NL7908868A - SUBSTITUTED FUROPYRIDINONES AND FUROPYRAZINONES. - Google Patents

Description

LS 874-190 J

P&C

f

Substituted furopyridinones and furopyrazinones.

The invention relates to furopyridinones and furopyrazinones which are suitable as color formers in pressure-sensitive duplicating systems without carbon paper and in thermal marking systems, as well as methods for preparing these compounds and pressure-sensitive duplicating systems and thermal marking systems containing these compounds.

Different classes of organic compounds with widely differing structures are known, which are suitable as color formers for duplication systems without carbon paper. Among the important classes are listed phenothiazines, for example, benzoyl-leucomethylene blue; fluoro-10 grains, for example 2-anilino-6'-diethylaminofluorane; phthalides, such as crystal violet lactone; and various other types of color formers currently used in commercially acceptable carbonless copy systems. Representative of the many known systems are those described in U.S. Pat. Nos. 2,712,507, 2,800,457, and 3,041,289. However, many of the known color formers have one or more disadvantages, such as low color strength, low stability to light, low resistance to sublimation, and low solubility in conventional organic solvents.

U.S. Patent 3,775,424 and Belgian Patent 412,406 describe furopyridinones and furopyrazines for pressure sensitive recording material, and Belgian Patent 862,217 describes a series of phthalides suitable as color formers in pressure sensitive duplicating systems, thermal marking systems and hectographic or alcoholic copy systems.

The invention relates to a series of 7- (and 5-) (2-R ^ -4-NR ^ Rg-phenyl) and (1-Rg-2-R7 ~ 3-indolyl) -7- (and 5- ) [(Y ^ -Y ^ -phenyl) (Y ^ -Y ^ -phenyDamino] -furo [3,4-b] -pyridine-5 (7H) - [and 7 (5H) -] ones, 3- ( and 1 -) (2-R3 ~ 4-NR ^ R, - phenyl) and (1-R8 ^ -R ^ -S-indolyl) -3- (and 1-) [(Y ^ - ^ - phenyl) (Y ^ -Y ^ -phenyl) amino] furo [3,4-c] pyridine-1 (3H) - [and 3 (1H) -] ones and 7- (2-R3 ~ 4-NR4R5-phenyl) and 30 (1-Rg-2-R7-3-indolyl) -7 - [(Y ^ -Y ^ -phenyl) (Y ^ -Y ^ -phenyl) amino] furo [3,4-b] pyrazine -5 (7H) ones suitable as color formers in pressure-sensitive duplication systems without carbon paper and thermal marking systems The compounds develop colored images with good to excellent color strength, have high resistance to sublimation and improved solubility in conventional organic solvents and have the particular advantage of exhibiting excellent stability to light.

More particularly, the present compounds are those according to formula (1) 735 8 8 6-8 w - 2 - ♦ ·, wherein A is a divalent group of the formula (2), (3), (4) , (5) or (6) of the formula sheet; each of the symbols Y ^, Y2f Y3 and Y4 '° f may be different, a hydrogen atom, a halogen atom, a lower alkoxy group, an alkyl group with 1-9 carbon-5 atoms, a phenyl-lower alkyl group or a group -NR ^ R 1 represents, in which last group R 1 is a hydrogen atom or a lower alkyl group and a hydrogen atom, a lower alkyl group, a lower alkanoyl group, a phenyl sulfonyl group or a lower alkyl substituted phenyl sulfonyl group; and Z represents a monovalent group of the formula (7) or (8) of the formula sheet 10, in which formulas R 1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom or a di (lower alkyl) amino group, R ^ a lower alkyl group, R1 - a lower alkyl group or a benzyl group, R ^ a hydrogen atom or a non-tertiary alkyl group with 1-18 carbon atoms and R ^ a hydrogen atom, a phenyl group or a non-tertiary lower alkyl group . Preferably A is a group of the formula (2) or (5) and Z is a group of the formula (7). Preferred compounds are: 7- [4- (dimethyl amino) phenyl] -7- (diphenylamino) furo [3,4-b] pyridine-5 (7H) -one; 5- [4- (dimethylamino) phenyl] -5- (diphenylamino) furo [3,4-b] pyridine-7 (5H) -one; 7_ [4_ (dimethylamino) phenyl] -7- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-20 (7H) -one; 5- [4- (dimethylamino) phenyl] -5- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-7 (5H) -one; 7- [4- (diethylamino) -2-methylphenyl] -7- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-5 (7H) -one; 5- [4- (diethylamino) -2-methylphenyl] -5- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-7 (5h) -one; 7- (1-ethyl-2-methyl-3-indolyl) -7- (diphenylamino) furo [3,4-b] pyridine-5 (7H) -one; 5- (1-ethyl-2-methyl-3-indolyl) -5- (diphenylamino) furo [3,4-b] pyridine-7 (5H) -one; 7- (1-ethyl-2-methyl-3-indolyl) -7- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-5 (7H) -one and. 5- (1-ethyl-2-methyl-3-indolyl) -5- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-7 (5H) -one.

The compounds of formula (1) can be prepared by a process in which a pyridine carboxylic acid of formula (9) of the formula sheet is reacted with a diarylamine of formula (10) of the formula sheet, in the presence of an anhydride of an alkane carboxylic acid with 2-5 carbon atoms; in formulas (9) and (10), A, Z,, Y ^, Y ^ and Y ^ have the meanings given above.

The compounds of formula (1) can also be prepared by reaction 7908888

X

- 3 -

«C

t of a pyridine carboxylic acid of formula (9) with thionyl chloride, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride, followed by reaction of the obtained product with a diarylamine of formula (10) in the presence of an organic base; herein A, Z, Y ^, Y ^ and 5 Y4 in formulas (9) and (10) have the meanings given above.

The invention also relates to a pressure-sensitive duplication system without carbon paper and a thermal marking system containing as color-forming material a compound of formula (1). A particular embodiment includes a pressure-sensitive transfer sheet suitable for use with a receiver sheet having an electron acceptor layer, which transfer sheet is formed by a support sheet coated on one side with a layer of pressure-breakable microcapsules containing a liquid solution of a color-forming material, namely at least one compound of formula (1). Another system contains a heat-sensitive material formed by a support sheet coated on one side with a layer containing a mixture formed by at least one color-forming compound of formula (1) and an acid developer, all such that a marking-forming reaction between the color-forming compound and the acid developer takes place by heating.

The name "halogen" used here includes chlorine, fluorine, bromine and iodine. Chlorine is preferably the halogen present as a substituent because of the relatively low cost and ease of preparation of the required chlorine-substituted intermediates and because the other halogens do not offer any particular advantages over chlorine. However, the above mentioned other halogens as substituents are also satisfactory. The terms "lower alkyl group", "lower alkoxy group" and "didaagl alkyl) amino group" used herein refer to saturated, non-cyclic groups of 1-4 carbon atoms, which may be straight or branched chain, for example methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, isobutyl, tert.butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec.butoxy, iso-butoxy, tert.butoxy, dimethylamino, diethylamino, ethylmethylamino, di-propylamino, dibutylamino, isobutylmethylamino, di-tert-butylamino and the like.

The designation "lower alkanoyl group" used herein refers to saturated, non-cyclic acyl groups of 1 to 5 carbon atoms, which may be straight or branched chain, for example formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, 2-methylbutyryl , isovaleryl, pivalyl and the like.

The term "phenyl-lower alkyl group" used herein refers to 79 0 88 6 8-afo * - 4 - to groups such as benzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2,2-dimethyl -2-phenylethyl and the like. If desired, the phenyl group may contain a lower alkyl group or a lower alkoxy group as a substituent.

By "alkyl groups of 1-9 carbon atoms" are here meant saturated, monovalent, straight or branched chain aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 3- methylbutyl, hexyl, isohexyl, heptyl, iso-heptyl, octyl, iso-octyl, 2-ethylhexyl, nonyl, 3-ethylheptyl and the like. By "non-tert.alkyl groups of 1-18 carbon atoms", here, in addition to the above alkyl groups of 1-9 carbon atoms, of course, with the exception of tertiary alkyl groups, are meant saturated monovalent straight or branched chain aliphatic hydrocarbon groups, for example n.decyl, n.undecyl , c.tridecyl, n.dodecyl, n.tetradecyl, n.pentadecyl, 15 n.hexadecyl, n.heptadecyl, n.octadecyl, 1,3,5-trimethylhexyl, 1,5-dimethyl-4-ethylhexyl, 5- methyl-2-butylhexyl, 2-propylnonyl, 2-butyloctyl, 2-pentyl-nonyl, 1,2-dimethyltetradecyl and the like.

Examples of anhydrides of alkane carboxylic acids of 2-5 carbon atoms are: acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, isovaleric anhydride, α-methylbutyric anhydride, pivalic anhydride and the like.

Acetic anhydride is preferred because of the low price and high reactivity of this compound. However, the other anhydrides mentioned above are also satisfactory.

According to the conventional method of carrying out the above-described first method, approximately equimolar amounts of a pyridine carboxylic acid of formula (9) and a diarylamine of formula (10) are reacted in the presence of an anhydride of an alkane carboxylic acid with 2- 5 carbon atoms, such as acetic anhydride, with or without the use of an inert diluent, at a temperature of about 0®-100®C for about 10 minutes to about 72 hours. The conversion is usually performed in the absence of an inert diluent for about 0.5-2 hours at a temperature of about 20®-50®C. The product thus obtained can be isolated by filtration if it is insoluble in the reaction medium or by dilution of the reaction medium. medium with a miscible solvent in which the product is insoluble, such as a low alkanol or a low molecular weight hydrocarbon, for example, isopropanol or hexane, or a mixture thereof, to effect precipitation of the product. Alternatively, the 7908868 1 * - 5 reaction mixture can be poured into an aqueous base, for example, dilute ammonia, sodium hydroxide, sodium carbonate or sodium bicarbonate, and extract the product with an organic solvent, such as benzene or toluene, followed by evaporation of the organic solvent, leaving the product 5 as a residue. After isolation of the product, it can be purified by conventional methods, for example by trituration or re-purification. crystallize from a suitable solvent.

In the above-described conversion, the diarylamine of formula (10) serves as the basic catalyst. If desired, however, an organic base can also be used, for example pyridine, collidine, tri (lower alkyl) amines, urea and the like. Pyridine and urea are usually preferred.

According to the method normally used for the above-described second process, a compound of formula (1) can be prepared in two steps, first reacting a pyridine carboxylic acid of formula (9) with an excess of an inorganic acid chloride, such as thionyl chloride, phosphorus oxychloride , phosphorus trichloride or phosphorus pentachloride, whether or not using an inert diluent, such as benzene, toluene, chloroform, 1,2-dichloroethane or N, N-dimethylformamide, at a temperature of 20 ° -80®C for about 0.5- 2 hours, followed by a reaction of the resulting product (which, although not isolated, is believed to be a chloride of formula (11), in which formulas A and Z have the meanings given above) with a diarylamine according to formula (10) in an inert solvent in the presence of an organic base, such as pyridine, collidine, tri (lower alkyl) amines or urea, at a temperature of 0®-80®C for about 1-48 hours. The product can be isolated and purified in the usual manner.

The pyridine carboxylic acids and pyrazine carboxylic acids of formula (9), which are used as starting materials in the preparation of the final products of formula (1), are generally known, for example, from U.S. Pat. Nos. 3,936,564 and 3,775,424 and Japanese Patent Publications. 73/8727, 73/3205 and 73/8729. The pyridine carboxylic acids and pyrazine carboxylic acids which are new compounds can be prepared according to the methods described for the preparation of the known compounds, for example by reacting an anhydride of the formula (12) of the formula sheet with a suitable aniline of the formula (13) of the formula sheet or an indole of the formula (14) of the formula sheet, in which formulas A, R ^, R ^, R ^, Rg and R ^ have the meanings given above, in the presence of a Lewis acid, for example aluminum chlpride or zinc chloride, and using a diluent such as benzene, 7908868 * -6-chlorobenzene or o-dichlorobenzene, at a temperature of about 0® -100®C. The reaction is conveniently conducted in benzene in the presence of aluminum chloride at a temperature of about 0®-25®C. The relatively reactive indoles of formula (14) can be reacted with the anhydridides of formula (12) in the absence of a Lewis acid by simply reacting the reactants together in an inert solvent at a temperature of about 80®-150®C to heat.

Of course, reaction of the asymmetric anhydrides of formula (12), wherein A is a group of formula (2) or (3), with an aniline of formula (13) or an indole of formula (14) isomers or a mixture of isomers of Z-CO pyridinecarboxylic acids (formula (9)). For example, reaction of 2,3-pyridinedicarboxylic anhydride (Formula (12a) of Reaction Scheme A) with an aniline or an indole of Formula (13), respectively. formula (14) (ZH in reaction scheme A) a 2- (Z-CO) -3-pyridinecarboxylic acid 15 (formula (9a) in reaction scheme A) or a 3- (Z-CO-2-pyridinecarboxylic acid (formula (9b) in reaction scheme A) or a mixture thereof Obviously, the ratio of isomers obtained depends on various reaction conditions, such as temperature, solvent, catalyst and relative solubility of the isomers in the reaction medium.

When the preparation is carried out in the manner described above, a mixture of isomers is usually obtained, the 2- (Z-CO-3-pyridinecarboxylic acid (formula (9a) in reaction scheme A) in the isolated product being predominated. If desired, the mixture can be from isomeric Z-CO-pyridine carboxylic acids by conventional methods, for example, by selective precipitation at different pH values, fractional crystallization or chromatography, and each of the individual isomers (9a) and (9b) can then be reacted with a suitable diarylamine of formula (10) to obtain a furo [3,4-b] pyridine-5 (7H) -one of formula (1a) (reaction scheme A) or a furo [3,4-b] pyridine-7 (5H) -30one of formula (lb) (reaction scheme A) However, in general it is preferred to convert the isolated mixture of isomeric Z-CO pyridine carboxylic acids of formulas (9a) and (9b) with a diarylamine to obtain an isomer mixture of fu ropyridinones of formulas (1a) and (1b), which can be separated if desired by conventional methods. Since both isomers are suitable as color formers, it is economically advantageous to simply use the isolated mixture of these isomers according to the invention.

It has generally been found that the reaction of .2,3-pyridinedicarboxylic anhydride with an indole of formula (14) in the above-described 7908868-7 mode gives a mixture of isomers of formulas (9a) and (9b) (Z is a group of formula (8), wherein the isomer of formula (9a) predominates by a factor of more than about 7 in the isolated product In addition, it has further been observed that the predominant isomer (i.e., the isomer of formula (9a) )) is also the most reactive, therefore, the following reaction of the mixture of isomers of formulas (9a) and (9b) with a diarylamine of formula (10) yields almost exclusively furo [3,4-b] pyridine = 15 (7H ) -one (formula la), the isomer of formula (lb) being observed only in trace amounts.

The reaction of the above-described methods of 2,3-pyridinedi-carboxylic anhydride with an aniline of formula (13) also gives a mixture of isomers of formulas (9a) and (9b) (Z is a group of formula (7)), and although isomer (9a) in the isolated product predominates again, a significant amount of isomer (9b) is also obtained. Therefore, although isomer (9a) is more reactive, a sufficient concentration of the less reactive isomer (9b) is present in the mixture to react a reaction of isomeric furo [3,4-b] pyridinones upon reaction with a diarylamine of formula (10). formulas (1a) and (1b) in which isomer (1a) predominates and isomer (1b) is present in a small but substantial amount.

Similarly, by reacting 3,4-pyridine-dicarboxylic anhydride (formula (12b)) with an aniline of formula (13) or an indole of formula (14) (ZH in reaction scheme B), a mixture of 3- ( Z-CO) -4-pyridinecarboxylic acid (formula (9c)) and 4- (Z-CO) -3-pyridine carboxylic acid (formula (9d)). The resulting mixture is in turn reacted with a diarylamine of formula (10) to obtain an isomer mixture of furo [3,4-c] pyridine-1 (3H) -one (formula 1c)) and furo [3,4 -c] pyridine-3 (1H) -one (formula (Id)).

The diarylamines of formula (10), which are also used as starting materials in the present processes, are known compounds and are commercially available or can be easily obtained by known and conventional methods.

The new compounds of formula (1) are colorless or substantially colorless in the illustrated form. When contacted with an acidic medium, for example, silica gel or any of the materials commonly used in pressure-sensitive duplication systems without carbon paper, for example, silton clay or phenolic resins, the compounds of formula (1) develop a yellow to black colored image with a 7908868 ' *. Good to excellent tinting strength, while exhibiting sublimation resistance, xerographic copyability and, in particular, excellent stability to light. The present compounds are therefore very suitable as colorless precursors, ie color-forming materials in pressure-sensitive transfer systems without carbon paper. The compounds that give a yellow to red color can be used as "toners" in combination with other color-forming materials to provide images with a neutral tone, which are xerographically easy to copy. The compounds of formula (1), wherein one or more of the symbols, Y2, Y ^ and Y ^ represent an alkyl group with 1-9 carbon atoms, have excellent solubility in conventional and inexpensive organic solvents, such as fracture-free mineral oils, kerosene, vegetable oils and the like, which can avoid the need to use more expensive and special solvents, such as polyhalogenated or alkylated biphenyl compounds commonly used to obtain solutions of the known microcapsule color formers.

The compounds of the invention can be incorporated into any of the known commercially acceptable carbon paper duplicating systems. A representative embodiment for such an application proceeds as follows: Solutions of one or more colorless precursors according to formula (1), optionally mixed with other color formers, are introduced into a suitable solvent according to known methods (for example as described in the US patent specification). 3,649,649) in microcapsules. The micro-25 capsules are coated onto the back of a transfer sheet using an appropriate binder and the coated transfer sheet is then assembled into an assembly, the microcapsule-coated side being in contact with a receiver sheet coated with an electron acceptor material, for example, silton clay or a phenolic resin. Applying pressure to the assembly, for example, with a stylus, typewriter, or other form of writing or printing instrument, causes breakage of the capsules on the back of the transfer sheet. The solution of the color former released from the broken microcapsules flows to the receiver sheet and upon contact with the acid medium present thereon forms a yellow to black colored image with good tinting strength and superior stability to light. Of course, variations of this mode of application can also be used. For example, the receiver sheet in an assembly can be coated with the, if desired. present compounds, while the acidic 7908868 3 * 9 wrapper is contained in microcapsules, which are disposed in the rear of the top sheet; the receiver sheet may also be coated with a mixture containing both the acid developer and the microcapsule color-forming material.

It has also been found that when the compounds of formula (1) are intimately mixed with an acidic developer of the type commonly used in thermal copying paper, such as described in U.S. Pat. No. 3,539,375 (ie paper which, upon contact with a heated stylus or heated typer forms a colored image), for example bisphenol-A, heating the mixture produces a colored image with shades ranging from yellow to purple depending on the compound of the invention used. The ability of the compounds of formula (1) to form a type of color when heated in admixture with an acidic developer, such as bisphenol-A, makes them suitable in paper thermal marking systems, where an original or a duplicate Manufactured by contacting the thermal paper by any of the well-known methods with a heated stylus or a heated typing means.

The molecular structure of the compounds of the invention were determined based on the preparation method, elemental analysis, infrared spectrum, nuclear magnetic resonance spectrum and mass spectrum. The identity and the presence in a relatively large amount of individual isomers in mixtures of Z-CO pyridinecarboxylic acids and furopyridinones were determined from thin layer chromatography and the nuclear magnetic resonance spectrum using the shift reagent tris (dipivalomethanato) europium (III) [Eu (DPM).

The following non-limiting examples further illustrate the invention.

EXAMPLE I

30 A. To a mixture of 10 g of 2,3-pyridinedicarboxylic anhydride and 26 g of Ν, Ν-diethyl-m-phenetidine in 100 ml of benzene, 27 g of aluminum chloride were added. After stirring at about 40 ° C for 20 hours, the reaction mixture was filtered; the solid obtained was added to 800 ml of ice-water.

The resulting precipitate was collected, washed with water and then dissolved in 600 ml of 10% aqueous sodium hydroxide. After filtration to remove a small amount of soluble material, the basic aqueous solution was acidified with dilute hydrochloric acid to a pH of 6.

The resulting precipitate was collected, washed with water and dried to obtain 13.4 g of product. The filtrate was set aside to be further processed as described in Part B of this example below. This 13.4 g of solid material was redissolved in aqueous base. The resulting solution was filtered and the filtrate was adjusted to pH 6 with dilute hydrochloric acid. The precipitated light-yellow solid was collected, washed with water and dried. The dried material was then slurried in a mixture of 100 ml of toluene and 10 ml of ethanol; the light yellow solid was collected and dried to give 2.6 g of 3- [4- (diethylamino) -2-ethoxybenzoyl] -2-pyridinecarboxylic acid, mp 264 ° - 270 ° C (decomposition).

B. The separated filtrate was further acidified to a pH value of 2. The resulting pale yellow precipitate was collected, washed with water and dried, yielding 6.0 g of product. After recrystallization from ethanol-toluene, 4.0 g of 2- [4- (diethylamino) -2-ethoxybenzoyl] -3-pyridinecarboxylic acid, mp 209 ° - 210 ° C, were obtained.

C. A mixture of 1.7 g of 2- [4- (diethylamino) -2-ethoxybenzoyl] -3-pyridine carboxylic acid, 1.0 g of diphenylamine, 0.5 g of urea and 20 ml of acetic anhydride was stirred for 20 hours at stirred at room temperature. Almost immediately after the reactants were added together, the mixture turned a deep red color, indicating a rapid reaction. The reaction mixture 20 was poured into 300 ml of toluene and 200 ml of 5% aqueous ammonium hydroxide.

The toluene layer was separated, washed successively with water and saturated aqueous sodium chloride, then passed through a short column of silica gel. The desired product was extracted with acetone. silica gel column eluted. After evaporation of the acetone under reduced pressure and crystallization of the residue from 2-propanolhexane, 1.7 g of 7- [4- (diethylamino) -2-ethoxyphenyl] -7- (diphenylamino) furo [3, 4-b] pyridine-5 (7H) -one in the form of a light tan solid, mp 183.5®-185®C. This product gave a red image on acid clay and phenolic resin.

D. By a similar method as described in Part C, but using 2.5 g of 3- [4- (diethylamino) -2-ethoxybenzoyl] -2-pyridine carboxylic acid, 1.5 g of diphenylamine, 0.5 g of urea and 30 ml of acetic anhydride, stirring the reaction mixture at room temperature for 2 days (absence of a color change in the reaction mixture after 5 hours indicated a slow reaction), 0.2 g of 5- [4- (diethyl-) were obtained. 35 amino) -2-ethoxyphenyl] -5- (diphenylamino) furo [3,4-b] pyridine-7 (5H) -one in the form of a brown, gummy material. This product gave a red image on acid clay and phenolic resin.

EXAMPLE II

According to a similar procedure as described in Example 1C, 7908868 + - 11 - but using 1.7 g 2- [4- (diethylamino) -2-ethoxybenzoyl] -3-pyridinecarboxylic acid, 1.1 g 3-chloro- N-phenylaniline, 0.5 g urea and 20 ml acetic anhydride, 1.0 g 7 - [(3-chlorophenyl) phenylamino] -7- [4- (diethvlamino) -2-ethoxyphenyl] furo [3,4- b] pyridine-5 (7H) -one in the form of a light-tan solid, melting point 130®-131®C. This product gave a red colored image on acidic clay and phenolic resin.

EXAMPLE III

A mixture of 2.0 g of an isomer mixture of 3- [4- (diethylamino) -2-methylbenzoyl] -2-pyridinecarboxylic acid and 2- [4- (diethylamino) -2-methylbenzoyl] -10 3-pyridinecarboxylic acid, 0 81 g of 4,4'-bis (dimethylamino) diphenylamine, 6 ml of acetic anhydride and 0.5 ml of pyridine were stirred at room temperature for 1 hour and then poured into 200 ml of 5% aqueous ammonium hydroxide and 100 ml of toluene. The toluene layer was separated, washed with water and saturated aqueous sodium chloride and evaporated to dryness under reduced pressure. The residue was slurried in a minimal amount of acetone to obtain 0.5 g of an isomer mixture of 7- [4- (diethylamino) -2-methylphenyl] -7-bis [4- (dimethylamino) phenyl] amino furo [3 , 4-b] pyridine-5 (7H) -one and 5- [4- (diethylamino) -2-methylphenyl] -5- {bis [4- (dimethylamino) -phenyl] amino} furo [3,4-b ] pyridine-7 (5H) -one, in the form of a light green solid, mp 184®-186®C. A solution of the product in chloroform contacted with acid clay or phenolic resin developed a black image.

EXAMPLE IV

A. A mixture of 3.2 g of an isomeric mixture of 2- [4- (diethylamino) -25 2-methylbenzoyl] -3-pyridinecarboxylic acid and 3- [4- (diethylamino) -2-methylbenzoyl] -2- pyridine carboxylic acid, 2.05 g of 4,4'-dioctyldiphenylamine, 6 ml of acetic anhydride and 1.1 ml of pyridine were stirred at room temperature for 45 minutes. After diluting the reaction mixture with 6 ml of 2-propanol and 3 ml of hexane, the product was collected, washed with 2-propanol and dried to give 1.5 g of an isomer mixture of 7- [4- (diethylamino) -2-methylphenyl] -7- [bis- (4-octylphenyl) amino] furo [3,4-b] pyridine- '5 (7H) -one and 5- [4- (diethylamino) -2-methylphenyl] -5- [bis (4-octylphenyl) amino] furo [3,4- b] pyridine-7 (5H) -one in the form of a light purple colored solid, mp 194®-195®C (decomposition).

The filtrate was poured into 5% aqueous ammonium hydroxide and the product was extracted with toluene. The organic extracts were washed with water and saturated aqueous sodium chloride and evaporated to dryness under reduced pressure. After crystallization of the residue, a further 1.0 g of product was obtained in the form of a white solid. One with acidic 7908868 '♦ *. Solution of clay or phenolic resin contacted solution of the product in toluene developed a reddish-purple colored image.

B. To a mixture of 1.4 g of an isomeric mixture of 2- [4- (diethyl-amino) -2-methylbenzoyl] -3-pyridinecarboxylic acid and 3 - 4 - (diethylamino) -2-5 methylbenzoyl] -2 pyridine carboxylic acid, 1.0 ml of thionyl chloride and 60 ml of N, N-dimethylformamide, a solution of 1.84 g of 4,4'-dioctyldiphenylamine and 0.5 ml of pyridine in 40 ml of Ν, Ν-dimethylformamide was added at room temperature. After stirring for 1 hour, the reaction mixture was poured into 5% aqueous ammonium hydroxide. The precipitate was collected, washed with water and air dried. The solid was then slurried in a mixture of 30 ml of hexane and 10 ml of 2-propanol and filtered to give 1.03 g of product identical to the product of Part A.

C. A mixture of 3.13 g of an isomeric mixture of 2- [4- (diethylamino) -2-methylbenzoyl-3-pyridinecarboxylic acid and 3- [4- (diethylamino) -2-methylbenzoyl] -1 2-pyridinecarboxylic acid, 3 94 g of 4,4'-dioctyldiphenylamine, 6 ml of acetic anhydride, 6 ml of acetic acid and 0.75 g of urea were stirred at room temperature for 2 hours, then poured into 5% aqueous ammonium hydroxide and extracted with toluene. The organic extract was washed with water and saturated aqueous sodium chloride and evaporated to dryness. The residue was examined by thin layer chromatography and infrared spectroscopy and found to contain the desired product, which was identical to the product of Part A.

D. Part C conversion was performed in the absence of urea. The reaction mixture was poured into 5% aqueous ammonium hydroxide and extracted with toluene. The toluene extract was washed with water and with saturated aqueous sodium chloride and evaporated to dryness. The residue was examined by thin layer chromatography and infrared spectroscopy and found to contain the desired product, which was identical to the product of Part A.

30 EXAMPLE V

According to a similar procedure as described in Example IVA, but using 1.6 g of an isomer mixture of 2- [4- (diethylamino) -2-methylbenzoyl] -3-pyridinecarboxylic acid and 3— [4— (diethylamino) -2 methylbenzoyl] -2-pyridinecarboxylic acid. 0.6 g of 4-isopropoxy-N-phenylaniline, 0.5 ml of pyridine and 6 ml of acetic anhydride, 0.7 g of an isomer mixture of 7- [4- (diethylamino) -2-methylphenyl] -7- [ 4-isopropoxy-phenyl) phenylamino] furo [3,4-b] pyridine-5 (7H) -one and 5- [4- (diethylamino) -2-methylphenyl] -5 - [- (4-isopropoxyphenyl) phenylamino ] furo [3,4-b] pyridine-7 (5H) -one in the form of a white solid, mp 180 ° - 181 ° C. One with acid 7908868

•X

Clay or phenolic resin contacted solution of the product in toluene developed a reddish-purple colored image.

EXAMPLE VI

According to a similar method as described in Example IVA, 5, however, using 1.55 g of an isomer mixture of 2- [4- (diethylamino) benzoyl] -3-pyridinecarboxylic acid and 3- [4- (diethylamino) benzoyl] -2 pyridine carboxylic acid, 1.2 g of 4-isopropoxy-N-phenylaniline, 0.5 ml of pyridine and 6 ml of acetic anhydride, 0.7 g of an isomer mixture of 7- [4-] diethylamino) phenyl] -7 - [( 4-isopropoxyphenyl) phenylamino] furo [3,4-b] pyri-10dine-5 (7H) -one and 5- [4- (diethylamino) phenyl] -5 - [(4-isopropoxyphenyl) phenylamono] -furo [ 3,4-b] pyridine] -7 (5H) -one in the form of a white solid, mp 173®-185®C. A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange-colored image.

EXAMPLE VII

According to a similar method as described in Example III, but using 1.55 g of an isomer mixture of 2- [4- (diethylamino) benzoyl] -3-pyridinecarboxylic acid and 3- [4- (diethylamino) benzoyl] -2-pyridinecarboxylic acid, 1.33 g of 4,4'-bis (dimethylamino) diphenylamine, 0.5 ml of pyridine and 6 ml of acetic anhydride, 0.83 g of an isomeric mixture of 7- [4- (diethylamino) were obtained. ) phenyl] -7 | bis [4- (dimethylamino) phenyl] amino} -furo [3,4-b] pyridine-5 (7H) -one and 5- [4- (diethylamino) phenyl] -5-bis [4- (dimethyl-amino) phenyl] amino-furo [3,4-b] -7 (5H) -one in the form of a light gray-brown colored solid, mp 187 ° C (decomposition). A solution of the product in toluene contacted with acid clay or phenolic resin developed a dark brown image.

EXAMPLE VIII

A mixture of 0.2 g of an isomeric mixture of 2- [4- (diethylamino) -benzoyl] -3-pyridine carboxylic acid and 3- [4- (diethylamino) benzoyl] -2-pyridine carboxylic acid, 0.15 g of diphenylanine and 5 ml of acetic anhydride was stirred at room temperature for 3 hours. The reaction mixture was poured into 100 ml of toluene and 100 ml of 5% aqueous ammonium hydroxide. The toluene layer was separated, washed successively with water and saturated aqueous sodium chloride and evaporated under reduced pressure. After crystallization of the residue from hexane, 0.1 g of an isomer mixture of 7- [4- (di-35 ethylamino) phenyl] -7- (diphenylamino) furo [3,4-b] pyridine-5 (7H) were obtained ) -one and 5- [4- (diethylamino) phenyl] -5- (diphenylamino) furo [3,4-b] pyridine-7 (5H) -one in the form of a tan solid, melting point 168® - 169®C. This product gave a deep orange image on acidic clay and phenolic resin.

7908368 4f - 14 -

EXAMPLE IX

A mixture of 2.7 g of an isomer mixture of 2- [4- (dimethylamino) -benzoyl] -3-pyridine carboxylic acid and 3- [4- (dimethylamino) benzoyl] -2-pyridine carboxylic acid and 25 ml of acetic anhydride was 50 ®C heated. After a solution was formed, 1.7 g of diphenylamine was added. The mixture was stirred at 25 ° C for 2.5 hours and at 50 ° C for 1.5 hours and then cooled to 5 ° C. The resulting solid was filtered and washed with isopropanol to give 1.3 g of an isomer mixture of 7- [4- (dimethylamino) phenyl] -7- (diphenylamino) furo [3,4-b] pyridine-10 5 (7H) -one and 5- [4- (dimethylamino) phenyl] -5- (diphenylamino) furo [3,4-b] pyridine-7 (5H) -one in the form of a very light orange solid mp 175 ° -179®C. A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange image.

EXAMPLE X

According to a similar method as described in Example IX, but using 2.7 g of an isomer mixture of 2- [4- (dimethylamino) benzoyl] -3-pyridinecarboxylic acid and 3- [4- (dimethylamino) benzoyl] -2 pyridine carboxylic acid, 4.0. g of 4,4'-dioctyl diphenyl amine and 25 ml of acetic anhydride, 2.7 g of an isomer mixture of 7- [4- (dimethyl-20 amino) phenyl] -7- [bis (4-octylphenyl) are obtained amino] furo [3,4-b] pyridine-5 (7H) -one and 5- [4- (dimethylamino) phenyl] -5- [bis (4-octrylphenyl) amino] furo [3,4-b] pyridine -7 (5H) -one in the form of a light peach solid, mp 203 ° - 208®C. A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange image.

EXAMPLE XI

According to a similar procedure as described in Example III, but using 1.6 g of an isomer mixture of 3- [4- (diethylamino) -2-methylbenzoyl] -4-pyridinecarboxylic acid and 4- [4- (diethylamino) -2-methylbenzoyl] -3-pyridinecarboxylic acid, 1.3 g of 4,4'-bis (dimethylamino) diphenyl-30 amine and 6 ml of acetic anhydride, 1.5 g of 3- [4- (diethylamino) -2-methylphenyl were obtained ] -3 bis [4- (dimethylamino) phenyl] amino furo [3,4-c] pyridin-1 (3H) -one and 1- [4- (dimethylamino) -2-methylphenyl] -2 bis [4- ' (dimethylamino) phenyl] amino furo [3,4-c] pyridine-3 (1H) -one in the form of a semi-solid. A solution of the product 35 in toluene contacted with acid clay or phenolic resin developed a black image.

EXAMPLE XII

According to a similar method as described in Example III, however, using 1.6 g of an isomer mixture of 3- [4- (diethylamino) -2-methylbenzoyl] -4-pyridinecarboxylic acid and 4- [4- (diethylamino) - 7908868 - 15 - 2-methylbenzoyl] -3-pyridinecarboxylic acid, 0.9 g of diphenylamine and 6 ml of acetic anhydride, an isomer mixture of 3- [4- (diethylamino) -2-methylphenyl] -3- (diphenylamino) furo [3,4-c] pyridine-1 (3H) -one and 1- [4- (diethylamino) -2-methylphenyl] -1- (diphenylaroino) furo [3,4-c] pyridine-3 (1H ) -on.

A solution of the product in toluene contacted with acid clay or phenolic resin developed a red grape-green colored image.

EXAMPLE XIII

According to a similar procedure as described in Example III, but using 1.55 g of an isomer mixture of 3- [4- (di-10-ethylamino) benzoyl] -4-pyridinecarboxylic acid and 4- [4- (diethylamino) benzoyl] - 3-Pyridinecarboxylic acid, 1.3 g of 4,4'-bis (dimethylamino) diphenylamine, 0.5 ml of pyridine and 6 ml of acetic anhydride, 1.5 g of an isomer mixture of 3- [4- (diethylamino) phenyl] were obtained. -3 ^ bis [4- (dimethylamino) phenyl] amino] furo [3,4-c] pyridine-1 (3H) -one and 1— [4— (dimethylamino) phenyl] -1 bis [4- (di Methylamino) phenyl] amino furo [3,4-c] pyridine-3 (1H) -one in the form of a viscous oil. A solution of the product in toluene contacted with acid clay or phenolic resin developed a brown-colored image.

EXAMPLE XIV

According to a similar procedure as described in Example III, 20, however, using 1.55 g of an isomer mixture of 3- [4- (diethylamina) benzoyl] -4-pyridinecarboxylic acid and 4- [4- (diethylamino) benzoyl] - 3-pyridinecarboxylic acid, 1.2 g of 4-acetamido-N-phenylaniline, 0.5 ml of pyridine and 6 ml of acetic anhydride, 1.5 g of an isomer mixture of 3- [4- (diethylamino) phenyl] -3- were obtained [(4-acetamidophenyl) phenylamino] furo [3,4-c] pyridine-1 (3H) -one and 1- [4- (diethylamino) phenyl] -1 - [(4-acetamidophenyl) phenylamino] furo [3,4-c] pyridine-3 (1H) -one in the form of a red-brown colored solid, mp 102 ° - 116®C. A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange-red colored image.

30 EXAMPLE XV

3.0 g of a mixture of isomers, namely 3- [4- (diethylamino) benzoyl] -4-pyridinecarboxylic acid and 4- [4- (diethylamino) benzoyl] -3-pyridinecarboxylic acid in 30 ml acetic anhydride, were heated at 40 ° C heated. After a solution was formed, 4.0 g of 4,4'-dioctyldiphenylamine was added, the mixture was stirred for 7 hours and then left to stand for 40 hours. The resulting solution was poured into 100 ml of ice-water containing 76 ml of concentrated ammonium hydroxide. The product was taken up in 75 ml of toluene by extraction; the toluene layer was separated, dried over anhydrous calcium chloride and evaporated to leave an oil. After crystallization 79 0 8 8 6 8 ·,. α-16 - 2.8 g of a mixture of the isomers 3- [4- (diethylamino) phenyl] -3- [bis (4-octylphenyl) amino] furo [3,4-] was obtained from hexane c] pyridine-1 (3H) -one and 1- [4- (diethylamino) phenyl] -1- [bis (4-octylphenyl) amino] furo [3,4-c] pyridine-3 (1H) -one in in the form of a tan solid, melting point 114®-117®C.

A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange-colored image.

EXAMPLE XVI

According to a similar procedure as described in Example III, but using 3.0 g of an isomer mixture of 3- [4- (di-10 ethylamino) benzoyl] -4-pyridinecarboxylic acid and 4- [4- (diethylamino) benzoyl] - 3-pyridinecarboxylic acid, 1.7 g of diphenylamine and 30 ml of acetic anhydride, 1.4 g of an isomer mixture of 3- [4- (diethylamino) phenyl] -3- (diphenylamino) furo [3,4-c] pyridine were obtained -1 (3H) -one and 1- [4- [diethylamino) phenyl] -1- (diphenylamino) furo [3,4-c] pyridine-3 (1H) -one in the form of a light orange solid dust, melting point 135® - 141®C. A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange-colored image.

EXAMPLE XVII

2.6 g of a mixture of isomers 3- [4- (diethylamino) -2-methylben-20 zoyl] -4-pyridinecarboxylic acid and 4- [4- (diethylamino) -2-methylbenzoyl] -3-pyridinecarboxylic acid in 30 ml of acetic anhydride was heated to 40 ° C, after which 4.0 g of 4,4'-dioctylphenylamine was added. The mixture was stirred at room temperature for 3 hours and then poured into 100 ml ice-water and 76 ml concentrated ammonium hydroxide to obtain 5.7 g of a mixture of isomers 3- [4 - (diethylamino) -2-methylphenyl ] -3- [bis (4-octylphenyl) amino] furo [3,4-c] pyridine-1 (3H) -one and 1- [4- (diethylamino) -2-methylphenyl] -1- [bis (4 octylphenyl) amino] furo [3,4-c] pyridine-3 (1H) -one in the form of a red solid, mp 58®-105®C. A solution of the product in toluene contacted with acid clay or phenolic resin developed a violet-colored image.

EXAMPLE XVIII

According to a similar procedure as described in Example III, but using 1.63 g of 3- [4- (diethylamino) -2-methylbenzoyl] -2-pyrazine carboxylic acid, 1.3 g of 4,41-bis (dimethylamino) diphenylamine, 0.5 ml of pyridine and 6 ml of acetic anhydride, 0.9 g of 7- [4- (diethylamino) -2-methylphenyl] -7 ^ bis [4- (dimethylamino) phenyl] amino} furo [3.4 -c] pyrazine-5 (7H) -one in the form of a light orange-colored solid, melting point 193.5®-195®C (decomposition). A solution of the product in toluene contacted with acid clay or phenolic resin developed a black image.

7908868 4 - 17 -

EXAMPLE XIX

According to a similar procedure as described in Example III, but using 1.6 g of 3- [4- (diethylamino) -2-methylbenzoyl] -2-pyrazine carboxylic acid, 0.9 g of diphenylamine, 0.5 ml of pyridine and 6 ml acetic acid-5 anhydride, 0.1 g of 7- [4- (diethylamino) -2-methylphenyl] -7- (di-phenylamino) furo [3,4-c] pyrazine-5 (7H) -one, m.p. 189.5 ° - 191 ° C (decompn.). A solution of the product in toluene contacted with acid clay or phenolic resin developed a red-brown-green image.

EXAMPLE XX

According to a similar procedure as described in Example III, but using 0.43 g of 3- [4- (diethylamino) benzoyl] -2-pyrazine-carboxylic acid, 0.34 g of 4,4'-bis (dimethylamino) diphenylamine , 0.5 ml of pyridine and 6 ml of acetic anhydride, 0.59 g of 7- [4- (diethylamino) phenyl] - 7 bis- [4- (dimethylamino) phenyl] amino furo [3,4-b] pyrazine- 5 (7H) -one, melting point 61 ° -74 ° C. A solution of the product in toluene contacted with acid clay or phenolic resin developed a red-brown image.

EXAMPLE XXI »

According to a similar procedure as described in Example III, but using 0.5 g of 3- [4- (diethylamino) benzoyl] -2-pyrazine-carboxylic acid, 0.38 g of 4-isopropoxy-N-phenylaniline, 5 ml of pyridine and 6 ml of acetic anhydride, 0.6 g of 7- [4- (diethylamino) phenyl] -7 - [(4-iso-propoxyphenyl) phenylamino] furo [3,4-b] pyrazine-5 (7H) were obtained -one, melting point 75 ° -82 ° C. A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange-brown image.

EXAMPLE XXII

A mixture of 0.7 g of 3- [4- (dimethylamino) benzoyl] -2-pyrazine carboxylic acid, 1.0 g of 4,41-dioctyldiphenylamine and 7 ml of acetic anhydride was gently heated in a warm water bath for 1 hour with stirring. The product, 7- [4- (dimethylamino) phenyl] -7- [bis (4-octylphenyl) amino] furo [3,4-b] pyrazine-5 (7H) -one, was isolated by column chromatography in the rust-colored solid, melting point 158 ° - 168 ° C. A solution of the product in toluene contacted with acid clay or phenolic resin developed a reddish-brown image.

EXAMPLE XXIII

A mixture of 0.1 g of 3- [4- (diethylamino) benzoyl] -2-pyrazine carboxylic acid, 0.1 g of diphenylamine and 2 ml of acetic anhydride was heated for several hours, then the mixture was allowed to stand for 3 hours. The product, 7- [4- (diethylamino) phenyl] -7- (diphenylamino) furo [3,4-b] pyrazine-5 (7H) -one, was isolated by column chromatography as a light orange 7908868 4 - 18 - solid, melting point 140 ° - 140.2®C. A solution of this product in toluene contacted with acid clay or phenolic resin developed a red image.

EXAMPLE XXIV

A mixture of 0.15 g of 3- [4- (diethylamino) benzoyl] -2-pyrazine carboxylic acid, 0.18 g of 4,4'-dioctyldiphenylamine and 3 ml of acetic anhydride was gently heated for 5 hours, after which the mixture was left overnight. The product, 7- [4- (diethylamincr) phenyl] -7- [bis (4-octyl-phenyl) amino] furo [3,4-b] pyrazine-5 (7H) -one, was isolated by column chroma-10 tography, followed by crystallization from hexane, to give a peach solid, mp 180®-181®C. A solution of this product in toluene contacted with acid clay or phenolic resin developed a red image.

EXAMPLE XXV

A mixture of 3.1 g of 3- [4- (diethylamino) -2-methylbenzoyl] -2-pyrazine carboxylic acid, 3.1 g of 4,4'-dioctyldiphenylamine and 25 ml of acetic anhydride was stirred in a warm water bath for 3 hours. . The reaction mixture was poured into water and the resulting solid was collected and recrystallized from hexane to give 7- [4 - (diethylamino) -2-methylphenyl] -20 7- [bis (4-octylphenyl) amino] furo [3,4-b] pyrazine-5 (7H) -one in the form of a light tan solid, mp 180®-18.7®C. A solution of this product in toluene contacted with acid clay or phenolic resin developed a violet-colored image.

EXAMPLE XXVI

According to a similar method as described in Example III,.

however, using 4.5 g of an isomer mixture of 2 - [(1-ethyl-2-methyl-3-indolyl) carbonyl] -3-pyridine carboxylic acid and 3- [(1-ethyl-2-methyl-3) indolyl) carbonyl] -2-pyridinecarboxylic acid, 3.6 g of 4-ethoxy-N-phenylaniline, 1 ml of pyridine and 8 ml of acetic anhydride, 5.5 g of 7- (1-ethyl-2-methyl-3-) were obtained. indolyl) -7- [(4-ethoxyphenyl) phenylamino] furo [3,4-b] pyridine-5 (7H) -one in the form of a tan solid, melting point 122®-129®C (decomposition * ). A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange image.

EXAMPLE XVII

35 By a similar method as described in Example III, but using 1.6 g of an isomer mixture of 2 - [(1-ethyl-2-methyl-3-indolyl) carbonyl] -3-pyridine carboxylic acid and 3 - [( 1-ethyl-2-methyl-3-indolyl) carbonyl] -2-pyridinecarboxylic acid, 2.0 g of 4,4'-dioctyldiphenylamine, 0.5 ml of pyridine and 6 ml of acetic anhydride, 0.9 g of 7- (1 -ethyl- 7908868 '- 19 - 2-methyl-3-indolyl) -7- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-5 (7H) -one in the form of a light -tan-colored substance, melting point 187 ®C (decomposition).

A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange image.

5 EXAMPLE XXVIII

According to a similar method as described in Example III, however, using 1.6 g of a mixture of isomers 2 - [(1-ethyl-2-methyl-3-indolyl) carbonyl] -3-pyridine carboxylic acid and 3 - [( 1-ethyl-2-methyl-3-indolyl) carbonyl] -2-pyridinecarboxylic acid, 1.1 g 4- (dimethylamino) -N-phenyl-10 aniline, 0.5 ml pyridine and 6 ml acetic anhydride, 1, 3 g of 7- (1-ethyl-2-methyl-3-indolyl) -7 ^ [4- (dimethylamino) phenyl] phenylaminoj furo [3,4-b] pyridine-5 (7H) -one in the form of a gray solid, mp 191 ° - 192 ® C (decomposition). A solution of the product in chloroform contacted with acid clay or phenolic resin developed a brown image.

EXAMPLE XIX

According to a similar method as described in Example III, however, using 1.6 g of a mixture of the isomers 2 - [(1-ethyl-2-methyl-3-indolyl) carbonyl] -3-pyridine carboxylic acid and 3- [ (1-ethyl-2-methyl-3-indolyl) carbonyl] -2-pyridine carboxylic acid, -1.3 g 4,4'-bis- (dimethylamino) -20 diphenylamine, 0.5 ml pyridine and 6 ml acetic anhydride, obtained 0.35 g of 7- (1-ethyl-2-methyl-3-indolyl) -7- | bis [4- (dimethylamino) phenyl] amino} -furo [3,4-b] pyridine-5 (7H) -one in the form of a white solid, mp 205 ° - 206 ®C (decomposition). A solution of the product in chloroform contacted with acid clay or phenolic resin developed a brown image.

EXAMPLE XXX

According to a similar procedure as described in Example III, however, using 1.6 g of a mixture of the isomers 2 - [(1-ethyl-2-methyl-3-indolyl) carbonyl] -3-pyridine carboxylic acid and 3- [ (1-ethyl-2-30 methyl-3-indolyl) carbonyl] -2-pyridine carboxylic acid, 0.95 g N-phenyl-n.toluidine, 0.5 ml pyridine and 6 ml acetic anhydride, 7- (1- ethyl 2-methyl-3-indolyl) -7- (m.tolylphenylamino) furo [3,4-b] pyridine-5 (7H) -one in the form of a yellow solid, mp 178 ° - 190 ®C (decomposition). A solution of the product in contact with acid clay or phenolic resin in toluene developed an orange image.

EXAMPLE XXXI

A mixture of 4.5 g of a mixture of the isomers 2 - [(1-ethyl-2-methyl-3-indolyl) carbonyl] -3-pyridinecarboxylic acid and 3 - [(1-ethyl-2-methyl-3- indolyl) carbonyl] -2-pyridinecarboxylic acid, 2.5 g diphenylamine and 30 ml 7578868 * '. o-20-acetic anhydride was stirred for 6.5 hours and then treated with 1 ml of pyridine and the mixture was left overnight.

The mixture was poured into 750 ml of water and the resulting solid product was purified by column chromatography to obtain 7- (1-ethyl-2-methyl-3-5 indolyl) -7- (di-enylamino) furo [3, 4-b] pyridine-5 (7H) -one in the form of a light orange solid, mp 132.5®-136®C. A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange image.

EXAMPLE XXXII

According to a similar procedure as described in Example III, however, using 1.6 g of an isomer mixture of 3 - [(1-ethyl-2-methyl-3-indolyl) carbonyl] -4-pyridine carboxylic acid and 4- [ (1-ethyl-2-methyl-3-indolyl) carbonyl] -3-pyridine carboxylic acid, 0.9 g diphenylamine, 0.5 ml pyridine and 6 ml acetic anhydride, 1- (1-ethyl-2-methyl-3) was obtained indolyl) 1- (diphenylamino) furo [3,4-c] pyridine-3 (1H) -one in the form of a viscous oil. A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange image.

EXAMPLE XXXIII

According to a similar procedure as described in Example III, 20, however, using 3.1 g of 3 - [(1-ethyl-2-methyl-3-indolyl) carbonyl] -2-pyrazine carboxylic acid, 2.2 g of 4-ethoxy -N-phenylaniline, 2 ml pyridine and 10 ml acetic anhydride, 1.1 g of 7- (1-ethyl-2-methyl-3-indolyl) -7-] (4-ethoxyphenyl) phenylamino] furo [3,4 -b] pyrazine-5 (7H) -one in the form of a light brown solid, mp 120 ° - 135 ° C (decomposition). A solution of the product in toluene contacted with acid clay or phenolic resin developed a "reddish-orange image.

EXAMPLE XXXIV

According to a similar procedure as described in Example III, but using 0.8 g of 3 - [(1-ethyl-2-methyl-3-indolyl) carbonyl] -2-pyrazine carboxylic acid, 1.0 g 4.41- dioctyldiphenylamine, 0.25 ml pyridine and 3 ml acetic anhydride, 7- (1-ethyl-2-methyl-3-indolyl) -7- [bis (4-octylphenyl) amino] furo [3,4-b pyrazine-5 (7H) -one in the form of a semi-solid. A solution of the product in toluene contacted with acid clay or phenolic resin developed an orange image.

EXAMPLE XXXV

A mixture of 4 g of 3 - [(1-ethyl-2-methyl-3-indolyl) carbonyl] -2-pyrazine carboxylic acid, 1.7 g of diphenylamine and 15 ml of acetic anhydride was left at room temperature for 1 hour and then gently for 30 minutes heating stirred. The product, 7- (1-ethyl-2-methyl-3-indolyl) - 7 9 0 8 8 6 8 <3 -21- 7- (diphenylamino) furo [3,4-b] pyrazine-5 (7H) One was isolated by column chromatography as a red solid, mp 98 ° -100 ° C. A solution of this product in toluene contacted with acid clay or phenolic resin developed an orange image.

By similar procedures as described in the above examples, however, using the appropriate Z-CO pyridinecarboxylic acids of formula (9) and the suitably substituted diarylamines of formula (10), the compounds shown in the table below are obtained according to formula (1) (Examples XXXVI-LXV).

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EXAMPLE LXVI

A solution of 1.46 g of the color former of Example XXVIII in 60 ml of isopropylbiphenyk and a solution of 5 g of carboxymethyl cellulose in 200 ml of water were mixed and emulsified by rapid stirring. The desired 5 particle size (5 microns) was determined using a microscope. A solution of 15 g of pig skin gelatin in 120 ml of water was added to the emulsion. The pH was adjusted to 6.5 with 10% aqueous sodium hydroxide with rapid stirring, and after the gradual addition of 670 ml of water at 50 ° C, the pH was continued with 10% aqueous acetic acid under 10 rapidly stirring set to a value of 4.5. After 5 minutes, the mixture was cooled to 15 ° C, treated with 10 g of 25% aqueous glutaraldehyde and stirred quickly for 15 minutes. The resulting microcapsule dispersion was stirred more slowly overnight, diluted with water to 1120 g, and coated with approximately 0.0038 cm thick on 15 sheets of white typewriter paper. The sheets were air dried.

Duplicate images were applied to a receiver sheet coated with phenolic resin or acid clay. The colorformer vein Example XXVIII gave a brown image on both types of receiver sheets.

EXAMPLE LXVII

A dispersion of the color former of Example XXVIII in polyvinyl alcohol was prepared by a mixture of 2.0 g of the color former, 3.7 g of water, 8.6 g of 10% aqueous polyvinyl alcohol and 10 g of grits of zirconium for Shake for 1 hour in a paint shaker. A dispersion of bisphenol-A in polyvinyl alcohol was prepared by shaking a mixture of 9.8 g of bisphenol-A, 18.2 g of water, 42 g of 10% aqueous polyvinyl alcohol and 70 ml of zirconium grits. The coating mixture was prepared by mixing 2.1 g of the polyvinyl alcohol dispersion of the color former with 47.9 g of the polyvinyl alcohol dispersion of bisphenol-A. The coating mixture was applied (in thicknesses of about 0.0076 cm and about 0.0038 cm) on white mimeo paper sheets; the sheets were dried at room temperature. By contacting the coated sheets with a stylus heated to a temperature between 110 ° C and 150 ° C, a purple-colored image was obtained.

35 7908868

Claims (12)

Furopyridinones and furopyrazinones of formula (1), wherein A represents a divalent group of the formula (2), (3), (4), (5) or (6); each of the symbols Y ^, Y ^ and Y. ^, which may be the same or different, a hydrogen atom, a halogen atom, a lower alkoxy group, an alkyl group. 5 with 1-9 carbon atoms, represents a phenyl-lower alkyl group or a group -NR ^ ^, in which the last group R ^ represents a hydrogen atom or a lower alkyl group and R R represents a hydrogen atom, a lower alkyl group, a lower alkanoyl group, a phenylsulfonyl group or a lower alkyl substituted phenylsulfonyl group; Z represents a monovalent group of the formula (7) or (8) -10; R 1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom or a di (lower alkyl) amino group; R 1 represents a lower alkyl group; R ,. represents a lower alkyl group or a benzyl group; Rg represents a hydrogen atom or a non-tertiary alkyl group with 1-18 carbon atoms; and R 1 represents a hydrogen atom, a phenyl group or a non-tertiary lower alkyl group. Compounds according to claim 1, wherein A represents a group of the formula (2) or a group of the formula (5). Compounds according to claim 1 or 2, wherein Z represents a group of the formula (7), R 1 a hydrogen atom or a lower alkyl group and each of the symbols R 1 and R 1 represents a lower alkyl group. Compounds according to claim 1 or 2, wherein Z represents a group of the formula (8) and Y ^. and both are hydrogen. Compounds according to claims 1-3, wherein Y ^ and Y ^ are both hydrogen. Compounds according to claims 1-5, wherein each of the symbols Y ^ and Y ^, which may be the same or different, represents a hydrogen atom or an alkyl group with 1-9 carbon atoms. 7. 7- [4-Dimethylamino) phenyl] -7- (diphenylamino) furo [3,4-b] -5- (7H) -one. 8. 5- [4- (dimethylamino) phenyl] -5- (diphenylamino) furo [3,4-b] pyridine-7 (5H) -one. 9. 7- [4- (Dimethylamino) phenyl] -7- [bis (4-octylphenyl) amino] furo [3,4-b] - • amino] furo [, 34-b] pyridine ~ 5 (7H) - on. 10. 5- [4- (Dimethylamino) phenyl] -5- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-7 (5H) -one. 11. 7 - [4- (Diethylamino) -2-methylphenyl] -7- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-5 (7H) -one. 12. 5- [4- (Diethylamino) -2-methylphenyl] -5- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-7 (5H) -one. 13. 7- (1-Ethyl-2-methyl-3-indolyl) -7- (diphenylamino) furo [3,4-b] pyridine-7908868-27-5 (7Η) -one. 14. 5- (1-Ethyl-2-methyl-3-indolyl) -5- (diphenylamino) furo [3,4-b] pyridine-7 (5H) -one. 15. 7- (1-Ethyl-2-methyl-3-indolyl) -7- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-5 (7H) -one. 16. 5- (1-Ethyl-2-methyl-3-indolyl) -5- [bis (4-octylphenyl) amino] furo [3,4-b] pyridine-7 (5H) -one. Process for the preparation of new furopyridinones and furopyrazones, characterized in that a carboxylic acid according to formula (9) is reacted with 10 (1) a diarylamine according to formula (10) in the presence of the anhydride of an alkane carboxylic acid with 2-5 carbon atoms, or with (2) thionyl chloride, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride and reacting the product obtained by reaction with the chloride with a diarylamine of formula (9) in the presence of an organic base. 18. Process according to claim 17, characterized in that acetic anhydride is used as the anhydride of an alkane carboxylic acid with 2-5 carbon atoms. 19. Process according to claim 17, characterized in that the inorganic acid chloride is thionyl chloride and the organic base is diarylamine, pyridine or urea. Pressure-sensitive duplication system without carbon paper and thermal marking system, characterized in that the system contains a compound according to claims 1-16 as a color-forming material. Pressure-sensitive carbonless paper duplicating system according to claim 25, characterized by a support sheet coated on one side with a layer of pressure-breakable microcapsules containing a liquid solution of the color-forming material. 22. A thermal marking system according to claim 20, characterized by a support sheet coated on one side with a layer containing a mixture of the color-forming material and an acid developer, such that by applying heat a marking-forming reaction between the color-forming material material and the acid developer is accomplished. * 7908868 F- a LS 874-190 Ned. - Appendix 4 Sterling Drug Inc. in New York, New York, United States of America Z 'N- / 7 • Hs - ,,, · ·. / ^. (2) .. (3V '(4). (5) (6) r ^ N- ^ ί · ί [I Γ IT R.RcN * ^^ ïïï: v ^ A> n, s, * R- 4 5 -------- 3 ..I-7 · C7) -i ...... (8) \ o .. - C (J> ®γ '. I # - r ^ X ^ 3 __ (13) I (14). II ζ ^ NR4H5 '.' V. 7908868 - 2 - KEY SCHEDULE A 'cA αΓ' · ftr '^ wi · ZH ^^ ¢ ^ €: = 0 ^, / X = 0 γ / W ν = χγ I ü —— ^ | zi Z v (12a) I (9a). J (9b) | --- 7 .9 »Yy r ^ r ^ X ί ^ \ / \! L /) - s / y4 LL · / i — v ï II iy ^> s, Μ, (la) / X1 * 2 X1 X2 Clb) | REACTION SCHEDULE B (12b) I (9c)! C9d) I ^ ί <ίχΝν = ^ Ϊ3 Λ ^ “" ^ 3 •, M,> h, HO I1 2 1 2 X · 7808888