CA1113474A

CA1113474A - 3-aryl-3-heterylphthalides and preparations thereof

Info

Publication number: CA1113474A
Application number: CA296,986A
Authority: CA
Inventors: Nathan N. Crounse; Paul J. Schmidt
Original assignee: Sterling Drug Inc
Current assignee: STWB Inc
Priority date: 1977-03-01
Filing date: 1978-02-16
Publication date: 1981-12-01
Also published as: IT7820770A0; FR2382451A1; GB1600662A; DE2808798A1; GB1600663A; US4189171A; ES467393A1; LU79146A1; NL7802189A; IT1095468B; CH635835A5; BR7801192A; ES476038A1; MX150158A; AR229961A1; DK90278A; JPS53108967A

Abstract

ABSTRACT OF THE DISCLOSURE
3-(Aminophenyl- or indolyl-) 3-(indolyl-,pyrroly-or carbazolyl-)-phthalides, of the formula ...I
prepared by interaction of the appropriate 2-(heteroaryl) carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonyl-benzoic acid and the appropriate indole, are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copyingsystems.

Description

~13474 This invention relates to 3-aryl-3-heteroaryl-phthalides and 3,3-bis(heteroaryl~phthalides useful as color ~recursors, particularly in the art of carbonless duplicating as, for example, in pressure-sensitive systems, in thermal marking systems and in hectographic or spirit-reproducing copying systems; to substituted 2-(indolylcarbonyl)-benzoic acids and 2-(pyrrolylcarbonyl)benzoic acids useful as intermediates to the sub~ect phthalide color precursors;
to processes for preparing said ~hthalides and benzoic acids; and to pressure-sensitive duplicating systems, thermal marking systems and hectographic copying systems containing the same.
Several classes of organic compounds of widely diverse structural types are known to be useful as colorless precursors for carbonless duplîcating systems. Among the more important classes, there may be named phenothiazines, for example, benzoyl leuco methylene blue; phthalides with which this invention is concerned, for example, crystal violet lactone; fluorans, for example, 2'-anilino-6'-diethyl-aminofluoran and 2'-dibenzylamino-6'-diethylaminofluoran;
and various other types of colorless precursors currently employed in commercially accepted carbonless copy systems.
Typical of the many such systems taught in the prior art are those described in U.S. Patents 2,712,507, 2,800,457 and 3,041,289. Many of the color formers in the prior art ~L
q~

suffer one or more disadvantages such as low tinctorial strength, poor light stability, low resistance to sublimation, low susceptibility to copia~ility of the color-developed form in standard copying machines, for example, a xerox copier, S and low solubility in common organic solvents, the latter dis-advantage thus requiring the use of specialized and expensive solvents in order to obtain microencapsulated solutions of sufficient concentration for use in pressure-sensitive ing systems.
u~s~ Patent 3,491~112 discloses in most pertinent part a series of normally colorless phthalides stated to be useful as color formers in pressure-sensitive copying paper which are represented by the structural formula z~
15 ~ G
N

/ \

wherein ~ N is a heterocyclic radical selected from the group consisting of ~3 ~ ¢~ and ~

Rl Rl Rl in which Rl and R2 are cl to C4 alkyl, phenyl and hydrogent Z and Y are hydrogen and dialkylamino in which alkyl is cl to C4 alkyl with the proviso that only one Z and Y can be said ~1134`74 . .
dialkylamino while the other is hydrogen; and R3 and R4 are Cl to C4 alkyl.

U.S. Patent 3,779,753 discloses the phthalide having the formula HOOf S f`~
f~ 0~

which is stated to be useful as an optlcal filter agent "in photographic processes'lto protect a selectively exposed photo-sensitive material from further exposure during processing in the presence of incident light.
British Patent l,427,318 discloses the interaction of trimellitic anhydride and m-diethylaminophenol to obtain a mixture of 4-diethylamino-2-hydroxybenzophenone-2',4'-di-carboxylic acid and the corresponding 2',5'-dicarboxylic acid isomer. The isomeric mixture is then interacted with 3,5-di-methylphenol in the presence of sulfuric acid followed by treatment with sodium hydroxide to obtain the compound having the structure (C2 5)2 1~13474 ~ \ H3 (NaOOC ~t I I /a ~ \co which is stated to be useful as a color former in a spirit reproducing process.
U.S. Patent 3,509,174 discloses 1,2-dimethyl-3-(2-carboxybenzoyl)indole which is stated to be an intermediate to a series of 3,3-bis(3-indolyl)phthalides useful as color formers in pressure-sensitive copying paper.
The present invention provides novel 3-aryl-3-hetero-arylphthalides among 3-aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides, 3-aryl-3-carbazolylphthalides and 3,3-bis-(heteroaryl)phthalides, particularly 3,3-bls(indolyl)phthalides, which are useful as color formers in pressure-sensitive duplicating systems, in thermal marking systems and in hecto-graphic or spirit-reproducing systems. The compounds develop colored images of good to excellent tinctorial strength, and have the advantages of improved light stability, high resistance to sublimation and enhanced solubility in common organic solvents. Certain species are also soluble in water and lower alcohols and are therefore of particular utility as color formers in hectographic or spirit-reproducing copying systems. The present invention also provides 2-heteroaryl-carbonyl benzoic acids useful as intermediates to the sub~ect phthalide color formers.
One aspect of the present invention resides in the novel phthalides, which are particularly useful as color-1~13474 less precursors in the art of carbonless duplicating, thermal marking and hectograph duplicating, which are 3-X-3-Z-4-R-5-Rl-6-R2-7-R3-phthalides having the formula ~`~0 Rl/~l/~
X Z
Formula I
wherein R, Rl, R and R each represent hydrogen or halo and when R, R and one of Rl and R are each hydrogen, the other of R and R represents nitro, amino, acetamido, dialkyl-amino wherein alkyl is non-tertiary Cl to C4 alkyl or ~-B in which B represents -OY or -N wherein Y is hydrogen, ~y -an alkali metal cation, an ammonium cation, a Cl to C18 mono-, di- or trialkylammonium cation, Cl to C18 alkyl, Cl to C18 alkenyl, benzyl or benzyl substituted in the benzene ring thereof by Cl to C12 alkyl, halo or Cl to C8 alkoxy; Y' is hydrogen or Cl to C18 alkyl; Y" is hydrogen, Cl to C18 alkyl or C4 to C12 N,N-dialkylaminoalkyl; X repr~sents a monovalent radical having the formula l ~ ~ or A B C

Z represents a monovalent radical havlng the formula ~13474 R ~ or ~ ~ yl' R ~ D R6 E

where, in the above, R represents non-tertiary Cl to C4 alkyl, benzyl or benzyl substituted in the benzene ring by one or two of halo or Cl to C3 alkyl, R represents acetamido, dialkylamino in which alkyl is non-tertiary Cl to C4 alkyl, and when one of Rl or R2 represents any of said carboxy or said carbonyl substituents, R4 further represents hydrogen, Cl to C3 alkyl, Cl to C4 alkoxy or halo, RS and R5 represent hydrogen, Cl to C3 alkyl or phenyl, R6 and R6 represent hydrogen, Cl to C18 alkyl, C2 to C4 alkenyl, benzyl or benzyl substi-tuted in the benzene ring by one or two of halo or Cl to C3 alkyl, R7 and R8 represent hydrogen, Cl to C3 al~yl or phenyl, and Y and yl represent no or one or two Cl to C3 alkyl, C1 to C3 alkoxy, halo or nitro substituents in the benzenoid portion of the indolyl radical with the provisos ~i) that X
and Z can both simultaneously represent monovalent indolyl moieties only when at least one of Rl and R2 represent said b~ z ~J~/
-B and (ii) X represents a pyrrolyl or a e~Y~r~t~ moiety only when Z represents a 2-R -4-N-(R)2-phenyl moiety. The yl and Y2substituents referred to throughout are preferably at the 5- or 6- position of the indole ring.
In a particular embodiment in accordance with the above invention of Formula I, Z is a radlcal of Formula D above and X is a radical of Formula A, B or C above 5 (referred to as Formulas III, IV and V, .respectively).

~.~13474 In a second particular embodlment in accordance with the above invention of Formula I, X is a radical of Formula A
above and E is a radical of Formula E above (referred to as Formula VI) wherein the indolyl radicals A and E can be the same or different; R and R3 and at least one of Rl and R
represent hydrogen and the other represents ~C-B in which B
represents -OY or - ~ wherein Y is hydrogen, an alkali ~"

metal cation, an ammonium cation, a Cl to C18 mono-, di- or trialkylammonium cation, Cl to C18 alkyl, Cl to C18 alkenyl, benzyl or benzyl substituted in the benzene ring thereof by Cl to C12 alkyl, halo or Cl to C8 alkoxy; Y' is hydrogen or Cl to C18 alkyl; Y" is hydrogen, Cl to C18 alkyl or C4 to C12 N,N-dialkylaminoalkyl; and R5, R5, R6, R6 , y and Y
each have the same respective meanings given ln relation to Formula I.
~his invention also relates to the novel 2-(X-carbonyl)-3-R-4-R -5-R -6-R -benzoic acids which are useful as intermediates to the final products and having the formula R ~f OOH

Rl /~X

Formula VII
wherein R~, Rl, R2 and R3 each represent hydrogen, or halo and when R , R3 and one of Rl and R2 are each hydrogen, the other of Rl and R2 represents amino or carboxy; X represents a monovalent radical having the Formula A or B above in which R5 represents hydrogen, Cl to C3 alkyl or phenyl, R6 ~13474 represents C4 to C18 alkyl, C2 to C4 alkenyl, benzyl or benzyl substituted in the benzene ring by one or two of halo or Cl to C3 alkyl or represents hydrogen or Cl to C3 alkyl only when yl is other than hydrogen and~or when one of Rl and R2 is amino or carboxy; R7 represents hydrogen, Cl to C3 alkyl or phenyl; and yl represents no or one or two Cl to C3 alkyl, Cl to C3 alkoxy, halo or nitro substituents in the benzenoid portion of the indolyl radical. The compounds of Formula VII
when X are radicals A and B are referred to as Formulas VIII
and IX, respectively.
The invention also deals with a pressure-sensitive carbonless duplicating system, thermal marking system or hectographic copy system containing as a color-forming sub-stance a 3-X-3-Z-4-R-5-Rl-6-R -7-R -phthalide according to Formula I, as defined above, and particularly a pressure-sensitive transfer sheet, adapted Cor use with a receiving sheet having an electron accepting layer, comprising a support sheet coated on one side with a layer of pressure-rupturable microcapsules, said microcapsules containing a liquid solution of a color forming substance comprising at least one compound having Formula I. The invention also deals particularly with a heat responsive record material comprising a support sheet coated on one side with a layer containing a mixture comprising at least one color-forming compound having Formula I and an acidic developer arranged such that application of heat will produce a mark-forming reaction between the color-forming compound and the acidic developer.
Preferred embodiments a~ove-descri~ed are those wherein the color-forming component comprises a 3-[2-R4-4-N(R)2-phenyl]-3-(1-R5-2-R6-5/6-Y -3-indolyl)-4-R-5-R -6-_g _ - ~i.13474 R -7-R -phthalide wherein R, R, R , R , R , R , R , R and yl ~ave the same respective meanings gi~en in relation to Formula III or a 3-(1-R5-2-R6-5~6-Yl-3-indolyl)-3-(1-R5 -

2-R '-5/6-Y -3-indolyl)-4-R-5-Rl-6-R2-7-R3-phthalide wherein R, ~ , R2, R3, R5, R6 R5' R6l yl d 1~
the same respective meanings given in relation to Formula VI.
A further particular aspect of the invention resides in a hectographic or spirit reproducing copying system com-prising a transfer sheet coated on one side with a layer containing a color-forming substance comprising a compound according to Formula I wherein R, R3 and one of Rl and R2 are each hydrogen, the other of Rl and R2 represents ~-OY
wherein Y is hydrogen, an alkali metal cation, an ammonium cation or a Cl to C18 mono-, di- or trialkylammonium cation.
AS used herein the term "halo" includes chloro, fluoro, bromo and iodo. Chloro is the preferred halo substituent because of the relatively low cost and ease of preparation of the required chloro-substituted intermediates and because the other halogens offer no particular advantages over chloro. However the other above-named halo substituents are also satisfactory.
The terms "Cl to C4 alkoxy" and "dialkylamino ~n which alkyl is non-tertiary Cl to C~ alkyl" denote saturated, acyclic groups which may be straight or b~anched as exempli-fied by methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy, dîmethylamino, dlethylamino, ethylmethylamino, dipropylamino, dibutylamino, lsobutylmethyl-amino, and the like.

As used herein ~he terms "Cl to C3 alkyl", "Cl to C12 alkyl" and "Cl to C18 alkyl" denote saturated monovalent 1~3474 straight or branched aliphatic hydrocarbon radicals includ-ing methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, l-methylbutyl, 3-methylbutyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, 3-ethylheptyl, n-decyl, n-undecyl, n-dodecyl, _-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, 1,3,5-trimethylhexyl, 1,5-dimethyl-4-ethylhexyl, 5-methyl-2-butyl-hexyl, 2-propylnonyl, 2-butyloctyl, 2-pentyl-nonyl, 1,2-dimethylhexadecyl, and the like.

As used herein the term "alkali metal cation" includes lithium, sodium and potassium cations.
The term "Cl to C18 alkylammonium cation" includes ammo-nium cations substituted by from 1 to 3 alkyl groups as above de-scribed. The alkyl groups can be the same or different provided the ammonium cation contains no more than 18 carbon atomsO As exam-ples there can be named methylammonium, t-butylammonium, t-octyl-ammonium, n-dodecylammonium, n-octadecylammonium, di-n-butylamnonium, di-n-nonylammonium, isopropyl-n-butylammonium, dimethyl-n-butylamino-nium, triethylsmmonium, N-ethyl-N,N-diisopropylammonium, tributyl-ammonium, di-n-butyl-n-octylammonium and the like.
The term~ "Cl to C8` alkoxy and "Cl to C18 alkoxy" in-clude~ saturated, acyclic, straight or branch-chained groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, i90-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyl-oxy, n-nonyloxy, _-decyloxy, n-undecyloxy, n-dodecyloxy, n-tri-decyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-hepta-decyloxy, n-octadecyloxy, l-methylpentyloxy, 2,2-dimethylbutyloxy, 2~methylhexyloxy, 1,4-dimethylpentyloxy, 3-ethylpentyloxy, 2-methyl-heptyloxy, l-sthylhexyloxy, 2-propylpentyloxy, 2-methyl-3-ethyl-pentyloxy, 1,3,5-trimethylhexyloxy, 1,5-dimethyl-4-ethylhexyloxy, 5-methyl-2-butylhexyloxy, 2-propylnonyloxy, 2-butyloctyloxy, 1,1-dimethylundecyloxy, 2-pentylnonyloxy, 1,2-dimethyltetradecyloxy, 1,l-dimethylpentadecyloxy and the like.
The term "C4 to C12 N,N-dialkylaminoalkyl" includes branched and straight chain alkyl groups which can be the same or di~ferent provided the total number of carbon atoms is not less than ~our nor more than twelve. As examples there can be named 2-di-methylaminoethyl, diethylaminomethyl, 3-dimethylaminopropyl l-di-methylamino 2 propyl, 3-diethylaminopropyl, 1-diethylamino-2-propyl, 2-dipropylaminoethyl, 2-di-i-propylaminoethyl, 3-dipropyl-~3474 aminopropyl, 3-dimethylaminopropyl, 4-diethylamino-n-butyl,

3-dibutylaminopropyl, 4-dimethylamino-n-butyl, 5-diethylamino-pentyl, 5-dipropylaminopentyl, 6-dimethylamino-n-hexyl, 6-di-ethylamino-6-ethylhexyl, 4-dibutylamino-n-butyl, 8-dimethyl-amino-n-octyl, 8-diethylamino-n-octyl, 10-dimethylamino-n-decyl, 5-dipropylamino-2-pentyl and the like.
As used herein, the term ~Cl to C18 alkenyl" means a monovalent aliphatic radical possessing a single double bond, for example, ethenyl (or vinyll, 2-propenyl ~or allyl), 1-methylethenyl (or isopropenyl~, 2-methyl-2-propenyl, 2-methyl-l-propenyl, 2-butenyl, 3-butenyl, l-pentenyl, 2-pentenyl, 3-methyl-2-butenyl, 2-methyl-1-butenyl ~isoamylenyl), 3-methyl-l-butenyl, l-hexenyl, 2-h~nyl, 3~nyl, 2-heptenyl, l~x~nyl, 1-hexadecenyl, 9-octadecenyl, 9-decenyl, 1-methyl-4-butenyl, 4-pentenyl, l-ethyl-l-propenyl, 1-ethyl-3-propenyl, 10-un-decenyl and the like.
Anhydrides of alkanoic acids of two to five carbon atoms include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, isovaleric anhydride, ~-methylbutyric anhydride, pivalic anhydride and the like. Acetic anhydride is preferred because of its low cost and high reactivity, however the other above-named anhydrides are also satis~actory.
The novel compounds of Formula I hereinabove are essentially colorless in the depicted form. When contacted with an acidic medium, for example silica gel or one of the types ordinarily employed in pressure-sensitive carbonless du-plicating systems such as silton clay or phenolic resins the compounds of Formula I develop an orange-red through green to a blackish-purple colored image of good to excellent tinctorial strength, and possessing excellent light stability, resistance ~3474 to sublimation and xerographic copiability. The compounds are thus highly suitable for use as colorless precursors, that is color-forming substances in pressure-sensitive carbonless du-plicating systems. The darker violets and bluish-black colors can be used alone as color formers to produce images which are readily copiable, whereas the reds, greens and blue colors can be used as toners in adm~xture with other color formers to pro-duce images of a neutral shade which desirably are readily copiable by xerographic means. Moreover, the compounds of Formula I, in particular those wherein one of R and R2 repre-sents ~-B in which B represents -OY or -N wherein Y is C
~ yll to C18 alkyl, Cl to C18 alkenyl, benzyl or benzyl substituted in the benzene ring thereof by Cl to C12 alkyl, halo or Cl to C8 alkoxy; Y' is hydrogen or Cl to C18 alkyl; Y" is hydrogen, Cl to C18 alkyl or C4 to C12 N,N-dialkylaminoalkyl have en-hanced solubility in common and inexpensive organic solvents such as odorless mineral spirits, ~erosene, vegetable oils and the like; and hose wherein one of Rl and R is an alkali-metal cation, an ammonium cation or a Cl to C18 mono-, di-or trialkylammonium cation salt of the carboxy group are soluble in water and lower-alkanols thereby avoiding the need for more expensive, specialized solvents such as polyhalo-genated or alkylated biphenyls which have ordinarily been used to prepare mic~La~ated solutions of the color formers of the priorart.
Ihe a~ of this invention may be incorporated in any of the co~c ~ ly accep~ sys~ bx~ in the carbonless duplicat ~ art.
A typical technique for such application is as follows. Solutions contain-ing o~e or more colsrless precursor o~o~nds of Fornwla I, optionally inad-~ixture with o~ color f~rmers, in ~ table solYents are microencapsulated by well-k~ ~x~edures for ~le as de ~ ibed Ln U S~ Patent 3,649,649.

~`3L3474 The microcapsules are coated on the reverse side of a transfer sheet with the aid of a suitable binder and the coated transfer sheet is then assembled in a manifold with the microcapsule coated side in contact with a receiving sheet coated with an electron accepting substance, for example, silton clay or a phenolic resin~ Applica-tion of pressure to the manifold such as that exerted by a stylus~
typewriter or other form of writing or printing causes the capsules on the reverse side to rupture. The solution of the color former released from the ruptured microcapsules flows to the receiving sheet and on contact with the acidic medium thereon forms orange-red to violet-black colored images of good tinctorial strength~
It is, of course, obvious that variants of this mode of application can be utilized~ For example, the receiving sheet in a manifold can alternatively be coated with the subject compounds and the acidic developing agent can be contained in microcapsules applied to the reverse side of the top sheet in the manifold; or the receiving sheet can be coated with a mixture containing both the acidic developing agent and the microencapsulated color formerO
It has also been found that when the compounds of Formula ~ are intimately mixed with an acidic developer of the type gener ally employed in thermal papers such as described in U.SO Patent 3,539,375, that is, papers which produce a colored image when con-tacted with a heated stylus or heated type, for example, bisphenol A, heating of the mixture produces a colored image of varying shades from orange-red to violet-black depending on the particular compound of the invention employedO The ability of the compounds of Formula I to form a deep color when heated in admixture with an acidic developer such as bisphenol A, makes them useful in thermal paper marking systems, either where an original or a duplicate copy is prepared by contacting the thermal paper with a heated stylus or heated type in any of the methods generally known in the art~

The compounds of this invention which are soluble in water and lower-alkanols may be incorporated in any of the commercial hectographic or spirit-reproducing copying systems such as described in British Patent 1,427,318. In such systems a transfer sheet coated on one side with a layer containing one or more water- or lower alkanol-soluble color formers of Formula I is placed with its coated surface against one surface of a master paper which is then typed, written or marked on, causing transfer of the coating as a substantially colorless reverse image to the master paper at the points where the transfer sheet and master paper have been pressed together. The master paper is then brought into contact with a succession of sheets of paper moistened with a suitable spirit-reproducing fluid such as ethanol. The fluid dissolves a part of the color former and transfers it to each paper sheet where it combines with an electron-accept-ing substance, to give a orangish-red to violet-black colored image which duplicates the original typing or writing on the master paper.
The 3-X~3-Z-4-R-5-Rl-6-R2-7-R3-phthalides of Formula I wherein R, Rl, R and R each represent hydrogen or halo and when R, R3 and one of Rl and R2 are each hydrogen and the other represents nitro, dialkylamino or carboxy are obtained by interacting approximately an equi-molar quantity of the appropriate 2-(X-carbonyl)-3-R-4-R -5-R -6-R -benzoic acid of the Formula VII with the appro-priate 3-R -N,N-(R)~-aniline or a l-R6 -2-R5 _yl -indole.
The reaction is conveniently carried out in the presence of an anhydride of an alkanoic acid having from 2 to 5 carbon atoms, for example, acetic anhydride at a temperature in the range of 1~13474 10 to 140C. for from approximately thirty mlnutes to eighteen hours. The 3-X-3-Z-4-R-5-Rl-6-R2-7-R3-phthalide thus obtained can be isolated ky filtration if it is insoluble in the reaction medium or by dilution of the reaction medium with a miscible solvent in whlch the product is insoluble, for example, a lower-alkanol or low molecular weight hydro-carbon, for example, isopropyl alcohol or hexane to effect precipitation of the phthalide. Alternatively, the reaction mixture can be poured into an aqueous base or an aqueous base added to the reaction mixture, for example, dilute ammonium hydroxide, sodium hydroxide or sodium carbonate and the phthalide extracted with an organic solvent, for example, benzene or toluene followed by evaporation of the organic solvent leaving the product as a residue. The phthalide once isolated can be purified by conventlonal means such as trituration or recrystallization from a suitable solvent.
In a second alternative method, the reaction mixture can be added to an aqueous acid, for example, dilute hydrochloric acid and the pH adjusted by the addition of a dilute alkali, for example, dilute aqueous ammonium hydroxide or an alkaline salt, for example, sodium acetate and the product filtered or extracted as described above.
The 3-(1-R6-2-R5-5~6-Yl-3-indolyl)-3-(1-R6 -2-R -5j6 Y -3-indolyl)-4-R-5-R -6-R -7-R3-phthalides of Formula VI in which the indole moieties are the same can be pre-pared by interacting a corresponding 3-R-4-Rl-5-R2-6-R -phthalic anhydride, e.g., trimellitic anhydrlde with approxim-ately two molecular proportions of the appropriate l-R6-2-R5-Y -indole. The reaction is conveniently carried out in 0 the presence of an anhydride of an alkanoic acid having ~13474 from two to five carbon atoms, for example acetic anhydride at a temperature in the range of 10 to 140C., but more desirably, at a temperatur~ in the range of 75 to 140C. to obtain the desired 3-(1-R6-2-R5-5~6-Yl-3-indolyl)-3-(1-R6 -2-2R5'-5/6-Yl -3-indolyl)-5~6-carboxyphthalide. The phthalides are isolated in a manner similar to that indicated in the first mode of synthesis descrlbed abo~e.
The 3-X-3-Z-5~6-amlnophthalides of Formula I can be prepared by reducing the corresponding 3-X-3-Z-5/6-nitro-phthalide. The reduction is conveniently carried out in an acidic medium, for example, hydrochloric acid using a metal salt reducing agent, for example, stannous chloride at a temperature in the range of 0 to 809C., but more desirably, at a temperature in the range of 50-80C. The desired phthalide is collected by filtration and purified by conventional means for example recrystallization from a suitable solvent after an aqueous alkali extraction.
The 3-X-3-Z-5~6-acetamidophthalide according to Formula I can be conveniently obtained by interacting the ap~ropriate compound of Formula VII, wherein one of R
and R~ is amino and the other and each of R and R3 are hydrogens, with approximately an e~uimolar quantity of an appropriate 3-R -N,N-(R)2-aniline or a 1-R6 -2-R5 -Y -indole in the presence of at Least two molecular proportions of acetic anhydride. The product is isolated by adding water and dilute alkali to the reaction mixture and the product extracted with an organic solvent, for example, benzene or toluene followed by evaporation of the organic solvent leaving the phthalide as a crystalline material.
The 3-X-3-Z-5/6-COOY-phthalldes of Formula I in which Y is a Cl to C18 alk~l, a Cl to C18 y or a benzyl substituted in the benzene ring thereof by Cl to C12 alkyl, halo or Cl tO C8 alkoxy are obtained by inter-acting a 3-X-3-Z-5/6-COOH-phthalide with an appropriate alkylating agent, for example, dimethyl sulfate, diethyl sulfate or Y-halogen, e.g~, ethyl lodide, butyl bromide, allyl chloride, octyl bromide, hexadecyl bromide or benzyl bromide, in an inert diluent, for example, acetone, N,N-dimethylformamide or hexamethylphosphoramide in the presence of an alkali metal salt, particularly an alkali metal hydroxide or carbonate, for example, sodium hydroxide, sodium cabonate, pota~sium hydroxide or potassium carbonate.
The reaction is conveniently carried out at a temperature in the range of 10~ to 100'C. for approximately one to three hours. The 3-X-3-Z-5/6-COOY-phthalide thus obtained is iso-lated by adding the reacting mlxture to water with subsequent extraction into and subse~uent isolation from an aromatic solvent, for example, ~enzene or toluene. The organic layer is separated, dried over a suitable drying agent, followed by evaporation of the organic solvent leaving the phthalide as a residue. The product once isolated can be purified by conventional means such as trituration or recrystallization from a suitable solvent.
The 3-X-3-Z-5~6-CONY'Y"-phthalides of Formula I
are obtained by amidating the corresponding 3-X-3-Z-5/6-COOH-phthalide or the appropriate corresponding carboxyllc ~unctional derivative thereof, 3-X-3-Z-5f6-COOY-phthalide, with the appropriate Y'Y"NH amine, for example, 3-(di-_-butylamino)propylamine. The reactlon is convenlently carrled 3~ out op~ionally in the presence of an inert diluent or in the absence of an inert diluent at a temperature in the range of 90 to 150C. for approximately five hours. The phthalide thus obtained can be isolated by adding the re-action mixture to water and the product extracted with an organic solvent, for example, benzene or toluene. The organic layer is separated and evaporated or distilled in vacuum to leave the product as a residue or oil.
The 3-X-3-Z-5/6-COOY-phthalides wherein the Y is an alkali metal cation, an ammonium cation or a mono-, di or trialkylammonium cation are obtained by interacting the a~propriate 3-X-3-Z-5/6-COOH-phthalide with approximately an equimolar quantity of an appropriate alkali metal salt, for example, sodium hydroxide, potassium hydroxide or lithium hydroxide, ammonium hydroxide or a suitable primary amine, for example, 1,1,3,3-tetramethylbutylamine. The reaction is conveniently carried out in an inert diluent, for example, acetone at a temperature in the range of 10 to 50C. for approximately five minutes to one hour. The phthalide thus obtained is isolated by dilution of the reaction medium with a miscible solvent in which the product is insoluble, for examPle, low molecular weight hydrocarbons such as hexane in order to effect precipitation of the product. The phthalide once isolated can be purified by conventional means such as trituration or recrystallization from a suitable solvent.
Both the known and the novel 2-X-carbonyl-3-R-4-R -5-R -6-R -benzoic acids of Formula VII are prepared in similar fashion, by interacting a 3-Ro-4-Rl-5-R2-6-R3-phthalic anhydride with a l-R6-2-R5-Yl-indole, a l-R -0 pyrrole, or a 9-R -carbazole wherein R, R , R2, R3, R5, :~S 13474 R6, R7, R8 and yl each have the same meanings given in relationto Formula VII usually in the presence of a Lewis acid, for example, aluminum chloride or zinc chloride, and with a diluent such as benzene, toluene, x~lene, chlorobenzene, l,2-dichloro-ethane or _-dichlorobenzene at a temperature of about 0 to 150C. The reaction is conveniently carried out in toluene in the presence of aluminum chloride at about 0 to 25C.
Alternatively, the more reactive indoles can be interacted in the absence of a Lewis acid by simply heating the reactants together in an inert solvent at about 80 to 150C. The 2-tX-carbonyl)-3-R-4-Rl-5-R2-6-R3-benzolc acids in which Lewis acids are used in their preparation are isolated by adding water to the reaction mixture or the reaction mixture to water or dilute mineral acid, for example, hydrochloric acid and subsequently separating the organic layer. The product is extracted from the organic layer with a dilute aqueous alkali solution and precipitated by the addition of a mineral acid, for example, hydrochloric acid. The benzoic acid is collected by flltration and may be purified by con-ventional means but is generally dried and used as ls. Alterna-tively, in the case where the more reactive indoles are utilized, it is preferable not to use a Lewis acid and the 2-(X-carbonyl)-3-R-4-Rl-5-R2-6-R3-benzoic acids are obtained by cooling the reaction mixture to ambient temperature and collecting the product by filtration. The product once isolated can be purified by conventional means but preferably the benzoic acid is dried and used as is.
The 2-(X-carbonyl)-5/6-aminobenzoic acids of Formula VII are obtained by reducing the corresponding 2-(X-carbonyl)-5/6-nitrobenzoic acid. The reduction is con-1~13474 veniently carrled out in an acidlc medium, for example, hydrochloric acid using a metal salt reducing agent, for example, stannous chloride at a temperature in the range of 0 to 80C., but preferably at a temperature in the range of 50-80C. The desired benzoic acid is collected by filtra-tion and purified if desired by conventional means but preferably it is dried and used as is.
It will, of course, be appreciated that reaction of an unsymmetrically substituted phthalic anhydride with an indole, pyrrole or carbazole can produce isomers or a mixture of isomers of 2-(heteroarylcarbonyl7benzoic acids.
For example, reaction of a 4-substituted phthallc anhydride with an indole, pyrrole or carbazole can produce either a

4- or 5-substituted 2-(heteroarylcarbonyl)benzoic acid or a mixture thereof. Similarly a 3-substituted phthalic anhydride can produce either a 3- or a 6-substituted 2-(heteroaryl-carbonyl)benzoic acid or a mixture of these. The mixtures of isomeric 2-(heteroarylcarbonyl7 benzoic acids can be separated by conventional means such as fractional crystal-~0 lization or chromatography. Alternatively, the isomeric mixtures can be reacted directly with appropriate 3-R4-N,N-(R)2-anilines or l-R -2-R _5/6_yl -indoles to produce isomeric mixtures of phthalides of Formula I. Thus, reaction of a mixture or 4- and 5-substituted 2-(heteroarylcarbonyl)-benzoic acids with a 3-R -N,N-(R72-aniline or a 1-R6 -2-R5 -

5~6-Y -indole will produce a mixture of 5- and 6-substituted phthalides. The mixtures of phthalides can, if desired, be separated by conventional means or simply and preferably used as mixtures in the practice of this invention. Throughout this application where the possibility of different isomeric 1~13474 products being formed is present, the nomenclature 4/5, 5/6 and so forth is adopted meanlng the product obtained or claimed is a mixture of the lsomers.
Indole~, the substituted indoles, pyrrole, the substituèd pyrroles, carbazole and the substituted carbazoles required as intermediates for the preparation of the carbonyl-benzoic acid intermediates of Formula VII, VIII and IX and for the final products of Formulas I, III IV, V and VI
form an old and well-known class of compounds which are readily obtained by conventional procedures well known in the art. The following compounds are exemplary of indoles, pyrroles and carbazoles useful in the practice of this invention:
indole, l-methylindole, 2-methylindole, 1,2-dimethylindole, l-ethyl-2-methylindole, 2-phenyl~ndole, 1-propyl-2-methylindole, 1-benzyl-2-methylindole, 1-butyl-2-methylindole, 1-octyl-2-methylindole, 2-ethyl-5-methylindole, 1-benzyl-5-fluoroindole, l-methyl-6-nitroindole, 5-methoxy-1-butylindole, 1-allyl-2-methylindole, 1~2-dimethyl-6-nitroindole, 1-t4-chlorobenzyl)-2-methyl-5-nitroindole, 2-ethyllndole, 2-ethyl-1-methylindole, l-isopropylindole, 2-isopropylindole, 1-methyl-5-bromo-6-nitroindole, 2,5,6-trimethylindole, 1-isobutyl-2-methylindole,

6-bromo-2-methylindole, l-hexylindole, 1-(2,5-dimethylbenzyl)-2-methylindole, 2-propylindole, 6-chloro-2-phenyllndole, 1-(2-ethylhexyl)-2-methyllndole, 1-(2,6-dichlorobenzyl)-2-methylindole, 1-vinyl-2-methylindole, 2-ethyl-6-methylindole, 6-fluoro-1-benzylindole, 1-(4-bromobenzyl)-2-1sopropylindole, 1-(3-chlorobenzyl)-2-ethylindole, 5-chloro-1-benzylindole, 1-(2-fluorobenzyl)-2-methylindole, 5-1odo-l-(l-methylhexyl)-indole, 5,6-dimethoxyindole, 1-t2-methylbenzyl)-2-methylindole, 5,6-dichloro-2-phenylindole, l-lsoamyllndole, 1-[3-(2-methyl)-~3474 l-propenyl]-2-methoxyindole, pyrrole, N-methylpyrrole, N-ethylpyrrole, N-propylpyrrole, N-isopropylpyrrole, N-phenylpyrrole, carbazole, 9-methylcarbazole, g-ethylcarbazole, 9-propylcarbazole, 9-isopropylcarbazole, and 9-phenyl-carbazole.
The 3-R -N,N-~R~2-anilines, which are ~equired for interaction with the 2-(X-carbonyl~-3-R-4-R -5-R -6-R -benzoic acids of Formula VII to obtain the 3-X-3-[2-R4-4-NtR)2-phenyl]-4-R-~-Rl-6-R2-7-R3-phthalides of Formula II
form an old and well-known class of compounds readily obtained by conventional procedures well known in the art. The following anilines exemplify compounds falling within the ambit of the formula Z-H which are useful in the practice of the step in the processes of this invention for producing the aforesaid lS phthalides of Formula II: N,N,N',N'-tetramethyl-_-phenylene-diamine, N,N-dibutylaniline, N,N-diethyl-3-ethoxyaniline, N,N-diethyl-m-anisidine, N,N-dimethylaniline, N-benzyl-N-ethylaniline, N,N-diethyl-m-toluidine, N,N-diethylaniline, N-ethyl-N-methylaniline, N-benzyl-N-methylaniline, N-benzyl-N-propylaniline, N,N-dimethyl-3-bromoaniline, N,N,N',N'-tetra-isopropyl-m-phenylenediamine, N,N-dibutyl-3-fluoroanlline, N,N-diethyl-2-methoxy-3-chloroaniline, N-benzyl-N-methyl-3-ethylaniline, N,N,N',N'-tetra-sec-butyl-m-phenylenediamine, N-benzyl-N-butyl-3-iodoaniline, N,N-dlisopropyl-3-chloro-aniline, N-benzyl-N-sec-butylaniline, N,N-di-sec-butylaniline, N,N-diethyl-3-isopropylaniline, N,N-dlisobutylaniline, N,N-diethyl-2-propoxyaniline, N,N-dipropylaniline, N-isopropyl-N-methylaniline, N-methyl-N-propylanlllne, N,N,N',N'-tetra-butyl-m-phenylenediamine, N,N-dipropyl-_-anisldlne, N-iso-butyl-N-ethylaniline, N,N,N',N'-tetraethyl-m-phenylenediam~ne, `` 1~13474 N-propyl-N-ethylaniline, N,N-diethyl-2-ethoxyaniline, N-benzyl-N-sec-butyl-2-propoxyaniline, and N,N-dimethyl-_-toludine.
The molecular structures of the compounds of this invention were assigned on the basis of the modes of synthesis, elemental analysis and study of their infrared, nuclear magnetic resonance, and mass spectra.
The following examples will further illustrate the invention without, however, limiting it thereto.

Example 1 A. To a stirred suspension of 22.5 g ~0.15 mole~ of phthalic anhydride and 61.Q g ~0.30 mole~ of 77.5 percent active l-ethyl-2-methylindole in 120 ml of ethylene dichloride chill-ed to 0 to 5C. by means of an ice bath, there was added insmall portion~ 32 0 g ~0~24 mole~ of aluminum chloride~ The mixture was maintained at 0-5Cc for an additional 15 minutes, allowed to warm to room temperature and stirred overnight.
Then, 240 ml of water was added to the reaction mixture and the ethylene dichloride layer was separated from the acidic aqueous layerO The organic layer was extracted with 60Q ml of 3O5 percent aqueous sodium hydroxide. The alkaline extract was acidified with dilute hydrochloric acid and the separated solid collected, washed with water and dried to obtain 24.0 g of 2-~(1-ethyl-2-methyl-3~indolyl)carbonyl]
benzoic acid ~Formula VIII: Ro=Rl~R2=R3=Yl=~; R5=CH3; R6=
CH2CH3~, a slightly pink solid having a melt ~ pom~ of 184-185C.
B. A mixture of 12.28 g ~0.04 mole~ of 2-~ ethyl-2-methyl-3-indolyl~carbonyl~benzoic acid, prepared a~ described in part A above, 1OD7 g ~0.043 mole~ of 90 percent active N,N,N',N'-tetraethyl-m-phenylenediamine and 6.0 ml of acetic anhydride was stirred at room temperature for seventeen hours.
The reaction mixture was diluted with 26.0 ml of ethanol, stirred and filtered. The separated solid was washed with di-25 ethylether and dried bo yleLd 11.8 g oftl-ethyl-2imethyl-3-~bLyl~phthallde (Fonm~a III: Ro=Rl--R2~R3~H; R~
R6=CH2CH3; R --N(CH2CH3)2; R5=CH3), a shite crystalline materi~1 which melted at 139-140C~ The infrared sp~um showed a sigmflcant band at 1760 cm 1 ~C-O; s~ and the nuclear magnetic resonance ~K~Um was in acaord with the 3Q sbn~ture. A solution of this product in benzene developed a deep blue-black color when spotted on silica gel.

~13474 C. In a procedure similar to that described above in part B
of this example, 12.28 g ~0.04 mole~ of 2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, prepared as described in part A
above, 8,57 g ~0,05 mole L of N,N,N',N'-tetramethyl-m-phenylene-diamine and 600 ml of acetic anhydride were interacted with stirring at room temperature overnightO The reaction mixture was then diluted with 13.0 ml of ethanol and the precipitate which separated was filtered and washed with 6.0 ml of ethanol~ The filter cake was then reslurried in 30 ml of methanol, filtered and washed succesi-vely with methanol and diethylether. The material was dried in vacuo to obtain 15.8 g of 3-~2L4-bistdimethylamino)phenyl]-3-(1-eth 1-2-meth 1-3-indolyl)phthalide (Formula III: R =Rl=R2=R3=Yl=H;
Y Y
R=R5-CH3; R4zN(CH3)2; R =CH2CH3), a white crystalline solid which melted at 218-222C, The infrared spectrum was consistent with the structure. A benzene solution of the above product developed an intense grape-red color when streaked on a phenolic resin coated paper.
Example 2 A. To a stirred suspension of ~o66 g (0.017 mole) of tetra-chlorophthalic anhydride and 1305 g ~0.034 mole) of 80 percent active l-ethyl-2-methylindole in 30 ml of benzene maintained at 0-5C by means of an ice bath, 10.6 g (00079 mole) of aluminum chloride was added in small increments. The reaction mixture was then maintained at O to 5CO for an additional twenty minutes, al-lowed to warm to room temperature and stirred overnightO The mix-ture was transferred to a beaker and triturated successively with hexane, 10 percent hydrochloric acid, and lastly with 5 percent a~ueous sodium hydroxide which had been heated to 70Co The residual oil was filtered, acidified with dilute hydrochloric acid and allowed to stand overnight~ On standing, the oil gave way to 1~13474 a solid which was collected by ~iltration~ washed with water and dried to yield 6O8 g of 2-[~1-ethyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachlorobenzoic acid ~Formula VIII: R =Rl=R2=R3-Cl;
R5=CH3; R6=CH3CH2; Yl=H), an off white solid melting at 214-216Co Analysis by mass spectrum showed m/e peaks at 443 (M+, Cl=35) and 398 (M -COOH).
Bo A stirred mixture of 8~86 g of 2-~(1-ethyl-2-methyl-3-indolyl~carbonyl]-3,4~5,6-tetrachlorobenzoic acid, prepared as described in part A above, 4.0 g of N,N,N',N'-tetramethyl-m-phenyl-enediamine, and 10.0 ml of acetic anhydride was heated at reflux for a period of three hoursO The reaction was then allowed to cool to room temperature, and the tan precipitate which formed was filtered and washed with isopropanolO The material thus obtained was dissolved in 500 ml of benzene and the resulting solution ex-tracted with 70 ml of 10 percent aqueous sodium hydroxideO The benzene solution was filtered and evaporated to dryness at ambient temperature yielding 1,5 g of 3-~2,4-bis(dimethylamino)ph ~
U-ethyl-2-methYl-3-indolyl)-4~5~6~7-tetrachlorophthalide (Formula III~ R Rl=R2=R3=Cl; RzP5=CH3; R4=N~CH3)2; R6=CH2CH3; Yl=H)~ a white solid which melted with decomposition at 227-229Co A sig-nificant infrared maximum occurred at 1770 cm 1 ~C=O; s)~ The nu-clear magnetic resonance spectrum was in complete agreement with the assigned structure. A benzene solution of this product spotted on silica gel developed an intense purple colorO
Example 3 A. A solution of 67c2 g ~0.4 mole) of 4-nitrophthalic an-hydride and 63.0 g ~0,32 mole) of 80O6 percent active 1-ethyl-2-methylindole in 50 ml of ethylene dichloride was heated at reflux for two hours~ The reaction mixture was then allowed to cool to room temperature. The yellow precipitate which separated was col-~34'74 lected by filtration, washed with fresh ethylene dichloride and dried to obtain 64,5 g of 2-[~1-ethyl-2-methyl-3-indolyl)carbonyl-5-nitrobenzoic acid (Formula VIII: R =R2=R3=Yl=H; Rl=NO2; R5=CH3;
R6=CH2CH3) having a melting point of 203-204C.
B. A m~xture of 3,68 g ~OoOl mole) of 2-[(1-ethyl-2-methyl-3-indolyllcarbonyl~-5-nitrobenzoic acid, prepared as described in part A above, and 2.0 g ~0012 mole~ of N,N,N',N'-tetramethyl-m phenylenediamine in 10~0 ml of acetic anhydride was heated at 90CO
for one hour and then allowed to cool to 25C. The solid which separated was collected by filtration, washed with diethylether and dried to obtain 3.8 g of 3-~2,4-bis~dimethylamino)phenyl]-3-(1-ethYl-2-methYl-3-indolyl~-6-nitrophthalide (Formula III: R =Rl=
R3-Yl=~ R2=NO2; ~=RS=CH3; R4=N~CH3)2; R5=CH2CH3) as an orange solid which melted over the range 185-187Co The nuclear magnetic reso-nance spectrum was in accord with the assigned structureO A benzene solution of this product developed a black-purple color when spotted on silica gel.
C. A solution of 2500 g ~0O054 mole~ of 3-[2,4 bis(dimethyl-amino~phenyl]-3-~1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide, pre-pared as described in part B above, in 285 ml of concentrated hydro~
chloric acid was heated to 60Co at which temperature 31025 g (00142 mole) of stannous chloride dihydrate was added at such a rate as to maintain the temperature at 60Co After the addition was complete, the solution was heated to 70C. and he~d there for a period of one hour and then allowed to cool to 25Co The green-colored solid which separated was collected by filtration and was slurried in five percent aqueous sodium hydroxide solutionO The resulting sus-pension was extracted with S00 ml of toluene at room temperature and the toluene extract was filtered, decolorized, and dried over sodium sulfateO On standing, a cream solid separated from the tolu~

~13474 ene solution~ The solid was filtered off and dried to obtain 209 g of 6-aminophthalide ~ormula III: R -Rl=R3=Yl=H; R2=NH2; R=R5=CH3;
R4=N(CH3)2; R6=CH2CH3) having a melting point of 206-209Co Infra-S red analysis showed a maximum at 1727 cm 1 (C=0; s)~ The nuclear magnetic resonance spectrum was concordant with the assigned struc-ture. A toluene solution of the above compound developed an intensive grape-black color when spotted on a paper coated with phenolic resin~
D. To a solution of 7004 g ~0002 mole) of 2- [ ~1-ethyl-2-methyl-3-indolyl)carbonyl~-5-nitrobenzoic acid, prepared as de-scribed in part A of this example, in 70 ml of concentrated hydro-chloric acid, there was added 13c5 g ~0006 mole) of stannous chlo-ride dihydrate at such a rate as to allow the reaction to exotherm to 55Co The temperature was maintained at 55Co for an additional one-half hour. The reaction was then cooled to room temperature and the pH adjusted to six by the addition of 10 percent aqueous sodium hydroxide solutionO The red precipitate thus formed was filtered off and extracted into acetoneO The acetone solution was evaporated and the paste-like residue was slurried in diethylether and then the solid was collected by filtration to obtain 3.5 g of ~ (For-mula VIII: R3=R2=R =Yl=H; Rl=NH2; R5=CH3; R6=CH2CH3)~ a red solid which melted at 187-189C
E~ A mixture of 3022 g ~0.01 mole) Of 2-[(1-ethyl-2~methyl-3-indolyl)carbonyl~-5-aminobenzoic acid, 118 g (0 oOl mole) of N,NtN',N'-tetramethyl-m-phenylenediamine in lOoO ml of acetic an-hydride was heated to 50C~ for one~half hourO After cooling to ambient temperature, 50 ml of water was added and the reaction mixture was ilteredO The f.iltrate was rendered alkaline with di-lute aqueous sodium hydroxide in the presence of 100 ml of toluene~

1~3474 The toluene layer was separated, ~ried and evaporated to obtain as tan crystals (Formula III R=Rl=R3=yl=H
R2=NHCOCH3; R=R5~CH3; R4-N~CH3)2; R6~CH2CH3) having a melting point of 204-206C. Infrared analyses showed maxima at 1733 cm 1 ~C=O; s) and 1695 cm 1 ~C=O; s). Nuclear magnetic resonance analy-sis was consistent with the structure. An acetone solution of the above compound developed an intense grape color when spotted on silica gel~
Example 4 A. Following the procedure described in part A of Example 1,

7.4 g (0.05 mole) of phthalic anhydride, 16.0 g (0~07 mole) of 79 percent active l-n-butyl-2-methylindole and 13.3 g ~.01 mole of aluminum chloride were interacted in 50 ml of benzene to obtain 2-~(1-n-butyl-2-methyl-3-indolyl)carbonyl~benzoic acid (Formula VIII:
Ro-Rl-R2=R3=Y1=H; R5=CH3; R6=(CH2)3CH3) a pale pink solid melting over the range 88-92C. The nuclear magnetic resonance spectrum was consistent with the structure. Infrared maxima were recorded at 1720 cm 1 ~C-O; s) and 1700 cm 1 (C=O; s), Bo A mixture of 3O35 g ~0.01 mole) of 2-[(1-n-butyl-2-methyl-3-indolyl)carbonyl~benzoic acid, prepared as described in part A
above, 1.80 g ~0.011) mole) of N,N,N',N'-tetramethyl-m-phenylene-diamine and five ml of acetic anhydride was stirred at ambient temperature for a period of approximately 18 hoursO The reaction mixture was then poured into a mixture of 40 ml of water, 40 ml of ligroin and 20 ml of 10 percent aqueous sodium hydroxide. The ligroin layer was separated and the white crystals which separated from the solution on standing, were collected by filtration and dried to obtain 3-~2,4-~is~dimethylamino)phenyl~-3-(1-n-butyl-2-methyl~3-indolyl)phthalide ~Formula III: ~ =Rl=R2=~3=Yl=H; R=R5=CH ;
R4=N(CH3)2; R =~CH2)3CH3) which melted at 165-167Co A character-~:;
.

istic infrared maximum appeared a 1752 cm 1 ~C=O; s). A toluene solution of the product spotted on silica gel developed an intense purple-colored image.
C. In a manner similar to that described in part B above, 3.35 g (0.01 mole~ of 2-[~1-n-butyl-2-methyl-3-indolyl)carbonyl~-benzoic acid and 2.42 g (0.011 mole) of N,N,N',N'-tetraethyl-m-phenylenediamine were interacted to obtain 3-[2,4-bis(diethylamino)-phenyl]-3-(1-n-butyl-2-methyl-3-indolyl~phthalide (Formula III:
R =RlsR2-R3'Yl=~; R=CH2CH3; R4=N~CH2CH3)2; R5=CH3; R6=(CH2)3CH3), as tan-colored crystals which melted at 78-80C. A toluene solution of the product spotted on silica gel developed an intense blue-black-colored image.
~.
Ao In a manner similar to that described in part A of Example 1 hereinabove, 7.4 g ~0.05 mole) of phthalic anhydride, 16O0 g (0.053 mole) of 76.5 percent active 1-n-octyl-2-methyl-indole, and 13.3 g ~0.1 molel of aluminum chloride were interacted in 50 ml of benzene to obtain 6.9 g of 2-[(1-n-octyl-2-methyl-3-indolyl)carbon-~ , . . .
~ ~ormula VIII: R =Rl-R2=R3=Yl=H R5 C
R6'(CH2)7CH3~, as a pink-colored powder which melted at 121-123C~
The nuclear magnetic spectrum was in agreement with the structure and a significant maxima occurred at 1717 cm 1 (C=O; s)~
B. Proceedin~ in a manner similar to that described in part B of Example 4 above, 3.91 g (0.01 mole) of 2-[(1-n-octyl-2-methyl-3-indolyl)carbonyl]benzoic acid, 1.80 g (0.011 mole) of N,N,N',N~-tetramethyl-m-phenylenediamine and five ml of acetic anhydride were interacted at ambient temperature for a period of approximately 24 hours to obtain, after recrystallization from methanol, 3-[2~4-bis~dimethylamino)phenyl]-3-~1-n-octyl-2-methyl-3-indolyl)phthalide .
~Formula III: R =R =R =R =Y =H; R=R5=CH3; R =N(CH3)2; R =(CH2)7CH3) ~.~13474 which melted over the range 64-~8C. A significant infrared absorp-tion was observed at 1750 cm 1 (C=O; s)~ Analysis by mass spectrum showed m/e peaks at 537 ~M+~ and 493 ~M+-C02)~ A toluene solution of the product when spotted on a phenolic resin coated paper developed an intense grape-colored imageO
Example 6 A~ Proceeding in a manner similar to that described in part A of Example 2, 14.3 g ~0.05 molel of tetrachlorophthalic anhydride, 16O0 g ~OOO7 mole) of 76 percent active 1-n-butyl-2-methylindole and 13.3 g (0.10 mole) of aluminum chloride were interacted in 100 ml of benzene. The reaction mixture was drowned in 200 ml of five percent hydrochloric acid with stirring. The solid which formed was collected by filtration, washed with water and dried to obtain 2-[(1-n-butyl-2-methyl-3-indolyl)carbonyl]-3,4,5,6-tetrachloro-benzoic acid (Formula VIII: R =Rl=R2=R3=Yl=H; R5=CH3; R6=5CH2)3CH3), a pale yellow solid melting at 162-164C. The nuclear magnetic resonance spectrum was in accord with the structure.
Bo A mixture of 5,20 g ~OoOl mole) of 2-t(l-n-butyl-2-methyl-3-indolyl~carbonyl)]-3,4,5,6-tetrachlorobenzoic acidf prepared in part A above, 2.0 g ~0~012 mole) of N,N,N',N'-tetramethyl-m-phenylenediamine and five ml of acetic anhydride was warmed over a period of approximately forty minutes at 110C. The reaction mix-ture was then cooled to ambient temperature, set aside overnight, rendered alkaline with 10 percent aqueous sodium hydroxide solution and extracted with benzeneO Petroleum ether was slowly added to the separated benzene extract and the solid which slowly separated was collected by filtration and dried to ~`

obtain 3-[2~4-blstdimethylamino~phenyl]-3-~l-~-butyl-2-methyl-3-indolyl~-4,5,6,7-tetrachlorophthalide tFormula III: R=Rl=R =
R3=Cl; R=R5=CH3; R4=N(CH3)2; R6=~CH2~3CH3; Yl=H), as white crys-tals having a melting point of 173-175C. The nuclear magnetic resonance spectrum was consistent with the structure; a maximllm of 1770 cm 1 tC=O; s~ appeared in the infrared spectrum; the spectrum showed a m/e peak at 617 (M , 4 Cl).
Example 7 A. Proceeding in the same manner as that described in part A of Example 6 above, 14.3 g (0.05 mole) of tetrachloro-phthalic anhydride, 16.0 g (0.052 mole) of 76.5 percent active l-n-octyl-2-methylindole and 13.3 g (0.10 mole) of aluminum chloride were interacted to obtain 2-[(1-~-octyl-2-methyl-3-indolyl)carbonyl~-3,4,5,6-tetrachlorobenzoic acid (Formula VIII:
R=R1=R2=R3=Cl; R5=CH3; R6=(CH2)7CH3; Yl-H), a pale orange solid melting at 132-134C. The infrared spectrum, showing a maximum at 1745 cm 1 (C=O; s~ and the nuclear magnetic resonanoe spectrum was in accord with the structure.

8, A mixture of 2O64 g ~0.005 mole~ of 2-[1-n-octyl-2-methyl-3-indolyl~carbonyl]-3,4,5,6-tetrachlorobenzoic acid, pre-pared as described in part A above, 1.0 g (0.006 le) of N,N,N',N'-tetramethyl-m-phenylenediamine and three ml of acetic anhydride were interacted as described in Example 2, part C
above to obtain 3- ~ -2-methYl-3-indolyl-4,5,6,7-tetrachlor~hthalide (Formula III:
R=Rl=R2=R3=Cl; R=CH3; R4=NtCH3~2; R5=CH3; R =(CH2)7CH3;
Yl=H), a pale yellow powder melting at 145-147C~ The in~rared spectrum showed a maximum appearing at 1770 cm 1 tC=O; s) and the nuclear magnetic resonance spectrum was concordant with the structure.

Exam~le 81 ~1 347 4 A. A suspension of 14~8 9 (0.10 mole) of phthalic anhy-dride, lO.S g (0.05 mole) of 2-phenylindole and 82 ml of xylene was heated to 110C briefly, cooled toand maintained at 95C
for approximately two hours. The solution was cooled to ambient temperature and the solid which separated was collected by fil-tration and dried to obtain 10.6 g of carbonYllbenzoic acid (Formula VIII: Ro=Rl=R2=R3=R =Y1=H; R5=
C6H5) which melted at 106-107C and had a nuclear magnetic resonance spectrum consistent with the assigned structure.
B. A mixture of 4.82 g (0.014 mole) of the ~-~(2-phenyl-3-indolyl)carbonyl~benzoic acid from part A above, 3.60 g (0.02 ~ole) of N,N,N ,r~ -tetramethyl-m-phenylenediamine, and five ml of acetic anhydride was slowly heated until a purple color formed lS and maintained at this temperature for approximately two hours.
After cooling to room temperature, sufficient 3N hydrochloric acid w~s added to the mixture to effect solution and stirring was continued for approximately 1.5 hours. The resultins solu-tion was filtered and the pH ad~usted to five by the addition of sodi~m acetate. The precipitate which separated from the solution was collected by filtration and dried to obtain 3-[2,4-bis(dim~othy}amino)phenvl~-3-(2-phenvl-3-indolvl)phthalide SFormula III Ro=Rl=R2=R3=R6=yl=H; R=CH3; R =N(C1l3)2; R =C6H5)~
After recrystallization from toluene and hexane, the off white-co}ored solid melted at 153-155~C. Significant infrared maxima were observed at 33B0 cm 1 (NH; m) and 1750 cm 1 ~C-O; s). The nuclear magnetic resonance spectrum was consistent with the structure. A toluene solution of this product spotted on si}ica gel developed an intense grape-red-colored image.

l~i3474 Example 9 Ac Proceeding in a manner similar to part A of Example 8, but substituting 2-methylindole for 2-phenylindole, there was obtained 2-~(2-methyl-3-indolyl)carbon~l]benzoic acid (Formula VIII: Ro=Rl=R2=R3=R6=Yl=H; R5=CH3~, as pale pink-colored crystals melting at 198-200C.
. A mixture of 8037 g (0.03 mole) of 2-[(2-methyl-3-indolyl)carbonyl~benzoic acid, prepared as described in part A
above, ~.37 g (0.05 mole) of N,N,N',N'-tetramethyl-m-phenylene-diamine and 10 ml of acetic anhydride was interacted at 50C.
as described in part B of Example 8 above to obtain 3-[2,4-bis-(dimethylamino)phenyll-3-(2-methyl-3-indolyl)phthalide (Formula 1 2 3 R6 yl=H; R=R5=CH3; R =N(CH3)2) cation by slurrying in a benzene and ligroin mixture, the col-lected and dried product melted at 183-186C. The product had mass spectrum with a m/e peak at 425 (M~). Both the infrared and nuclear magnetic resonance spectra were consistent with this structureO ~ toluene solutior,of the product spotted on a phenolic resin coated paper developed an intense grape-colored image.
E~ample 10 A. A mixture of 5.0 g (O.Q3 mole~ of 5-methoxy-2-methyl-indole and 4.6 g (0.03 mole~ of phthalic anhydride in 25 ml of ethylene dichloride was refluxed for ten hours, cooled to room temperature and the separated solid was collected by filtration and dried to obtain 2-[~2-methyl-5-methoxy-3-indolyl)carbonyl~-benzoic acid ~Formula VIII: Ro=Rl=R2=R3=R6=~; R =CB3; Y =OCH3), as a pale pink-colored solid which decomposed at 203-204C.
The nuclear magnetic resonance and infrared spectra were consistent with the assigned structure.

~13474 B. A mixture of 2rO g lOoO06 mole) of 2-[(2-methyl-5-methoxy-3-indolyl)carbonyl~benzoic acid, obtained as described in part A
above, 1.1 g ~000067 mole) of N,N~N',N'-tetramethyl-m-phenylene-diamine and six ml of acetic anhydride were interacted at 50-55Co in a manner similar to that described in Example 2 ~ part B to obtain 205 g of 3-[2,4-bis~dimethylamino)phenyl]-3-(2-methyl-5-methoxY-3-mula III: R =Rl=R2=R3=R6=H; R Rs 4 tCH3)2; Y zOCH3), as a light pink-colored solid melting at 196-198Cc with decompositiont The infrared spectrum, showing a significant maximum at 1740 cm 1 ~C=0; s) and the nuclear magnetic resonance spectrum were in accord with the structureO A toluene solution of this product spotted on a phenolic resin coated paper developed an intense violet-colored imagec Example 11 Ao A mixture of 500 g ~0.034 mole) of phthalic anhydride and 500 g ~00034 molel of 2,5-dimethylindole in 30 ml of ethylene di-chloride was refluxed for 20 hours, cooled and the separated solid filtered off and dried to obtain 308 g of ~ ~Formula VIII: R =Rl=R2=R3=R6=H; R5 CH
Yl=CH3) as a pink-colored solid melting at 198-200Co B. A mixture of 200 g (00007 mole) of 2-[(2~5-dimethyl-3-indolyl~carbonyl~benzoic acid from part A above, 151 g (00007 mole) of N,N,NI,N'-tetramethyl-m-phenylenediamine and seven ml of acetic anhydride was interacted in a manner similar to that described in Example 3; part E above, to obtain 2.35 g of 3-~2,4-bis(dimethyl-~ ~Formula III:
R =Rl=R2=R3=R6=H, R=R5=CH3; R4=N(CH3)2; Yl=CH3), a light purple solid melting over the range of 100-125Cc The infrared showed a characteristic absorption maximum at 1760 cm 1 ~C=0; s)0 A toluene solution of this product spotted on acid clay or phenolic resin developed an intense violet-colored imagec ~13474 Example 12 A mixture of 1.55 g ~0.0036 mole? of 2-~(1,2-dimethy1-3-indolyl)carbonyl~-3,4,5,6-tetrachlorobenzoic acid prepared in a manner similar to part A of Example 2, 0.58 g (0.0035 m~le) of N,N,N',N'-tetramethyl-m-phenylenediamine and ten ml of acetic anhydride was heated to reflux for approximately one hourO After cooling to room temperature, the reaction mixture was poured into 20 ml of 10 percent hydrochloric acid and the mixture then rendered alkaline by the addition of concentrated ammonium hydroxide. The purple solid which separated was col-lected by filtration, dried, and recrystallized twice from isopropyl acetate to obtain 3-[2,4-bis(dimethylamino)phenyl]-3-(1,2-dimethyl-3-indolYl~-4,5,6,7-tetrachloxoPhthalide (FormLla III: R=R =R2=R3=C1; R=R5=R6=CH3; R4=N~CH3)2; Yl=H) which de-composed at 228-229~C. The mass spectrum showed an m/e at 5i5 (M , 4 Cl~ A toluene solution of the productspotted on silica gel developed an intense purple-colored image.
Example 13 A suspen~sion of 1.36 g (0.01 mole~ of m-amino-N,N-dimethylaniline in 20 ml of acetic anhydride was heated to 80-90C. for approximately thirty minutes and then cooled to room temperature. Three grams (0~01 mole) of 2-[(1-ethyl-2-methyl-3-indolyl~carbonyllbenzoic acid, prepared as described in part A of Example 1, was added and the resulting mixture was heated at 60-,0C~ for approxlmately thirty minutes~ After cooling, the reaction mixture was poured into 100 ml of 10 percent hydrochloric acid and the mixture made alkaline with 10 percent aqueous sodium ~ydroxide with the additio~ of ice. Ihe solid which separated was collecbed by filtra~ion and dried t~ obtain 3-~2-aoetamido -dimethyl-aminophenyl~-3~ e~y~-2-methyl-3-indolyl)ph~ide ~Fonmula III: R =R =
;~ -38-~13474 R2=R3=Yl=H; R4=NH-C-CH3; R=R5=CH3; R6=CH2CH3) as a pale blue-colored solid melting over the range 180-195Co Infrared absorption maxima appeared at 1757 cm 1 ~C=O; s) and 1696 cm 1 ~C=O; s)O
Example 14 A mixture of 0O34 g ~0l001 mole) of 2-~1,2-dimethyl-3-indolyl)carbonyl]-5-dimethylaminobenzoic acid prepared as described in Example 1 of UOSO Patent 3,540,910 was interacted with 0016 g ~O oOOl mole) of N,N,N',N'-tetramethyl-m-phen~lenediamine in 5 ml of acetic anhydride in a similar manner to the procedure described in Example 1, part C hereinabove to obtain 3-[2,4-bis(dimethy~lamino)-(Formula ~ =Rl=R3=~1=H; R2=N~CH3)2; R=R5=R6=CH3; R4=N(CH3)2) which melts over the range of 146-152Co A significant infrared absorption maximum appeared at 1760 cm 1 lC=O; s)O A toluene solution of this product spotted on silica gel developed an intense grape-red-colored imageO
Example 15 Ao To a mixture of 8~17 ~ (0.05 mole) of N-ethylcarbazole and 3O7 g ~0O25 mole) of phthalic anhydride in 112 g of chloro~
benzene, 6065 g ~0.05 mole) of aluminum chloride was added in small increments at ambient temperature after which the mixture was warmed in the range of 50-70C~ for two hours~ The reaction mix ture was poured onto ice and rendered acidic by the addition of 10 percent hydrochloric acidO The chlorobenzene layer was separated and steam-distilled to remove the chlorobenzeneO The residue was extracted with 10 percent aqueous sodium hydroxide, filtered to remove the insolubles and then acidified with dilute hydrochloric acidO The solid which separated was collected by filtration, washed with water and dried to obtain 2-[~9-ethyl-3-carbazolyl)~
carbonyl]benzoic acid (~ormula VII R =Rl=R2=R3=H; R8=CH2CH3) ~i~3474 melting over the range 120-130Co Bo A mixture of 3.43 g (OoOl mole) of 2-[(9-ethyl-3-carba-zolyl~carbonyl]benzoic acid, 1080 g (0.011 mole) of N,N,N',N'-tetra-methyl-m-phenylenediamine and 4.0 of acetic anhydride was interacted in a manner similar to that described in Example 1, part C above to yield phthalide ~ormula V: R =Rl=R2=R3=H; R=CH3; R4=N(CH3)2; R3=CH2CH3) which mel~ed over the range 134-142C. A significant infrared ab-sorption maximum appeared at 1753 cm 1 (C=O; s). A toluene solution of this product spotted on silica gel developed a bordeaux-colored image~
Example 16 Ao To a mixture of 2.96 g ~0.02 mole) of phthalic anhydride and 5072 g (0O04 mole) of N-phenylpyrrole in 50 ml of chlorobenzene~
maintained at 0-5C in an ice bath, 810 g (0.06 mole) of aluminum chloride was added in small portionsO The reaction mixture was held at 0-5C for approximately two hoursO The reaction was allowed to warm to room temperature and then set aside overnight at ambient temperature. The reaction mixture was worked up in a manner similar to that described in part A of Example 15 to obtain 2-[(l~he~1 2-~Formula IX: R =Rl=R2=R3=H; R7-C H ) which melted over the range 159-168C
B~ A mixture of 2.91 g ~0.01 mole) of 2-[(1-phenyl-2-pyrrol yl)sarbonyl]benzoic acid prepared in part A above, 2034 g (00017 mole) of 84~6 percent active N,N,N',N'-tetramethyl-m-phenylene-diamine in 4.0 ml of acetic anhydride was interacted in a manner similar to that described in Example 1, part C to obtain 2~61 g of ~Formula IV: R =Rl=R2=R3=H; R=C~3; R4=N~CH3)2; R7=C6H5)~ a peach-colored powder melting at 193-194Co ~he infrared spectrum showed a maximum at 1760 cm (C~O; s). A toluene solution of this product spotted on silica gel developed an immediate orange-red-colored imageO

~`- Example 17 A. Proceeding in a manner similar to that descrlbed ~n par~ ~ of Example 16, 14.8 g (0.1 mole~ of phthalic anhydride, 16.2 ~ (0.2 mol~) of N-methylpyrrole and 39.0 g (0.3 mole) of S aluminum chloride were interacted in 50 ml of chlorobenzene to obtain ?-~ methyl-2-pYrrolYl)carbonYllbenzoic acid (Formula IX:
Ro=Rl=R2=R3=H; R =CH3) melting at 165-167C. A significant in-frared absorption maximum appeared at 1710 cm 1 (C=0; s).
B. A mixture of 4.58 g ~0.02 mole) of 2-[tl-methyl-Z-pyrrolyl)carbonyl]benzoic acid, from part A above, 3.61 9 (0.022 mole) of N,N,N ,N -tetramethyl-m-phenylenediamine and 3.0 ml o acetic anhydride was interacted in a manner similar to that descri~ed above in Example 1, part C to obtain 1.92 g of 3-~2,4-b~s~dimethYlamino)phenyl~-3-(l-methyl-2-p~rrolyl~phthalide lS (Formula IV: Ro=Rl=R2=R3=H; R=R7=CH3; R =N(CH3)2), a tan powder melting at 14B-lS0C. A toluene solution of this p~oduct spotted on silica gel developed an intense red-colored image.
Example 18 A. A stirred solution of 48.0 g (0.250 mole) of trimellitic anhydride and 45.0 9 (0.314 mole) of 1-ethyl-2-methylindole in 350 ml of ethylene dichloride was heated at reflux for a period of approximately two hours~ and then allowed to cool to ambient temperature. The solid, which separated, was collected by fil-tration, washed with 200 ml of ethylene dichloride and dried in vacuo at 60C to obtain 66.0 g.of 4/S-carboxy-2-r(l-ethYl-2-methyl-3-indolyl)carbonvllbenzoic acid ~Formula VIII: Rl=R2=H~COOH;
Ro=R3=Yl=H; R5=CH3; R6=CH2CH3), a yellowish-orange solid melting over the range 198-201C. Infrared maxima appeared at 1730 (C=0; s) and 1700 cm 1 (C=0; vs). The nuclear ma~netic resonance spectrum was in agreement with the ass1gned .tructure.

'74 B. A stirred mixture of 17.S g (0.05 mole) of the 4~5-carboxy-2-[(1-et}-yl-2-methyl-3-indolyl)carbonyl]benzoic acid, prepared as described in part A above, 8 5 g (0.052 mole) of N,N,N ,N -tetramethyl-m-phenylenediamine and 25 ml of acetic anhydride was heated at 50C for a period of two hours and then allowed to cool to ambien~ temperature. After the addition of 25 ml of isopropyl alcohol, the resulting mixture was poured int~ water with vigorous stirring. The solid which separated was collected by filtration, washed with water and dried in vacuo at 60~C to obtain 22.0 9 of ~-r2,4-bis~dimethylamino)-phenYll-3-(l-ethyl-3-methvl-3-indolyl)-s/6-carboxyphthalide , (Formula III: R=R5=CH3; Ro=R3=Yl=H; Rl=R2=H/COOH; R4=N(CH3)2;
R6=CH2CH3) as a dark purple solid melting over the range 149-151C. Infrared maxima appeared at 1775 (C=0; s) and 1720 cm 1 (C=0; s).
C. Three milliliters of dimethyl sulfate was added to a refluxing mixture of 3.0 g of the 3-~2,4-bis(dimethylamino)-phenyl~-3-(1-ethyl-2-methyl-3-indolyl)-5f6-carboxyphthalide prepared as described in part B above, 3.0 g of potassium carbonate and 100 ml of acetone. The reaction mixture was heated at reflux for a period of t~o hours and was then poured into water and the aqueous mixture extracted with toluene. The toluene extract was washed successively with water and saturated salt solution and then evaporated to dryness. The residue was triturated with ligroin ~b.p. 60-90C) and the solid separated and dried to obtain 1.0 g of 3-~2,~-bis(dim~thvlamino)~heryll-3-(1-ethvl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide (Formula III: R=R5=CH3; Ro-R3=Yl=H; Rl=R2=H~COOCH3; R4=N(CH3)2;
R6=CH2CH3), a light purple solid melting over the range 72-F35~C. Infrarcd maxima appeared at 1760 (C=0; s) and 1730 cm I

~.~13474 (C=O; s). Analysis by mass spectrum showed m/e peaks at 511 (M ) and at 452 (M -CO2CH3). A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic re-sin developed a grape-colored image.
Example 1~
To a stirred mixture of 6.38 g ~0.013 mole) of 3-[2,4-bis~dimethylamino~phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide, prepared as described above in part B of Example 18, 150 ml of hexamethylphosphoramide and 10 ml of 25 percent aqueous sodium hydroxide, there was added 7.0 ml of ethyl iodide. The mixture was stirred at room temperature for a period of two hours. The reaction mixture was then drowned in water and the aqueous mixture was extracted with toluene.
The toluene layer was washed with water, dried over anhydrous so~ium sulfate, and evaporated. The residue was triturated with ligroin ~b.p. 60-90C.) and the separated solid collected and dried to obtain 0.92 g of 3-12,4-bis~dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide (Formula III: R=R5=C~3î Ro=R3=Yl=H; Rl=R2=~/COOCH2CH3; R4=
N(CH3)2; R6=CH2CH3), a light brown powder melting over the range 88-~7Co Infrared maxima appeared at 1765 (C=O; s) and 1725 cm 1 (C=O; s). The nuclear magnetic resonance spectrum was in agreement with the assigned structure. Analysis by mass spectrum showed m~e peak at 525 (M ). A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a grape-colored image.
Example 20 Following a procedure similar to that described above in part C of Example 18 but substituting dimethylformamide for acetone and n-octyl bromide for dimethyl sulfate, there was ob-1~13474 tained 3-[2,4-bis~dimethylamino)phenyl]-3-~1-ethyl-2-methyl-3-_ndolyl~-5/6-~-octyloxycarbonylphthalide ~Formula III: R=R5=
CH3; R =R3=Y =H; R =R2=H/COO~CH217CH3; R =N~C~3)2; R =CH2CH3) as a light brown oil. Infrared maxima appeared at 1770 tC=O;
s) and 1730 cm 1 (C=O; s), A benzene solution of the product spotted on silica gel, an acidic clay or a phenolic resin de-veloped a grape-colored image.
Example 21 Following a procedure similar to that described above in Example 20 except that ~-bromotoluene was used in place of n-octyl bromide, there was obtained 2.52 g of 3-[2,4-bis~dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-phenylmethoxy carbonylphthalide (Formula III: R=R5=CH3; R =
R =Y =H; R =R =H/COOCH2C6H5; R =N~CH3)2; R =CH2CH3), a light purple powder melting over the range 72-78C. Infrared ma~ma appeared a~ 1770 cm 1 (C=O; s)O Analysis by mass spectrum showed m/e peaks at 587 (M ) and 543 ~M -C02~. A toluene so-lution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a grape-colored image.
Example 22 Ao A mixture of 35 g (0.10 mole~ of 4/5-carboxy-2-[~1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid prepared as de-scribed in Example 18, part A above, 20 g (0.103 mole) of N,N-diethyl-m-phenetidine and 6~ ml of acetic anhydride was stir-red at room temperature for a period of approximately eighteen hours. Af~er the addition of 100 ml of isopropyl alcohol, the resulting mixture was poured into water with vigorous stirring.
lhe solid which separated was oollected by filtration, washed with water and dried to ~btain 53.4 g of 3-~2-ethoxy-4-diethylaminophenyl)-3~
ethyl-2-methyl-3-indolyl~-5/6-carboxyphthalide (Formula III:
_ ~ -44-1~13474 `
R=R -C2H5; R =R =Y ~H; Rl=R2~HfCOOH; R4~oC2H5; R5-CH3), a dark blue solid melt~ng over the range of 130-144C. Infrared maxima appeared at 1765 (C=O; s) and 1725 cm 1 (C=O; s).
Analysis by mass spectrum showed m/e peaks at 526 (M ) and 481 (M -CO2H).
B. Employing a procedure similar to that described in part C of Fxample 18, but interacting 5.0 9 t0.0095 mole) of 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-3-methyl-3-indolyl)-5/6-carboxyphthalide prepared as described in part A of this example lQ with dimethyl sulfate instead of 3-[2,4-bis(dimethylamino)phenyl]-3-~1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide, there was o~tained 4.9 9 of 3-(2-ethoxv-4-diethvlaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxvcarbonvlphthalide (Formula III:
R=R6=C2H5; Ro=R3=Yl=H; Rl=R2=H/COOCH3; R -OC2H5; R5=CH3), a light green-colored solid melting over the range 96-103C.
Infrared maxima appeared at 1765 (C-O; s) and 1730 cm 1 (C=O; s). The nuclear magentic resonance spectrum was in agree-ment wi~h the assigned structure. Analysis by mass spectrum showed m/e peaks at 540 (M ), 496 ~M -CO2) and 418 (M -COOCH3).
A toluene s~lution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a deep blue-colored image which had good lightfastness.
: Example 23 When diethyl sulfate was substituted for dimethyl sulfate for interaction with 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide according to the pro-cedure described in part B of Example 22, there was obtained 1.5 9 of 3-(~-ethoxv-4-diethylamino~henvl)-3-(1-ethvl-2-methyl-3-in~olvl)-Sf6-ethoxycar~onvlph~halide (Formula III: R=R6=C2H5; Ro=R3--Yl=H;
Rl=R2=H/COOCH2CH3; R =OC2H5; RS=CH3;), a light yello~ solid " lil3474 melting ove,r thc range 1~1-148C~ Infrared maxima appeared at 1750 (C=0; s) and 1732 cm (C~0; s). Analysis by mass spec-trum showed m/e peaks at 554 (M ), S10 (M -C0) and 481 (M+-C02C2H5). A toluene solution of the product spotted on S silica gcl, an acidic clay or a phenolic resin develop~d a deep ~lue-colored lmage which had ~ood lightfastness.
Example 24 Following a procedure similar to that described above in Example 22, part B, 5.0 g (0.0095 mole) of 3-(2-ethoxy-4-di-ethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxy-phthalide prepared as described in Example 22, part A was inter-acted with 2.0 g (0.0117 mole) of ~-bromotoluene to o~tain 3.4 g of 3-(2-ethoxY-4-diethvla~ino~henyl)-3-(1-ethyl-2-methvl-3-. indolYl)-5/6-phenylmethox~carbonylphthalide (Formula III: R=R6=
lS C2~5; Ro=R3=Yl=H; Rl=R2=H/COOCH2C6H5; R4=oC2H5; R5=CH3), a light yellow solid melting over the range 82-87C. Infrared maxima appeared at 1765 (C-0; s) and 1725 cm 1 (C=O; s). Analysis by mass spectrum showed m/e peaks at 616 (M~) and 572 (M~-CO2).
A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a deep blue-colored image which had good lightfastness.
Example 25 When n-octyl bromide was substituted for a-bromotoluene for interaction with 3-(2-ethoxy-4-diethylaminophenyl)-3~
ethyl-2-methyl-3-indolyl)-S/6-carboxyphthalide according to the procedure described in Exa~ple 24, there was obtained 3-(2-:~:5e:!aD~ henvl)-3-(l-ethyl-2-methvl-3-indo~ )-5/~
n-octoxycarbonylphthalide (~ormula III: R=R -C2~S; R =R =Y =~;
Rl=R2=H~C00-n-(CH2)7CH3; R =OC2H5j R5 CH~), a l~ght blue solid melting over the range 13~-162C. A toluenc .c,1ution of the pro-~ 6-1~ 474 duct spott~d on sil~ca gel, an acidic clay or a phenolic resln developed a dcep blue-colored image which had good li~htfast-ness.
Example 26 Substltuting l-bromohexadecane for n-octyl bromide for ;, ~nteraction with 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide according to the procedure described in Example 25, there was obtained 7.1 9 o~ 3-t2-ethoxy-4-diethylaminophenYl)-3-(1-ethvl-2-methvl-3-indolyl)-5/6-hexa-decanoxvcarbonYlphthalide (Formula III: R=R6=C2H5; R=R~=Yl=
H/COO(C~2) 5CH3; R =OC2H5; R5=CH3), a light brown oil. Infrared . ~
maxima appeared at 1765 (C=0; s) and 1725 cm (C=0; s). The nuclear magnetic resonance spectrum was in agree~ent with the assigned structure. Analysis by mass spectrum showed m/e peaks at 750 (M~ and 706 (S~ -C02)~ A ~enzene solution of the product , spotted on silica gel, an acidic clay or phenolic resin developed a deep blue-colored image which had good lightfastness.
Sxample 27 , To a stirred solution of 5.3 g of 3-(2~ethoxy-4-diethyl-aminophenyl)-3~ ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide prepared as described in Example 22, part A, in 25 ml of acetone there was added 2.6 9 of 1,1,3,3-tetramethylbutylamine. The mix-ture was stirred at ambient temperature for approximate,ly ten minutes and then 160 ml of n-hexane was added. The supernatant liq~id was decanted and the insoluble, brown, gummy residue tri-turated with n-hexane to obtain 6,2 9 of th~ 1,1,3,3-t~tramethvl-butylammonlum salt of 3-(2-ethoxY-4-diethY]~minophenvl)-3-(l-eth~l-2-methYl-3-in~olY})-5/6-carbox~hthalide ~Formula III: Ro=R3=
yl=~; R =R =H/cooN~t3c(c~3)2cH2c(cH3)2cH3; R-R =C2lt5; R =
OC2H5; R5=CH3), a beige-colored solid melting over the rarlge ~13474 of 80-105C with decomposit~on. Infrared spectral analysls showcd significant maxima in the range from 2350 cm 1 to 2150 cm 1, and a strong absorpt~on at 1760 cm 1 (C=O; s). Thè assigned struc-tur~ was corroborated by a concordant nuclear magnetic resonance S spectrum. A toluene sol~tlon of the product spotted on silica gel, an acidic clay or a phenolic resin developed a deep blue-colored image which had good lightfastness. This product is also a water-soluble color-former.
Example 28 A. Following a procedure similar to that described in part A of Example 22 but interacting N,N-dimethylaniline instead of N,N-diethyl-m-phenetidine, with 4/5-carboxy-2-[(1-ethyl-2-~ethyl-3-indolyl)carbonyl]benzoic acid, there was obtained 3-(4-dimethvl-aminophenYl)-3~ ethvl-2-methyl-3-indol~l)-sJ5-carbox~ph _alide lS (Formula }II: R=RS-C~3; Ro=~3=R =Yl=H, R~=R2-H!C0OH, R =C?H5), a blue-colored solid melting over the range.l41-100C. Infrared maxima appeared at 1770 tC=O; s) and 1730 cm 1 (C=O; s) Analysis by mass spectrum showed m/e peaks at 454 (M+), 410 (M+-CO2) and 409 (M+-COOH).
B. Employing a procedure similar to that described in part C of Example 18, but substit~ting 3-(4-dimethylaminophenyl)-3-~1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide prepared as de-scribed in part A above for 3-~2,4-bis(dimethylamino)phenyl]-3-(l-ethyl-2-methyl-3-indolyl)-5~G-carboxyphthalide for interaction with dimethyl sulfate, there was obtained 3-(4-dimethYlamino~henYl)-3-(1-eth 1~2-methvl-3-indol l)-S/G-m~thoxvcarbonvl~hthalide Y Y - - .
(Formula III: R-RS-CH3; Ro=R3=R =Yl=H; Rl=R2=HJCOOCH3; R6=
C2H5) t a light yellow solid melting over the range 101-110C.
Infrared maxima appeared at 1760 ~C-O; s) and 1730 cm 1 (C=O; s).
- 30 The nuclear magnetic resonance spectrum ~as in c~greement with the -48~

~13474 ~ssi~ned structure. Analys~s by mas~s spectrum showed m/e peaks at 468 (M ), 424 (M -CO2) and 409 (M -COQCH3). A tolu~ne solu-tion of the product spotted on silica gel, an acidic clay or a phenolic resin developed a blue-colored image had good light-fastness.
Example 29 Proceeding in a manner similar to that described above ~n Example 23, 3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide prepared as described in Example 28, part A, was interacted with diethyl sulfate to obtain 3-(4-dimethYlaminoDhen~ 3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxy-carbonylphthalide (Formula III: R=R5-CH3; Ro=R3=R4=YlcH; R =
R2=H/COOC2H5; R6=C2H5), a li~ht green solid melting Over the range 114-131C. Infrared maxima appeared at 1765 (C=O; s~
and 1725 cm 1 ~C=O; s). Analysis by mass spectrum showed m/e peaks at 482 (M ), 438 (M -CO2) and 409 (M~-CO2C2H5). A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a blue-colored image which had good lightfastness.
Example 30 When ~-bromotoluene was substituted for diethyl sulfate in Example 29, there was obtained 3-(4-dimethvlaminophenyl~-3-(l-ethyl-2-methyl-3-indolyl)-5/6-phenylmethox~carbon~lphthalide (Formula III: R-RS=CH3; Ro=R3=R4=Yl=H; Rl=R2-H/COOCH C H ;
R6= C2H5), a light green-colored solid melting over the range 93-98~C. Infrared maxima appeared at 1770 (C=O; s) and 1728 cm 1 (C=O;-s). Analysis by mass spectrum showed m/e peaks at 544 (M ) and 500 (M -CO2). A tol~ene solution of the product spotted on silica gel9 an acidic clay or a phenolic resin developed a blu~-colored image which had good llqhtfastness.

Example 31 A. Following a procedure similar to that described in part A of Example 22, but using 15 g of N,N-diethylaniline instead of N,N-diethyl-m-phenetidine for interaction with 4/5-S carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, there was obtained 3-(4-diethylamino~henyl)-3-(1-eehq~ b~l -indolyl)-5/6-carboxyphthalide (Formula III: R=R6=C2HS; Ro=R3-R =Yl=H; Rl=R2=H/COOH; R5=CH3), a blue solid melting over the range 169-182C. Infrared maxima appeared at 1765 (C=O; s) and 1730 cm 1 ~C=O; s). The nuclear magnetic resonance spectrum was in agreement with the assigned structure.
B. Proceeding in a manner ~imilar to that described in part r of Example 18, but using 3-~4-diethylaminophenyl)-3-~1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide prepared as de~cribed in part A above in place of 3-[2,4-bis(dimethylamino) phenyl)-3-~1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide for interaction with dimethyl sulfate, there was obtained 3-(4-diethylaminophenyl)-3-(l-ethyl-2-methyl-3-indolyl~-5/6-meth c~rbonylphthalide (Formula III: R-R6-C2~5; RozR3=R4=Yl=H; Rl2 R~sH/COOCH3; R5=CH3), a light green solid melting over the range 114-128Cc Infrared maxima appeared at 1765 (C-O; 8) and 1730 cm 1 (C=O; s). A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a blue-colored image which had good lightfastnes~.
Example 32 A. Employing a procedure similar to that described in part A of Example 22, but using m-chloro-N,N-dimethylaniline ins~ of N,N-diethyl-m~phenetidine for interaction with 4/5-carboxy-2-~ ethyl-2-me~hyl-3-indolyl)cæbonyl]benzoic acid, there was obta~ 3-(2-chloro-4-dimethvlammo~ 3-(1-ethyl-2 ~ thyl-3-indolyl)-5/6-carboxyphthalide (Formula III: R=R5=C~3; Ro-R3=Yl=H;
-50~

1~13474 Rl=R2=H/COOH; R4=Cl; R6=C2H5), as a greenish-blue solid melting over the range 130-142C G Infrared maxima appeared at 1770 (C=O; s) and 1725 cm (C=O; m).
B. PDxY#s~ng in a manner similar to that described in part C of Example 18, but using 3-~2-chloro-4-dimethylamino-phenyl)-3-(1-ethyl-2-methyl-3-indolyl~-5/6-carboxyphthalide prepared as described in part A above instead of 3-[2,4-bis (dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide for interaction with dimethyl sulfate, there was obtained 3-(2-chloro-4-dimethylaminophenyl~-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide (Formula III:
R=R5=CH3; R =R3=Y1=H; Rl=R2=H/COOCH3; R =Cl; R6=C2H5), as a light blue solid melting over the range 168-193C. Infrared maxima appeared at 1770 (C=O; s) and 1730 cm 1 ~C=O; s). A
toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a pale green-colored image.
Example 33 A. Following a procedure similar to that described in part A of Example 22, but using N,N-m-diethyltoluidine instead of N,N-diethyl-m-phenetidine for interaction with 4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, there was obtained 3-(2-methYl-4-diethYlamlnoPheny~L-3-(l-ethyl-2-methyl-3-indol~1~-5/6-carboxyphthalide (Formula III: R=R6=C2H5;
R=R =Y =H; R =R2--H/COOH; R4=R =CH3~, a turquoise-colored solid melting o~er the range 146-162C. Infrared maxima ap-peared at 1765 (C=O; s) and 1720 cm 1 (C=O; s~. Analysis by mass spe~m showed m~e p~ at 4~6 ~ ), 452 ~M -CO2~ and 451 ~M -COOH).
B. Employing a pxocedure similar to that described in part C of Example 18, but using 2-~2-methyl-4-diethy~nophenyll-3~ ethyl-2-methyl-3-indolyl~-5/6-carboxyphthalide prepared as 1~3474 ~escribed in part A above instead of 3-[2,4-bls(dimethylamino)-phenyl]-3-~1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide, there was obtalned 3-(2-methyl-~-dieth~laminophenvl)-3-(1-ethyl-2-methyl-3-indolyl)-S/6-methoxvcarbonylphthalide (Formula III: R=R6=C2~5;
Ro=R3=Y =H; Rl=R2=H/COOCH3; R4=R5=CH3), a light yellow solid ; melting over the range 113-120C. Infrared maxima appeared at 1770 (C=0; s) and 1730 cm 1 (C=0; s). The nuclear magnetic resonance spectrum was in agreement with the assigned struc-ture. Analysis by mass spectrum showed m/e peaks at S10 (M ) and 495 (M -COOC~3). A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a tur-quoise-colored image which had good lightfastness.
Example 34 Proceeding in a manner similar to that described above lS in Example 23, 3-(2-methyl-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl~-5/6-carboxyphthalide prepared as described in Example 33, part A was interacted with diethyl sulfate to obtain ~-(2-methvl-4-diethYlaminophen~rl)-3-(l-ethyl-2-methvl-3-indolyl) S/~-ethoxycarbonYl~hthalide (Formula III: R=R6=C2H5; Ro=R3=Yl=H;
Rl=R2=H/COOC2H5; R4=RS=CH3), a tan solid melting over the range 89-144C. Infrared maxima appeared at 1~65 (C=0; s) and 1725 cm 1 (C=0; s). Anaiysis by mass spectrum showed m/e peaks at 524 (M ), 480 (M -C02) and 451 (M -C02C2H5). A toluene solution of the product spotted on sili~a gel, an acidic clay or a phenolic resin developed a turquoise-colored image which had good lightfastness~
Example 35 When ~-bromotoluene was substituted for diethyl sulfate in Example 3~ for interaction with 3-(2-methyl-~-diethylamino-phenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyph~halide pre-.:
pared as descri~ed in Example 33, part A, there was obtained 3-(2-methvl-4~di~?thylami!lophenyl)_3-(1-~thyl-2-methyl-3-indolvl)-Sf6-phen~rlmethoxycarbonylphthalide (Formula III: R=R6=C2H5;
Ro=R3=Yl=H; Rl=R2-H~COOCH2C6H5; R4=~5=CH3), a light yellow S solid melting over the range 92-98C. Infr~red maxima appeared at 1765 (C=O; s) and 1725 cm 1 (C=O; s). Analysis by mass spec-trum showed m/e peaks at 586 (M+) and 542 (M+-C02). A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a turquoise-colored image having good lightfastness.
E:xample 36 A. Following a procedure similar to that described in part A of Example 22, but using N,N-di-n-butylaniline instead of N~N-diethyl-m-phenetidine for interaction with 4/S-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, there was obtained 3-(4-di-n-butylaminol~henvl)-3-(1-ethyl-2-methyl-3-indolyl)-St6-car~oxv-phthalide (Formula III: R=CH2(CH?)2CH3; R =R3=R =Yl=H; Rl=R2=H/COOH;
R5 = CH3; R6 = C2H5), as a blue-colored solid melting over the range 81-94C. Infrared maxima appeared at 1760 (C=0; s) and 1725 cm 1 (C=0; m).
B. Employing a procedure similar to that described in part C of Example 18 but using 3-(4-di-n-butylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide prepared as described in part A above instead of 3-~2,4-}:)is(dimethylamino)phenyl3-3-(1-ethyl-2-methyl-3-indolyl~-5~6_carboxyphthalide for interaction with dimethyl sulfate, there was obtained 3-(4-di-n-butvlamino-h ~1~ 3 (1 ~th 1 2 meth 1-3-indol 1)-5~6-methox car~onvlr~nthali.de p en~ y - - Y v Y
tFormula III: R-CH2(CH2~2CH3; Ro=R3=R4=Yl.-H; Rl=R2=H/COOCH3; R =CH3;
R - C2H5), a light yellow solid rnelting over the ran~e 72-9~'`C.
Infrared maxima appeared at 1765 (C=0; s) and 172~3 cm 1 (C~=C~
.--53--~13474 Analysis by mass spectrum showed m~e peaks at 552 (M ), 508 (M -C02) and 493 (M -C02CH3). A toluene solut~on o~ the pro-duct spotted on s~lica gel, an acidic clay or a phenolic ~esin developed a blue-colored image which had good lightfastness.
S Exam~le 37 A. Followinq a procedure similar to that described in part A of Example 22, but using N,N-dimethyl-m-anisidine inste~d of N,N-diethyl-m-phenetidine for interaction with 4/5-carboxy-2-t(l-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, there was obtained 3-(2-methoxy-4-dimeth~laminophenYl)-3-(1-ethyl-2-methYl_ 3-indolyl)-~/6-carboxYphthalide (Formula III: R=R -CH3; Ro~R3=
Yl=H; Rl=R2=H/COOH; R4=oC~3, R6=C2H5), a deep ~lue solid melting over the range 128-133C. Infrared maxima appeared at 1760 (C=0; s) and 1730 cm 1 (C=O; m). Analysis by mass spectrum lS showe~ m/e peaks at 484 (M~), 440 (M+-C02) and 439 (M~-CO0~) B. Employing a procedure similar to that described ln part C of Example 18, but using 3-(2-methoxy-4-dimethylamino-phenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide pre-pared as described in part A above instead of 3-[2,4-bis(di-methylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5~6-carboxy-phthalide for interaction with dimethyl sulfate, there was obtained 2-(2-methox -4-dimeth laminoDhenvl)-3-(1-ethyl-2-methvl-3-indol~1)-..- Y Y
5~6-methoxycarbonylphthalide (Formula II~: R=RS=CH3; Ro=R3=Yl=H;
Rl=~2=H/COOCH3; R4=oCH3; R6=C2H~), as a light blue solid melting over the range 131-135C~ Infrared maxima appeared at 1760 (C-O; s) and 1730 cm 1 (C=O; s)~ Analysis by mass spectrum showed mJe peaks at 498 (M~), 454 (M -C02) and 439 (M -CO2C~3).
A toluene solution of the product spotted on silica gcl, an acidic clay or a phenolic rcsin develop~d a deep blue-colorcd image ~hich had good lightfastness `` 1~13474 - Example 38 A. Proceeding in a manner similar to that described in part A of Example 22, but using 3-n-butoxy-N,N-diethylaniline instead of N,N-diethyl-m-phenetidine for interaction with 4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl]benzoic acid, there was obtained 3-(2-~-butoxy-4-diethylaminophenyl)-3-(1-ethYl-2-methyl-3-indolyl~-S/6-carboxyphthalide (Formula III:
R=R6=C2H5; Ro=R3=Yl=H; Rl=R2=H/COO~; R4=oC~2(CH2)2CH3; R5=CH3), a deep blue solid melting over the range 113-125C. Infrared maxima appeared at 1760 (C=O; s) and 1725 cm 1 (C=O; m).
Analysis by mass spectrum showed a m/e peak at 510 (M -CO2).
B. Following a procedure similar to that described in part C of Example 18, but using 3-(2-n-butoxy-4-diethylamino-phenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide prepared as described in part A above instead of 3-[2,4-bis (dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide for interaction with dimethyl sulfate, there was obtained 3-(2-~butoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-_ndolyl~-5/6-methoxycarbonylphthal_de (Formula III:
R=R6=C2H5; Ro=R3=Yl=H; Rl=R2=H/C~OCH3; R4=ocH2~c~2)2cH3iR =
CH3), a light green oil. Infrared maxima appeared at 1765 (C=O; s~ and 1730 cm 1 (C=O; s). A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a deep blue-colored image which had good lightfastness.
Example 39 A. A stirred mixture of 19.2 g (0.10 mole) of trimelli-tic anhydride, 35 g (0.22 mole) of 1-ethyl-2-methylindole and 75 ml of acetic anhydride was heated at reflux for approximate-3Q ly one hour, then cooled slightly below reflux after which 1~13474 there was slowly added 100 ml of methanol. The resulting so-lution was cooled to ambient temperature and slowly poured with stirring into a mixture of ice and water. The solid that formed was collected by filtration and dried in vacuo at 60C.
to obtain 3,3-bis(l-ethyl-2-methyl-3-indolyl)-5/6-carboxy-phthalide (Formula VI: Rl=R2=H/COO~; R5=R5 =C~3; R6=R6 =
CH2CH3; Ro=R3=Yl=Yl =H), as a deep red solid melting over the range of 110-119C. Infrared maxima appeared at 1760 ~C=O; s) and 1720 cm 1 (C=O; m). The nuclear magnetic resOnanCe spectrum was in accord with the assigned structure.
B. Following a procedure similar to that described above in part C of Example 18, but using 3,3-bis(l-ethyl-2-methyl-3-indolyl)-5/6-carboxyphthalide prepared as described above in part A of this example instead of 3-[2,4-bis~dimethyl-amino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl~-5/6-carhoxy-phthalide for interaction with dimethyl sulfate, there was obtained ~ ~
onylphthalide ~Formula VI: Rl=R2=H/COOCH3; Ro=R3=Yl=Yl =H;
R5=R5 =CH3; R6=R6 =CH2CH3), a tan solid melting over the range of 226-229C. with decomposition. Infrared maxima appeared at 1765 (C-O; s) and 1735 cm 1 (C=O; s). The nuclear magnetic resonance spectrum was concordant with the assigned structure.
Mass spectrum analysis showed m/e peaks at 506 (M ), 462 (M -CO2) and 447 (M -CO2CH3)~ An acetone solution of the product spotted on silica gel, an acidic clay or a phenolic resin developed a deep red-colored image which had good xero-graphic copia~ility and good lightfastness.
Example 4Q
A stirred mixture of 3.0 g (0.006 mole) of 3,3-bis-1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide prepared ~i3474 as in Example 39, part B and 35 ml of 3- ~di-n-butylamino) propylamine was heated at 125-130C. for approximately five hours and then allowed to cool to ambient temperature. The brown solution was poured into a mixture of water and toluene and the toluene layer was separated, washed with water and concentrated under reduced pressure. The excess amine was re-moved by vacuum distillation. There was thus obtained 3,3-bis (l-ethyl-2-methyl-3-indolyl) -5~6= ~3-N,N-di-a-butylamino) propyl=
aminocarbonylphthalide (Formula VI: Rl=R2=H/CONH(CH2) 3N(n-C4Hg) 2; R =R =CH3; R6=R6 =C2H5; Ro=R3=Y =Y =~), as a light brown oil. Infrared maxima appeared at 1770 (C=O; s) and 1650 cm 1 (C=O; s). The nuclear resonance spectrum was concordant with the assigned structure. When a soy oil solution of the product was spotted on silica gel, an acidic clay or a phenolic resin, a dark red-colored image developed which had good lightfastness.
Example 41 A. Eollawing a pmcedure similar to that described in Example 18, part B above, for interacting 10.6 g of 4/S-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carkonyl]benzoic acid, prepared as described in Example 18, par~ A, and 7.0 g of 1-n-butyl-2~nethylindole, there was obtained 16 g of 3-(1-ethyl-2-~thyl-3-indolyl)-3~ -butyl-2-methyl-3-indolyl)-5/6-carbo~ph~alide (E~rr~mla VI: R =R =H/COOH; R =R =CH3; R ~2H5; R =n-C4Hg; Ro--R3--Yl=Yl =H), a deep red solid melting over the range of 128-138C.
with dec~qnposition. Infrared maxi~ appeared at 1762 (C=O; s) and 1738 cm 1 (~0; s) B. Employing a procedure similar to that descr~ above in part B of Example 39, except that 3-(1-ethyl-2-methyl-3-indolyl)-3-(1-n-butyl-2-methyl-3-indolyl)-5/6-carbo~phthalide prepared as described above in part A of this example was used in place of 3,3-bis(l-ethyl-2-methyl-3-indolyl-5/6-carb~thalideJ there was obtained 3-(l~thyl-2~nethyl-3-indolyl)-3-(1-~-butyl-2-methyl-3-indolyl)-5/6-met oxycarbonylphthalide (Formula VI: Rl=R2=H/COOCH3; R5=R5 =CH3; R6=C2H5; R6 =n-C4Hg;
R =R3eYl =H), a light orange solid melting over the range of 82-94Co Significant infrared maxima appeared at 1765 (C=O; s) and 1730 cm 1 ~C~O; s)O Mass spectral analysis showed m/e peaks at 534 ~M ) and 490 ~M -CO2). A toluene solution of the product spotted on silica gel, an acidic clay or a phenolic resin devel-oped a deep red-colored image which possessed good lightfastnessO

A, Proceeding in a manner similar to that described in : 10 Example 41, part A above, but using l-allyl-2-methylindole in-stead of l-n-butyl-2-methylindole for interaction with 4/5-carboxy-2-[ ~-ethyl-2-methyl-3-indolyl)carbonyl~benzoic acid, there was obtained ~
~ (Formula VI: Rl=R2=H/COOH; R5=R5 =
CH3; R6=~2H5; R 'CH2-CH=CH2; R =R3=Y =Y -H), a deep red solid melting at 135Co with decompositionO Significant infrared maxima appeared at 1765 (C=O, s) and 1730 cm 1 (C=O; m)~
Bo When 3-~1-ethyl-2-methyl-3-indolyl)-3-(1-allyl-2-methyl-3-indolYl)-5/6-carboxyphthalide prepared as described in part A
of this example was substituted for 3,3-bis U-ethyl-2-methYl-3-indolyl)-5/6-carboxyphthalide in the procedure described in part B of Example 39, there was obtained 3-(1-ethyl-2-methyl-3-indolyl)-~ ~ _ t =
~Formula VI: R =R2=H/COOCH; R5=R =CH3; R6=C2H5; R =CH2-CH=CH2;
R =R3=Y =~ , an orange solid melting over the range of 152-164Co Infrared spectral analysis showed maxima at 1760 (C=O; s) and 1732 cm 1 ~C=O; s). Nuclear magnetic resonance analysis was in accord with the assigned structure. Analysis by mass spectrum showed m/e peaks at S18 ~M ), 474 (M -CO2) and 459 (M -COOCH3)o A toluene solution of the product spotted on silica gel, an acid '~

1S~13474 clay or a phenolic resin developed a deep red-colored image which had good lightfastnes~.
Example 43 Employing a procedure similar to that described in Example 18, part B above, for interacting 4/5-carboxy-2-[(1-ethyl-2-methyl-3-indolyl)carbonyl~benzoic acid, prepared as described in Example 18, part A and l-ethyl-2-methylindole, there was obtained 3,3-bis ~-ethyl-2-methyl-3-indolyl)-5/6-carboxy;~hthalide (Formula VI: Rl-R~aH/COOH; R5-R5 =CH3; R6-R6 sCH2CH3; R -R3~Yl=Yl =H)~
Proceeding in a manner similar to that described in Example 39, part B, the following esters of the thus prepared 3,3-bis(l-ethyl-2-methyl-3-indolyl)-5j6-carboxyphthalide of Formula VI (R SR3=Yl=
yl -H; R5-R5 ~CH3; R6~R6 ~CH2CH3; Rl/R2=E/COOH~ above were prepared by e~terification employing the appropriate dialkyl sulfate or organic hal~de. A toluene 801ution of these individual ester~, when ~potted on silic~ gel, an acidic clay or a phenolic re~in, each developed a deep red-colored image which had good lightfastne~s~ The infrared analyses, nuclear magnetic resonance analyses and mass spectral analy~es obtained for the products of Example~ 44 to 48 inclusive were concordant for the assigned struc-ture given in those examples.

phthalide (Formula VI: Rl~R2-H/COOC2H5; R5-R5 =CH3; R6=R6 =
CH2CH3; R =R3=Yl=Yl sH) was obtained as a pale yellow solid melt-ing over the range of 176-179C.

3,3-Bis~l-ethyl-2-methyl-3-indolyl)-5/6-n-butoxycar-b ~ ~Formula VI: R~=R =H/COO(CH2)3CH3; R =R =CH3;
R6=R~ =CH2CH3; R -R3=Yl=Yl =H) was obtained as a light orange ~.

" 1~13474 solid melting at 88C. with decomposition~
Example 4 6 3,3-Bis~l-ethyl-2-methyl-3-indolyl)-5/6-n-octyloxy=
carbonylPhthalide ~ormula VI: Rl=R2=H/COO(CH2)7CH3; R5=R5 =CH3;
S R6=R6 =CH2CH3; R =R3-Yl-Yl =H) was obtained as an orange oilO

~L_b~
carbonylPhthalide ~Formula VIo Rl=R2=H/COOCH2C6H5; R5=R5 =CH3;
6 6' Ro=R3=Yl=Yl =H) was obtained as a light orange solid melting over the range of 94-100Co with decomposition~
: ~.
3,3-Bis(l-ethyl-2-methyl-3-indolyl)-5/6-allyloxy~car-(Formula VI: R =R2-H/COOCH2CH=CH2; R5=R5 =CH~; R6=
R6 =CH2CH3, R -R3=Yl=Yl =H~ was obtained as a light orange solid melting over the range of 75-87C.
, ~
=~=~
~ormula VIs Rl=R2-H/COOtCH2)15CH3; R5=R5 =CH3, R6=R6 =CH2CH3; R -R3=Yl=Yl =H~ was obtained as a dark red oilO
Infrared maxima appeared at 1770 (C=O7 s) and 1730 cm 1 ~C=O~ s)~
Example 50 Proceeding in a manner similar to that described in Example 13 above, 4.43 g ~OoOl mole) of 2-[(1-ethyl-2-methyl-3~
indolyl)carbonyl~-3,4,5,6-tetrachlorobenzoic acid, prepared as de-scribed in Example 2, part A above, was interacted with 2~0 g ~0c015 mole~ of m-amino-N,N-dimethylaniline in the presence of ten -ml of acetic anhydride to obtain phthallde (Formula III: R =Rl=R2=R3=Cl; R=R5=CH3, R4=NH-~-CH3;
R6=CH2CH3; Yl=H) which developed a blue~green color when spotted X

1~3474 on silica gel in the form of a toluene solutionO
Example Sl Following a procedure similar to that described in part B
of Example 2 above~ 4O45 g (ODO1 mole) of 2~ ethyl-2-methyl-3-indolyl~carbonyl-3,4,5,6 tetrachlorobenzoic acid and 2~20 g (0~01 mole) of N,N,N',NI-tetraethyl-m-phenylenediamine were interacted in the presence of ten ml of acetic anhydride to obtain 3~2,4-bis-(diethylamino]phenyl]-3-~1-eth~
~ (Formula III: ~ 'Rl=R2=R3=Cl; R~R6=CH CH 4 ~CH2CH3)2; RS=CH3; Y =H) melting at 100-103C. and showing a ~ignificant infrared absorption maxima at 1770 cm 1 ¢C=O; s)O A
toluene solution of this compound developed an intense blue color when spotted on silica gelO
Example_52 Employing a procedure similar to that described in part C of Example 1, 9072 g (0O04 mole) of 2-~1~2-dimethyl-3-indolyl)-carbonylbenzoic acid prepared as described in UOSO Patent 3,50~,173, 8057 g ~0005 molel of N,N~N~N'-tetramethyl-m-phenylene-diamine and 6O0 ml of acetic anhydride are interacted to obtain (Formula III: ~ =Rl-R2-R3~Yl-H; R=R5=R6=CH R4 Example 53 A~ Employing a procedure similar to that described in part A of Example 10 above, 7clS g ~00025 mole) of tetrachlorophthalic anhydride and 3.65 g (00028 mole) of 2-methylindole were interacted in 100 ml of ethylene dichloride to obtain 2-~2-methyl-3-1ndolyl)-(Formula VIII: R =R ~
R2~R3=Cl; R5=CH3; R6=Yl=H)~ an orange solid melting at 200-201Co Bo A stirred mixture of 4017 g of 2-~2-methyl-3-indolyl)-carbonyl]-4,5,6,7 tetrachlorobenzoic acid~ prepared as described ~' in part A above and 3 o28 g (0 ~02 mole) of N,N~Na,N'-tetramethyl-m-phenylenediamine were interacted in the presence of 40 ml of acetic anhydride after the manner described in Example 2, part B
above to obtain ~
~ (Formula III: R =Rl=R2=R3=
Cl; R=R5=CH3; ~4=N~CH3)2; R6=Yl=H) which showed an infrared carbonyl absorption maximum at 1775 cm 1~ A toluene solution of the compound developed a blue-black color when spotted on silica gel, ~
Proceeding in a manner similar to that described in part B of Example 5 above, 2034 g ~00006 mole) of 2-[~1-n-octyl-2-methyl-3-indolyl)carbonyl~benzoic acid prepared according to Example 50 part A, and 2~40 g of N,N~Ni~N~-tetraethyl m-phenylene-diamine were interacted in the presence of 2O40 g of acetic an-hydride to obtain 3-[2,4 bis~diethylamino)phenyl]-3-(1-n-octyl-2-~ 3-ind~lvl~ht~alide ~Formula III~ R =Rl=R2=R3=Yl=H;
R=cH2cH3; ~ =N~CH2CH3)2~ R =CH3; R -(CH2~7CH3) as a tar-like semlsolid. A toluene solution of this material developed a purple color when spotted on silica gel, A. Proceeding in a manner similar to that described in part A of Example 10, 2906 g (0.20 mole~ of phthalic anhydride and 35~2 g ~0.20 mole) of 5-nitro-2-methylindole were interacted in 100 ml of ethylene dichloride to obtain ~ ~Formula VIII: R =Rl=R2=R3=R6=H; R5=CH3, Yl-5-NO2)~ a red brown solid melting at 144-148C~ and showing a strong carbonyl absorption maximum at 1700 cm 1 in the infrared spectrum~
B. Following a procedure similar to that descrîbed in part i~
~h~

B of Example 18 for interacting 3 24 g (OtOl mole) of 2-~(2-methyl-5-nitro-3-indolyl~carbonyl~benzoic acid, prepared as described in part A above, and lo6 g (0~01 mole~ of N,N,N',N'-tetramethyl-m-phenylenediamine in the presence of 500 ml of acetic anhydride, there is obtained ~ ~ormula III R =Rl=~2=R3=R6=H; R Rs CH3; R =N~CH3)2; Yl=N02), Example 56 A. Using a procedure similar to the one described in part A of Example 18, 48.0 g ~0~25 mole) of trimellitic anhydride and 3208 g (0~25 mole) of 2-methylindole were interacted in 250 ml of ethylene dichloride to obtain 66.1 g of m ~ (Formula VIII: Rl=R2=
H/COOH; R =R3=R6=Yl=H; R5=CH3) melting at 237-241Co Bo A procedure similar to that described in part B of Example 18 above, was followed for interacting 10 g (00023 mole) of 4/5-carboxy-2-~2-methyl-3-indolyl)carbonyl]benzoic acid, pre-pared as described in part A above, and 800 g (0006 mole) of 2-methylindole in the presence of 50 ml of acetic anhydride~ There was thus obtained ~Formula VI: Rl=R2=H/CooH; R =R3=R6=R6~=yl=yl~=H Rs Rs~ CH ) pink solid melting over the range of 145-165C.
Example 57 AD Proceeding in a similar fashion to the one described in part A of Example 17, 28.6 g (0~01 mole) of tetrachlorophthalic anhydride, 16.2 g lO~2 mole~ of N-methylpyrrole and 40 g (0~3 mole~ of aluminum chloride were interacted in 50 ml of dry chloro-benzene to o~tain ~hl~r~be~z~i- aci ~ormula IX: R =Rl=R2=R3=Cl; R7=CH3) having a melting point of 203-205C~

r.

~13474 B. Employing the procedure of part B of Example 17 hereinabove, 3.70 g (0.01 mole) of 2-[~1-methyl-2-pyrrolyl)carbonyl]-3,4,5,6-tetrachloro-benzoic acid, prepared as described in part A above, and 2.0 g (0.012 mole) of N,N,N',N'-tetramethyl-m-phenylenediamine were interacted in the presence S of 10 ml of acetic anhydride to obtain 3-[2,4-bis(dimethylamino)phenyl]-3-(l-methyl-2-pyrrolyl)-4,5,6,7-tetrachlorophthalide (Formula IV: R=Rl=R =
R =Cl; R=R =CH3; R4=N(CH3)2).

- 63a -X

` Example S~ l~i3474 ~o a stirred solution of 5.3 9 of 3-(2-cthoxy-4-di-ethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-carboxy-phthalidc, prepared as described in Example 22, part A, in 25 ml of acetone, there was added 30 ml of a 0.5 N methan~lic so~ium hydroxide solution. The mixture was stirred for approximately fifteen minutes at ambient temperature and concentrated to a syrup under vacuum. A small portion of fresh acetone was added to the syrup and the dark blue crystals which formed were col-1~ lected by filtration. A small portion of hexane was added to the crystals resulting in a gummy residue. The residue was then triturated with more hexane to obtain a bright blue powder~which was collected by filtration and dried to yield 4.8 g of the sodium salt of 3-t2-ethoxy-4-dieth lamino henyl)-3-(1-cthYl-2-~ P
1~ methYl-3-indolvl)-5/6-carboxvohthalide (Formula III: Ro=R3=Yl=H;
R =R =H/C~O Na ; R=R -C2H5; R -OC2H5; R5=CH3), a bright blue colored powder melting over the range 82-95CC. Infrared spectral analysis showed significant maxima at 1752 (C=O, s) and 1735 cm~l (C=O, s).

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1~3474 Example 113 The use of the compounds o~ Formulas I through VI and described in Examples 1 through 112 as color forming components in pressure sensitiYe microencapsulated copying systems is illus-trated with reference to the product of Example 1, part B.
Ao A mixture of 196 ml of distilled water and 15~0 g of pigskin gelatin was stirred at approximately 50C. for approxi-mately 45 minutes. There was then added to the mixture a warmed ~approximately 50C~ solution of 49.0 g of alkylated biphenyls and 0O5 g of 3-r2,4-bisldiethylamino~phenyll-3-~1-ethyl-2-methyl-3-indolyl~phthalide, prepared as described above in Example 1, part B. The resulting solution was stirred for approximately fifteen minutes. A second solution of 81.0 ml of distilled water and lOoO
g of gum arabic was then prepared and warmed to approximately 50C~
for approximately one hour.
B~ The two solutions, the first containing water~ gelatin, alkylated biphenyls and the product, and the second containing water and gum arabic were mixed and the pH adjusted to 9 by the addition of approximately 0~7 ml of 20 percent aqueous sodium hydroxideO The resulting mixture was transferred to a larger reactor equipped with a variable speed one-half horsepower Eppenbach Homo-Mixer ~Gifford-Wood Co., Hudson, N ~Y o ) and there was added over a period of two to three minutes 650 ml of distilled water which had been heated to 50C~ With the stirrer running at an applied voltage of between 20 to 25 volts there was slowly added sufficient ten percent aqueous acetic acid to set the pH at 4O5J
this being the point where coacervation was initiated~ The stirrer speed was increased by raising the applied voltage to approximately thirty volts and approximately four drops 2-ethylhexanol were added 0 to suppress foaming~ After approximately twenty minutes, a `-"` 1113474 sample of the suspension was examined microscopically and found to have stabilized in the range of 20 to 25 microns particle size whereupon an external ice/water bath was immediately placed around the reactor containing the suspensionO At approximately 20C~
the agitation speed was reduced by decreasing the applied voltage to the range o 20 to 25 voltsO Cooling was continued and at approximately 15Co~ 10~0 ml of glutaraldehyde was added over a period of five minutes. When the internal temperature reached 10Co~ the agitation speed was further reduced by lowering the applied voltage to approximately 20 volts and these conditions maintained for approximately thirty minutesO At this time, the Eppenbach Homo-Mixer was replaced with a conventional blade type laboratory agitator and the suspension was stirred an additional three hours during which period the temperature was allowed to warm to room temperature. The microencapsulated product was isolated by pouring the slurry through an ASTM #18 stainless steel sieve to remove any large agglomerates and then collecting the capsules by filtration. The collected capsules were washed successively with four 100 ml portions of distilled water each and stored as a water wet pulpo A sample of the pulp analyzed by drying in vacuo at 80Co was found to consist of 37O5 percent solidsO
CO To 125 ml of distilled water, 10.6 g of oxidized corn starch was added over a period of ten to fifteen minutes with stirringO This mixture was heated to a temperature in the range of 70-80Co and maintained until all the starch dissolvedO The starch solution was cooled to ambient temperature and there was added 100 g of the capsule-containing water wet pulp from part B
a~ove and 4300 ml of distilled waterO The capsules and starch solution were mixed at room temperature using an Eppenbach Homo-Mixer set at an applied voltage of 25 volts for five minutes and ~13474 then at an applied voltage of 30 volts for an additional five minutes to complete the suspension of the capsules of the starch solution.
D. The stock starch-microcapsule suspension prepared in part C above was coated on paper sheets to a thickness of approximately 0.0015 inch and the coated paper air dried.
The paper thus coated with the microencapsulated colorless precursor was assembled as the top sheet in a manifold system by positioning the coated side in contact with the coated side of a commercially available receiving sheet coated with a color developer of the electron accepting type. More speci-fically, papers coated with a phenolic resin and with an acidic clay were employed in this test. An image was then drawn with a stylus on the top sheet bearing the microencap-sulated colorless precursor on its reverse side causing theaffected microcapsules to rupture thus allowing the solution of the colorless precursor held by said microcapsules to flow into contact with the color developing substance on the re-ceiving sheet whereupon a deep blue-colored image promptly formed. The developed image exhibited good lightfastness when exposed to daylight or to a daylight fluorescent lamp for ex-tended periods.
When evaluated in a duplicating system prepared and tested as described above, the product of Example 1, part C
3-[2,4-bis~dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl) phthalide produced a grape-colored developed image.

;~;

~134'74 The use of the compounds o~ Formulas I through VI and described in Exa~ples 1 through112 as color forming components in pressure sensitive microencapsulated copying systems is S similarly illustrated with reference to the product of Example 23.
A. A mixture of 196 ml of dlstilled water and 15.0 9 of pigs~n gelatin was stirred at approximately 50C for approxi-mately 45 minutes There was then added to the mixture a warmed (approximately 50C) solution of 49.0 g of alkylated biphenyls and 1.0 g of 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide prepared as de-scribed above in Example 23. The resulting solution was stirred for approximately fifteen minutes. A second solution of 81.0 ml of distilled water and 5.0 g of carboxymethylcellulose was then prepared and warme~ to approximately 50C for approximately one hour.
B. The two solutions, the first containing water, gelatin, alXylated biphenyls and the prod~ct, and the second containing water with car~oxymethylcellulose were mixed by means of an Eppenbach Homo-Mlxer (Gifford-Wood Co., Hudson, N.Y.). The pH
was adjusted to 6.5 by the addition of approximately 0.7 ml of 20 percent aqueous sodium hydroxide. To the resultant mixture was added over a period of two to three minutes 650 ml of distilled water which had been heated to 50C. With the stirrer running at an applied voltage of between 35 to 40 volts there was slowly added sufficient ten percent aqueous acetic acid to set the pH
at 4.5, this being the point where coacervation was initiated.
Four drops of 2-ethylhexanol were added to suppress foaming~

After approximately twenty minutes an external ice,/water b~th was placed around the reactor containlng the suspension. Coollng was continued and at approximately 15C, 10.0 ml of glutaraldehyde was added over a period of five minutes. When the internal temperature reached 10C, the Eppenbach Homo-Mixer was replaced w~th a conventional blade type laboratory agitator and the thus prepared suspension of microcapsules was stirred an additional three hours during which period the temperature was allowed to warm to room temperature.
C. The microcapsule suspension prepared as described in part B above was coated on paper sheets to a thickness of approxi-mately 0.0015 inch and the coated paper air dried. The paper thus coated with the microencapsulated colorless precursor was assembled as the top sheet in a manifold system by positioning the coated side in contact with the coated side of a commercially available receiving sheet coated with a color developer of the electron accepting type. More specifically, papers coated wit~
a phenolic resin and with an acidic clay ~ere emp7Oyed in this test. An image was then drawn wïth a stylus on the top sheet bearing the microencapsulated colorless precursor on its reverse side causing the affected microcapsules to rupture thus allowing the solution of the colorless precursor held by said microcapsules to flow into contact with the color developing substance on the receiving sheet whereupon a deep blue-colored image promptly formed. The developed image exhibited good lightfastness ~hen exposed to daylight or to a daylight fluorescent lamp for extended periods.
When evaluated in a duplicatin~ system prepared and tested as described above, the product of Example 29, 3~ dimethyl-aminophenyl)-3-~1-ethyl-2-methyl-3-indolyl)_5/6-~t~loxycar~or)yl-1~3474 phthallde, produc~d a blue-colored develop~d lma~e; th~ produc~
of Exanlple 34, 3-(2-methyl-4-diethyla~lnophenyl)-3-(1-ethyl-~-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide, produced a tur-quolse-colored developed image; th~ product of Exampl~ 39B, 3,3-S bis(l-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide, produced a deep red-colored developed image; the product of Example 2B, 3-[2,4-bis(dimethylamino)phenyl~-3-(1-ethyl-2-methyl-3-indolyl)-4,5,6~7-tetrachlorophthalide, produced a deep grape-colored developed ima~e; thé product of Example 3B, 3-[2,4-bis-(dimethylamino)phenyl~-3-(1-ethyl-2-methyl-3-indolyl)-6-nitro-phthalide, produced a blue-black-colored image.

When evaluated in a carbonless duplicatin~ system by proceeding in a manner similar to that described in Example 114 lS above, except that soy oil was used in place of alkylated bi-phenyls, the product of Example 20, 3-[2,4-bis(dimethylamino)-phenyl]-3~ ethyl-2-methyl-3-indolyl)-5/6-n-octyloxycarbonyl-phthalide, produced a grape-colored developed image; and the product of Example 46, 3,3-bis(l-ethyl-~-methyl-3-indolyl)-5/6-n-octyloxycarbonylphthalide, produced a deep red-colored developed . .
imaqe.
Example 116 Followin~ a procedure similar to that described in Example 114 but using kerosene instead of alkylated biphenyls for evaluation in a car~onless duplicatin~ system, the product of Example 26, 3-(2-ethoxy-4-diethylaminophenyl)-3~ ethyl-2-~ethyl-3-indolyl)-SJ6-hexadecyloxycarbonylphthalide, produced a deep blue-colored developed image.

l~i34~4 xample ll7 The utillty of the phthalides of Formulas I to IV who-e pr~parations are de~cribed in the foregoing exa~ples as color forming components in thermal marking systcms is ~llustratcd by the incorporation and testing of the compound of Example 22B, 3-t2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl~-5/6-methoxycarbonylphthalide in a thermal sensitive marking paper.
The test paper was prepared by a procedure similar to that de-scribed in U.S. Patent 3,S39~375.
A. A mixture of 2.0 g of 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide, 8.6 9 of a ten percent aqueous solution of polyvinyl alcohol ~approxi-mately 99 percent hydrolyzed), 3.7 g of water and 31.6 g of 1/16 inch diameter zirconium grinding beads was charged into a container which was placed in a mechanical shaker. Shaking was erfected for one hour. The zirconium beads were then removed by straining the mixture throught a No. 40 sieve.
B. Similarly, a mixture of 9.8 g of 4,4'-isopropylidine diphenol (Bisphenol A), 42.0 9 of a ten percent aqueous polyvinyl alcohol solution (approximately 99 percent hydrolyzed), 18.2 9 of water and 221.2 9 of 1/16 inch diameter zirconium ~rinding beads was charged into a container which was placed in a mechan-ical shaker. After shaking was effected for one hour, the zir-conium beads were removed by straining throught a No. 4~ sieve.
C. A coating composition was prepared by mixing 2.1 g of the siurry from A and 47.9 9 of the slurry from B. The mixture was then uniformly coated on sheets of paper at thicknesses of approximately 0.003 inch and the coated sheets air-dried. The coated paper was tested by tracin~ a design on the coated side of the paper placed on a smooth flat surface ~ith a stylus heclte~
to approximately 125C. A deep blue-colored ima~e corrcs~ondin~
to the traced design promptly dcveloped.

en evaluated in thermal marking paper prepar~d and tested as described above, the product of Example 39B, 3,3-b~s-~l-ethyl-2-methyl-3-indolyl)-S/6-methoxycarbonylphthalide, pro-duced a violet-colored image; the-product of ~xample 21, 3-~2,4-bis(dimethylaminO)phenyl]-3 (1-ethyl-2-methyl-3-indolyl)-S/6_ phenylmethoxycarbonylphthalide, produced a grape-colored ilnage;
th~ product of Example 28B, 3-(4-dimethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-methoxycarbonylphthalide, produced a blue-colored image; the product of Example 33B, 3-(2-methyl-4-diethyl-aminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-m~thoxycarbonyl-phthalide, produced a turquoise-colored image; the product of Example 1~, 3-r2,4-bis(diethylamino)phenyl]-3-(1-e'hyl-2-methyl-3-indolyl)phthalide, produced a blue-black-colored image; the product of Example lC, 3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide, produced a grape-colored imag~; the product of Example 2B, 3-[2~4~bis(dimethylamino)phenyl1-3-(1-ethyl~2-methyl-3-indolyl)-4,5,6,7-tetrachlorophthalide, pro-duced a deep grape-colored developed image; the product of Exampl.e 3B, 3-[2,4-bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)-6-nitrophthalide, produced a blue-bl~ck-colored image.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula ...I

wherein R°, R1, R2 and R3 each represent hydrogen or halo when R°, R3 and one of R1 and R2 are each hydrogen, the other of R1 and R2 represents nitro, amino, acetamido, dialkylamino wherein alkyl is non-tertiary C1 to C4 alkyl, or in which B represents -OY or wherein Y is hydrogen, an alkali metal cation, an ammonium cation, a C1 to C18 mono-, di- or trialkylammonium cation, C1 to C18 alkyl, C1 to C18 alkenyl, benzyl or benzyl substituted in the benzene ring thereof by C1 to C12 alkyl, halo or C1 to C8 alkoxy; Y' is hydrogen or C1 to C18 alkyl; Y" is hydrogen, C1 to C18 alkyl or C4 to C12 N,N-dialkylaminoalkyl;
X represents a monovalent radical having the formula , and ...A ...B ...C

Z represents a monovalent radical having the formula and ...D ...E
in which R represents non-tertiary C1 to C4 alkyl, benzyl or benzyl substituted in the benzene ring by one or two of halo or C1 to C3 alkyl, R4 represents acetamido, dialkylamino in which alkyl is non-tertiary C1 to C4 alkyl, and when one of R1 or R2 represents any of said carboxy or said carbonyl substitu-ents, R4 further represents hydrogen, C1 to C3 alkyl, C1 to C4 alkoxy or halo, R5 and R5' represent hydrogen, C1 to C3 alkyl or phenyl;
R6 and R6' represent hydrogen, C1 to C18 alkyl, C2 to C4 alkenyl, benzyl or benzyl substituted in the benzene ring by one or two of halo or C1 to C3 alkyl, R7 and R8 represent hydrogen, C1 to C3 alkyl or phenyl, and Y1 and Y1' represent no or one to two C1 to C3 alkyl, C1 to C3 alkoxy, halo or nitro substituents in the benzenoid portion of the indole radical with the provisos (i) that X and Z can both simultaneously represent mono-valent indolyl moieties only when one of R1 and R2 represents said and (ii) X represents a pyrrolyl of a carbazolyl moiety only when Z represents a 2-R4-4-N(R)2-phenyl moiety.

2. 3-[2,4-Bis(dimethylamino)phenyl]-3-(1-ethyl-2-methyl-3-indolyl)phthalide according to claim 1.

3. 3-(2-Ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxycarbonylphthalide according to claim 1.

4. 3-(2-Ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methyl-3-indolyl)-5/6-hexadecyloxycarbonylphthalide accord-ing to claim 1.

5. 3,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-ethoxy-carbonylphthalide according to claim 1.

6. 3,3-Bis(1-ethyl-2-methyl-3-indolyl)-5/6-n-hexa-decyloxycarbonylphthalide according to claim 1.

7. A process for preparing a compound according to claim 1, which comprises interacting a compound of the formula ...VII
with approximately one molecular proportion of a 3-R4-N,N-(R)2-aniline or a 1-R6'-2-R5'-Y1'-indole in the presence of an anhydride of an alkanoic acid having from 2 to 5 carbon atoms wherein R°, R1, R2 and R3 each represent hydrogen or halo and when R°, R3 and one of R1 and R2 are each hydrogen, the other of R1 and R2 represents nitro, dialkylamino wherein alkyl is non-tertiary C1 to C4 alkyl, or carboxy; and R, R4, R5', R6', X, Y1' and Z each have the same respective meanings given in claim 1; or interacting a corresponding 3-R°-4-R1-5-R2-6-R3-phthalic anhydride with approximately two molecular proportions of an 1-R6-2-R5-Y1-indole to prepare a compound of Formula I as defined in claim 1, wherein X is a radical of the Formula A and Z is a radical of Formula E and A and E are the same; or reducing the compound of Formula I as defined in claim 1, wherein one of R1 and R2 is nitro to prepare a corresponding compound of Formula I wherein one of R1 and R2 is amino; or interacting a compound of Formula (VII) as defined above, where one of R1 and R2 is amino and the other of R1 and R2 and each of R° and R3 are hydrogen, with approximately one molecular proportion of a 3-R4-N,N-(R)2-aniline or a 1-R6'-2-R5'-Y1'-indole in the presence of at least two molecular proportions of acetic anhydride wherein R4, R5', R6', X, Y1' and Z each have the same respective meanings given in claim 1 to prepare a compound of Formula I as defined above wherein one of R1 and R2 acetamido; and if desired, esterifying the compound of Formula I as defined above where one of R1 and R2 is COOH with a corresponding alkylating agent to prepare corresponding compounds of Formula I in which one of R1 and R2 is COOY and Y is C1 to C18 alkyl, C1 to 18 benzyl or benzyl substituted in the benzene ring thereof by C1 to C12 alkyl, halo or C1 to C8 alkoxy; and, if desired admidating the compound of Formula I as defined above in which one of R1 and R2 is COOY with a corresponding compound of the formula to prepare a corresponding compound of Formula I in which one of R1 and R2 is CON(Y')(Y"); and, if desired, reacting a compound of Formula I as defined above wherein one of R1 and R2 is COOH with a corresponding alkali metal or ammonium salt or a primary amine to prepare a corresponding compound of Formula I in which one of and R2 is COOY wherein Y is an alkali metal cation, an ammonium cation, or a C1 to C18 mono-, di- or trialkylammonium cation.

8. A pressure-sensitive carbonless duplicating system, thermal marking system or hectographic copying system con-taining as a color-forming substance a compound according to any one of claims 1, 2 and 3.

9. A thermal marking system comprising a support sheet coated on one side with a layer containing a mixture of the color-forming substance and an acidic developer arranged such that application of heat will produce a mark-forming reaction between the color-forming substance and the acidic developer, said system containing as a color-forming substance a compound according to any one of claims 1, 2 and 3.

10. A hectographic copying system comprising a support sheet coated on one side with a layer containing a color-forming substance comprising a compound according to claim 1, wherein R°, R3 and one of R1 and R2 are each hydrogen and the other of R1 and R2 represents wherein Y is an alkali metal cation, an ammonium cation or a C1 to C18 mono-, di- or trialkylammonium cation.