Powder                                    
         acetylphenothiazine                                              
36   5.9 g                                                                
         7-(Dimethylamino)-3-(N--                                         
                      II: R═R.sup.5 ═H; R.sup.1 ═             
                                Blue   280- 1675 cm.sup.-1                
         trichloroacetyl-N--meth-                                         
                      Cl.sub.3 C; R.sup.2 ═R.sup.3 ═              
                                Powder 285° C.                     
                                            (C═O;s)                   
         ylamino)-10-trichloro-                                           
                      R.sup.4 ═CH.sub.3                               
         acetylphenothiazine                                              
37   0.95 g                                                               
         2-Methyl-3-acetamido-7-                                          
                      II: R═2-CH.sub.3 ; R.sup.1 ═                
                                Tan    157- 1668 cm.sup.-1                
                                                  Consistant              
                                                        Gray              
         dimethylamino-10-acetyl-                                         
                      R.sup.3 ═R.sup.4 ═CH.sub.3 ;                
                                Powder 159° C.                     
                                            (C═O;s)                   
                                                  (Mass Spec.             
         phenothiazine                                                    
                      R.sup.2 ═H              Consistent)             
38   1.8 g                                                                
         2-Methyl-3-benzamido-7-                                          
                      II: R═2-CH.sub.3 ; R.sup.1 ═                
                                Yellow 167- 1650 cm.sup.-1                
                                                        Gray              
         dimethylamino-10-ben-                                            
                      C.sub.6 H.sub.5 ; R.sup.2 ═H;                   
                                Powder3 ═                             
                                       175° C.                     
                                            (C═O;s)                   
         zoylphenothiazine                                                
                      R.sup.4 ═CH.sub.3                               
39   2.65 g                                                               
         2-Methyl-3-(4-methyl-                                            
                      II: R═2-CH.sub.3 ; R.sup.1 ═                
                                Pale   238- 1650 cm.sup.-1                
                                                        Blue-             
         phenylamido)-7-dimeth-                                           
                      4-CH.sub.3 C.sub.6 H.sub.4 ; R.sup.2 ═H;        
                                Yellow 242° C.                     
                                            (C═O;s) gray              
         ylamino-10-(4-methyl-                                            
                      R.sup.3 ═R.sup.4 ═CH.sub.3                  
                                Powder                                    
         phenylcarbonyl)pheno-                                            
         thiazine                                                         
40   1.46 g                                                               
         2-Methyl-3-butyryl-                                              
                      II: R═2-CH.sub.3 ; R.sup.1 ═                
                                White  208- 1665 cm.sup.-1                
                                                  Consistent              
                                                        Blue-             
         amido-7-dimethylamino-                                           
                      C.sub.3 H.sub.7 ; R.sup.2 ═H;                   
                                Powder3 ═                             
                                       210° C.                     
                                            (C═O;s) gray              
         10-butyrylcarbonylpheno-                                         
                      R.sup.4 ═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 2  -amino)-7-(N--R 3  --N--R 4  -amino)phenothiazinium halide or phenoxazinium halide of Formula IV with a 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 2  --N--COR 1  -amino)-7-(N--R 3  --N--R 4  -amino)-10-(R 1  --CO)phenothiazine or phenoxazine of 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     Br  Cl.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.6 H.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.2 H.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.4 CH.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.6 H.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.6 H.sub.4 CH.sub.2                   
                            CH.sub.3  CH.sub.3  C.sub.4 H.sub.9           
__________________________________________________________________________