3-[4-Disubstituted-amino)phenyl] or (9-julolidinyl)-3-(diphenylamino)phthalides useful as color formers in pressure-sensitive and thermal marking systems are prepared by reaction of 2-[4-disubstituted-amino)benzoyl] or (9-julolidinyl-carbonyl)benzoic acids with diphenylamines.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a group of compounds classified in the field or 
organic chemistry as 3-[4-(disubstituted amino)phenyl] or 
(9-julolidinyl)-3-(diphenylamino)phthalides useful in the art of 
carbonless duplicating as color formers in pressure-sensitive and thermal 
marking systems; to processes for the preparation thereof; and to 
pressure-sensitive duplicating systems and thermal marking systems 
containing the same. 
2. Description of the Prior Art 
Several classes of organic compounds of widely diverse structural types are 
known to be useful as color formers for carbonless duplicating systems. 
Among the more widely recognized classes, there may be named 
phenothiazines, for example, benzoyl leuco methylene blue; fluorans, for 
example, 2'-anilino-6'-diethylaminofluoran; phthalides, the class with 
which this invention is concerned, for example, crystal violet lactone; 
and various other types of color formers currently employed in 
commercially accepted carbonless duplicating systems. Typical of the many 
such systems taught in the prior art are those described in U.S. Pat. Nos. 
2,712,507, 2,800,457 and 3,041,289 which issued July 5, 1955 and June 26, 
1957 and June 26, 1962, respectively. Many of the color formers in the 
prior art suffer one or more disadvantages such as low tinctorial 
strength, poor light stability, low resistance to sublimation and low 
solubility in common organic solvents, the latter disadvantage thus 
requiring the use of specialized and expensive solvents in order to obtain 
microencapsulated solutions of sufficient concentration for use in 
pressure-sensitive copying systems. 
The following appear to constitute the most relevant prior art relative to 
the present invention. 
Japanese Patent Publication No. 71/4616 published Feb. 4, 1971 discloses a 
series of compounds having the formula 
##STR1## 
wherein R.sub.1 is hydrogen or lower-alkyl; R.sub.2 is hydrogen, halogen 
or lower-alkyl; and R.sub.3 and R.sub.4 are each lower-alkyl. The 
compounds are prepared by reaction of a 
2-[4'-(dialkylamino)benzoyl]benzoic acid with an appropriate aniline, and 
are stated to be useful as color formers in pressure-sensitive copying 
paper. 
R. Valters and V. Tsiekure in Khim. Geterotsikl. Soedin. 1975, (11) 1476-8 
discuss ring-chain tautomerism in 3-(N,N-diphenylamino)-3-phenylphthalide 
but disclose no utility for the compound. 
3. Patent Activities of Others 
German Offenlegungsschrift No. 2,537,776 published Mar. 11, 1976, based on 
Japanese Application No. 97934-74 published Mar. 2, 1976 as Japanese 
Patent Publication No. 76/25529, discloses in most pertinent part a series 
of phthalides stated to be useful as color formers and having the formula: 
##STR2## 
wherein inter alia R.sub.1 and R.sub.2 are the same or different and are 
lower-alkyl, a benzyl group which can be substituted in its aromatic ring 
with a di-lower-alkylamino group having 1 to 4 carbon atoms in its alkyl 
portions; or a phenyl group which can be substituted with a lower-alkoxy 
group with 1 to 4 carbon atoms; R.sub.3 is a chlorine atom, a lower-alkyl 
group with 1 to 4 carbon atoms or a lower-alkoxy group with 1 to 4 carbon 
atoms; R.sub.4 is hydrogen or a lower-alkyl group with 1 to 4 carbon 
atoms; R.sub.5 is a phenyl group which can be substituted with a 
lower-alkyl group of 1 to 4 carbon atoms or a chlorine atom. 
SUMMARY OF THE INVENTION 
The present invention provides novel 3-[4-(disubstituted amino)phenyl] or 
(9-julolidinyl)-3-(diphenylamino)phthalides useful as color formers in 
pressure-sensitive duplicating systems and thermal marking 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. 
In a composition-of-matter aspect the invention relates to a series of 
3-(2-R.sub.1 -4-NR.sub.2 R.sub.3 -phenyl) or (9-julolidinyl)-3-[N-(Y.sub.1 
-Y.sub.2 -phenyl)-N-(Y.sub.3 -Y.sub.4 -phenyl)amino]-4-Q.sub.4 -5-Q.sub.5 
-6-Q.sub.6 -7-Q.sub.7 -phthalides which are useful as color formers in 
pressure-sensitive carbonless duplicating systems or thermal marking 
systems. 
In a process aspect the present invention provides a process for preparing 
3-(2-R.sub.1 -4-NR.sub.2 R.sub.3 -phenyl) or (9-julolidinyl)-3-[N-(Y.sub.1 
-Y.sub.2 -phenyl)-N-(Y.sub.3 -Y.sub.4 -phenyl)amino]-4-Q.sub.4 -5-Q.sub.5 
-6-Q.sub.6 -7-Q.sub.7 -phthalides which comprises reacting a 2-(2-R.sub.1 
-4-NR.sub.2 R.sub.3 -benzoyl) or (9-julolidinylcarbonyl)-4-Q.sub.4 
-5-Q.sub.5 -6-Q.sub.6 -7-Q.sub.7 -benzoic acid with a N-(Y.sub.1 -Y.sub.2 
-phenyl)-N-(Y.sub.3 -Y.sub.4 -phenyl)amine. 
This invention further provides a second process for preparing 3-(2-R.sub.1 
-4-NR.sub.2 R.sub.3 -phenyl) or (9-julolidinyl)-3-[N-(Y.sub.1 -Y.sub.2 
-phenyl)-N-(Y.sub.3 -Y.sub.4 -phenyl)amino]-4-Q.sub.4 -5-Q.sub.5 
-6-Q.sub.6 -7-Q.sub.7 -phthalides which comprises reacting a 2-(2-R.sub.1 
-4-NR.sub.2 R.sub.3 -benzoyl) or (9-julolidinylcarbonyl)-4-Q.sub.4 
-5-Q.sub.5 -6-Q.sub.6 -7-Q.sub.7 -benzoic acid with an inorganic acid 
chloride followed by reaction of the product so-obtained with a N-(Y.sub.1 
-Y.sub.2 -phenyl)-N-(Y.sub.3 -Y.sub.4 -phenyl)amine. 
In an article-of-manufacture aspect the present invention relates to a 
pressure-sensitive carbonless duplicating system or thermal marking system 
containing a color-forming substance comprising a 3-(2-R.sub.1 -4-NR.sub.2 
R.sub.3 -phenyl) or (9-julolidinyl)-3-[N-(Y.sub.1 -Y.sub.2 
-phenyl)-N-(Y.sub.3 -Y.sub.4 -phenyl)amino]-4-Q.sub.4 -5-Q.sub.5 
-6-Q.sub.6 -7-Q.sub.7 -phthalide.

DETAILED DESCRIPTION INCLUSIVE OF THE PREFERRED EMBODIMENTS 
More specifically, this invention in a composition-of-matter aspect resides 
in a compound having Formula I 
##STR3## 
wherein: Q.sub.4 is hydrogen or halo; 
Q.sub.5 is the same as Q.sub.4 ; or di-lower-alkylamino, COX or halo when 
Q.sub.4, Q.sub.6 and Q.sub.7 are each hydrogen; 
Q.sub.6 is the same as Q.sub.4 ; or di-lower-alkylamino, COX or halo when 
Q.sub.4, Q.sub.5 and Q.sub.7 are each hydrogen; 
Q.sub.7 is the same as Q.sub.4 ; 
X is hydroxy, benzyloxy, alkoxy having from 1 to 18 carbon atoms or OM 
where M is an alkali metal cation, an ammonium cation or a mono-, di- or 
trialkylammonium cation having from 1 to 18 carbon atoms; 
Y.sub.1, y.sub.2, y.sub.3 and Y.sub.4 are the same or different and are 
selected from the group consisting of hydrogen, halo, hydroxyl, 
lower-alkoxy, alkyl having from 1 to 9 carbon atoms, phenyl-lower-alkyl, 
COOR.sub.4 and NR.sub.5 R.sub.6 where R.sub.4 and R.sub.5 are hydrogen or 
lower alkyl and R.sub.6 is hydrogen, lower alkyl, cycloalkyl having from 5 
to 7 carbon atoms or lower alkanoyl; 
Z is selected from the group consisting of 9-julolidinyl and a radical 
having the formula 
##STR4## 
in which: R.sub.1 is selected from the group consisting of hydrogen, halo, 
lower-alkyl, lower-alkoxy and di-lower-alkylamino; 
R.sub.2 is lower-alkyl; and 
R.sub.3 is selected from the group consisting of lower-alkyl, benzyl, 
phenyl, and phenyl substituted with a lower-alkyl or lower-alkoxy group. 
The compounds are useful as color formers in pressure-sensitive carbonless 
duplicating systems and in thermal marking systems. 
A particular embodiment sought to be patented resides in a compound having 
Formula II 
##STR5## 
wherein R.sub.1, R.sub.2, R.sub.3, Q.sub.4, Q.sub.5, Q.sub.6, Q.sub.7, 
Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 have the previously given meanings. 
Preferred compounds within the ambit of this particular embodiment are 
those wherein: 
(a) Q.sub.4, Q.sub.5, Q.sub.6 and Q.sub.7 are each hydrogen, 
(b) Q.sub.4, Q.sub.5 and Q.sub.7 are each hydrogen and Q.sub.6 is 
di-lower-alkylamino; and 
(c) Q.sub.4, Q.sub.5, Q.sub.6 and Q.sub.7 are each halo, especially: 
3-[4-(dimethylamino)phenyl]-3-[N-(4-ethoxyphenyl)-N-phenylamino]phthalide; 
3-[4-(dimethylamino)phenyl]-3-[N-(4-isopropoxyphenyl)-N-phenylamino]phthal 
ide; 
4,5,6,7-tetrachloro-3-[4-(dimethylamino)phenyl]-3-[N-(4-ethoxyphenyl)-N-ph 
enylamino]phthalide; 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(4-ethoxyphenyl)-N-phenylamino]ph 
thalide; 
3-[4-(dimethylamino)phenyl]-3-[N,N-bis-(4-octylphenyl)amino]phthalide; 
6-(dimethylamino)-3-[4-(dimethylamino)phenyl]-3-[N-(4-ethoxyphenyl)-N-phen 
ylamino]phthalide; 
3-[4-(dimethylamino)-phenyl]-3-(N,N-diphenylamino)phthalide; 
6-(dimethylamino)-3-[4-(dimethylamino)phenyl]-3-[N,N-bis-(4-octylphenyl)am 
ino]phthalide; 
3-[4-(ethylbenzylamino)phenyl]-3-[N-(4-ethoxyphenyl)-N-phenylamino]phthali 
de and 
3-[4-(diethylamino)-2-methylphenyl]-3-{N,N-bis[4-(dimethylamino)phenyl]ami 
no}phthalide. 
In one of its process aspects the invention sought to be patented resides 
in the process which comprises reacting a 2-substituted benzoic acid 
having Formula III 
##STR6## 
with a diarylamine having Formula IV 
##STR7## 
in the presence of the anhydride of an alkanoic acid having from 2 to 5 
carbon atoms, and an organic base; where in Formulas III and IV, Z, 
Q.sub.4, Q.sub.7, Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 have the 
previously given meanings; Q.sub.5 is the same as Q.sub.4 ; or 
di-lower-alkylamino, halo or COX when Q.sub.4, Q.sub.6 and Q.sub.7 are 
hydrogen; Q.sub.6 is the same as Q.sub.4 ; or di-lower-alkylamino, halo or 
COX when Q.sub.4, Q.sub.5 and Q.sub.7 are hydrogen; and X is hydroxy, 
benzyloxy or alkoxy having from 1 to 18 carbon atoms. 
In another process aspect the invention sought to be patented resides in 
the process which comprises reacting a 2-substituted benzoic acid of 
Formula III with an inorganic acid chloride selected from the group 
consisting of thionyl, chloride, phosphorus oxychloride, phosphorus 
trichloride and phosphorus pentachloride followed by reaction of the 
resulting product with a diarylamine of Formula IV in the presence of an 
organic base; where in Formulas III and IV, Z, Q.sub.4, Q.sub.5, Q.sub.6, 
Q.sub.7, Y.sub.1, Y.sub.2, Y.sub.3 and Y.sub.4 have the meanings given in 
the preceding paragraph. 
In an article-of-manufacture aspect the invention sought to be patented 
resides in a pressure-sensitive carbonless duplicating system or thermal 
marking system containing a color-forming substance comprising a compound 
having Formula I. 
A particular embodiment sought to be patented resides in a 
pressure-sensitive transfer sheet, adapted for 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. 
Another particular embodiment sought to be patented resides in 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 articles within the ambit of the particular embodiments 
above-described are those wherein the color-forming component comprises a 
compound having Formula II, especially where in Formula II: 
(a) Q.sub.4, Q.sub.5, Q.sub.6 and Q.sub.7 are each hydrogen; 
(b) Q.sub.4, Q.sub.5 and Q.sub.7 are each hydrogen and Q.sub.6 is 
di-lower-alkylamine, and 
(c) Q.sub.4, Q.sub.5, Q.sub.6 and Q.sub.7 are each halo. 
As used herein the term "halo" includes chloro, fluoro, bromo and iodo. 
Chloro is the preferred hal 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 "lower-alkyl, lower-alkoxy and di-lower-alkylamino" denote 
saturated, acyclic groups having from 1 to 4 carbon atoms which may be 
straight or branched as exemplified by methyl, ethyl, propyl, isopropyl, 
butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, 
isopropoxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy, dimethylamino, 
diethylamino, ethylmethylamino, dipropylamino, dibutylamino, 
isobutylmethylamino, di-tert-butylamino and the like. 
As used herein the term "alkyl of one to nine carbon atoms" denotes 
saturated monovalent straight or branched chain aliphatic hydrocarbon 
radicals including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 
tert-butyl, amyl, 1-methylbutyl, 3-methylbutyl, hexyl, isohexyl, heptyl, 
isoheptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, 3-ethylheptyl and the 
like. 
As used herein the term "cycloalkyl having from 5 to 7 carbon atoms" 
includes cyclopentyl, cyclohexyl and cycloheptyl. 
The term "lower alkanoyl" denotes saturated acyclic acyl groups having from 
1 to 5 carbon atoms which may be straight or branched as exemplified by 
formyl, acetyl propionyl, butyryl, isobutyryl, valeryl, 2-methylbutyryl, 
isovaleryl, pivalyl and the like. 
The term "phenyl-lower-alkyl includes benzyl, 2-phenylethyl, 
2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2,2-dimethyl-2-phenylethyl 
and the like. If desired the phenyl group may contain a lower alkyl or 
lower alkoxy substituent. 
The term "alkoxy having from 1 to 18 carbon atoms" includes, in addition to 
the above-noted lower-alkoxy groups, saturated, acyclic, straight or 
branched-chain groups such as n-pentyloxy, n-hexyloxy, n-heptyloxy, 
n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, 
n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, 
n-heptadecyloxy, n-octadecyloxy, 1-methylpentyloxy, 2,2-dimethylbutyloxy, 
2-methylhexyloxy, 1,4-dimethylpentyloxy, 3-ethylpentyloxy, 
2-methylheptyloxy, 1-ethylhexyloxy, 2-propylpentyloxy, 
2-methyl-3-ethylpentyloxy, 1,3,5-trimethylhexyloxy, 
1,5-dimethyl-4-ethylhexyloxy, 5-methyl-2-butylhexyloxy-2-propylnonyloxy, 
2-butyloctyloxy, 1,1-dimethylundecyloxy, 2-pentylnonyloxy, 
1,2-dimethyltetradecyloxy, 1,1-dimethylpentadecyloxy and the like. 
As used herein the term "alkali metal" includes lithium, sodium and 
potassium. 
The term "mono-, di or tri-alkylammonium cation" includes ammonium cations 
substituted by from 1 to 3 alkyl groups as above described. The alkyl 
groups can be the same or different provided the ammonium cation contains 
no more than 18 carbon atoms. As examples there can be named 
methylammonium, t-butylammonium, t-octylammonium, n-dodecylammonium, 
n-octadecylammonium, di-n-butylammonium, di-n-nonylammonium, 
isopropyl-n-butylammonium, dimethyl-n-butylammonium, triethylammonium, 
N-ethyl-N,N-diisopropylammonium, tributylammonium, 
di-n-butyl-n-octylammonium and the like. 
The term "9-julolidinyl" of course refers to the radical having Formula V 
##STR8## 
Anhydrides of alkanoic acids of two to five carbon atoms include acetic 
anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, 
valeric anhydride, isovaleric anhydride, .alpha.-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 satisfactory. 
Organic bases include pyridine, collidine, tri-lower-alkyl amines, urea, 
diarylamines of Formula IV hereinabove and the like. Because of their low 
cost and ready availability pyridine and urea are preferred. 
In accordance with one of the process aspects of this invention the 
compounds having Formula I are obtained by reacting approximately 
equimolar amounts of a 2-substituted benzoic acid of Formula III and a 
diarylamine of Formula IV in the anhydride of an alkanoic acid having from 
two to five carbon atoms, such as acetic anhydride, with or without an 
inert diluent and in the presence of an organic base, for example pyridine 
or urea, at a temperature of from about 0.degree. to 100.degree. C. for 
from approximately 10 minutes to 24 hours. The reaction is usually carried 
out in the absence of an inert diluent at about 20.degree. to 40.degree. 
C. for approximately 0.5 to 2 hours. If desired an excess of the 
diarylamine reactant can be employed as the organic base. The product thus 
obtained can be isolated by filtration if it is insoluble in the reaction 
medium or by dilution of the reaction medium with a miscible solvent in 
which the product is insoluble such as a lower-alkanol or low molecular 
weight hydrocarbon for example isopropyl alcohol or hexane or a mixture of 
these in order to effect precipitation of the product. Alternatively, the 
reaction mixture can be poured into aqueous base such as dilute ammonium 
hydroxide, sodium hydroxide, sodium carbonate or sodium bicarbonate and 
the product extracted with an organic solvent such as benzene or toluene 
followed by evaporation of the organic solvent leaving the product as a 
residue. The product once isolated can be purified by conventional means 
such as trituration or recrystallization from a suitable solvent. 
In accordance with a second process aspect of the invention the compounds 
of Formula I can be prepared in two steps which comprise first reacting a 
2-substituted benzoic acid of Formula III with an excess of an inorganic 
acid chloride such as thionyl chloride, phosphorus oxychloride, phosphorus 
trichloride or phosphorus pentachloride with or without an inert diluent 
such as benzene, toluene, chloroform or 1,2-dichloroethane, at 20.degree. 
to 80.degree. C. for about 0.5 to 2 hours; and following removal of excess 
inorganic acid chloride, reaction of the resulting product which while not 
having been isolated is presumed to be a halide having Formula VI 
##STR9## 
in which Q.sub.4, Q.sub.5, Q.sub.6, Q.sub.7 and Z have the meanings 
previously given in Formula III, with a diarylamine of Formula IV 
hereinabove in an inert solvent in the presence of an organic base as 
previously described at a temperature in the range of 0.degree. to 
80.degree. C. for about 1 to 48 hours. The product can be isolated and 
purified in the manner previously described. 
When preparing compounds of Formula I wherein Q.sub.5 or Q.sub.6 is COX and 
X is benzyloxy, alkoxy having from 1 to 18 carbon atoms or OM where M is 
an alkali metal cation, an ammonium cation or a mono, di or 
trialkylammonium cation having from 1 to 18 carbon atoms it is ordinarily 
preferred to first prepare the compound of Formula I wherein Q.sub.5 or 
Q.sub.6 is COOH followed by conversion of the carboxyl group to the 
desired ester, alkali metal salt or ammonium salt in accordance with 
conventional procedures. 
The 2-substituted benzoic acids of Formula III required as starting 
materials in the preparation of the products of Formula I are generally 
known or if specifically new can be prepared in accordance with the 
procedures described for the preparation of the known compounds, for 
example as disclosed in British Pat. No. 1,435,179, published May 12, 
1976, i.e., by reacting a phthalic anhydride having Formula VII 
##STR10## 
with julolidine or an appropriate aniline having Formula VIII 
##STR11## 
under Friedel-Crafts conditions, where in Formula VII Q.sub.4, Q.sub.5, 
Q.sub.6 and Q.sub.7 have the meanings given above in Formula III, and in 
Formula VIII R.sub.1, R.sub.2 and R.sub.3 have the previously given 
meanings. It will, of course, be appreciated that when Q.sub.5 (or 
Q.sub.6) of the phthalic anhydride (Formula VII) is halo, COX or 
di-lower-alkylamino the reaction can produce isomers or a mixture of 
isomers, viz. 2-substituted benzoic acids of Formula III having a halo, 
COX or di-lower-alkylamino substituent at the 4-position (Q.sub.5) or the 
5-position (Q.sub.6) or a mixture of these. In the latter instance the 
isomeric 2-substituted benzoic acids can be separated by conventional 
means such as fractional crystallization or chromatography. Alternatively, 
the mixture of 2-substituted benzoic acids can be reacted with a 
diarylamine of Formula IV to produce a mixture of 5 and 6-substituted 
phthalides of Formula I which, if desired, can be separated or simply used 
as the mixture in the practice of this invention. 
The diarylamines of Formula IV which are also required as starting 
materials in the processes of the invention belong to a well known class 
of compounds and are either commercially available or readily obtained by 
conventional procedures well known in the art. 
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 duplicating systems such as silton clay or phenolic resins the 
compounds of Formula I develop a yellow to black colored image of good to 
excellent tinctorial strength, and possessing excellent light stability, 
resistance 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 duplicating 
systems. The compounds which produce a yellow to red color can be used as 
toners in admixture with other color formers to produce images of a 
neutral shade which desirably are readily copiable by xerographic means. 
The compounds of Formula I wherein at least one of Y.sub.1 and Y.sub.2 and 
at least one of Y.sub.3 and Y.sub.4 are simultaneously di-lower-alkylamino 
develop a purple to black image when contacted with an acidic medium and 
are accordingly of particular value as color precursors. Moreover, the 
compounds of Formula I, in particular whose wherein Q.sub.5 or Q.sub.6 is 
COX and X is alkoxy having from 1 to 18 carbon atoms, or those wherein one 
or more of Y.sub.1, Y.sub.2 Y.sub.3 and Y.sub.4 are alkyl of 1 to 9 carbon 
atoms, have enhanced solubility in common and inexpensive organic solvents 
such as odorless mineral spirits, kerosene, vegetable oils and the like; 
and those wherein Q.sub.5 or Q.sub.6 is COX and X is OM in which M has the 
previously given meaning are soluable in water and lower-alkanols thereby 
avoiding the need for more expensive, specialized solvents such as 
polyhalogenated or alkylated biphenyls which have ordinarily been used to 
prepare microencapsulated solutions of the color formers of the prior art. 
The compounds of this invention may be incorporated in any of the 
commercially accepted systems known in the carbonless duplicating art. A 
typical technique for such application is as follows. Solutions containing 
one or more colorless precursor compounds of Formula I, optionally in 
admixture with other color formers, in suitable solvents are 
microencapsulated by well-known procedures for example as described in 
U.S. Pat. No. 3,649,649. 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. 
Application 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 a yellow to red colored image 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 former. 
It has also been found that when the compounds of Formula I are intimately 
mixed with an acidic developer of the type generally employed in thermal 
papers such as described in U.S. Pat. No. 3,539,375, that is, papers which 
produce a colored image when contacted with a heated stylus or heated 
type, for example, bisphenol A. heating of the mixture produces a colored 
image of varying shades from yellow to purple depending on the particular 
compound of the invention employed. 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 Pat. 
No. 1,427,318 published Mar. 10, 1976. 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 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 mixture containing 5.4 g. of 2-[4-(dimethylamino)benzoyl]benzoic acid, 
3.4 g. of diphenylamine, 2 ml. of pyridine and 15 ml. of acetic anhydride 
was stirred at room temperature. After a few minutes the solid reactants 
were completely dissolved and after 15 minutes an orange solid 
precipitated. The reaction mixture was stirred an additional 15 minutes 
and then diluted with 20 ml. of 2-propanol and 50 ml. of ligroin. After 
stirring an additional 10 minutes the solids were collected, washed with 
ligroin and 2-propanol (which removed an orange impurity) and dried to 
give 5.9 g. of 3-[4-(dimethylamino)phenyl]-3-diphenylaminophthalide as a 
cream solid, m.p. 188.degree.-190.degree. C. (dec.). A toluene solution of 
the product contacted with acidic clay or phenolic resin developed an 
orange-colored image. 
EXAMPLE 2 
A mixture containing 5.4 g. of 2-[4-(dimethylamino)benzoyl]benzoic acid, 
4.3 g. of 4-ethoxy-N-phenylaniline, 0.5 g. of urea and 15 ml. of acetic 
anhydride was stirred 0.5 hr. at room temperature. Complete dissolution of 
the solid reactants was followed shortly by precipitation of the product. 
After diluting the reaction mixture with 20 ml. of 2-propanol the product 
was collected, washed with 2-propanol and dried to give 8.4 g. of 
3-[4-(dimethylamino)phenyl]-3-[N-(4-ethoxyphenyl)-N-phenylamino]phthalide 
as a white solid, m.p. 214.degree.-216.degree. C. (dec.). A toluene 
solution of the product contacted with acidic clay or phenolic resin 
developed an orange-colored image. 
EXAMPLE 3 
A mixture containing 6.24 g. (0.02 mole) of 
5-(dimethylamino)-2-[4-(dimethylamino)benzoyl]benzoic acid, 6.25 g. (0.03 
mole) of 4-ethoxy-N-phenylaniline and 20 ml. of acetic anhydride was 
stirred at room temperature for 20 hours. The reaction mixture was then 
diluted with 30 ml. of 2-propanol and stirred an additional 0.5 hr. The 
solids were collected, washed with ligroin and dried to give 9.3 g. of 
6-(dimethylamino)-3-[4-(dimethylamino)phenyl]-3-[N-(4-ethoxyphenyl)-N-phen 
ylamino]phthalide as a pale pink solid, m.p. 200.degree.-202.degree. C. 
(dec.). A toluene solution of the product contacted with acidic clay or 
phenolic resin developed an orange colored image, which, on acidic clay, 
became green after exposure to fluoroecent light. 
EXAMPLE 4 
A mixture containing 2.0 g. of 2-[2,4-bis-(dimethylamino)benzoyl]benzoic 
acid, 1.4 g. of 4-ethoxy-N-phenylaniline, 1 ml. of pyridine and 8 ml. of 
acetic anhydride was stirred 1.5 hrs. at room temperature. Dilution with 
20 ml. of 2-propanol and 50 ml. of ligroin produced no precipitate. The 
reaction mixture was therefore poured into 10% aqueous ammonia and the 
product was extracted with toluene. The organic extracts were washed with 
water and saturated aqueous sodium chloride and evaporated to dryness 
under vacuum. Trituration of the residue with ligroin afforded 2.18 g. of 
3-[2,4-bis-(dimethylamino)phenyl]-3-[N-(4-ethoxyphenyl)-N-phenylamino]phth 
alide as a pale orange solid, m.p. 111.degree.-117.degree. C. (dec.). A 
toluene solution of the product contacted with acidic clay or phenolic 
resin developed an orange-colored image. 
EXAMPLE 5 
A mixture containing 1.7 g. of 
3,4,5,6-tetrachloro-2-[4-(dimethylamino)benzoyl]benzoic acid, 0.5 ml. of 
thionyl chloride and 200 ml. of 1,2-dichloroethane was heated 0.5 hr. 
under reflux to produce a pale green solution. After cooling to 35.degree. 
C. a solution containing 1.0 g. of 4-ethoxy-N-phenylaniline and a few 
drops of pyridine in 10 ml. of 1,2-dichloroethane was added and stirring 
at room temperature was continued for 2 days. The reaction mixture was 
then poured into 10% aqueous ammonia and the product extracted with 
1,2-dichloroethane. The organic extracts were washed with water and 
saturated aqueous sodium chloride and evaporated to dryness under vacuum. 
The residue was slurried in 100 ml. of acetone and a white water-soluble 
solid was filtered off. The filtrate was evaporated to dryness and the 
residue was triturated with 2-propanol to give 1.5 g. of crude 
4,5,6,7-tetrachloro-3-[4-(dimethylamino)phenyl]-3-[N-(4-ethoxyphenyl)-N-ph 
enylamino]phthalide as a gray solid, m.p. 112.degree.- 121.degree. C. The 
nmr spectrum indicated the product to be a mixture containing the desired 
phthalide and unreacted 
3,4,5,6-tetrachloro-2-[4-(dimethylamino)benzoyl]benzoic acid in an 
approximate ratio of 60:40. A toluene solution of the product contacted 
with acidic clay developed a brown colored image; and when contacted with 
phenolic resin produced a pinkish-purple colored image. 
EXAMPLE 6 
Following a procedure similar to that described in Example 1 but employing 
6.24 g. of 5-(dimethylamino)-2-[4-(dimethylamino)benzoyl]benzoic acid and 
3.4 g. of diphenylamine there was obtained 8.67 g. of 
6-(dimethylamino)-3-[4-(dimethylamino)phenyl]-3-(diphenylamino)phthalide, 
m.p. 159.degree.-160.degree. C. A toluene solution of the product 
contacted with acidic clay or phenolic resin developed a red color image 
which, on acidic clay, became green after exposure to fluoroescent light. 
EXAMPLE 7 
Following a procedure similar to that described in Example 1 but employing 
3.1 g. of 2-[4-(diethylamino)-2-methylbenzoyl]benzoic acid and 2.1 g. of 
4-ethoxy-N-phenylaniline there was obtained 3.7 g. of 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(4-ethoxyphenyl)-N-phenylamino]ph 
thalide, m.p. 176.degree.-178.degree. C. (dec.). A toluene solution of the 
product contacted with acidic clay or phenolic resin developed a 
red-colored image. 
EXAMPLE 8 
Following a procedure similar to that described in Example 1 but employing 
2.7 g. of 2-[4-(dimethylamino)benzoyl]benzoic acid and 1.9 g. of 
3-methyl-N-phenylaniline there was obtained 2.7 g. of 
3-[4-(dimethylamino)phenyl]-3-[N-(3-methylphenyl)-N-phenylamino]phthalide, 
m.p. 185.degree.-187.degree. C. A toluene solution of the product 
contacted with acidic clay or phenolic resin developed an orange-colored 
image. 
EXAMPLE 9 
Following a procedure similar to that described in Example 1 but employing 
2.7 g. of 2-[4-(dimethylamino)benzoyl]benzoic acid and 2.5 g. of 
4-isopropoxy-N-phenylaniline there was obtained 4.34 g. of 
3-[4-(dimethylamino)phenyl]-3-[N-(4-isopropoxyphenyl)-N-phenylamino]phthal 
ide, m.p. 181.degree.-184.degree. C. A toluene solution of the product 
contacted with acidic clay or phenolic resin developed an orange colored 
image. 
EXAMPLE 10 
Following a procedure similar to that described in Example 1 but employing 
3.1 g. 2-[4-(diethylamino)-2-methyl)benzoyl]benzoic acid and 2.5 g. of 
4-isopropoxy-N-phenylaniline there was obtained 3.9 g. of 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(4-isopropoxyphenyl)-N-phenylamin 
o]phthalide, m.p. 176.degree.-178.degree. C. A toluene solution of the 
product contacted with acidic clay or phenolic resin developed a 
red-colored image. 
EXAMPLE 11 
Following a procedure similar to that described in Example 1 but employing 
3.61 g. of 2-[4-(N-p-anisoyl-N-methylamino)benzoyl]benzoic acid (m.p. 
235.degree.-242.degree. C.) and 2.13 g. of 4-ethoxy-N-phenylaniline there 
was obtained 1.88 g. of 
3-[4-(N-p-anisoyl-N-methylamino)phenyl]-3-[N-(4-ethoxyphenyl-N-phenylamino 
]phthalide, m.p. 63.degree.-68.degree. C. (dec.). A toluene solution of the 
product contacted with acidic clay or phenolic resin developed an 
orange-colored image. 
EXAMPLE 12 
Following a procedure similar to that described in Example 1 but employing 
3.21 g. of 2-(9-julolidinylcarbonyl)benzoic acid and 2.13 g. of 
4-ethoxy-N-phenylaniline there was obtained 4.61 g. of 
3-(9-julolidinyl)-3-[N-(4-ethoxyphenyl)-N-phenylamino]phthalide, m.p. 
143.degree.-147.degree. C. A toluene solution of the product contacted 
with acidic clay or phenolic resin developed a red-colored image. 
EXAMPLE 13 
Following a procedure similar to that described in Example 4 but employing 
5.4 g. of 2-[4-(dimethylamino)benzoyl]benzoic acid and 4.0 g. of 
4-hydroxy-N-phenylaniline there was obtained 5.6 g. of 
3-[4-(dimethylamino)phenyl]-3-[N-(4-hydroxyphenyl)-N-phenylamino]phthalide 
, m.p. 81.degree.-95.degree. C. (dec.). A toluene solution of the product 
contacted with acidic clay or phenolic resin developed an orange-colored 
image. 
EXAMPLE 14 
Following a procedure similar to that described in Example 4 but employing 
1.4 g. of 2-[4-(diethylamino)-2-methylbenzoyl] benzoic acid and 0.9 g. of 
diphenylamine there was obtained 1.36 g. of 
3-[4-(diethylamino)-2-methylphenyl]-3-(diphenylamino)phthalide, m.p. 
173.degree.-175.degree. C. (dec.) A toluene solution of the product 
contacted with acidic clay or phenolic resin developed a red colored 
image. 
EXAMPLE 15 
Following a procedure similar to that described in Example 4 but employing 
3.1 g. of 2-[4-(diethylamino)-2-methylbenzoyl] benzoic acid and 2.1 g. of 
3-methyl-N-phenylaniline there was obtained 1.2 g. of 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(3-methylphenyl)-N-phenylamino]ph 
thalide, m.p. 155.degree.-156.degree. C. A toluene solution of the product 
contacted with acidic clay or phenolic resin developed a red colored 
image. 
EXAMPLE 16 
Following a procedure similar to that described in Example 4 but employing 
1.0 g. of 2-[4-(dimethylamino)-benzoyl]benzoic acid and 1.4 g. of 
4,4'-dioctyldiphenyl-amine there was obtained 0.62 g. of 
3-[4-(dimethylamino)phenyl]-3-[N,N-bis-(4-octylphenyl)amino] phthalide, 
m.p. 158.degree.-169.degree. C. A toluene solution of the product 
contacted with acidic clay or phenolic resin developed an orange colored 
image. In another preparation carried out in a manner similar to that 
described in Example 2 the product was obtained as a solid, m.p. 
163.degree.-167.degree. C. 
A 2 percent (W/V) toluene solution of the product of this example was mixed 
in varying proportions with a 2 percent (W/V) toluene solution of the 
known color former crystal violet lactone (CVL) and the resulting solution 
was contacted with phenolic resin with the following results. 
______________________________________ 
Cpd of Ex. 16 
CVL 
(2% solution) 
(2% solution) 
color of image produced 
______________________________________ 
7.0 ml. 3.0 ml. brownish violet black 
6.5 ml. 3.5 ml. brownish violet black 
6.0 ml. 4.0 ml. violet black 
5.0 ml. 5.0 ml. bluish black 
______________________________________ 
EXAMPLE 17 
Following a procedure similar to that described in Example 4 but employing 
3.1 g. of 2-[4-(diethylamino)-2-methylbenzoyl] benzoic acid and 4.0 g. of 
4,4'-dioctyldiphenylamine there was obtained 0.41 g. of 
3-[4-(diethylamino)-2-methylphenyl]-3-[N,N-bis(4-octylphenyl)amino]-phthal 
ide, m.p. 85.degree.-110.degree. C. A toluene solution of the product 
contacted with acidic clay or phenolic resin developed a red colored 
image. Another preparation carried out in a manner similar to that 
described in Example 1 afforded a product m.p. 176.degree.-179.degree. C. 
EXAMPLE 18 
Following a procedure similar to that described in Example 4 but employing 
2.7 g. of 2-[4-(diethylamino)benzoyl]benzoic acid and 5 g. of 
3,3'-diethyl-5,5'-dinonyldiphenylamine there was obtained crude 
3-[4-(dimethylamino)phenyl]-3-[N,N-bis-(3-ethyl-5-nonylphenyl)amino]phthal 
ide as a gum. A toluene solution of the product contacted with acidic clay 
or phenolic resin developed a yellow-colored image. 
EXAMPLE 19 
Following a procedure similar to that described in Example 4 but employing 
6.1 g. of 2-[2-chloro-4-(dimethylamino)benzoyl]benzoic acid and 4.2 g. of 
4-ethoxy-N-phenylaniline there was obtained crude 
3-[2-chloro-4-(dimethylamino)-phenyl]-3-[N-(4-ethoxyphenyl)-N-phenylamino] 
phthalide as a gum. A toluene solution of the product contacted with acidic 
clay or phenolic resin developed a red-colored image. 
EXAMPLE 20 
Following a procedure similar to that described in Example 4 but employing 
2.7 g. of 2-[4-(dimethylamino)benzoyl]benzoic acid and 2.1 g. of 
3-chloro-N-phenylaniline there was obtained 1.6 g. of 
3-[4-(dimethylamino)phenyl]-3-[N-(3-chlorophenyl)-N-phenylamino]phthalide, 
m.p. 128.degree.-138.degree. C. A toluene solution of the product 
contacted with acidic clay or phenolic resin developed an orange-colored 
image. 
EXAMPLE 21 
Following a procedure similar to that described in Example 1 but employing 
2.6 g. of 2-[4-(dimethylamino)benzoyl]benzoic acid and 2.1 g. of 
4-dimethylamino-N-phenylaniline there was obtained 2.2 g. of 
3-[4-dimethylamino)phenyl]-3-[N-(4-dimethylaminophenyl)-N-phenylamino]phth 
alide, m.p. 163.degree.-166.degree. C. A toluene solution of the product 
contacted with acidic clay or phenolic resin developed a brown-colored 
image. 
EXAMPLE 22 
Following a procedure similar to that described in Example 1 but employing 
3.1 g. of 5-(dimethylamino)-2-[4-(dimethylamino)benzoyl]benzoic acid and 
3.0 g. of 4-dimethylamino-N-phenylaniline there was obtained 3.8 g. of 
6-(dimethylamino)-3-[4-(dimethylamino)phenyl]-3-[N-(4-dimethylaminophenyl) 
-N-phenylamino]phthalide, m.p. 163.degree.-164.degree. C. A toluene 
solution of the product contacted with acidic clay or phenolic resin 
developed a brown-colored image which changed to green on clay after 
fluorescent light exposure. 
EXAMPLE 23 
Following a procedure similar to that described in Example 1 but employing 
4.0 g. of 2-[4-(diethylamino)-2-methyl)benzoyl]benzoic acid and 4.0 g. of 
4-dimethylamino-N-phenylaniline there was obtained 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(4-dimethylaminophenyl)-N-phenyla 
mino]phthalide, m.p. 154.degree.-156.degree. C. A toluene solution of the 
product contacted with acidic clay or phenolic resin developed a dark 
grape-colored image. 
EXAMPLE 24 
Following a procedure similar to that described in Example 4 but employing 
2.6 g. of 2-[4-(dimethylamino)benzoyl]benzoic acid and 2.3 g. of methyl 
2-anilinobenzoate there was obtained 1.3 g. of 
3-[4-(dimethylamino)phenyl]-3-[N-(2-methoxycarbonylphenyl)phenylamino]phth 
alide, m.p. 92.5.degree.-102.degree. C. A toluene solution of the product 
contacted with acidic clay developed a yellow-colored image. 
EXAMPLE 25 
Following a procedure similar to that described in Example 4 but employing 
3.1 g. of 2-[4-(diethylamino)-2-methyl)benzoyl]benzoic acid and 2.3 g. of 
methyl 2-anilinobenzoate there was obtained 1.4 g. of 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(2-methoxycarbonylphenyl)phenylam 
ino]phthalide, m.p. 51.degree.-126.degree. C. A toluene solution of the 
product contacted with acidic clay or phenolic resin developed an 
orange-colored image. 
EXAMPLE 26 
Following a procedure similar to that described in Example 4 but employing 
5.2 g. of 2-[4-(dimethylamino)benzoyl]benzoic acid and 7.0 g. of 
4,4'-bis-(dimethylamino)diphenylamine there was obtained 10.7 g. of 
3-[4-(dimethylamino)phenyl]-3-[N-(4-dimethylaminophenyl)-N-(4-dimethylamin 
o)phenylamino]phthalide, m.p. 67.degree.-143.degree. C. A toluene solution 
of the product contacted with acidic clay or phenolic resin developed a 
brown-colored image. 
EXAMPLE 27 
Following a procedure similar to that described in Example 1 but employing 
4.0 g. of 2-[4-(dimethylamino)benzoyl]benzoic acid and 3.4 g. of 
4-acetamido-N-phenylaniline there was obtained 5.9 g. of 
3-[4-(dimethylamino)phenyl]-3-[N-(4-acetamidophenyl)-N-phenylamino]phthali 
de, m.p. 182.degree.-184.5.degree. C. An acetone solution of the product 
contacted with acidic clay or phenolic resin developed an orange-colored 
image. 
EXAMPLE 28 
Following a procedure similar to that described in Example 1 but employing 
4.6 g. of 2-[4-(diethylamino)-2-methyl)benzoyl]benzoic acid and 3.4 g. of 
4-acetamido-N-phenylaniline there was obtained 5.6 g. of 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(4-acetamidophenyl)-N-phenylamino 
]phthalide, m.p. 169.degree.-171.degree. C. An acetone solution of the 
product contacted with acidic clay or phenolic resin developed a 
red-colored image. 
EXAMPLE 29 
Following a procedure similar to that described in Example 4 but employing 
3.2 g. of 2-[4-(diethylamino)-2-methyl)benzoyl]benzoic acid and 2.9 g. of 
4,4'-diacetamidodiphenylamine there was obtained 0.82 g. of 
3-[4-(diethylamino)-2-methylphenyl]-3-[N,N-bis-(4-acetamidophenyl)amino]ph 
thalide, m.p. 179.degree.-182.degree. C. An acetone solution of the product 
contacted with acidic clay or phenolic resin developed a red-colored 
image. 
EXAMPLE 30 
Following a procedure similar to that described in Example 4 but employing 
4.0 g. of 5-(dimethylamino)-2-[4-(ethylbenzylamino)benzoyl]benzoic acid 
and 2.2 g of 4-ethoxy-N-phenylaniline there was obtained 3.0 g. of 
6-(dimethylamino)-3-[4-(ethylbenzylamino)phenyl]-3-[N-(4-ethoxyphenyl-N-ph 
enylamio]phthalide, m.p. 148.degree.-152.degree. C. A toluene solution of 
the product contacted with acidic clay or phenolic resin developed an 
orange-colored image which changed to green on clay after fluorescent 
light exposure. 
EXAMPLE 31 
Following a procedure similar to that described in Example 2 but employing 
5.4 g. of 2-[4-(ethylbenzylamino)benzoyl]benzoic acid and 3.1 g. of 
4-ethoxy-N-phenylaniline there was obtained 7.5 g. of 
3-[4-(ethylbenzylamino)phenyl]-3-[N-(4-ethoxyphenyl)-N-phenylamino]phthali 
de, m.p. 163.degree.-173.degree. C. A toluene solution of the product 
contacted with acidic clay or phenolic resin developed an orange-colored 
image. 
EXAMPLE 32 
Following a procedure similar to that described in Example 3 but employing 
3.2 g. of 2-[4-(diethylamino)-2-methyl)benzoyl]benzoic acid and 5 g. of 
4-octyl-4'-arylalkyldiphenylamine which is available from the B.F. 
Goodrich Chemical Company under the trade name Good-rite Antioxidant 3190 
there was obtained 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(4-octylphenyl)-N-(4-arylalkyl)ph 
enylamino]phthalide as an oil. A toluene solution of the product contacted 
with acidic clay or phenolic resin developed a red-colored image. 
EXAMPLE 33 
Following a procedure similar to that described in Example 1 but employing 
15.6 g. of 5-(dimethylamino)-2-[4-(dimethylamino)benzoyl]benzoic acid and 
19.6 g of 4,4'-dioctyldiphenylamine there was obtained 30.0 g. of 
6-(dimethylamino)-3-[4-(dimethylamino)phenyl]-3-[N,N-bis(4-octylphenyl)ami 
no]phthalide, m.p. 208.degree.-210.degree. C. A toluene solution of the 
product contacted with acidic clay or phenolic resin developed an 
orange-colored image which changed to green on the clay after fluoroescent 
light exposure. 
EXAMPLE 34 
Following a procedure similar to that described in Example 4 but employing 
3.4 g. of 2-[4-(diethylamino)-2-ethoxy)benzoyl]benzoic acid and 4.0 g. of 
4,4'-dioctyldiphenylamine there was obtained 
3-[4-(diethylamino)-2-ethoxyphenyl]-3-[N,N-bis-(4-octylphenyl)amino]phthal 
ide as an oil. A toluene solution of the product contacted with acidic clay 
or phenolic resin developed an orange-colored image. 
EXAMPLE 35 
Following a procedure similar to that described in Example 4 but employing 
5.1 g. of 2-[4-(diethylamino)-2-ethoxy)benzoyl]benzoic acid and 3.4 g. of 
4-acetamido-N-phenylaniline there was obtained 4.8 g. of 
3-[4-(diethylamino)-2-ethoxyphenyl]-3-[N-(4-acetamidophenyl)-N-phenylamino 
]phthalide, m.p. 126.degree.-131.degree. C. A toluene solution of the 
product contacted with acidic clay or phenolic resin developed an 
orange-colored image. 
EXAMPLE 36 
Following a procedure similar to that described in Example 1 but employing 
5.7 g. of 2-[4-(dimethylamino)-2-methylbenzoyl]benzoic acid and 8.0 g. of 
4,4'-dioctyldiphenylamine there was obtained 6.2 g. of 
3-[4-dimethylamino)-2-methylphenyl]-3-[N,N-bis(octylphenyl)amino]phthalide 
, m.p. 172.degree.-174.degree. C. A toluene solution of the product 
contacted with acidic clay or phenolic resin developed a red-colored 
image. 
EXAMPLE 37 
Following a procedure similar to that described in Example 4 but employing 
4.6 g. of 2-[4-(diethylamino)-2-methyl)benzoyl]benzoic acid and 4.5 g. of 
4,4'-bis-(diethylamino)diphenylamine there was obtained 0.53 g of 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(4-diethylaminophenyl)-N-(4-dieth 
ylamino)phenylamino]phthalide, m.p. 58.degree.-71.degree. C. A toluene 
solution of the product contacted with acidic clay or phenolic resin 
developed a black-colored image. 
EXAMPLE 38 
Following a procedure similar to that described in Example 4 but employing 
4.6 g. of 2-[4-(diethylamino)-2-methyl)benzoyl]benzoic acid and 5.0 g. of 
4-(diethylamino)-4'-(dimethylamino)diphenylamine there was obtained 5.9 g 
of 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(4-diethylaminophenyl)-N-(4-dimet 
hylamino)phenylamino]phthalide, m.p. 68.degree.-83.degree. C. A toluene 
solution of the product contacted with acidic clay or phenolic resin 
developed a black-colored image. 
EXAMPLE 39 
Following a procedure similar to that described in Example 4 but employing 
4.5 g. of 2-[4-(dimethylamino)-2-chloro)benzoyl]benzoic acid and 5.0 g. of 
4-(diethylamino)-4'-(dimethylamino)diphenylamine there was obtained 0.8 g 
of 
3-[4-(dimethylamino)-2-chlorophenyl]-3-[N-(4-diethylaminophenyl)-N-(4-dime 
thylamino)phenylamino]phthalide, m.p. 67.degree.-84.degree. C. A toluene 
solution of the product contacted with acidic clay or phenolic resin 
developed a black-colored image. 
EXAMPLE 40 
Following a procedure similar to that described in Example 4 but employing 
5.8 g. of 2-[4-(diethylamino)-2-ethoxy)benzoyl]benzoic acid and 3.9 g. of 
4,4'-bis(dimethylamino)diphenylamine there was obtained 2.26 g. of 
3-[4-(diethylamino)-2-ethoxyphenyl]-3-[N-(4-dimethylaminophenyl)-N-(4-dime 
thylamino)phenylamino]phthalide, m.p. 58.degree.-69.degree. C. A toluene 
solution of the product contacted with acidic clay or phenolic resin 
developed a grape-black-colored image. 
EXAMPLE 41 
Following a procedure similar to that described in Example 4 but employing 
5.7 g. of 2-[4-(dimethylamino)-2-methyl)benzoyl]benzoic acid and 5.0 g. of 
4,4'-bis(dimethylamino)diphenylamine there was obtained 0.22 g. of 
3-[4-(dimethylamino)-2-methylphenyl]-3-[N-(4-dimethylaminophenyl)-N-(4-dim 
ethylamino)phenylamino]phthalide, m.p. 97.degree.-113.degree. C. A toluene 
solution of the product contacted with acidic clay or phenolic resin 
developed a black-colored image. 
EXAMPLE 42 
Following a procedure similar to that described in Example 4 but employing 
5.7 g. of 2-[4-(dimethylamino)-2-methylbenzoyl]benzoic acid and 5.5 g. of 
4,4'-bis(diethylamino)diphenylamine there was obtained 1.62 g. of 
3-(4-(dimethylamino)-2-methylphenyl]-3-[N-(4-diethylaminophenyl)-N-(4-eith 
ylamino)phenylaino]phthalide, m.p. 59.degree.-72.degree. C. A toluene 
solution of the product contacted with acidic clay or phenolic resin 
developed a black-colored image. 
EXAMPLE 43 
A. Following a procedure similar to that described in Example 4 but 
employing 3.1 g. of 2-[4-(diethylamino)-2-methylbenzoyl]benzoic acid and 
3.0 g. of 4,4'-bis(dimethylamino)diphenylamine there was obtained 2.95 g. 
of 
3-[4-(diethylamino)-2-methylphenyl]-3-[N-(4-dimethylaminophenyl)-N-(4-dime 
thylaminophenyl)amino]phthalide, m.p. 67.degree.-83.5.degree. C. A toluene 
solution of the product contacted with acidic clay or phenolic resin 
developed a black-colored image. 
B. A mixture containing 6.2 g. of 
2-[4-(diethylamino)-2-methylbenzoyl]benzoic acid and 5.1 g. of 
4,4'-bis(dimethylamino)diphenylamine, 20 ml. of acetic anhydride and 2.0 
g. of urea was stirred 2 hours at room temperature and then poured into 5% 
aqueous ammonium hydroxide and extracted with toluene. The organic 
extracts were dried over anhydrous sodium sulfate and evaporated to 
dryness under vacuum. The residue was dissolved in 200 ml. of DMF and 
slowly added to 11/2 liter of water containing 1 g. of Dabco with vigorous 
stirring. The air dried product was weighed 5.0 g. and was essentially 
identical to the product of part A above. 
C. In a procedure similar to that described in Example 5 was employed, 1.7 
g. of thionyl chloride was added to a mixture of 100 ml. of benzene and 50 
ml. of 1,2-dichloroethane. After 4.7 g. of 
2-[4-diethylamino-2-methylbenzoyl]benzoic acid was added, the reaction 
mixture was warmed to 60.degree. C. to obtain a clear solution. When the 
solution had cooled to 40.degree. C., a solution of 3.5 g. of 
4,4'-bis(dimethylamino)diphenylamine and 1 ml. of pyridine in 50 ml. 
1,2-dichloroethane was added and the mix heated to 60.degree. C. for one 
hour, cooled and stirred overnight at room temperature. The tary material 
which separated was filtered, washed and dissolved in dimethylformamide. 
Addition to an excess of water yielded 4.2 g. of a light grape-colored 
solid which developed a black color on silica gel. 
EXAMPLE 44 
Following a procedure similar to that described in Example 4 but employing 
6.2 g. of 5-dimethylamino-2-[4-(dimethylamino)benzoyl]benzoic acid and 5.0 
g. of 4,4'-bis-(dimethylamino)diphenylamine there was obtained 6.6 g. of 
6-dimethylamino-3-[4-(dimethylamino)phenyl]-3-[N-(4-dimethylaminophenyl)-N 
-(4-dimethylamino)phenylamino]phthalide, m.p. 86.degree.-92.degree. C. A 
toluene solution of the product contacted with acidic clay or phenolic 
resin developed a brown-colored image which changed to green on clay after 
fluorescent light exposure. 
EXAMPLE 45 
Following a procedure similar to that described in Example 4 but employing 
1.4 g. of 5-dimethylamino-2-[4-(N-ethyl-N-benzylamino)benzoyl]benzoic acid 
and 0.8 g. of 4,4'-bis(dimethylamino)diphenylamine there was obtained 1.0 
g. of 
6-dimethylamino-3-[4-(N-ethyl-N-benzyl)aminophenyl]-3-[N-(4-dimethylaminop 
henyl)-N-(4-dimethylamino)phenylamino]phthalide, m.p. 
137.degree.-148.degree. C. A toluene solution of the product contacted 
with acidic clay or phenolic resin developed a dark brown-colored image 
which changed to green on clay after fluorescent light exposure. 
EXAMPLE 46 
A. To a stirred mixture containing 36 g. of 4-(and 5-) 
carboxy-2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid (prepared from 
trimellitic anhydride and 3-(diethylamino)phenol, 60 ml. of diethyl 
sulfate and 450 ml. of acetone at 35.degree. C. was added dropwise over 2 
hours a solution containing 25 g. of potassium hydroxide in 75 ml. of 
water. When the addition was complete stirring was continued an additional 
2 hours. Another 20 g. of potassium hydroxide in 60 ml. of water was added 
and the mixture was heated under reflux 1 hour. Solvent was then allowed 
to distill until the internal temperature reached 96.degree. C. The 
reaction mixture was maintained at 96.degree. C. 0.5 hour then stirred at 
room temperature overnight, diluted with 100 ml. of water and brought to 
pH 4.0 l with 3 N hydrochloric acid. The resulting red precipitate was 
collected, washed with water and air-dried to give 37 g. of 4 -(and 
5-)carboxy-2-(4-diethylamino-2-ethoxybenzoyl)benzoic acid, m.p. 
63.degree.-96.degree. C. which was used without further purification. 
B. A mixture containing 8.0 g. of 4-(and 
5-)carboxy-2-(4-diethylamino-2-ethoxybenzoyl)benzoic acid, 8.0 g. of 
4-dimethylamino-4'-diethylaminodiphenylamine, 25 ml. of acetic anhydride 
and 2 ml. of pyridine was stirred 2 hours at room temperature. The mixture 
was poured into toluene and the product extracted with 10% aqueous 
ammonia. The aqueous alkaline extracts were acidified to pH 5 with 3 N 
hydrochloric acid. The resulting precipitate was collected, washed with 
water and dried to give 4.8 g. of 5-(and 
6-)carboxy-3-[4-(diethylamino)-2-ethoxyphenyl]3-[N-(4-dimethylaminophenyl) 
-N-(4-diethylaminophenyl)amino]phthalide, m.p. 167.degree.-173.degree. C. 
C. To a mixture containing 4.0 g. of the above acid, 4.0 g. of potassium 
carbonate and 100 ml. of N,N-dimethylformamide was added 4.0 g. of 
dimethyl sulfate. After stirring for one hour, the reaction mixture was 
poured into 1 liter of water containing 10 ml. of concentrated ammonium 
hydroxide. The resulting precipitate was collected, washed with water and 
dried to give 0.2 g. of 5-(and 
6-)methoxycarbonyl-3-[4-(diethylamino)-2-ethoxyphenyl]-3-[N-(4-dimethylami 
nophenyl)-N-(4-diethylaminophenyl)amino]phthalide, m.p. 
87.degree.-93.degree. C. A toluene solution of the product contacted with 
acidic clay or phenolic resin developed a brown-black-colored image. 
It is contemplated that by following procedures similar to those described 
in Examples 1, 2, 3, 4 and 5 but employing the appropriate 2-substituted 
diarylamines of Formula IV there will be obtained the phthalides of 
Formula II, Examples 47-48 presented in Table A hereinbelow. 
3 TABLE A 
Phthalides of Formula II Ex. Q.sub.4 Q.sub.5 Q.sub.6 Q.sub.7 R.sub.1 
R.sub.2 R.sub.3 Y.sub.1 Y.sub.2 Y.sub.3 Y.sub.4 
47 H H H H n-C.sub.4 H.sub.9 CH.sub.3 CH.sub.3 H H 3-I H 48 H (C.sub.2 
H.sub.5).sub.2 N H H H CH.sub.3 C.sub.6 H.sub.5 CH.sub.2 H H 2-C.sub.2 
H.sub.5 H 49 H Br H H Br CH.sub.3 CH.sub.3 H H 4-Br H 50 Br Br Br Br 
(CH.sub.3).sub.2 N CH.sub.3 CH.sub.3 H H 3-(t-C.sub.4 H.sub.9) H 51 H H 
H H C.sub.2 H.sub.5 O C.sub.2 H.sub.5 C.sub.2 H.sub.5 2-CH.sub.3 H 
4-CH.sub.3 O H 52 H (C.sub.4 H.sub.9).sub.2 N H H H CH.sub.3 C.sub.2 
H.sub.5 3-Br H 5-Br H 53 H H F H H CH.sub.3 C.sub.6 H.sub.5 H H 2-F H 54 
H Cl H H H t-C.sub.4 H.sub.9 t-C.sub.4 H.sub.9 2-Cl H 4-F H 55 F F F F H 
CH.sub.3 p-CH.sub.3 C.sub.6 H.sub.4 3-CH.sub.3 O H 3-CH.sub.3 O H 56 H H 
H H (sec-C.sub.4 H.sub.9).sub.2 N sec-C.sub.4 H.sub.9 sec-C.sub.4 
H.sub.9 H H H H 57 I I I I H CH.sub.3 CH.sub.3 H H 4-OH H 58 H H H H I 
C.sub.4 H.sub.9 p-C.sub.4 H.sub.9C.sub.6 H.sub.4 3-CH.sub.3 4-CH.sub.3 
3-CH.sub.3 4-CH.sub.3 59 H H (C.sub.2 H.sub.5).sub.2 N H H C.sub.2 
H.sub.5 C.sub.4 H.sub.9 3-C.sub.4 H.sub.9 O H 3-C.sub.4 H.sub.9 O H 60 H 
H (C.sub.4 H.sub.9).sub.2 
N H H CH.sub.3 CH.sub.3 H H 
##STR12## 
H 61 H H H H (CH.sub.3).sub.2 CHCH.sub.2 O CH.sub.3 CH.sub.3 2-Cl 4-Cl 
2-Cl 4-Cl 62 H CO.sub.2 CH.sub.2 C.sub.6 H.sub. 5 H H H CH.sub.3 
CH.sub.3 4-CH.sub.2 C.sub.6 H.sub.5 H H H 63 H H CO.sub.2 C.sub.8 
H.sub.17 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 2-CO.sub.2 
C.sub.4 H.sub.9 H H H 64 H CO.sub.2 C.sub.18 H.sub.37 H H Cl CH.sub.3 
CH.sub.3 
##STR13## 
H H H 65 H CO.sub.2 C.sub.14 
H.sub.29 H H H CH.sub.3 CH.sub.3 2-CO.sub.2 C.sub.2 H.sub.5 H H H 66 H 
H 
##STR14## 
H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 4-CO.sub.2 CH.sub.3 H H H 67 
H CO.sub.2 H H H H CH.sub.3 CH.sub.3 2-CO.sub.2 H H H H 68 H H H H H 
CH.sub.3 CH.sub.3 4-NH.sub.2 H H H 69 H H H H CH.sub.3 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 4-NH.sub.2 H 4-NH.sub.2 H 70 Cl Cl Cl Cl H CH.sub. 3 
CH.sub.3 4-NHC.sub.4 H.sub.9 H 4-NHC.sub.4 H.sub.9 H 71 H H H H CH.sub.3 
C.sub.2 H.sub.5 C.sub.2 
H.sub.5 
##STR15## 
H H H 72 H H H H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 4-NHCOC.sub.4 
H.sub.9 H 4-NHCOC.sub.4 H.sub.9 H 73 H CO.sub.2.sup..crclbar. 
Na.sup..sym. H H H CH.sub.3 CH.sub.3 4-OC.sub.2 H.sub.5 H H H 74 H H 
CO.sub.2.sup..crclbar. NH.sub.4.sup..sym. H H CH.sub.3 CH.sub.3 H H H H 
75 H CO.sub.2.sup..crclbar. HN.sup..sym. (C.sub.2 H.sub.5).sub.3 H H H 
C.sub.2 H.sub.5 C.sub.6 H.sub.5 CH.sub.2 4-OC.sub.2 H.sub.5 H H H 76 H 
##STR16## 
H H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 
H.sub.5 H H H H 77 H H CO.sub.2.sup..crclbar. 
H.sub.3 .sup..sym.NC.sub.8 H.sub.17 H H CH.sub.3 CH.sub.3 4-OC.sub.2 
H.sub.5 H H H 78 H H H H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 
4-NHCH(CH.sub.3).sub.2 H H H 
EXAMPLE 79 
The color formers of Examples 2 and 7 were microencapsulated as follows. A 
solution containing 1 g. of the color former in 49 g. of isopropylbiphenyl 
and a solution containing 5 g. of carboxymethylcellulose in 200 ml. of 
water were mixed and emulsified by rapid stirring. The desired particle 
size (5 microns) was checked by microscope. To the emulsion was added a 
solution containing 15 g. of pigskin gelatin in 120 ml. of water. The pH 
was adjusted to 6.5 with 10% aqueous sodium hydroxide with rapid stirring, 
and following the gradual addition of 670 ml. of water with heating (at 
50.degree. C.) the pH was adjusted to 4.5 with 10% aqueous acetic acid 
with continued rapid stirring. After 5 minutes 10 g. of 25% aqueous 
glutaraldehyde was added and rapid stirring was continued an additional 15 
minutes. The resulting microcapsule dispersion was stirred more slowly 
overnight. 
Starch (12 g.) was gradually added to 60 ml. of water. The mixture was 
heated to 90.degree. C. and stirred 15 minutes. After cooling to room 
temperature the mixture was added to 473 g. of the above microcapsule 
dispersion and the resulting emulsion stirred vigorously for 2 minutes, 
and then coated on white typewriter paper sheets (0.0015 in. film 
thickness). The sheets were air dried. Duplicate typewritten images were 
made on receiving sheets coated with either phenolic resin or acidic clay. 
The color former of Example 2 produced an orange image on both types of 
receiving sheets, and the color former of Example 7 produced a red image 
on both types of receiving sheets. 
EXAMPLE 80 
Polyvinyl alcohol dispersions of the color formers of Examples 2, 3 and 7 
were prepared by shaking 1 hour on a paint shaker a mixture containing 2.0 
g. of the color former, 3.7 g. of water, 8.6 g. of 10% aqueous polyvinyl 
alcohol and 10 g. of zirconium grinding beads. A polyvinyl alcohol 
dispersion of bisphenol A was prepared by shaking a mixture containing 9.8 
g. of bisphenol A, 18.2 g. of water, 42 g. of 10% aqueous polyvinyl 
alcohol and 70 ml. of zirconium grinding beads. The coating mixture was 
made by combining and thoroughly mixing 2.1 g. of the polyvinyl alcohol 
dispersion of the color former with 47.9 g. of the polyvinyl alcohol 
dispersion of bisphenol A. The coating mixture was applied (at thicknesses 
of 0.003 in. and 0.0015 in.) to white mimeo paper sheets and the sheets 
were dried at room temperature. Contacting the coated sheets with a heated 
stylus at a temperature between 110.degree. C. and 150.degree. C. 
produced a dark orange image on the sheet coated with the color former of 
Example 2, a dark red image on the sheet coated with the color former of 
Example 3 and a dark purple image on the sheet coated with the color 
former of Example 7. 
EXAMPLE 81 
Following a procedure similar to that described in Example 79 but 
substituting kerosene for isopropylbiphenyl the color former of Example 32 
was microencapsulated and coated on a transfer sheet. The color former 
developed a red image on both types of receiving sheets. 
EXAMPLE 82 
Following a procedure similar to that described in Example 79 but omitting 
the addition of starch to the microcapsule dispersion, the color former of 
Example 43 was microencapsulated and coated on a transfer sheet. The color 
former developed a black image on both types of receiving sheets. The 
image formed on the clay-coated receiving sheet turned green on standing. 
EXAMPLE 83 
Following a procedure similar to that described in Example 79 but omitting 
the addition of starch to the microcapsule dispersion, a mixture 
containing 0.876 g. of the color former of Example 16 and 0.584 g. of 
crystal violet lactone was microencapsulated and coated on a transfer 
sheet. The mixture of color formers developed a blue to black image on 
resin-coated receiving sheets.