CH628923A5 - Preparation and use of 3-(diphenylamino)phthalides - Google Patents

Description

The present invention relates to the preparation of new 3- (diphenylamino) phthalides substituted in position 3 and their use as color formers in reproduction systems (or copy) without pressure-sensitive carbon paper, in thermal marking systems and in hectographic reproductive systems or colorless chemicals.

It is known that several categories of organic compounds of widely varied structural types can be used as color formers for reproduction systems without carbon paper. Among the most widely known categories, there may be mentioned phenothiazins, for example, benzoyl blue, leuco methylene; fluorans, for example, 2'-anilino-6'-diethylaminofluorane; phthalides, a category to which this invention relates, for example the lactone of crystallized violet; and various other types of color formers commonly used in commercially used carbonless reproduction systems. Typical examples of many systems described in the art are those described in U.S. patents. No. 2,712,507, io 2,800,457 and 3,041,289.

Many of the color formers in the prior art suffer from one or more disadvantages such as poor dyeing power, poor light stability, poor resistance to sublimation and poor solubility in common organic solvents, such as last disadvantage then requiring the use of specialized and expensive solvents to obtain microencapsulated solutions of sufficient concentration for use in pressure-sensitive reproduction systems. The prior art further includes U.S. patents. No. 3736 168, and 3491 112 and Japanese patent publication No. 71/4616.

R. Valters and V. Tsiekure in Khim. Geterotsikm. Soedin. 1975, (11) 1476-8 describe the chain-chain tautomerism of 3- (N, N-diphenylamino) -3-phenylphthalide, but describe no utility for the compound.

This invention relates to the preparation of the compounds of formula I

O

* -Y.

Y1 Y2

in which:

Q is a di- (lower alkyl) -amino, nitro group, a halogen atom or a COX group where X is a hydroxy, benzyloxy, alkoxy group having from 1 to 18 carbon atoms or OM where M is a cation of alkali metal, an ammonium cation or a mono-, di- or tri-alkylammonium cation having from 1 to 18 carbon atoms;

n is 0; or 1 when Q is a di- (lower alkyl) -amino, nitro or COX group; or from 1 to 4 when Q is a halogen atom; Yi, Y2, Y3 and Y4 are identical and different and are hydrogen or halogen atoms or hydroxy, lower alkoxy, alkyl having from 1 to 9 carbon atoms, phenyl-lower alkyl, COOR4 or NR5R6, where R4 and Rs are hydrogen atoms or lower alkyl groups and R6 is a hydrogen atom or a lower alkyl, cycloalkyl group having 5 to 7 carbon atoms or lower alkanoyl; Z is a group

55

60

R.

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;

R.

628,923

a 9-julolidinyle where:

R is a hydrogen atom or a non-tertiary alkyl group having from 1 to 4 carbon atoms;

Ri is a hydrogen atom or a non-tertiary alkyl group having from 1 to 18 carbon atoms;

R2 and a hydrogen atom or a phenyl or non-tertiary alkyl group having from 1 to 4 carbon atoms;

R.Ì is a hydrogen atom or a non-tertiary alkyl group having from 1 to 4 carbon atoms or non-tertiary alkoxy group having from 1 to 4 carbon atoms;

R? is a hydrogen or halogen atom or a lower alkyl, lower alkoxy or di-lower alkylamino group;

Rs and a lower alkyl group; and R9 is a lower alkyl, benzyl, phenyl or phenyl group substituted by a lower alkyl or alkoxy group.

The compounds are useful as color formers in pressure-sensitive carbonless reproduction systems, thermal marking systems and hectographic reproduction systems.

Particular embodiments relate to the preparation of the compounds of formula I

in which Q, n, Yi, Y2, Y3 and Y4 have the meanings given above and Z is

9

Ri, R :, R3, R ?, Rs and R? having the meanings previously given. The preferred compounds in the context of this particular embodiment are those in which:

a) nvautO;

b) n is 1 and Q is a lower dialkylamino group or COX where X is as defined above; and c) n is 4 and Q is a halogen atom, in particular 3- [N- (4-ethoxy-phenyl) -N-phenylamino] -3- (1-ethyl-2-methyl-3-indolyl ) phthalide, 3- (diphenylamino) -3- (1-ethyl-

2-methyl-3-indolyl) phthalide, 3- (l-ethyl-2-methyl-3-indoh l) -3- (N-Phenyl-N-m-tolylamino) phthalide,

3- (1-ethyl-2-methyl-3-indolyl) -3- [N, N-bis- (3-ethyl-5-nonyl-phenyl) aminoJphthalide, 5- (and 6-) carboxy-3- [N- (4-ethoxy-phenyl) -N-phenylamino] -3- (1 -ethyl-2-methyl-3-indolyl) -phthalide, 3- [N- (4-ethoxyphenyl) -N-phenyl- amino] -3- (1 -ethyl-2-methyl-

3-indoIyl) -5- (and 6-) methoxycarbonylphthalide, 5- (and 6-ethoxycarbonyl-3- [N- (4-ethoxyphenyl) -N-phenyla-mino] -3- (1 -ethyl-2- methyl-3-indolyl) phthalide, the

3- [N- (4-ethoxyphenyl) -N-phenylamino] -3- (1-ethyl-2-methyl-3-indolyl) -5- (and 6 -) - n-octyloxy-carbonylphthalide, 5- ( and

6-) benzyloxycarbonyl-3-N- [4- (ethoxy-phenyl) -N-phenyla-mino] -3- (1-ethyl-2-methyl-3-indolyI) phthalide, 4,5,6,

7-tetrachloro-3- [N- (4-ethoxyphenyl) -N-phenyla-mino] -3- (ethyl-2-methyl-3-indolyl) phthalide, 3- (1-ethyl-2-methyl-3 -indolyl) -3- [N, N-bis- (4-octyphenyl) -amino] phta-lide, 3- [4- (dimethylamino) phenyl] -3- [M- (4-ethoxy-phenyl) - N-phenylamino] -phthalide; 3- [4- (dimethyl-amino) phenyl] -3- [N- (4-isopropoxyphenyl) -N-phenyl-amino] -thalide; 4,5,6,7-tetrachloro-3- [4- (dimethyl-amino) -phenyl] -3- [N- (4-ethoxyphenyl) -N-phenyl-aminojphthalide; 3- [4- (dimethylamino) -2-methyl-phenyl] -3- [N- (4-ethoxyphenyl) -N-phenylamino] phthalide; 3- [4- (dimethylamino) phenyl] -3- [N, N-bis- (4-octyl-phenyl) aminojphthalide; 6- (dimethylamino) -3-Lyl [4- (dimethyl-amino) phenyl] -3- [N- (4-ethoxyphenyl) -N-phenylamino] phta-lide; 3 - [(4-dimethylamino) -phenyl] -3- (N, N-diphenyl-amino) phthalide; 6- (dimethylamino) -3- [4- (dimethyl-amino) phenyl] -3- [N, N-bis (4-octylphenyl) amino] -phthalide; 3- [4- (ethylbenzylamino) phenyl] -3- [N-4-ethoxyphenyl) -N-phenylaminojphthalide and 3- [4- (dimethylamino)) - 2-methyl-phenyl] -3- [N, N -bis- [4- (dimethylamino) phenyl] amino] -phta-lide.

The compounds of formula I are prepared by a process which consists in reacting a benzoic acid substituted in position 2, of formula II

(Q)

c = o z

with a diarylamine of formula III

.UH

in the presence of the anhydride of an alkanoic acid having from 2 to 5 carbon atoms as promoter of lactonic cyclization, and of an organic base; in formulas II and III, Z, n, Yi, Y2, Y3 and Y4 have the meanings given above and Q is chosen from the group comprising the di- (lower alkyl) -amino and nitro groups, the halogen atoms and COX groups where X is a hydroxy, benzyloxy or alkoxy group having from 1 to 18 carbon atoms.

Another process for the production of the compounds of formula I consists in reacting a benzoic acid substituted in position 2 of formula II with a mineral acid chloride such as thionyl chloride, phosphorus oxychloride, phosphorus tri-chloride or phosphorus pentachloride,

then reacting the resulting cyclic lactone with a diarylamine of formula III, in the presence of an organic base; in formulas II and III, Z, Q, n, Yi, Y2, Y3 and Y4 are as defined in the previous paragraph.

If desired, a compound of formula I is then formed where Q

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- -COOM, from a compound obtained where Q = -COOH, by reaction with an appropriate base.

The present invention also relates to the use of the compounds (I) in a reproduction system without pressure-sensitive carbon paper, by thermal marking or by hectography, containing a color-forming substance comprising a compound of formula I. special embodiment consists of a pressure-sensitive transfer sheet, designed for use with a receiving sheet having an electron-accepting layer, comprising a support sheet coated on one side with a layer of microcapsules which can rupture under pressure , said microcapsules containing a liquid solution of a color-forming substance comprising at least one compound of formula I. Another particular embodiment relates to a heat-reactive recording material, comprising a support sheet coated on one side a layer containing a mixture comprising at least one color-forming compound of formula I and an acid developer, designed so that the application of heat will produce a marking reaction between the color forming compound and the acidic developer.

Another particular embodiment consists of a hectographic reproduction system, comprising a transfer sheet coated on one side with a layer containing a color-forming substance comprising at least one compound of formula I, where n is 1 and Q is a COX grouping where X is OM and M is as defined above.

When used here, the term "halogen" refers to chlorine, fluorine, bromine or iodine. Chlorine is the preferred halogenated substituent because of its relatively low price and the ease of preparation of the necessary chlorine intermediates, and because other halogens do not offer any particular advantages over chlorine. However, the other halogenated substituents mentioned above are also satisfactory.

The terms "lower alkyl, lower alkoxy and lower dialkyl-amino" denote saturated acyclic groups having from 1 to 4 carbon atoms, which may be linear or branched, for example methyl, ethyl, propyl, isopropyl, butyl, s -butyl, isobutyl, t-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, isobutoxy, t-butoxy, dimethylamino, diethylamino, ethylmethylamino, dipropylamino, dibutylamino, isobutyl-methylamino, di-t-butylamino, etc. .

When used herein, the term "cycloalkyl having 5 to 7 carbon atoms" includes cyclopen-tyle, cyclohexyl and cycloheptyl.

The expression “lower alkanoyl” designates saturated acyclic acyl groups having from 1 to 5 carbon atoms, linear or branched, for example the for-myl, acetyl, propionyl, butyryl, isobutyryl, valeryl groups,

2-methylbutyryl, isovaleryl, pivalyl etc.

The expression “lower phenylalkyl” includes the benzyl, 2-phenylethyl, 2-phenylpropyl groups,

3-phenylpropyl, 1-phenylbutyl, 2,2-dimethyl-2-phenyl-thyle, etc ... If desired, the phenyl group may contain a lower alkyl or alkoxy substituent.

The term “alkoxy having from 1 to 18 carbon atoms” includes, in addition to the above-mentioned lower alkoxy groups, saturated straight or branched chain acyclic groups, such as n-pentyloxy, n-hexyl-oxy, n- heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octa-decyloxy, 1- methylpentyloxy, 2,2-dimethylbutyloxy,

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2-methylhexyloxy, 1,4-dimethylpentyloxy, 3-ethylpentyloxy, 2-methylheptyloxy, 1-ethylhexyloxy, 2-propylpentyloxy, 2-methyl-3-ethylpentyloxy, 1,3,5-trimethylhexyloxy, 1,5-dimethyl-4- ethylhexyloxy, 5-methyl-2-butyl-hexyloxy-2-propylnonyloxy, 2-butyIoctyloxy, 1,1-dimethylundecyloxy, 2-pentylnonyloxy, 1,2-dimethyltetradecyloxy, 1,1-dimethyl-pentadecyl-oxy, etc.

When used here, the expression “alkyl having from 1 to 9 carbon atoms” designates straight or branched chain aliphatic aliphatic hydrocarbon radicals comprising methyl, ethyl, propyl, isopropyl, butyl, isobutyl groups, t-butyl, amyl, 1-methylbutyl, 3-methyl-butyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, iso-octyl, 2-ethylhexyl, nonyl, 3-ethylheptyl, etc.

The expression “non-tertiary alkyl having from 1 to 18 carbon atoms” includes, in addition to the above-mentioned alkyl groups having from 1 to 9 carbon atoms, the saturated monovalent aliphatic hydrocarbon radicals, with straight or branched chain, excluding obviously from any tertiary alkyl group, such as n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-pentadecyl, n-hexa-decyl, n-heptadecyl, n-octadecyl, 1,3,5- trimethylhexyl, 1,5-dimethyl-4-ethylhexyl, 5-methyl-2-butylhexyl, 2-pro-pylnonyl, 2-butyloctyl, 2-pentylnonyl, 1,2-dimethyl-tetra-decyl, etc.

When used here, the term "alkali metal" refers to lithium, sodium or potassium.

The expression “mono-, di- or tri-alkylammonium cation” includes ammonium cations substituted by 1 to 3 alkyl groups as described above. The alkyl groups may be the same or different as long as the ammonium cation does not contain more than 18 carbon atoms. As examples, mention may be made of the methylam-monium, t-butylammonium, t-octylammonium, n-dodecyl-ammonium, n-octadecylammonium, di-n-butylammonium, di-n-nonylammonium, isopropyl-n-butylammonium cations. thyl-n-butylammonium, tri-ethylammonium, N-ethyl-N, N-diisopropylammonium, tributylammonium, di-n-butyloctilammonium, ect.

The expression “9-julolidinyle” obviously designates the radical of formula

Anhydrides of alkanoic acids having 2 to 5 carbon atoms include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, isovaleric anhydride, a- anhydride methylbutyric acid, pivalic anhydride, etc. Acetic anhydride is preferred because of its low price and high reactivity, however the other anhydrides mentioned above are also satisfactory.

Organic bases include pyridine, collidine, lower trialkylamines, urea, diarylamines of formula IV above, etc. Due to their low price and easy availability, pyridine and urea are preferred.

According to a practical embodiment, the compounds of formula I are obtained by reacting quantities approximately

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equimolars of a benzoic acid substituted in position 2 of formula II and of a diarylamine of formula III in the anhydride of an alkanoic acid having from 2 to 5 carbon atoms, such as acetic anhydride, with or without inert diluent , and in the presence of an organic base, for example pyridine or urea, at a temperature of about 0 to 100 ° C for about 10 minutes to 24 hours. The reaction is generally carried out in the absence of an inert diluent at a temperature of about 20 to 40 ° C for about 0.5 to 2 hours. If desired, an excess of the diarylamine reagent can be used as the organic base. The product thus obtained can be isolated by filtration if it is insoluble in the reaction medium or by dilution of the reaction medium with a miscible solvent in which the product is insoluble, such as a lower alkanol or a low molecular weight hydrocarbon, for example l isopropyl alcohol or hexane, or a mixture thereof, to effect precipitation of the product. Alternatively, the reaction mixture can be poured into an aqueous base such as dilute ammonium hydroxide, sodium hydroxide, sodium carbonate or sodium bicarbonate, and extract the product with an organic solvent such as benzene and toluene, then evaporate the organic solvent, which leaves the product in the form of a residue. Once isolated, the product can be purified by conventional methods such as trituration or recrystallization from an appropriate solvent.

According to the second method, the compounds of formula I can be prepared in practice in two stages which firstly comprise the reaction of a benzoic acid substituted in position 2 of formula II, with an excess of an organic acid chloride such as thionyl chloride, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride, with or without an inert diluent such as benzene, toluene, chloroform or 1,2-dichloroethane, at a temperature of 20 to 80 ° C for about 0.5 to 2 hours; and after removal of the excess mineral acid chloride, the reaction of the resulting product which, although not having been

in which Q, n and Z have the meanings given for formula II, with a diarylamine of formula III, in an inert solvent in the presence of an organic base as described above, at a temperature between 0 and 80 ° C for d '' about 1 to 48 hours. The product can be isolated and purified as described above.

When preparing the compounds of formula I, in which Q is COX and X is a benzyloxy or alkoxy group having from 1 to 18 carbon atoms or OM where M is an alkali metal cation, an ammonium cation or a mono-cation , di- or trialkylammonium having from 1 to 18 carbon atoms, it is usually preferred to prepare the compound of formula I where Q is COOH, then transform the carboxy group into the desired ester, alkali metal salt or ammonium salt according to procedures classics.

Some of the position 2 substituted benzoic acids of formula II, required as starting materials in the preparation of products of formula I, are known, for example those described in the U.S. Patent. No. 3,812,146, German Patent Application No. 2,423,534, Journal of the

Chemical Society 107,885 (1915) and Chemical Abstracts 83, 77938h (1975). Those which were not previously known can be prepared according to the procedures described for the preparation of the known compounds, for example s such as those described in British Patent No. 1,435,179. The benzoic acids substituted in position 2 are prepared by reaction of a phthalic anhydride of formula VII

O

With an appropriate indole of formula VI, a pyrrole of formula VIII, a carbazole of formula IX, an aniline of formula X or julolidine,

X

Q and n in formula VII having the meanings given previously in formula II and R, R7, Rs and R9 in formulas VIII, IX and X having the meanings previously given, in the presence of a Lewis acid, for example the aluminum chloride or zinc chloride, with a diluent such as benzene, chlorobenzene or o-dichlorobenzene, at a temperature of about 0 to 100 ° C. The reaction is conveniently carried out in benzene in the presence of aluminum chloride at about 0-25 ° C. Alternatively, the more reactive indoles (formula V) can be reacted with phthalic anhydrides (formula VII) in the absence of a Lewis acid, by simply heating the reactants in an inert solvent to about 80-150 ° C.

It will obviously be seen that the reaction of an asymmetrically substituted phthalic anhydride (formula VII) with an indole, a pyrrole, a carbazole, an aniline (formulas V, VIII, IX or X) or julolidine, can give isomers or a mixture of isomers of 2-Z-CO-benzoic acids (formula II). For example, the reaction of a phthalic anhydride substituted in position 3 (formula VII where n is 1 and Q occupies position 3) with an indole, a pyrrolle, a carbazole, an aniline or julolidine, can give a 2- 3- or 6-substituted Z-CO-ben-zoic (formula II where n is 1 and Q occupies position 3 or position 6) or a mixture thereof. Similarly, a phthalic anhydride substituted in position 4 (formula VII or n is 1 and Q occupies position 4) can give a 4- or 5-substituted 2-Z-CO-benzoic acid (formula II where n

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is 1 and Q occupies position 4 or position 5) or a mixture of these. The mixture of isomeric 2-Z-CO benzoic acids can be separated by conventional means such as fractional crystallization or chromatography. Alternatively, the isomeric mixtures can be reacted directly with the appropriate diarylamines of formula III to obtain isomeric mixtures of the phthalides of formula I. Thus, the reaction of a mixture of 2-Z-CO-benzoic acids 3- and 6-substituted (formula II where n is 1 and Q occupies position 3 or 6) with a diarylamine of formula III will give a mixture of 4- and 7-substituted phthalides (formula I where n is 1 and Q occupies position 4 or 7); and similarly, a mixture of 4- and 5-substituted 2-Z-CO-benzoic acids (formula II where n is 1 and Q occupies position 4 or 5) will give a mixture of phthalides 5- and 6 -substituted (formula I where n is 1 and Q occupies position 5 or 6). It is possible, if desired, to separate the mixtures of the phthalides by conventional methods, or one can simply and preferably use them as mixtures in the practice of this invention.

The diarylamines of formula III which are also necessary as starting materials in the methods of the invention, belong to a well-known category of compounds and are available commercially or easily obtained by standard procedures well known in the art.

The new compounds of formula I above are essentially colorless in the form described. When in contact with an acidic medium, for example silica gel or one of the media generally used in carbon-free reproduction systems sensitive to pressure such as clay loam or phenolic resins, the compounds of formula I give an image of yellow to black color having a good to excellent dyeing power, and having an excellent light stability, an excellent resistance to sublimation and an excellent ability to reproduce by xerographic processes. The compounds are thus entirely suitable for use as colorless precursors, that is to say as color-generating substances in pressure-free carbon-free reproduction systems. Compounds which produce a yellow to red color can be used as "inks" (like "toner") in admixture with other color formers to give neutral tint images which are preferably easily reproducible by xerographic means. The compounds of formula I or at least one of Yi and Y2 and at least one of Y3 and Y4 are simultaneously lower dialkylamino groups, give a grape-brown image when they are in contact with an acid medium and are therefore particularly interesting as color precursors. In addition, the compounds of formula I, in particular those in which n is 1, Q is COX and X is an alkoxy group having from 1 to 18 carbon atoms, or those in which one or more of the groups Yi, Y2, Y3 and Y4 are alkyl groups of 1 to 9 carbon atoms, have improved solubility in common and inexpensive organic solvents such as odorless mineral spirits, kerosene, vegetable oils, etc .; and those where n is 1, Q is

COX and X is OM where M is as defined above, are soluble in water and lower alkanols, which avoids the need to use more expensive specialized solvents such as polyhalogenated or alkylated biphenyls which are usually used to prepare the micro-encapsulated solutions of color formers of the prior art.

The compounds obtained according to this invention can be incorporated into any of the industrially used systems known in the field of carbon-free reproduction. A typical technique for such an application is as follows. Microencapsulation of solutions containing one or more colorless precursors of formula I is carried out, optionally in admixture with other color-forming agents, by well known procedures, for example such as those described in the U.S. Patent. No. 3,649,649. The microcapsules are coated on the back of a transfer sheet using an appropriate binder, then the coated transfer sheet is then assembled in a bundle, the side coated with microcapsules being in contact with a receiving sheet coated with an electron accepting substance, for example clay silt or a phenolic resin. Applying pressure to the bundle, such as that from a stylus, typewriter, or other form of writing or printing, causes the capsules on the back to break. The solution of color-forming agent released from the broken microcapsules flows towards the receiving sheet and, on contact with the acid medium which it carries, forms a yellow to red colored image having good dyeing power. It is obvious that variants of this mode of application can be used. For example, the receiving sheet in a bundle can be coated with the compounds in question and the acid developer can be contained in microcapsules applied to the back of the upper sheet of the bundle; or the receiving sheet may be coated with a mixture containing both the revealing agent and the micro-encapsulated color forming agent.

It has also been found that when the compounds of formula I are intimately mixed with an acid developer of the type commonly used in thermal papers as described in the U.S. Patent. No. 3,539,375, i.e. paper which gives a colored image when in contact with a heated stylus or a heated character, for example bisphenol A, heating the mixture produces a colored tint image variable ranging from yellow to purple, depending on the particular compound of the invention used. The ability of the compounds of formula I to form a dark color when heated in admixture with an acid developer such as bisphenol A makes them usable in thermal paper marking systems, whether an original or a copy by bringing the thermal paper into contact with a heated stylus or heated character, in any of the methods generally known in the art.

Compounds of formula I which are soluble in water and lower alkanols can be introduced into any of the hectographic or commercial fluid reproduction systems, such as those described in British Patent No. 1,427,318. such systems, a transfer sheet coated on one side with a layer comprising one or more color formers of formula I soluble in water or lower lacanols, is placed so that its coated surface is against a surface d '' an original paper on which we type, write or introduce marks, which causes the transfer of the coating, in the form of an essentially colorless reverse image, to the original paper at the points where the transfer sheet and the paper original were pressed together. The original paper is then brought into contact with a series of sheets of paper moistened with a suitable reproduction fluid such as ethanol. The fluid dissolves part of the color forming agent and transfers it to each sheet of paper where it combines with an electron accepting substance, giving a yellow to red image that reproduces typing or initial writing original paper.

The molecular structures of the compounds obtained according to the invention have been assigned on the basis of the modes of synthesis, elementary analysis and the study of their infrared spectrum, of nuclear magnetic resonance and of mass.

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The following examples will illustrate the invention without, however, limiting it.

Example 1

A. A mixture containing 24 g of 2- (I-ethyl-2-methyl-3-indo-lylcarbonyl) -benzoic acid, 16.5 g of 4-ethoxy-N-phenylaniline is stirred for one hour at room temperature. , 7 ml of pyridine and 70 ml of acetic anhydride. Dilution with 30 ml of 2-propanol and 100 ml of ligroin does not produce a precipitate. The reaction mixture is then poured into 10% ammonia and the product is extracted with toluene. The organic extracts are washed with water and a saturated aqueous sodium chloride solution and evaporated to dryness in vacuo. Trituration of the residue with ligroin provides 25.3 g of 3- [N- (4-ethoxyphenyl) -N-phenyl-mino] -3- (1-ethyl-2-methyl-3-indolyl) phthalide, m.p.

110-135 ° C. Recrystallization of an analytical sample from a mixture of 2-propanol and ligroin provides colorless crystals, m.p. 161-163 ° C. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an image of yellow color.

B. A mixture containing 7.86 g (0.02 mole) 2- (1-ethyl-2-methyl-3-indolylcarbonyl) benzoic acid, 6.38 g (0 is stirred overnight at room temperature). , 03 mol) of 4-ethoxy-N-phenylaniline and 12 ml of acetic anhydride and then poured into 200 ml of 10% aqueous sodium hydroxide and 100 ml of toluene. After one hour of stirring, the layers are separated. The toluene layer is dried over anhydrous sodium sulfate, treated with bleaching charcoal and filtered. The filtrate is concentrated to 50 ml and diluted slowly with 900 ml of hexane. The precipitated product is collected, washed with hexane and dried, giving 6.0 g of a product essentially identical to the product in part A above.

Example 2

A. A mixture containing 3.1 (2- (1-ethyl-2-methyl-3-indo-lylcarbonylj-benzoic acid, 5 g of 3,3'-diethyl-5) is stirred for one hour at room temperature. 5-di-nonyIdi-phenylamine, 10 ml of acetic anhydride and 1 ml of pyridine, then it is poured into a 10% aqueous solution of sodium hydroxide and the product is extracted with toluene. The toluene extracts are dried over anhydrous sodium sulfate and evaporated to dryness in vacuo. Trituration of the residue with ligroin and 2-propanol provides 0.8 g of 3- [N, N-bis- (3-ethyl-5-nonylphenyl ) amino] -3-l- (ethyl-2-methyl-3-indolyl) phthalide, mp 76-90 ° C with decomposition A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an image of Red color.

B. A mixture containing 6.2 g of 2- (1-ethyl-2-methyl-3-indo-lylcarbonyI) benzoic acid, 9.3 g of 3.3 ′ is stirred for 2 hours at room temperature. diethyl-5,5'-di-nonyldi-phenylamine, 25 ml of acetic anhydride and 1 g of urea, then poured into 5% aqueous ammonium hydroxide and extracted with toluene . The organic extracts are dried over anhydrous sodium sulfate and evaporated to dryness in vacuo. The residue is triturated with cyclohexane and 4.96 g of a product essentially identical to the product of part A above is obtained.

Example 3

A. A stirred solution containing 48.0 g (0.250 mole) of trimellitic anhydride and 45.0 g (0.314 mole) of 1-ethyl-2-methylindole in 350 ml of 1,2-dichloroethane is heated at reflux for two hours. . The reaction mixture is allowed to cool to room temperature and the precipitated solid is collected, washed with 1,2-dichloroethane and dried, giving 66.0 g of a 4- acid mixture and 5-car-boxy-2- (1-ethyl-2-methyl-3-indolylcarbonyl) benzoic, mp 198-201 ° C. This substance is used in subsequent reactions without further purification;

B. A mixture containing 7.0 g of 4- (and 5-) carboxy-2- (1-ethyl-2-methyl-3-indolylcarbonyl) benzoic acid, 4.3 g, is stirred for two hours at room temperature. of 4-ethoxy-N-phenylaniline, 25 ml of acetic anhydride and 2 ml of pyridine. Dilution with 20 ml of 2-propanol and 100 ml of ligroin does not give a precipitate. The mixture is then poured into toluene and the product is extracted with 5% ammonia. The aqueous alkaline extracts are neutralized with 3N hydrochloric acid. The resulting precipitate is collected, washed with water and dried, which gives 5.6 g of 5- (and 6-) carboxy-3- [N- (4-ethoxyphenyl) -N-phenylamino] -3- (1-ethyl-2-methyl-3-indolyl) phthalide, mp 145-148 ° C.

C. To a stirred solution containing 2 g of the above acid in 30 ml of acetone, 2 ml of t-octylamine are added. After

10 minutes of stirring, the mixture is diluted with 200 ml of hexane. The solvents are decanted and the residue is triturated with hexane, to give 1.8 g of 3- [N- (4-ethoxyphenyl) -N-phenylamino] -3- (1-ethyl-2-methyl- 3-indolyl) phthalide-5- (and

6-) t-octyl ammonium carboxylate, m.p. 141 ° C with decomposition.

Example 4

A mixture containing 4.5 g of 3,4,5,6-tetrachloro-2- (1-ethyl-2-methyl-3-indolylcarbonyl) benzoic acid, 1.0 ml of chloride is heated to reflux temperature. tionyl and 200 ml of 1,2-dichloroethane, then cooled to 30 ° C and treated with a solution containing 2.1 g of 4-ethoxy-N-phe-nylaniline in 20 ml of 1,2- dichloroethane. After stirring overnight at room temperature, the reaction mixture is poured into 5% ammonia and the product is extracted with 1,2-dichloroethane. The organic extracts are washed with water and a saturated aqueous solution of sodium chloride and evaporated to dryness. The residue is triturated with cyclohexane, which gives 3.1 g of 4.5.6,

7-tetrachloro-3- [N- (4-ethoxyphenyl) -N-phenyl-amino] -3- (1-ethyl-2-methyl-3-indolyl) phthalide, m.p.

182-188 ° C. The infrared spectrum indicates that this substance is contaminated with unreacted 3,4,5,6-tetra-chloro-2- (1-ethyl-2-methyl-3-indolylcarbonyl) benzoic acid. By evaporating the triturated product to dryness and then triturating the residue successively in ligroin and acetone, 0.4 g of pure phthalide is obtained, m.p. 143-149 ° C with decomposition. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an orange color image.

Example 5

A. Following a procedure similar to that described in Example 1 A, but using 3.1 g of 2- (1-ethyl-2-methyl-3-indolylcarbonyl) benzoic acid and 1.8 g of diphenylamine, 0.78 g of 3- (1-ethyl-2-methyl-3-indolyl) -3- (diphenylamino) phthalide, mp is obtained 125-130 ° C with decomposition. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an image of yellow color.

B. A mixture containing 3.0 g of N, N-diphenylphthalamic acid, 1.6 g of 1-ethyl-2-methylindole, 7 ml of acetic anhydride and 0.5 ml is stirred for several hours at room temperature. of pyridine. The reaction mixture is filtered to remove unreacted N, N-diphenylphthalamic acid. The filtrate is analyzed by thin layer chromatography and shown to contain the desired 3- (1-ethyl-2-methyl-3-indolyl) -3- (diphenylamino) phthalide identical to the pro-

s

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65

from Part A above, contaminated with a certain amount of 3,3-bis- (1-ethyl-2-methyl-3-indolyl) phthalide.

C. The reaction of part B above is carried out in the absence of pyridine. The reaction mixture is poured into 5% ammonia and the product is extracted with toluene. The toluene extracts are washed with water and a saturated aqueous sodium chloride solution and evaporated to dryness. The residue is essentially identical to the product in Part B above, as indicated by thin layer chromatography.

Example 6

A mixture containing 7.0 g of 2- (1-ethyl-2-methyl-3-indo-lylcarbonyl) -4- (and 5-) nitrobenzoic acid, 4.4 g of 4-ethoxy-N-phenylaniline, 10 ml of acetic anhydride and 2 ml of pyridine. The reaction mixture is diluted with 10 ml of 2-pro-panol and 50 ml of ligroin, which causes 3.73 g of 2- (1-ethyl-2-methyl-3-indolylcarbonyl) -4- (and 5-) nitroben-zoic. The filtrate is poured into 5% ammonia and the product is extracted with toluene. The toluene extracts are washed with water and a saturated aqueous sodium chloride solution and evaporated to dryness in vacuo. The residue is triturated successively with ligroin and 2-propanol, which gives 1.4 g of 3- [N- (4-ethoxyphenyl) -N-phenyla-mino] -3- (1 -ethyl-2- methyl-3-indolyl) -5- (and 6-) nitrophthalide, mp 171-173 ° C. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an orange color image.

Preparation A

To a stirred solution containing 7.4 g of phthalic anhydride and 16.0 g of 1-butyl-2-methylindole at 0-5 ° C, 13.3 g of aluminum chloride are added in portions. The mixture is diluted with 50 ml of benzene and stirred overnight at room temperature. The reaction mixture is poured into 200 ml of 5% hydrochloric acid and the product is extracted with benzene. The benzene extracts are stirred with a dilute aqueous solution of potassium hydroxide. The aqueous alkaline layer is separated, cooled with ice and brought to pH 4 with acetic acid. The precipitated product is collected and dried, giving 2- (1-butyl-2-methyl-3-indolylcarbonyl) benzoic acid, m.p. 88-92 ° C. This intermediate is used in the preparation of the compound of Example 9.

Preparation B

By following a procedure similar to that described in Preparation A, but using 7.4 g of phthalic anhydride and 16.0 g of ln-octyl-2-methylindole, 6.9 g of 2- acid is obtained. (1 -n-octyl-2-methyl-3-indolylcarbonyl) benzoic, mp 121 -123 ° C. This intermediate is used in the preparation of the compound of Example 10.

Preparation C

A mixture is refluxed for 20 hours for 628,923

yield 5.0 g of phthalic anhydride, 5.0 g of 2,5-dimethylindole and 30 ml of 1,2-dichloroethane. The reaction mixture is cooled and the resulting precipitate is collected, washed with 1,2-dichloroethane and dried, giving 3.8 g of 2- (2,5-dimethyl-3-indolylcarbonyl) acid benzoic, pf

198-200 ° C with decomposition. This intermediate is used in the preparation of the compound of Example 11.

Preparation D

By following a procedure similar to that described in Preparation C, but using 10 g of phthalic anhydride and 10 g of 5-methoxy-2-methylindole, 4.6 g of 2- (5-methoxy acid) are obtained. -2-methyl-3-indolylcarbonyl) benzoic, mp 202-203 ° C with decomposition. This intermediate is used in the preparation of the compound of Example 12.

Example 7

A. To a stirred mixture of 14.8 g of phthalic anhydride, 16.2 g of N-methylpyrrole and 50 ml of chlorobenzene at 0-5 ° C, one quarter is added in portions over one hour 39.0 g of aluminum chloride. The mixture is kept at 2-5 ° C during the addition. After dilution with an additional 20 ml of chlorobenzene, the reaction mixture is left to stand for a weekend. Add an excess of water and stir the mixture. The solids are allowed to settle and the supernatant water-chlorobenzene mixture is decanted. The residue is taken up in 50 ml of 5% aqueous sodium hydroxide. The resulting solution is filtered and the filtrate is acidified to pH 3 with dilute hydrochloric acid. The yellow solid which precipitated is collected and dried, which gives 9.46 g of 2- (N-methyl-2- (and 3-) pyrrolylcarbonyl) benzoic acid, m.p. 165-167 ° C.

B. By following a procedure similar to that described in Example 1A but using 2.3 g of acid

2- (N-methyl-2- (and 3-) pyrrolylcarbonyl) benzoic acid and 2.2 g of 4-ethoxy-N-phenylaniline, 1.6 g of

3- [N- (4-ethoxyphenyl) -N-phenylamino] -3- (N-methyl-2- (and 3-) pyrrolyl) phthalide, m.p. 115-134 ° C. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an image of yellow color.

Example 8

By following a procedure similar to that described in Example 1A but using 3.43 g of 2- (9-ethyl-3-car-bazolylcarbonyl) benzoic acid and 2.13 g of 4-ethoxy-N- phenyla-niline, 0.73 g of 3- [N- (4-ethoxyphenyl) -N-pheny-lamino] -3- (9-ethyl-3-carbazolyl) phthalide, mp is obtained. 75-85 ° C with decomposition. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an image of orange yellow color.

By following a procedure similar to that described in Example 1 A, but using the appropriate 2- (3-indolyl) benzoic acids of formula II and the substituted diphenylamines of formula III, the following compounds of formula are obtained I, examples 9 to 21 where n is O and Z is

9

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628923

Example

R.

R1 / R2 / R3 Y, / Y2 Y3 / Y4

11-C4H9

CH3

H

mp (° C)

Color formed

H H 54-92

H 4-C2H5O yellow-orange

10

n-C8Hi7

CHs

H

H H

H 4-C2H5O yellow-orange

11

H

ch3 5-CHs

H H

H 145-157

4- (CH3) 2CHO yellow

12

H

ch3 5-ch3o

H H 68-75 (dec.)

H 4-C2H5O yellow-orange

13

C2H5

CH3

H

H H

H

3-CHs

171-174 yellow

14

H

ch3 H

H H 66-75 (dec.)

H 4-c2h5o orange-yellow

15

H

ch3 H

H H 103-125 (dec.)

H 4- (CH3) 2CHO yellow

16

C2H5

CH3

H

H H

H 77-90

4- (CH3) 2N brown

17

18

c2h5

ch3

H

c2h5

ch3

H

H H 80-115

H 2-COOCH3 pink

H H 76-85

4- (CH3> N 4- (CH3> N grape

19

c2h5

ch3

H

H H

H 93-116

4-CH3CONH yellow

20

C2H5

CH3

H

H H 105-121

4-C8Hi7 4-arylalkyl yellow

21

c2h5

ch3

H

H H 106-108

4-CgHn 4-CsHi7 yellow

Example 226s tion containing 5 g of carboxymethylcellulose in 200 ml Mixed and emulsified with rapid stirring of water. The desired particle size is checked under the microscope (5 solution containing 1.46 g of micron color-forming agent). To the emulsion, a solution containing 15 g of Example 1B in 60 ml of isopropylbiphenyl and a solution of pigskin gelatin in 120 ml of water is added. We adjust the

11

628923

pH at 6.5 with a 10% aqueous solution of sodium hydroxide with rapid stirring, and after the gradual addition of 670 ml of water at 50 ° C., the pH is adjusted to 4.5 with 10% aqueous acetic acid while continuing to stir rapidly. After 5 minutes, the mixture is cooled to 15 ° C, treated with 10 g of 25% aqueous glutaraldehyde and stirred rapidly for 15 minutes. The resulting dispersion of microcapsules is stirred more slowly overnight, diluted with water to 1120 g and placed on sheets of white typewriter paper (film thickness 38 microns). The leaves are air dried. Duplicate typed images are obtained on receiving sheets coated with phenolic resin or acid clay. The color forming agent of Example 1B gives a yellow image on the two types of receiving sheets.

Example 23

By using a procedure similar to that described in Example 22 but by substituting soybean oil for isopropylbiphenyl, microencapsulation of 5- (et6-) n-octyloxycarbonyl-3- [N- (4) is carried out. -ethoxyphenyl) -N-phe-nylamino] -3- (1 -ethyl-2-methyl-3-indoIyl) phthalide and deposited on a transfer sheet. The color forming agent gives an orange image on the two types of receiving sheets.

Example 24

A dispersion in polyvinyl alcohol of 5- (and 6-) benzyloxycarbonyl-3- [N- (4-ethoxy-phenyl) -N-phe-nylamino] -3- (1-ethyl-2-methyl-) is prepared. 3-indolyl) -phthalide, with stirring for one hour in a paint stirrer, a mixture containing 2.0 g of the color-forming agent, 3.7 g of water, 8.6 g of aqueous polyvinyl alcohol to 10% and 10 g of zirconium grinding balls. A dispersion of bisphenol A in polyvinyl alcohol is prepared by stirring a mixture containing 9.8 g of bisphenol A, 18.2 g of water, 42 g of 10% aqueous polyvinyl alcohol and 70 ml of zirconium grinding balls. The coating mixture is prepared by combining and carefully mixing 2.1 of the color forming agent dispersion with 47.9 g of the bisphenol A dispersion. The coating mixture is deposited (at thicknesses of 76 microns and 38 microns) to sheets of white paper for duplicator and the sheets are dried at room temperature. Contact of the coated sheets with a stylus heated to a temperature between 110 ° C and 150 ° C gives a dark orange image.

Example 25

A mixture containing 5.4 g of 2- [4- (dimethylamino) benzoyl] benzoic acid, 3.4 g of diphenylamine, 2 ml of pyridine and 15 ml of acetic anhydride is stirred at ambient temperature. After a few minutes, the solid reagents are completely dissolved and after 15 minutes an orange solid precipitates. The reaction mixture is stirred for an additional 15 minutes and then diluted with 20 ml of 2-propanol and 50 ml of ligroin. After stirring for an additional 10 minutes, the solids are collected, washed with ligroin and 2-propanol (which removes an orange impurity) and dried, which gives 5.9 g of 3- [4- (dimethylamino) phenyl] -3-diphenyla-minophthalide in the form of a cream solid, mp 188-190 ° C with decomposition. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an orange color image.

Example 26

A mixture containing 5.4 g of 2- [4-dimethyla-mino) -benzoyl] benzoic acid, 4.3 g of 4-ethoxy-N-phenylani- is stirred for half an hour at room temperature.

line, 0.5 g of urea and 15 ml of acetic anhydride. The total dissolution of the solid reactants is followed rapidly by the precipitation of the product. After diluting the reaction mixture with 20 ml of 2-propanol, the product is collected, washed with 2-propanol and dried, which gives 8.4 g of 3- [4-dimethylamino) phenyl] -3 - [N- (4-ethoxyphenyl) -N-phe-nylamino] phthalide in the form of a white solid, mp 214-216 ° C with decomposition. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an orange color image.

Example 27

A mixture containing 6.24 g (0.02 mol) of 5- (dimethyla-mino) -2- [4- (dimethylamino) benzoyl] benzoic acid, 6.25 g (6.25 g) is stirred at room temperature for 20 hours. 0.03 mol) of 4-ethoxy-N-phenylaniline and 20 ml of acetic anhydride. Then the reaction mixture is diluted with 30 ml of 2-propanol and stirred for an additional half hour. The solids are collected, washed with ligroin and dried, giving 9.3 g of 6- (dimethyla-mino) -3- [4- (dimethylamino) phenyl] -3- [N- ( 4-ethoxy-phenyl) -N-phenylamino] phthalide in the form of a pale pink solid, mp 200-202 ° C with decomposition. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an orange color image which, on acid clay, becomes green after exposure to fluorescent light.

Example 28

A mixture containing 2.0 g of 2- [2,4-bis- (dimethyla-mino) benzoyl] benzoic acid, 1.4 g of 4-ethoxy-N-phenylaniline is stirred for 1.5 hours at room temperature. , 1 ml of pyridine and 8 ml of acetic anhydride. Dilution with 20 ml of 2-propanol and 50 ml of ligroin does not produce a precipitate. The reaction mixture is therefore poured into 10% aqueous ammonia and the product is extracted with toluene. The organic extracts are washed with water and a saturated aqueous sodium chloride solution and evaporated to dryness in vacuo. Titration of the residue with ligroin provides 2.18 g of 3- [2,4-bis- (dimethyla-mino) phenyl] -3- [N- (4-ethoxyphenyl) -N-phenylamino] phta-lide under shape of a pale orange solid, pf 111-117 ° C with decomposition. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an orange color image.

Example 29

It is heated for half an hour at reflux to obtain a pale green solution a mixture containing 1.7 g of 3,4,5,6-tetrachloro-2- [4- (dimethylamino) benzoyl] benzoic acid, 0.5 ml of thionyl cloride and 200 ml of 1,2-dichloroethane. After cooling to 35 ° C., a solution containing 1.0 g of 4-ethoxy-N-phenylaniline and a few drops of pyridine in 10 ml of 1,2-dichloroethane is added and stirring is continued at room temperature for 2 days. Then the reaction mixture is poured into 10% ammonia and the product is extracted with 1,2-dichloroethane. The organic extracts are washed with water and a saturated aqueous sodium chloride solution and evaporated to dryness in vacuo. The residue is diluted in 100 ml of ethanol and a white solid soluble in water is filtered. The filtrate is evaporated to dryness and the residue is triturated with 2-propanol, which gives 1.5 g of 4, 5, 6, 7-tetrachloro-3- [4- (dimethyla-mino) phenyl] -3- [N- (4-ethoxyphenyl) -N-phenylamino] raw phta-lide in the form of a gray solid, mp 112-121 ° C. The NMR spectrum indicates that the product is a mixture containing the desired phthalide and 3,4,5,6-tetra-chloro-2- [4- (dimethylamino) benzoyl] benzoic acid which does not have s

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628923

12

reacted in an approximate ratio of 60:40. A toluene solution of the product brought into contact with an acid clay gives an image of brown color; and when it is in contact with a phenolic resin, one obtains an image of pinkish purple color.

Example 30

Following a procedure similar to that described in Example 25, but using 3.21 g of 2- (9-juloli-dinyl-carbonyl) -benzoic acid and 2.13 g of 4-ethoxy-N- phenyl-aniline, 4.61 g of 3- (9-julolidinyl) -3- [N- (4-ethoxy-phenyl) -N-phenylamino] phthalide, pf are obtained 143-147 ° C. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an image of red color.

Example 31

Following a procedure similar to that described in Example 28, but using 1.0 g of 2- [4- (dimethyla-mino) -benzoyl] benzoic acid and 1.4 g of 4.4'- dioctyldiphenyI-amine, 0.62 g of 3- [4- (dimethyla-mino) phenyl] -3- [N, N-bis- (4-octylphenyl) amino] phthalide, mp are obtained 158-169 ° C. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives an orange color image. In another preparation carried out in a similar manner to that described in Example 2, the product is obtained in the form of a solid, m.p. 163-167 ° C. A 2% (weight / volume) solution of the product of this example is mixed in variable proportions with a 2% (weight / volume) solution in the toluene of the known color forming agent, the crystallone violet lactone (LVC) and the resulting solution is brought into contact with a phenolic resin, with the following results.

Composed of Ex. 30 LVC Color of the image produced

(solution (2% solution)

7.0 ml 3.0 ml black purple brownish

6.5 ml 3.5 ml black purple brownish

6.0 ml 4.0 ml black purple

5.0 ml 5.0 ml bluish black

Example 32

A. Following a procedure similar to that described in Example 28 but using 3.1 g of 2- [4- (diethylamino) -2-methylbenzoyl] benzoic acid and 3.0 g of 4 , 4'-bis (dimethyl-amino) -diphenylamine, 2.95 g of 3- [4- (dimethylamino) -2-methylphenyl] -3- [N- (4-minethyl-aminophenyl) -N- are obtained (4 -dimethylaminophenyl) amino] phthalide, mp 67-83.5 ° C. A toluene solution of the product brought into contact with an acid clay or a phenolic resin gives a black color image.

B. A mixture containing 6.2 g of 2- [4- (dimethylamino) -2-methylbenzoyl] -benzoic acid and 5.1 g of 4,4'-bis (dimethyl- amino) diphenylamine, 20 ml of acetic anhydride and 2.0 g of urea, then poured into 5% aqueous sodium hydroxide and extracted with toluene. The organic extracts are dried over anhydrous sodium sulfate and evaporated to dryness in vacuo. The residue is dissolved in 200 ml of DM F and added slowly to 1 liter / 2 of water containing

1 g of Dabco with vigorous stirring. The air-dried product weighs 5.0 g and is essentially identical to the product in part a above.

C. In a procedure similar to that described in Example 29, 1.7 g of thionyl chloride are added to a mixture of 100 ml of benzene and 50 ml of 1,2-dichloroethane. After adding 4.7 g of 2- [4- (dimethyl-

amino-2-methylbenzoyl] -benzoic, the reaction mixture is heated to 60 ° C to obtain a clear solution. When the solution has cooled to 40 ° C., a solution of 3.5 g of 4,4'-bis (dimethylamino) diphenylamine and 1 ml of pyridine in 50 ml of 1,2-dichloroethane is added and the mixture is heated at 60 ° C for one hour, cooled and stirred at room temperature overnight. The tarry substance which separates out is filtered, washed and dissolved in dimethylformamide. The addition of an excess of water gives 4.2 g of a light grape solid which gives a black color on silica gel.

Example 33

A. To a stirred mixture containing 36 g of 4- (and 5-) car-15 boxy-2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid (prepared from trimellitic anhydride and 3- (diethyl -amino) phenol), 60 ml of diethyl sulphate and 450 ml of acetone at 35 ° C., a solution containing 25 g of potassium hydroxide in

20 75 ml of water. Once the addition is complete, the stirring is continued for two additional hours. 20 g of potassium hydroxide in 60 ml of water are added and the mixture is heated under reflux for one hour. The solvent is then allowed to distil until the internal temperature reaches 96 ° C. The reaction mixture is kept at 96 ° C for 1 hour and then stirred at room temperature overnight, diluted with 100 ml of water and brought to pH 4.0 with hydrochloric acid 3N. The resulting red precipitate is collected, washed with water and air dried to give 37 g of 4- (and 5-) carboxy-2- (4-diethylamino-2) acid -ethoxy-benzoyl) benzoic, mp 63-96 ° C, which is used without further purification.

B. A mixture containing 8.0 g of 4- (and 5-) carboxy-2- (4-diethyl-) acid is stirred for two hours at room temperature.

35 amino-2-ethoxybenzoyl) benzoic, 8.0 g of 4-dimethyl-amino-4'-diethylamino-diphenylamine, 25 ml of acetic anhydride and 2 ml of pyridine. The mixture is poured into toluene and the product is extracted with 10% ammonia. The aqueous alkaline extracts are acidified to pH 5 with 3N hydrochloric acid. The resulting precipitate is collected, washed with water and dried, which gives 4.8 g of 5- (and 6-) carboxy-3- [4- (dimethylamino) -2-ethoxy-phenyl ] -3- [N- (4-dimethylaminophenyl) -N- (4-diethylaminophenyl) amino] phthalide, pf 167-173 ° C.

45 C. To a mixture containing 4.0 g of the above acid, 4.0 g of potassium carbonate and 100 ml of N, N-dimethylformamide, 4.0 g of dimethyl sulfate are added. After one hour of stirring, the reaction mixture is poured into a liter of water containing 10 ml of concentrated ammonium hydroxide. The resulting precipitate is collected, washed with water and dried, which gives 0.2 g of 5- (and 6-) methoxy-carbonyl-3- [4- (diethylamino) -2-ethoxyphenyl ] -3- [N- (4-dimé-thylaminophényl) -N- (4-diéthylaminophényl) -amino] phta-lide, pf 87-93 ° C. A toluene solution of the product put in contact with an acid clay or a phenolic resin gives an image of black-brown color.

By following procedures similar to those of Examples 25 to 28 but using the appropriate 2- (4-aminodi-substituted) benzoyl benzoic acids of formula II and the diphenylamine of formula III suitably substituted, the phthalides of formula I of Examples 34 to 70, where Z is

65

S8R9N

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

13

628923

Q / n Rt / Rü / R »Y1 / Y2 Y3Y4 m.p. (° C)

Color formed

6- (CH3) 2N h 1 CH3

CH3

chs

0 C2H5

C2H5

h

0 ch3

CH3 h

0 CHa

CH3

CH3

0 C2H5

C2H5

h h h h h h h h h h h

CH3

P-CH3O-C6H4 H

CH3 CHa h h ch3

0 C2H5

C2H5

CH3

0 C2H5

C2H5

ch3

0 C2H5

C2H5

h

0 CH3

CH3

Cl

0 CH3

CH3

h

0 CHs

CH3

h

0 CH3

ch3

6- (CH3) 2N h

1 CH3 CH3

CH3

0 C2H5

C2H5

h h h h h

4-cshi?

3-C2H5 5-C9H19

h h h h h h h h h h h h

H

4-C2H5O

h

3-CH3

159-160 red

176-178 (dee.) Red

185-187 orange h 181-184

4- (CH3) 2CHO orange h 176-178

4- (CH3) 2CHO red h

4-C2H5O

h

4-oh h h h

3-CH3

h

4-cshn

3-C2H5 5-C9H19

h

3-C1

h

4- (CH3) 2N

h

4- (ch3) 2N

63-68 (dee.) Orange

81-95 (dee.) Orange

173-175 (dee.) Red

155-156 red

85-110 red yellow

H

4-C2H5O red

128-138 orange

163-166 brown

163-164 brown h 154-156

4- (CH3) 2N grape

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

14

Q / n

Ri / Rs / Rs

Y1 / Y2

YJY <

m.p.rc)

Color formed

H

cm

CHa

H H

H 92.5-102

2-COOCH3 yellow

CHs

C2H5

C2H5

H H

H 51-126

2-COOCH3 orange

H

CH3 CH3

H

4- (CH3> N

H 67-143

4- (CH3) 2N brown

H

CHs CHs

H H

H 182-184.5

4-NHCOCH3 orange

CHa

C2H5

C2H5

H H

H 169-171

4-NHCOCH3 red

CHs

0 C2H5 C2H5

6- (CH3) 2N H

1 C2H5 C6H5CH2

H H 179-182

4-NHCOCH3 4-NHCOCH3 red

H H

H

4-C2H5O

148-152 orange0

H

C2H5 C6H5CH2

H H

H

4-C2H5O

163-173 orange

CHs

C2HS

C2H5

H H -

4-CsHn 4-arylalkyl red

6- (CH3) 2N H 1 CH3

CH3

H

4-CSHit

H

4-CsHi?

208-210 orangeb

C2H5O

C2H5

C2H5

H

4-CsHn

H

4-CsHn orange

C2H5O

C2H5

C2H5

H H

H 126-131

4-NHCOCH3 orange

CH3 CHs CH3

H

4-CsHn

H

4-C8H17

172-174 red

CHs

C2H5

C2H5

H

4- (C2H5) 2N

H 58-71

4- (C2Hs) 2N black

CHa

C2H5

C2H5

H

4- (C2Hs) 2N

H 68-83

4- (CH3) 2N black

CHs CH3

H

4- (C2H5) 2N

H 67-84

4- (CH3) 2N black

15

628,923

Example Q / n Rt / Rk / R * Y1 / Y2 Y3Y4 m.p. (° C)

Color formed

66

C2H5O

C2H5

C2H5

H H 58-69

4- (CH3) 2N 4- (CH3) 2N black reason

67

CH3 CH3 CH3

H

4- (CH3) 2N

H 97-113

4- (CH3) 2N black

68

CHa C Hs CH3

H

4- (C2Hs) 2N

H 59-72

4- (C2Hî) 2N black

69 6- (CH3) zN H

1 CH3

CH3

H

4- (CH3) 2N

H

4- (ch3) 2n

86-92 brundb

70 6- (CH3) 2N H H H 137-148

1 C2H5 4- (CH3) 2N 4- (CH3) 2N brunb

C6H5CH2

a) Prepared according to the procedure of Example 28. Another preparation carried out in a manner similar to that described in Example 25 provides a product having a melting point of 176-179 ° C.

b) Turns green on acid clay after exposure to fluorescent light.

Example 71

The micro-encapsulation of the color-forming agents of Examples 26 and 34 is carried out as follows. A solution containing 1 g of the color-forming agent in 49 g of isopropylbiphenyl and a solution is mixed and emulsified with rapid stirring. containing 5 g of carboxymethylcellulose in 200 ml of water. The desired particle size (5 microns) is checked under a microscope. To the emulsion, a solution containing 15 g of pigskin gelatin in 120 ml of water is added. The pH is adjusted to 6.5 with 10% aqueous sodium hydroxide with rapid stirring, and after gradual addition of 670 ml of water with stirring (at 50 ° C), the pH is adjusted to 4.5 with 10% aqueous acetic acid, continuing to stir rapidly. After 5 minutes, 10 g of 20% aqueous glutaldehyde are added and rapid stirring is continued for an additional 15 minutes. The resulting dispersion of microcapsules is stirred more slowly overnight.

12 g of starch are gradually added to 60 ml of water. The mixture is heated to 90 ° C and stirred for 15 minutes. After cooling to room temperature, the mixture is added to 473 g of the preceding dispersion of microcapsules and the resulting emulsion is vigorously stirred for 2 minutes and then deposited on sheets of white paper for typewriters (film thickness 38 microns). The leaves are air dried. Typed duplicate typed images are prepared on receiving sheets coated with phenolic resin or acid clay. The color forming agent of Example 26 gives an orange image on the two types of receiving sheets, and the color forming agent of Example 34 gives a red image on the two types of receiving sheets.

Example 72

Polyvinyl alcohol dispersions of the color formers of Examples 26,27 and 34 are prepared by stirring for one hour in a paint stirrer a mixture containing 2.0 g of the color former, 3.7 g of water, 8.6 g of 10% aqueous polyvinyl alcohol and 10 g of zirconium grinding beads. A dispersion of bisphenol A in polyvinyl alcohol is prepared by stirring a mixture containing 9.8 g of bisphenol A, 18.2 g of water, 42 g of 10% aqueous polyvinyl alcohol and 70 ml of beads. zirconium grinding. The coating mixture is prepared by combining and thoroughly mixing 2.1 g of the dispersion of color forming agent in polyvinyl alcohol with 47.9 g of the dispersion of bisphenol A in polyvinyl alcohol. The coating mixture is applied (at thicknesses of 76 and 38 microns) to sheets of white paper for duplicators and the sheets are dried at room temperature. Contact of the coated sheets with a stylus heated to a temperature between 100 ° C and 150 ° C gives a dark orange image on the sheet coated with the color forming agent of Example 26, a dark red image on the sheet coated with the color former of Example 27 and a dark purple image on the sheet coated with the color former of Example 34.

50

Example 73

By following a procedure similar to that described in Example 71 but by substituting kerosene for isopropylbphenyl, the microencapsulation of the color-forming agent of Example 58 is carried out and a coating is coated therewith. transfer sheet. The color forming agent gives a red image on the two types of receiving sheets.

60 Example 74

By following a procedure similar to that described in Example 71 but omitting the addition of starch to the dispersion of microcapsules, the formative agent of Example 32 is microencapsulated and deposited on a 65 transfer sheet. The color forming agent gives a black image on the two types of receiving sheets. The image formed on the receiving sheet coated with clay turns green at rest.

40

628923

16

Example 75

By following a procedure similar to that described in Example 71 but omitting the addition of starch to the dispersion of microcapsules, the microencapsulation of a mixture containing 0.876 g of the color-forming agent of the product is carried out. Example 31 and 0.584 g of the crystallone violet lactone, and it is deposited on a transfer sheet. The mixture of color forming agents gives a blue to black image on resin coated receiving sheets.

By following procedures similar to those described in the previous examples, but using appropriate 2- (3-indolyl) or (4-amino disubstituted) benzoyl benzoic acids of formula II and the appropriate substituted diphenylamines of formula III, phthalides of formula I where Z is

10

15

(Examples 76 to 109), where Z is

(Examples 110 to 141).

20

25

30

35

40

45

50

55

60

65

NOT

E

U

~ X

hU <N

o o U

■ I I

u

* x u

o er o *

m fn r \

a x V

U ta tt, fc, U U c

I I I I I I I I

x u

Kïïïïïïïa: ï4a:

x u ta

O

m

- x a o a u

u u u c

T1 T1 T1 T1 T4 T "" 1 I> r <I I I I

a u a u

(N Ci a a o a u

o a a a

Bu "Suo

* "(M l-r <I I M I I I I

O

l

VS

l,

as? a-Saaaaaaa u ouauuuuuuuuo a

u

D

-o u • O

d3 cu a a a u

- —m m wi “n \ o c-> u £ a a u i i r? r) .rj i,

"" 'S a u £ a i I, "M r \ fN <N r rjcN i. ,,

c c u Buo a a u u cuu

^ "t M M m

Aa k a u "

MM r-l I O

I I I I I i i i in \ o "5f" -> CQ

—I ■ c * v

U PQ ci

\ b ^

iL * ^

vor-oooNO ^ c ^ m ^ mvoc-oo h-h-t ^ h'ooooûoûoooûoooooûo

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

Exen

110

111

112

113

114

115

116

117

118

119

6-CO2-11-C18H37

5-C02- (CH2) SCH (CH3) 2

6-CO2-11-C4H9 5-CO2-11-C14H29

5-CO ^ Na ©

6-COf NH4 © 6-CO £ HN © (C2H5) 3 6-CO £ H2N © (n-C4H9) 2

5-CO ^ C2H5 N © H (i-C3H?) 2

6-COfH3N © -n-Ci8H37

5-COfHN © - (n-C4H9) 3

6-Cof n-CsHn NH® (n-C4H9) 2

5-CO2C2H5

6-CO2CH3

Cl n

R.

A:

R3

Y,

Y;

Yl

Y "

1

C2H5

CH3

H

2-C1

4-C1

2-C1

4-C1

1

C2H5

CH3

H

H

H

H

H

1

CH3

CH3

5-11-C4H9O

H

H

4-n-CóHi3

H

1

C2H5

CH3

H

H

H

4-C2H5O

H

1

H

H

H

H

H

4-C2H5O

H

1

CHa

CHa

H

H

H

3-CHa

H

1

C2H5

CHa

H

H

H

4- (CHa) 2CHO H

1

C2H5

CHa

H

H

H

H

H

1

H

CHa

6-CH3

H

H

4-C2H5O

H

1

C2H5

CHa

H

H

H

4-C1

H

1

C2H5

CHa

6-CHaO

H

H

4-CH3O

H

1

CHa

CHa

H

H

H

4-C2H5O

H

0

C2H5

CHa

H

4-NH2

H

4-NH2

H

0

C2H5

CHa

H

4-NHCOC4H9

H

H

H

0

C2H5

CHa

H

4-NHC4H9

H

4-NHC4H9

H

1

CHa

CHa

H

2-CO2C4H9

H

H

H

1

C2H5

CHa

H

4-CO2C2H5

H

H

H

0

C2H5

CHa

H

4-CH2C6H5

H

H

H

0

C2H5

CHa

H

4-CH-CH2C0H5 1

H

H

H

1

CH3

0

C2H5

CH3

H

4-NH - ([[)

H

H

H

4

CH3

CH3

6-CHa

4-NHCH (CHa) 2

H

H

H

Phthalides of formula I = Z =

RgRgN

Rj

Rs

R9

Y:

5- (C2H5) zN 5-Br

4,5,6,7- (Br) 4

5- (C4H9) 2N

6-F 5-C1

4,5,6,7- (F) 4 4,5,6,7- (I) 4

11-C4H9

h

Br

(CH3) 2N

C2H5O

h h

h h

(sec-C4H9) 2N h

CH3

ch3

CH3 CHs C2H5 CH3

ch3

t — C4H9 CH3

sec- C4H9 CH3

CH3

C6H5CH2

CHs

CHs

C2H5

C2H5

CôHS

t — C4H9

P-CH3C6H4

sec-C4H9

CH3

h h h h

2-CH3

3-Br h

2-c1

3-ch3o h h

h h h h h h h h h h h

3-1

2-C2H5

4-Br

3- (t-C4H9)

4-CH30

5-Br

2-F 4-F

3-CH3O H

4-OH

h h h h h h h h h h h

Example

Q

not

R;

Rk

R ..

Y,

Y. '

Y.

.

121

-

0

I

cth "

p-c4h9-c6h4

3-ch3

4-ch3

3-chs

4-

122

6- (c2h5) 2n

1

H

c2h5

c4h9

3-c4h90

H

3-C4H90

h

ch.? 1

123

6- (c4h9) 2n

1

H

ch3

ch3

H

h

3-c2h5-c [

h

ch3

124

-

0

(ch3) 2chch20

ch3

ch3

2-C1

4-C1

2-C1

4-

125

5-cooch2c6h5

1

H

ch3

ch3

4-ch2c6h5

H

H

h

126

6-cooc8h17

1

c2h5

c2h5

c2h5

2-co2c4h9

H

H

H

127

5-COOCI8H37

1

Cl ch3

ch3

4-chch2c6h5 1

H

H

h

1

ch3

128

5-cooci4h29

1

H

ch3

ch3

2-c02c2h5

H

H

h

129

6-coo (CH2) sch (ch3) 2

1

ch3

c2h5

c2h5

4-c02ch3

h h

h

130

5-cooh

1

h ch3

ch3

2-C.02H

H

h h

131

-

0

H

ch3

• ch3

4-NH2

H

H

h

132

-

0

CHs c2h5

c2h5

4-NH2

h

4-NH2

H

133

4,5,6,7- (Cl) 4

4

H

ch3

ch3

4-nhc4h9

h

4-nhc4h9

h

134

-

0

CHs c2h5

c2h5

4-NH- ^

H

H

H

135

_

0

ch3

c2h5

c2h5

4-nhcoc4h9

H

4-nhcoc4h9 h

136

5-COO © Na®

1

H

ch3

ch3

4-oc2h5

h h

H

137

6-COO © Na®

1

H

ch3

ch3

H

H

H

H

138

5-coo0hn® (c2h5) 3

1

H

c2h5

c6h5ch2

4-oc2h5

H

H

H

139

5-coo © h3®ncl8h37

ch3

c2h5

c2h5

h h

h

H

140

6-COO © H3®nc8hi7

1

H

ch3

ch3

4-oc2h5

H

H

H

141

-

0

ch3

c2h5

c2h5

4-nhch (ch3) 2

H

H

H

Claims (5)

628923 1 Z with a diarylamine of formula III in the presence of the anhydride of a C2 to Cs alkanoic acid and of an organic base and, if desired, a salt of the compound obtained in which Q = -COOH, of formula I in which Q = -COOM, is prepared, M being an alkali metal cation, an ammonium cation or a mono-, di- or trialkylammonium-C1-Cis cation. 2. Process for the preparation of a compound of formula I, characterized in that the benzoic acid of formula II is first reacted with thionyl chloride, phosphorus oxychloride or phosphorus pentachloride, and l the compound obtained is then reacted with the diarylamine of formula III in the presence of an organic base and, if desired, a salt of the compound obtained in which Q = -COOH, of formula I in which Q = -COOM, is prepared, M being an alkali metal cation, an ammonium cation or a C 1 to C 6 mono-, di- or trialkylammonium. 2 CLAIMS 1. Process for the preparation of a new compound of formula I 0 (Q) Y Y in which: Q is a di- (lower alkyl) -amino, nitro group, a halogen atom or a -COX group where X is a hydroxy, benzyloxy, alkoxy group having from 1 to 18 carbon atoms; n is 0; or 1 when Q is a di- (lower alkyl) -amino, nitro or COX group; or from 1 to 4 when Q is a halogen atom; Yî, Y2, Y3 and Y4 are identical or different and are hydrogen or halogen atoms or hydroxy, lower alkoxy, alkyl having from 1 to 9 carbon atoms, phenyl-lower alkyl, COOR4 or NR5R6 where R4 and R5 are hydrogen atoms or lower alkyl groups and R6 is a hydrogen atom or a lower alkyl, cycloalkyl group having 5 to 7 carbon atoms or lower alkanoyl; Z is a group b a in which: R is a hydrogen atom or a non-tertiary alkyl group having from 1 to 4 carbon atoms; Ri is a hydrogen atom or a non-tertiary alkyl group having from 1 to 18 carbon atoms; R2 is a hydrogen atom or a phenyl or non-tertiary alkyl group having from 1 to 14 carbon atoms; R3 is a hydrogen atom or a non-tertiary alkyl group having from 1 to 4 carbon atoms or non-tertiary alkoxy group having from 1 to 4 carbon atoms; R7 is a hydrogen or halogen atom or a lower alkyl, lower alkoxy or di- (lower alkyl) -amino group; Rs is a lower alkyl group; and R9 is a lower alkyl, benzyl, phenyl or phenyl group substituted by a lower alkyl or alkoxy group, characterized in that a benzoic acid of formula II is reacted 3 628923 3. Use of a compound of formula I, the symbols of which are defined in claim 1, in a carbon-free, pressure-sensitive reproduction system, by thermal marking or by hectographic printing as a color-forming substance, the compound used in hecto -graphy corresponding to formula I in which R3 is a hydrogen atom; R7 is a hydrogen atom or a lower alkyl group; R9 is a lower alkyl or benzyl group; Yi and Y3 are each a hydrogen atom; Y2 and Y4 are the same or different and are hydrogen atoms or lower alkoxy, C1-C9 alkyl or NR5R6 groups where R5 and R6 are each lower alkyl groups; n is 1 and Q is -COOM where M is an alkali metal cation, an ammonium cation or a mono-, di- or tri-C1 to Cis alkylammonium cation. s 10 15 20 25 30 35 40 45 50 55 60 65 4. Use according to claim 3, characterized in that the pressure reproduction system comprises a support sheet coated on one side with a layer of microcapsules breaking under pressure containing a liquid solution of the color-forming substance of formula I. 5. Use according to claim 3, characterized in that the reproduction system by thermal marking contains a mixture of the color formatticele substance of formula I and an acid developer, designed so that the application of heat produces a formation reaction of marks between the color-forming substance and the acid developer.