Note: Descriptions are shown in the official language in which they were submitted.
10 ~ ~'7~ ~
This invention relates to 3~substituted-3-
~diphenylamino)phthalides u~eful as color form0rs in
pressure-~ensitive carbonless duplicating systems, ~hermal
marking system~ and hectographic or spirit-reproducing
cbpy~ng system~t to processe~ for the prepar~tion therflof5
and to pressure-sen~itive duplicating ~ystems, thermal
marking ~ystem~ and hectographic copying systems con~ining
the same.
Several cla~ses o organic compounds of widely di-
ver~e structural types are known to be useful a~ color
formere ~or carbon;ess duplicating sy6tems. Among the more
widely recognized classes, there may be named phenothiazines,
for example, benzoyl leuco methylene blue; fluorans, for
example, 2'-anllino-6'-diethylaminofluoran; phthalides, the
class wlth which this invention is concerned, for examplo,
crystal violet lactone; and various other types of color
formers currently employed in commercially accepted carbon-
less duplicating systems. Typical of the many such sy3tems
taught ln the prior art are those described in U.S. Patents
2,712,507, 2,800,4S7 and 3~041,289~
Many of the color formers in the prior art suffer
one or more dieadvantages ~uch as low tinctorial strength,
poor l$ght stability, low resistance to ~ublimation and low
solubility in common organic solvent , the latter disadvan-
2S tage thus requiring the use of specialized and expensive
-2-
-
.
. .
iLOti ;~'70~
801vent8 in order to obtain microencapeulated 801ution8 Of
8ufficient concentration for u8e in pr~8ur8-8ensitive
copying 8y8tem8. Other prior art includes U.S. Pat~nt8
3,736,168 and 3,491,112 and Japane3~ Patent Publication No.
71/4616.
R. Valters and V. ~8iekuro in Khim. G~terot~ikl.
Soedin. 1975, (llJ 1476-8 di~CU88 ring-chain tautomeri8m
in 3-(N,N-diphenylamino)-3-phanylphthalide but di~cloee no
utility for the compound.
Thi~ invention relate8 to compound9 having
Formula I
(Q)n ~ ~
Yl Y2
Formula I
wherein
Q i9 ai-lower-alkylamino, nitro, halo or COX,
where X i8 hydroxyl, benzyloxy, alkoxy having frcm 1 to 18
carbon atoms or OM where M i9 an alkali metal cation, an
ammoniUm cation or a mono-, di- or tri-alkylammonium cation
having from 1 to 18 carbon atom8;
n is O; or 1 when Q i8 di-lower alkylamino, nitro
or COX; or from 1 to 4 when Q i8 halo;
Yl, Y2, Y3 and Y4 are the 8ame or different and are
hydrogen, halo, hydroxyl, lower-alkoxy, alkyl having from 1 to 9
1 3
S
} ~ ;1 V ~
carbon atoms, phenyl-lower-alkyl, COOR4 or NR5R6, where R4
and R5 are hydrogen or low~r-alkyl and R6 is hydrogen, lower-
alkyl, cycloalkyl having from S to 7 carbon atoms, or lower
alkanoyl; Z i8
~ j A3~R2
,
l ll and 9-julolidinyl
R8Rg ~ R7
in which:
R is hydrogen or non-tertiary alkyl having from l
to 4 carbon atoms;
Rl is hydrogen, or non-tertiary alkyl having from
1 to 18 carbon atoms;
R2 i9 hydrogen, phenyl or non-tertiary alkyl having
from 1 to 4 carbon atoms;
R3 is hydrogen, non-tertiary alkyl having from l to
4 carbon atoms or non-tertiary alkoxy having from l to 4 car-
~on atoms;
R7 is hydrogen, halo, lower-alkyl, lower-alkoxy or
di-lower-alkylamino;
R8 is lower-alkyl; and
Rg is lower-alkyl, benzyl, phenyl or phenyl sub-
stituted with a lower-alkyl or lower-alkoxy group.
The compounds are useful as color formers in pres-
~ure-sensitive carbonless dupli¢ating systems, thermal
marking ~ystems and hectographic copying systems.
Particularly embodiment~ relat~ to compounds
having Formula I
wherein Q, n~ Yl, Y2, ~3 and Y4 have the previously given
meanings and 2 is
3 ~ ~ ~ ~2Rg~- l`` ~
Rl, R2, R3, R7, R~ and Rg having the previously given
meanings. Preferred compound~ within the ambit of this
particular embodiment are those wherein:
a) n is O;
b) n is 1 and Q is di-lower-alkylamino or COX
where X has the previously given meanings; and
c) n is 4 and Q is halo; especially 3-~N-(4-
ethoxy-phenyl)-N-phenylamino~-3- ~-ethyl-2-methyl-3-
indolyl)phthalide, 3-(diphenylamino~-3-~1-ethyl-2-methyl-
3-indolyl)phthalide, 3-~1-ethyl-2-methyl-3-indolyl3-3-~N-
phenyl-N-m-tolylamino)-phthalide, 3-~1-ethyl-2-methyl-3- ::
indolyl)-3-~N,N-bis(3-ethyl-5-nonylphenyl)amino]phthalide,
5-(and 6-)carboxy-3-[N-(4-ethoxyphenyl)-N-phenylamino]-3-
(l-ethyl-2-methyl-3-indolyl~-phthalide, 3-[N-¢4-ethoxyphenyl)-
2n N-phenylamino]-3-(1.-ethyl-2-methyl-3-indolyl)-5-~and 6-)
methoxycarbonylphthalide, 5-~and 6-ethoxycarbonyl
3 { N -t4--ethoxyphenyl)- N -phenylamino] - 3 ~
ethyl-2-methyl-3-indolyl~phthalide, 3-[N-~4-ethoxyphenyl)-N-
phenylamino]-3-(1-ethyl-2-methyl-3-indolyl)-5-~and 6-)-n-
octyloxy-carbonylphthalide, 5-~and 6-)benzyloxycarbonyl-3-
N-[4-(ethoxy-phenyl)-N-phenylamino]-3- ~-ethyl-2-methyl-3-
indolyl)phthaliae, 4,5,6,7-tetrachloro-3-[N-~4-ethoxyphenyl)-
. -5-
. ..
.
` ' ' - `
., ~ .
`': :'~ `, ':: `
N-phenylamino]-3-(ethyl-2-methyl-3-indolyl)phthalide, 3-
(l-ethyl-2-methyl-3-indol~ 3- [N,N-bi8- ~4-octylphenyl)-
amino]phthalide, 3-[4-(dimethylamino~phenyl]-3-[N-(4-
ethoxyphenyl)-N-phenylamino~-phthalid~; 3-~4-dimethyl-
amino)phenyl]-3-[N-~4-isopropoxyphenyl)-N-phenylamino]-
phthalide; 4,5,6,7-tetrachloro-3-[4-~dimethylamino)
phenyl]-3-[N-(4-ethoxyphenyl)-N-phenylamino~phthalide;
3-14-(diethYlamino)-2-methylphonyl~-3-lN-~4-ethoxyphenyl)-
N-phenylamino]amino]phthalide; 3 ~4-~dimethylamino)phenyl]-3-
~N,N-~is-(4-octylphenyl)aminQ~phthalid2; 6-~dimethylamino)-
3-[4-(dimethylamino)phenyl~-3-[N-(4-ethoxyphenyl)-N-
phenylamino]phthalide; 3-[4-(dimethylamino)-phenyl]-3-
(N,N-diphenylamino)phthalide; 6-(dimethylamino)-3-[4-
(dimethylamino)phenyl]-3-[N,N-bis(4-octylphenyl)amino]-
phthalide; 3-[4-(ethylbenzylamino)phenyl]-3-~N-(4-ethoxy-
phenyl)-N-phenylaminolphthalide and 3-[4-~diethylamino)-
2-methylphenyl]-3-{N,N-bis~4-~dimethylamino)phenyl]amino}-
phthali~e.
One can prepare the compounds of Formula I, by
a process which comprises reacting a 2-sub~tituted benzoic
acid havin~ Formula II
,~02H
(Q) ~ 11
~=0
~ Formula II
with a diarylamine having Formula III
Yl ~ ~ Y3
Y2 ~ ~ 4
Formula III
-6-
'7~3~
in the presence of the anhydride of an alkanoic acid having
from 2 to 5 carbon atoms, and an organic baee; where in
Formulas II and III, Z, n, Yl, Y2, 3, 4
previously given meanings and Q is selected from the group
consisting of di--lower-alkyl-amino, nitro, halo and COX
where X is hydroxy, benzyloxy or alkoxy having from 1 to 18
carbon atom~ .
Another process for producing the compounds of
Formula I, compri~es reacting a 2-substituted benzoic acid
1~ of Formula II, with an inorganic acid chloride which is
thion~l chloride, phosphorus oxychloride, phosphorus tri-
chloridè or phosphorus pentachloride, followed by reaction
of the resulting product with a diarylamine of Formula III,
in the presence of an organic base; where in Formulas II
and III, Z, O, n, Yl, Y2~ Y3 and Y4 have the meanings given
in the preceding paragraph.
A further process for preparing the compounds of
Formula I, wherein Z is
~L
comprises reacting a phthalamic acid having Formula IV
~,~ /C02H
(Q) n~ 1-l
~ 4
~/
.~,
Y~ 2 _7_ Formula IV
.. ~.,. .~., . , -
10~;~'70~
with an indole having Formula V
Formula V
in the presence of the anhydride of an alkanoic acid having
from 2 to 5 carbon atoms; where in Formulas IV and V Q, n,
Yl, Y2, y3, v4, Rl, R2 and R3 have the abo~e-given meanings
The present invention also deals with a pressure-
sensitive carbonless duplicating system, thermal marking
s~stem or hectographic copying system containing a color-
forming sub~tance comprising a compound having Formula I.
A particular smbodiment 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
resides in a heat responsi~e 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 applica-
tion of heat will produce a mark-forming reaction between the
color-forming compound and the acidic developer~
A further particular embodiment resides in a hecto-
graphic or spirit reproducing copying system comprising a
tran~fer sheet coated on one side with a layer containing a
color-forming substance comprising at least one compound
having Formula I, wherein n is l and Q is COX where X is
-8-
,...... . ~ , . .
~, . .
~ '7~ ~
OM and M ha~ the previously given meanings.
As uced herein the term "halo" includes chloro,fluoro, bromo and iodoO Chloro iB the preferred halo sub-
stituent because of the relatively low cost and ea~e of pre-
paration of the required chloro-substituted intermediates and
because the other halogens offer no particular advantage6
over chloro. However the other a~ove-named halo aubstituents
are also satisfactory.
The termQ "lower-alkyl, lower-alkoxy and di-lower-
alkylamino" denote saturated, acyclic groups having from 1te 4 carbon atoms which may be straight or branched as
exemplified by methyl, ethyl, pr~pyl, isopropyl, butyl, sec-
butyl, isobutyl, ert-butyl, methoxy, ethoxy, propoxy, i80-
propoxy, butoxy, sec-butoxy, i~obutoxy, tert-butoxy, dimeth-
ylamino, diethylamino, ethylmethylamino, dipropylamino,dibutylamino, isobutylmethylamino, di-tert-butylamlno and
the like.
A~ used herein the term "cycloalkyl having from
5 to 7 carbon atoms" include6 cyclopentyl, cyclohexyl and
cycloheptyl.
The term "lower alkanoyl" denotes saturated acyclic
acyl groupR having from 1 to 5 caxbon atoms which may be
straight or branched as exemplified by formyl, acetyl,
propionyl, butyryl, isobutyryl, valeryl, 2-methylbutyryl,
isovaleryl, pivalyl and the likeO
The term "phenyl-lower-alkyl" include~ benzyl,
2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, l-phonyl-
butyl, 2,2-dimethyl-2-phenylethyl and the like. If desired
the phenyl group may contain a lower alkyl or lower alkoxy
substituentO
~ :~
-{r ~
, ~ '
'~ '
.lV~;~710~
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-nonyl-
oxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy,
n-tetradecyloxy, n-pentadecyloxy, n-hexahecyloxy, n-hepta-
decyloxy, n-octadecyloxy, l-methylpentyloxy, 2,2-dimethyl-
butyloxy, 2-methylhexyloxy, 1,4-dimethylpentyloxy, 3-ethyl-
pentyloxy, 2-methylheptyloxy, l-ethylhexyloxy, 2-propyl-
10pentyloxy, 2-methyl-3-ethylpentyloxy, 1,3,5-trimethylhexyl-
oxy, l,S-dimethyl-4-ethylhexyloxy, 5-methyl-2-butylhexyl-
oxy-2-propylnonyloxy, 2-butyloctyloxy, l,l-dimethylundecyl-
oxy, 2-pentylnonyloxy, 1,2-dimethyltetradecyloxy, l,l-dimeth-
yl-pentadecyloxy and the like
15As used herein the term "alkyl having from 1 to 9
carbon atoms" denotes saturated monovalent straight or
branched chain aliphatic hydrocarbon radicals including meth-
yl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,
amYl, l-methylbutyl, 3-methylbutyl, hexyl, isohexyl, heptyl,
isoheptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, 3-ethyl-
heptyl and the like.
The term "non-tertiary alkyl having from 1 to 18
carbon atomsl includes, in addition to the above-named alkyl
groups having from 1 to 9 carbon atoms, excluding o~ course
any tertiary alkyl groups, saturated, monovalent, straight
or branched-chain aliphatic hydrocarbon radicals such as n-
decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-
pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, 1,3,5-
trimethylhexyl, 1,5-dimethyl-4-ethylhexyl, 5-methyl-2-butyl-
3~ hex~l, 2-propylnonyl, 2-butyloctyl, 2-pentylnonyl, 1,2-dimeth-
--10--
,
yl-tetradecyl, 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 substitute by from 1 to 3 alkyl
group~ as above described, The al~yl groups can be the same
or different provided the ammonium cation contain~ no more
than 18 carbon atoms. As examples there can be named methyl-
ammonium, t-butylammonium, t-octylammDnium, n-dodecylammonium, n-
octadecylammDnium, di-n-butylammonium, di-n-nonylammonium, isopropyl-n-butyl-
ammonium, dimethyl-n-butylammonium, tri-ethylammonium, N-
ethyl-N,N-diisopropylammonium, tributylammonium, di-n-butyl-
octylanmonium and the like.
The term "9-3ulolidinyl" of course refers to the
radical having the formula
Anhydrides of alkanoic acids of two to five carbon
atoms include acetic anhydride, propionic anhydride, butyric
anhydride, isobutyric anh~dride, valeric anhydride, iso-
valeric anhydride, ~-methylbutyric anhydride, pivalic anhydr-
ide and the like. Acetic anhydride is preferred because of
i~s low oost 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, herein-
--11--
:, .. . . .:
' . ' :
~ '7~U~
above and the like~ Because of their low cost and readyavailability pyridlne and urea are preferred.
In accordance with one process the compounds
having Formula I, are obtained by reacting approximately
equimolar amounts of a 2-substituted benzoic acid of
Formula II and a diarylamine of Formula III in the anhydr-
ide 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 to 1005C. for
from approximately 10 minutes to 24 hours. The reaction
is usually carried out in the absence of an inert diluent
at about 20 to 40C. 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 iso-
propyl alcohol or hexane or a mixture of these in order toeffect precipitation of the product. Alternatively, the
reaction mixture can be poured into aqueous base such as
dilute ammonium hydroxide, sodium hydroxide, sodium carb-
onate or sodium bicarbonate and the product extracted with
an organic solvent such as benzene or tolue~e followed by
evaporation of the organic solvent leaving the pxoduct as
a residue. The product once isolated can be purified by
conventional means such as trituration or recrystallization
from a suitable solvent.
3~ In accordance with a second process the compounds
-12-
'708
of Formula I, can be prepared in two steps which compris~
first reactin~ a 2-substituted benzoic acid of Formula II,
with an excess of an organic acid chloride such as thionyl
chloride, phosphorus oxychloride, phosphorus trichloride
or phosphorus pentachloride with or without an inert
diluent such as benzene, toluene, chloroform or 1,2-dichloro-
ethane, at 20 to 30C. for about 0.5 to 2 hours; and
following removal of excess inorganic acid chloride, reac-
tion of the resulting product which while not having been
isolated is presumed to be a halide having Formula VI
p
(Q)n I ~ P
'"' '``>~
Formula VI
in which ~, n and Z have meanings previously given in
Formula II, with a diarylamine Of Formula III, hereinabove
in an inert solvent in the presence of an organic base as
pre~iously described at a temperature in the range of 0 to
80C. for about 1 to 48 hours, The product can be isolated
and purified in the manner previously described.
In accordance with a urther process the compounds
having Formula I, wherein Z is
r'~
R3 ~" ~
`R2
~an be prepared by reacting a phthalamic acid of Formula IV
with an indole of Formula V in the anhydride of an alkanoic
-13-
- , . ~ .
-:, -
.. , .
' ' `'-~ ' ` '`' ` '' " ' ~' '" ' ' '~ ,
: ' , . . . . ..
"7(~
acid having from two to five carbon atoms, such as acetic
anhydride, w~th or without an inert diluent and optionally
in the presence of an organic base, for example pyridine
or urea, at a temperature of from 0 to 100C. for from
approximately 1 to 24 hoursO The reaction is usually
carried out at about 20 to 40C. for approximately 2 to 12
hours. The product so-obtained can be isolated and purified
in accordance with the above-described procedures.
When preparing compounds of Formula I, wherein Q
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 pre-
pare the compound of Formula I, wherein Q is COOH followed by
conversion of the carboxyl group to the desired ester, alkali
metal salt or ammonium salt in accordance with conventional
procedures.
Some of the 2-substituted benzoic acids of Formula
II required as starting materials in the preparation o the
products of Formula I are known, for example as disclosed in
U~S. Patent 3,812,146, issued May 21, 1974, German
Offenlegungsschrift 2,423,534, published December 12, 1974,
Journal of the Chemical Society 107, 885 ~1915~ and Chemical
Abstracts 83, 77938h ~1975~ Those previously not known
can be prepared in accordance with the procedures described
for the preparation of the known compounds, e.g. as disclosed
in British Patent 1,435,179, The 2-substituted benzoic acids
are prepared by reacting a phthalic anhydride having Formula
VII
,i
-14-
' ~
'7U~
!
~ ``~
(Q)~ o
~ ..
Formula VII
with an appropriate indole of Formula VI, a pyrrole of
Formula VIII, a carbazole of Formula IX, an aniline of
Formula X or julolidine,
R8Rg
Formula VIII rFormula IX Formula X
and n in Formula VII having the meanings given above in
~ormula II and R, R7, R8 and Rg in Formulas VIII, IX and ;~
X having the previously given meanings, in the presence of
a Lewis acid, for example, aluminum chloride or zinc chloride,
with a diluent such as benzene, chlorobenzene or o-dichloro-
benzene at a temperature of about 0 to 100C. The reaction
is conveniently carried out in benzene in the presence of
aluminum chloride at about 0 to 25C. Alternatively, the
more reactive indoles ~Formula V~ can be reacted with the
phthalic anhydrides ~Formula VII) in the absence of a
Lewis acid by simply heating the reactants together in an
inert solvent at about 80 to 150C.
It will, of course, be appreciated that reaction
of an unsymmetrically substituted phthalic anhydride
(~ormula VII) with an indole, p~rrole, carbazole~ aniline
(Formula V, VIII, IX or X~ or julolidine can produce isomers
or a mixture of isomers of 2-2-CO-benzoic acids ~ormula II~. :
-15-
. . - . . : . . -
,. - . , . . - : . .
.. ~, ,, . . .
;. - ~ . . - : : . . '
,
For example, reactlon of a 3-substituted phthalic anhydride
tFormula VII where n i9 l and Q occupies position 31 with an
indole, pyrrole, carbazole, aniline or julolidine can produce
either a 3- or 6-~substituted 2-Z-CO-benzoic acid ~Formula
II where n i5 l and Q occupies either position 3 or position
6) or a mixture of these. Similarly, a 4-substituted phthalic
anhydride (Formula VII where n is l and Q occupies position
4) can produce either a 4- or a 5-substituted 2-Z-CO-benzoic
acid ~Formula II, where n is l and Q occupies position 4 or
position 5) or a mixture of these. The mixture of isomeric
2-Z-CO-benzoic acids can be separated by conventional means
such as fractional crystallization or ~hromatography. Alter-
natively, the isomeric mixtures can be reacted directly with
appropriate diarylamines of Formula III to produce isomeric
mixtures o~ phthalides of Formula I. Thus reaction of a
mixture of 3- and 6-substituted 2-Z-CO-benzoic acids ~Formula
II where n is l and Q occupies position 3 or 6) with a
diarylamine of Formula III will produce a mixture of 4- and
7-substituted phthalides ~ormula I where n is l and Q
occupies position 4 or 7~; and in like fashion a mixture of
4- and 5-substituted 2-Z-CO-benzoic acids (Formula II where
n is 1 and Q oacupies position 4 or 5~ will produce a mixture
of 5- and 6-substituted phthalides ~ormula I where n is l
and Q occupies position 5 or 6~. The mixtures of phthalides
can, if desired, be separated by conventional means or simply
and preferably used as mixtures in the practice of ~his inven-
tion.
The diarylamines of Formula III which are also
required as starting materials in the processes of the
0 invention belong to a well known class of compounds and
-16-
'7(~
are either commercially available or readily obtained byconventional 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 possess- -
ing excellent light stability, resistance to sublimation and
xerographic copiabilityO The compounds are thus highly
suitable for use as colorless precursors, that is color-
forming substances in pressure-sensitive carbonless duplica-
ting 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 ~ormula I wherein at least one of Yl and Y2 and at least
one of ~3 and Y4 are simultaneously di-lower-alkyl~mino
develop a brown to grape image when contacted with an acidic
medium and are accordingly of particular value as color
precursors. Moreover, the compounds of Formula I, in par-
ticular those wherein n is 1~ Q is COX and X is alkoxy ;:
having from 1 to 18 carbon atoms, or those where one or more .
of Yl, Y2, Y3 and Y4 are alkyl of 1 to 9 carbon atoms, have
enhanced solubility in common and inexpensive organic
solvents such as odorless mineral spirits, kerosene, vege-
tablè oils and the like; and those wherein n is 1, Q is COX
and X is OM in which M has the previously given meaning are
soluble in water and lower-alkanols thereby avoiding the
-17-
- - .
-~o~ v~
need for more expenslve, speclalized solvents such as poly-
halogenated or alk~lated 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,Sc Patent 3~649~649O 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~ ~or 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 ~rom 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 utilizedQ For example, the receiving sheet in a
manifold can alternatively be coated with the subject com- :
pounds and the acidic developing agent can be contained in
microcapsules applied to the reverse side of the top sheet
:. 30 in the manifold: or the receiving sheet can be coated with
-18-
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. Patent 3,539,375, that is, paper which
produce a colored image when contacted with a heated
stylus or heated t~pe, 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 ~ormula ~ 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 ~ormula 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 togetherD The master paper is then brought
~;~ 30 into contact with a succession of sheets of paper moistened
--19--
7V~
with a suitable spirit~reproduclng 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-
accepting substance, to give a yellow to red colored image
which duplicates the original typing or writing on the
master paper.
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 I
A. A mixture containing 24 g. of 2~ ethyl-2-methyl-
3-indolylcarbonyl)benzoic acid, 16.5 g~ of 4-ethoxy-N-phenyl-
aniline, 7 ml~ of pyridine and 70 ml. of acetic anhydride
was stirred 1 hrb at room temperature Dilution with 30 ml.
of 2-propanol and 100 mlO of ligroin produced no precipitate.
The reaction mixture was therefore poured into 10% aqueous
2n 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
25~3 g. of 3-~(4 ethoxyphenyl~ N-phenylamino~-3-~1-ethyl-2-
methyl-3-indolyl)phthalide, m,p~ 110-135C. Recrystalliza-
tion of an analytical sample from 2-propanol-ligroin provided
colorless crystals, m p. 161-163~C. A toluene solution of
the product contacted with acidic clay or phenolic resin
developed a yellow colored imageO
B. A mixture containing 7O86 g. ~0~02 mole) of 2- ~-
.,
-20-
, . ., ,, ., - ,
7(~
ethyl-2-methyl-3-indolylcarbor.yl)benzoic acid, 6.38 g. ~0.03
mole) of 4-ethoxy-N-phenylaniline and 12 ml~ of acetic anhydr-
ide was stirred overnight at room temperatur~ and then poured
into 200 ml. of 10% aqueous sodium hydroxide and 100 ml. of
toluene. After stirring 1 hr. the lay~r~ were separated.
The toluene layer was dried over anhydrou6 ~odium sulfatQ,
treated with decolorizing oarbon and filter~d The filtrate
was concentrated to 5Q ml. and slowly diluted with 900 ml.
of hexane. The precipitated product was collected, washed
with hexane and dried to give 6.0 g. of product essentially
identical to the product of part A above.
~XAMP~ 2
A. A mixture containing 3cl g. of 2~ ethyl-2-methyl-
3-indolylcarbonyl)benzoic acid, 5 g. of 3,3'-diethyl-5,5'-
di-nonyldiphenylamine, 10 ml. of acetic anhydride and 1 mlO
of pyridine was stirred 1 hr. at room temperature and then
poured into 10% aqueous sodium hydroxide and the product
extracted with toluene. The toluene extracts were dried
over anhydrous sodium sulfate and evaporated to dryness
under vacuum. Trituration of the residue with ligroin
and 2-propanol afforded 0.8 g. of 3-[N,N-bis-~3-ethyl-5-
nonylphenyl)amino-]3-~1-ethyl-2-methyl-3-indolyl)phthalide,
m.p. 76-90C. ~dec.). A toluene solution of the product
contacted with acidic clay or phenolic resin d~veloped a
red colored image.
Bo A mixture containing 6.2 g. of 2-~1-ethyl-2-meth-
yl-3-indolylcarbonyl)benzoic acid, 903 g. of 3,3'-diethyl-
5,5'-di-nonyldiphenylamine, 25 mlO of acetic anhydride and
1 g. of urea was stirred 2 hrs. at room temperature and then0 poured into 5% aqueous ammonium hydroxide and extracted
21
with toluene~ The organic extracts were dried over anhydrous
sodium sulfate and evapo~ated to dryness under vacuum. The
residue was triturated with cyclohexane to give 4.96 g. of
product essentially identical to the product of part A above.
EXAM
A, A stirred solution containing 48.0 9. ~0O250 mole)
of trimellitic anhydride and 45O0 g~ ~0.314 mole) of l-ethyl-
2-methylindole in 350 ml~ of 1,2-dichloroethane was heated 2
hrsO under refluxO The reaction mixture was allowed to cool
to room temperature and the precipitated solid was collected,
washed with 1~2-dichloroethane and dried to give 66.0 g.
of a mixture of 4- and 5 carboxy-2~ ethyl-2-methyl-3~
indolyl-carbonyl~benzoic acid, mOp~ 198-201C. This material
was used in subsequent reactions without further purification.
B~ A mixture containing 7O0 gO of 4-¢and 5-)carboxy-
2-~1-ethyl-2 methyl~3YindoLylcarbonyl~benzoic acid, 4.3 g. of
4-ethoxy-N-phenylaniline, 25 mlO of acetic anhydride and ~-
2 mlO of pyridine was stirred 2 hrs~ at room temperature.
Dilution with 20 mlO o 2-propanol and 100 ml. of ligroin
produced no precipitateO The mixture was therefore poured
into toluene and the product extracted with 5% aqueous
ammonia~ The aqueous alkaline extracts were neutralized with
3N hydrochloric acidO The resulting precipitate was collec-
ted, washed with water and dried to give 5.6 g. of 5-land
6-)carboxy-3-~NYt4-ethoxyphenyll-N-phenylamino~-3-~l-ethyl-
2-methyl-3-indolyljphthalide~ mOpO 145-148C.
CO To a stirred solution containing 2 g. of the above
acid in 30 ml~ o~ acetone was added 2 ml. t-octylamine. After
stirring 10 minutes the mixture was diluted with 200 ml. of
hexaneO The solvents were decanted and the residue was tri-
-22-
;"7~3~
turated with hexane to give 1 8 g~ of t-octylammlonium 3-~N-
(4-ethoxyphenyl)-N-phenylaminv~-3-~1-ethyl-2-methyl-3-indol-
yl)-phthalide-5-(and 6-)carboxylate, m~p 141C. ~dec.lO
EXAMPLE 4
To a re~luxing mixture containing 5.5 g. of 5-
(and 6-)car~oxy-3-[N-~4-ethoxyphenyl~-N phenylamino]-3~
ethyl-2-methyl-3~indolyl~phthalide, 3 g~ of potassium carb-
onate and 150 ml~ of acetone was added 4 g~ of dimethyl-
sulfate, A~ter heating 1 hr~ under reflux the mixture was
poured into 300 ml. of 5~ aqueous ammonia and extracted
with 400 mlO of tolueneO The toluene extracts were washed
with water and saturated aqueous sodium chloride and evap-
oratèd to dryness~ Trituration of the residue with ligroin
afforded 0~6 g of 5-~and 6-)methoxycarbonyl-3-[N-~4-ethoxy-
phenyl)-N-phenylaminoJ 3~ ethyl-2-methyl-3-indolyl)
phthalide as a tan solid~ m.p~ 79-84C (decO)O A toluene
solution of the product contacted with acidic clay or phenolic
resin developed a yellow orange colored image~
EXAMPLE 5
A mixture containing 3O0 g of 5-~and 6-~carboxy-
3-lN-(4-ethox~phenyl) N phenylamino~-3~ ethyl-2-methyl-3-
indolYl)phthalide/ 3 ml, of 25~ aqueous sodium hydroxide and
50 ml. of hexamethylphosphoramide was stirred 1 hr. at room
tem~erature and then treated with 3 ml of ethyl iodide.
After stirring at room temperature another 2 hrs. the reac-
tion mixture was poured into water and the product extracted
with toluene~ ~he toluene extracts were washed with water
and saturated aqueous ~odium chloride, dried over anhydrous
sodium sulfate and evaporated to dr~ness under vacuum. The
residue was triturated with ligroin to give 0 2 g. of 5-~and
23
. ' .
~V ~ ~ 7 V ~
6-)ethoxycarbonyl-3-[N-(4-ethoxyphenyll-N-phenylamino~-3-
~l-ethyl-2-me~hyl-3-indolyl)phthalide as a light brown
solid, m.p. 86-93C. (dec.~. A toluene solution of the
product contacted with acidic clay or phenolic resin
developed an orange colored image.
EXAMPLE 6
A mixture containing 5.5 g. of 5-~and 6-)carboxy-
3-[N-~4-ethoxyphenyl)-N-phenylamino]-3- ~-ethyl-2-methyl-3-
indolyl)phthalide, 8 ml. of n-octyl bromide, 6 g. of potassium
carbonate and 150 ml. of acetone was heated under reflux
overnight. The reaction mixture was then poured into 5%
aqueous ammonia and the product extracted with toluene. The
toluene extracts were washed with water and saturated aqueous
sodium chloride, dried over anhydrous sodium sulfate and
evaporated to dryness under reduced pressure. Excess n-octyl
bromide was removed from the residue by vacuum distillation
leaving as an oil 5-(and 6-)n-octyloxycarbonyl-3-[N-~4-ethoxy-
phenyl)-N-phenylamino~-3-ll-ethyl-2-methyl-3-indolyllphthal-
ide, A toluene solution of the product contacted with acidic
clay or phenolic resin developed an orange colored image.
EXAMPLE 7
To a mixture containing 3 . O g . of 5-~and 6-)carb-
oxy-3-[N-(4-ethoxyphenyl)-N-phenylamino]-3- ~-ethyl-2-methyl-
3-indolyl)phthalide, 3.0 g. of potassium carbonate and 100
ml. of N,N-dimethylformamide was added 2.0 g. of ~-bromotolu-
ene. After stirring 10 min. the reaction mixture was poured
into ice-water and the resulting precipitate was collected
and dissolved in acetone. The acetone solution was evap-
orated to dryne~s and the residue was triturated with ligroin
to give 5-(and 6-)benzyloxycarbonyl-3-~N-~4-ethoxyphenyl)-N-
-24-
' ' '
. . .
. .:, ~ '
,
".' ' ' ~,,~ ~ '
~ 7~
phenylamino~-3~ ethyl-2-methyl-3-indolyl~phthalide as a
pale orange solid, m~p~ 80 85C. A toluene solution of the
product contacted with acidic clay or phenolic resin developed
an orange-yellow colored image
EXAMPLE 8
.
A mixture containing 4.5 g~ of 3,4,5,6-tetrachloro-
2-(1-ethyl-2-methyl-3-indolylcarbonyl)benzoic acid, 1.0 ml.
of thionyl chloride and 200 ml. of 1,2-dichloroethane was
heated up to the reflux temperature, then cooled to 30C.
and treated with a solution containing 2.1 g. of 4-ethoxy-N-
phenylaniline in 20 ml. of 1,2-dichloroethane. After stirring
overnight at room temperature the reaction mixture was poured
into S~ 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 dry-
ness. The residue was triturated with cyclohexane to give
3.1 g. of 4,5,6,7-tetrachloro 3-[N-~4-ethoxyphenyl)-N-phenyl-
amino]-3-(1-ethyl-2-methyl-3-indolyl)phthalide, m.p. 182-
188~C. The infrared spectrum indicated this material to be
contaminated with unreacted 3,4,5,6-tetrachloro-2-~1-ethyl-
2-methyl-3-indolylcarbonyl)benzoic acid. Evaporating the
triturant to dryness and triturating the residue successively
from ligroin and acetone afforded 0.4 g. of the pure phthal-
ide, m.p. 193-194C. (dec ) A toluene solution of the pro-
duct contacted with acidic clay or phenolic resin developed
an orange colored image.
EXAMP~E 9
A. Following a procedure similar to that described
in Example lA but employing 3 1 g of 2-(1-ethyl-2-methyl-3-
indolylcarbonyl)benzoic acid and 1 8 g. of diphenylamine
-25-
.
.
7Sl~
there was obtained 0,78 g~ of 3~ ethyl-2-methyl-3-indolyl)-
3-(diphenylamino)phthalide, m~p. 125-130C. ~dec.). A tolu-
ene solution of the product contacted with acidic clay or
phenolic resin developed a yellow colored image.
B. A mixture containing 3,0 g~ of N,N-diphenylphthal-
amic acid, 1.6 g~ of 1-ethyl-2-methylindole, 7 ml. of acetic
anhydride and 0,5 mlO of pyridine was stirred several hours
at room temperature. The reaction mixture was filtered to
remove unreacted N,N-diphenylphthalamic acid. The filtrat~
was analyzed by thin layer chromatography and shown to contain
the desired 3-(1-ethyl-2-methyl-3-indolyl)-3-tdiphenylamino)-
phthalide identical to the product of part A above contami-
nated with some 3,3-bis-(1-ethyl-2-methyl-3-indolyllphthalide.
C. The reaction of part B above was carried out in the
ab~ence of pyridineO The reaction mixture was poured into
5% aqueous ammonia and the product extracted with toluene.
The toluene extract~ were washed with water and saturated
aqueou~ sodium chloride and evaporated to dryness. The
residue was e~sentially identical to the product of part
B above as indicated by thin layer chromatography.
EXAMPLE 10
~ . ..
A mixture containing 7.0 g. of 2- ~-ethyl-2-
methyl-3-indolylcarbonyl)-4-~and 5-)nitrobenzoic acid, 4.4
g. of 4-ethoxy-N-phenylaniline, 10 mlO of acetic anhydr-
ide and 2 ml. of pyridine was stirred 2 hrs. at roomtemperature. The reaction mixture was diluted with 10 ml.
of 2-propanol and 50 ml. of ligroin to precipitate 3.73 g.
of unreacted 2-(1-ethyl-2-methyl-3-indolylcarbonyl)-4-~and
5-)nitrobenzoic acid. The filtrate was poured into 5%
; 30 aqueous ammonia and the product extracted with toluene. The
-26-
'' ' ~ ' '
L(l 1~7V~
toluene extracts were wa~hed with water and ~aturated aqueou~
sodium chloride and evaporated to dryness under vacuum. The
resldue wa~ triturated successively with ligroin and 2-propanol
to glve 1.4 g. of 3-[N-(4-ethoxyphenyl)-N-phenylamino]-3-(1-
ethyl-2-methyl-3-indolyl)-5-(and 6-)nitrophthalide, m.p. 171-
173C. A toluene solution of the product contacted with acidic
clay or phenolic re~in developed an orange colored image.
EXAMPLE 11
To a stirred mixture containing 7.4 g. o~ phthalic
anhydride and 16.0 g. of 1-butyl-2-methylindole at 0-5C. wa~
added portionwi~e 13.3 g. o~ alum~num chloride. The mixture
was dlluted w~th 50 ml. o~ benzens and stirred overnight at
room temporature. The reaction mixture wa~ poured into 200
ml. o~ 5~ hydrochloric acid and the product extracted with
benzeno. The bonzone extract~ were shaken with dilute aqueous
pota~lum hydroxiao. The aqueous alkaline layer was separated,
cooled with loo and brought to p~ 4 with acetic acid. The
pr~cipitatod product wa~ collectod and driod to give 2-(1-
butyl-2-m~thyl-3-lndolylcarbonyl)~onsoic acid, m.p. 88-92C.
Thi~ intormodlat~ wa~ u~o~ ln tho praparation of th~ compound
of Exampl~ 17.
EXAMPTE 12
Followlng a proo-dur~ ~imllar to that d~crlb~d ln
Examplo 11 but mploying 7.4 g. of phthallc anhyarido and 16.0
g. of 1-n-octyl-2-mothylindols thoro wa~ obtainod 6.9 g. o~
2-~1-n-ootyl-2-mothyl-3-indolylcarbonyl)bonzoic acid, m.p.
121-123C. Thi~ intormediate W~B u~ed in the preparation o~
th~ co~pound o~ ExamplH 18.
EXAMPLE 13
`J 30 A mlxture contalning 5.0 g. of phthallc anhydrlde,
-27-
:10~
5.0 g. of 2,5-dimethylindole and 30 ml. of 1,2-dichloroethane
was heated under reflux for 20 hours. The reaction mixture
was cooled and the resulting precipitate was collected, wash-
ed with 1,2-dichloroethane and dried to give 3.8 g. of 2-(2,5-
dimethyl-3-indolylcarbonyl)benzoic acid, m.p. 198-200C.
(dec.). This intermediate was used in the preparation of the
compound of Example 19.
EXAMPLE 14
Following a procedure similar to that described in
Example 13 but employing lO g. of phthalic anhydride and lO
g. of 5-methoxy-2-methylindole there was obtained 4.6 g. of
2-(5-methoxy-2-methyl-3-indolylcarbonyl)benzoic acid, m.p.
202-203C. ~dec). This intermediate was used in the prepara-
tion of the compound of Example 20.
EXAMPLE 15
A. To a stirred mixture of 14.8 g. of phthalic -
anhydride, 16.2 g. of N-methylpyrrole and 50 ml. of chloro-
benzene at 0-5C. was added portionwise over 1.25 hrs. 39.0
g. of aluminum chloride. The temperature was maintained at
2-5C. throughout the addition. After diluting with an addi-
tional 20 ml. of chlorobenzene the reaction mixture was
allowed to stand over a weekend. Excess water was added
and the mixture was stirred. The solids were allowed to
settle and the supernatant water-chlorobenzene mix was de-
canted. The residue was taken up in 50 ml. of 5~ aqueous
sodium hydroxide. The resulting solution was filtered and the
filtrate was acidified to pH 3 with dilute hydrochloric acid.
The precipitated yellow solid was collected and dried to give
9.46 g. of 2-(N-methyl-2-(and 3-)pyrrolylcarbonyl)benzoic
, 30 acid, m.p. 165-167C.
-28-
-
,
~ '70 ~
B. Followlng a procedure similar to that described in
Example lA but employing 2.3 gO of 2-(N-methyl-2-(and 3-)-
pyrrolylcarbonyl)benzoic acid and 2.2 g. of 4-ethoxy-N-phonyl-
aniline there was obtained 1.6 g, of 3-~N-~4-ethoxyphenyl)-N-
phenylamino]-3-(N-methyl-2-(and 3-)pyrrolyl)phthalide, m.p.
115-134C. A toluene solution of the product contacted with
acidic clay or phenolic resin developed a yellow colored
image.
EXAM~E 16
Following a procedure similar to that described in
Example lA but employing 3.43 g. of 2-~9-ethyl-3-carbazolyl-
carbonyl)benzoic acid and 2.13 gO of 4-ethoxy-N-phenylaniline
there was obtained 0.73 g. of 3-[N-t4-ethoxyphenyl)-N-phenyl-
amino]-3-(9-ethyl-3-carbazolyl~phthalide, m.p. 75-85C. tdec.).
A toluene solution of the product contacted with acidic clay
or phenolic resin developed a yellow-orange colored image~
Following a procedure similar to that described in
Example lA but employing the appropriate 2-~3-indolyl~benzoic
acids of Formula II and substituted diphenylamines of Formula
III, the following compounds of Formula I, Examplos 17-29,
wherein n i8 0 and Z i8
R3
were obtained: -
ExAMæLE Rl/R2/ 3 l/ 2 3/ 4 mC P ~C )
.
17 n-C4Hg H H 54-92
HH3 H 4-C2H50 yellow-orange
18 n C8 17 H H ---
3Q CH3 H 4-C2H50 yellow-orange
~ H -29-
-:
7V8
EXAMPLE Rl/R2/R3 Yl/Y2 Y3/Y4 m p (C ) -
19 H H H 145-157
CH3 H 4-(CH3)2CHO yellow
5-CH3
H H H 68-75 (dec.)
CH3 H 4-C2H5O yellow-orange
5-CH3O
21 C2H5 H H 171-174
CH3 H 3-CH3 yellow
H
22 H H H 66-75 ~dec.)
HH3 H 4-C2H5O orange-yellow
23 H H H 103-125 tdec.)
CH3 H 4-tCH3)2cHO yellow
H
24 C2H5 H H 77-90
CH3 H 4-~CH3)2N brown
H
C2H5 H H 80-115
CH3 H 2-COOCH3 pink
H
26 C2H5 H H 76-85
CH3 4-(CH3)2N 4-(CH3)2N grape
H
27 C2H5 H H 93-116
CH3 H 4-CH3CONH yellow
H
28 C2H5 H H 105-121
CH3 C8 17 4-arylalkyl yellow
29 C2H5 H H 106-108
CH3 C8 17 C8 17 yellow
H
EXAMPLE 30
A solution containing 1.46 g. of the color former
of Example lB in 60 ml. of isopropyl~iphenyl and a solution
containing 5 g. of carboxymethylcellulose in 200 ml. of water
-30-
.
:~ , - . : - . .
.
,.- ,~
' ,~ ' .
were mixed and emulslfied by rapid stirrlng. The desired
particle size (S mlcron~) was checked by microscope. To
the emulsion was added a solutlon containing 15 g. of pig-
skin gelatin in 120 ml. of water. The pH was adjusted to 6.5
with 10~ aqueous sodlum hydroxide with rapid stirring, and
following the gradual addition of 670 ml. of water at 50C.
the pH was adjusted to 4.5 with 10% aqueous acetic acid with
continued rapid stirring. After 5 minutes the mixture was
cooled to 15C~, treated with 10 g. of 25~ aqueous glutaralde-
hyde and rapidly stirred for lS minutes. The resulting micro-
capsule dispersion was stirred more slowly overnight, diluted
with water to 1120 g. and 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 lB produced a yellow colored image on
both types of receiving sheets.
EXAMPLE 31
Following a procedure similar to that described
in Example 30 but substituting soy oil for isopropylbiphenyl,
the color former of Example 6 was microencapsulated and coat-
ed on a transfer sheet. The co~or former developed an orange
colored image on both types of receiving sheets.
EXAMPLE 32
A polyvinyl alcohol dispersion of the color former
of Example 7 was 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.
-31-
7V~3
of Bisphenol A, 18.~ g. of water, 42 g. of 10~ aqueous poly-
vinyl 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
110C. and 150C. produced a dark orange image.
EXAMPLE 33
A mixture containing 5.4 g. of 2-[4-Idimethylamino)-
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 com-
pletely dissolved and after 15 minutes an orange solid pre-
cipitated. 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 re-
moved an orange impurity) and dried to give 5.9 g. of 3-[4-
(dimethylamino)phenyl]-3-diphenylaminophthalide as a cream
solid, m.p. 188-190C. (dec.). A toluene solution of the
product contacted with acidic clay or phenolic resin developed
an orange colored image.
EXAMPLE 34
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 re-
-32-
: , . . .. .
~V~;Z70~
actants wa~ 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-ethoxy-
5 phenyl)-N-phenylamino]phthalide as a white solid, m.p. 214-
216C. (dec.) A toluene solution of the product contacted
with acidic clay or phenolic resin developed an orange color-
ed image.
EXAMPLE 35
A mixture containing 6.24 g. tO.02 mole) of 5-~di-
methylamino)-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 wa~ then diluted with 30 ml. of 2-propanol
15 and stirred an additional 0.5 hr. The solids were collected,
washed with ligroin and dried to give 9.3 g. of 6-(dimethyl-
amino)-3-[4-(dimethylamino)phenyl]-3-[N-(4-ethoxyphenyl)-N-
phenylamino]phthalide as a pale pink solid, m.p. 200-202C.
(dec.). A toluene solution of the product contacted with
20 acidic clay or phenolic resin developed an orange colored
image, which, on acidic clay, became green after exposure to
fluoroecent light.
EXAMPLE 36
A mixture containing 2.0 g. of 2-~2,4-bis-(dimeth-
25 ylamino)henzoyl]benzoic acid, 1.4 g. of 4-ethoxy-N-phenyl-
aniline, 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 1096 aqueous0 ammonia and the product was extracted with toluene. The
--33--
.
' .
~ 7 ~ ~
org~nlc extract~ were washed with water and ~aturated aqueous
sodium chloride and evaporated to dryness under vacuum. Tri-
turation of the residue with ligroin afforded 2.18 g. of
3-[2,4-bis-(dimethylamino)phenyl~-3-[N-~4-ethoxyphenyl)-N-phen-
ylamino]phthalide as a pale orange ~olid, m.p. 111-117C. (dec.).
A toluene solution of the product contacted with acidic clay
or phenolic resin developed an orange colored image.
ExAMæLE 37
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 35C. a ~olution containing 1.0 g. of 4-ethoxy-N-
phenyl-aniline 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 pour-
ed 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-phenylamino]phthalide as a gray solid, m.p. 112-121C. 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 con-
-34-
. ~.
. ~ : ; ~ .
'7Vl~
tacted with phenolic resin produced a pinkish-purple colored
image.
EXAMPLE 38
Following a procedure similar to that described in
Example 33 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. 143-147C. A toluene solution
of the product contacted with acidic clay or phenolic resin .
developed a red colored image.
EXAMPLE 39
.
Following a procedure similar to that described in
Example 36 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 3-14-~dimethylamino)phenyl~-
3-[N,N-bis-(4-octylphenyl)amino]phthalide, m.p. 158-169C. 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-
167C.
A 2 per cent (W/V) toluene solution of the product
of this example was mixed in varying proportions with a 2
per cent (W/V) toluene solution of the known color former
crystal violet lactone tCVL) and the resulting solution was
contacted with phenolic resin with the following results.
Cpd of Ex. 38 CVL
(2~ solution) (2~ solution) color of image produced
7 0 ml. 3.0 ml. brownish violet black
306.5 ml. 3.5 ml. brownish violet black
6.0 ml. 4.0 ml. violet black
5.0 ml. 5.0 ml. bluish black
-35-
7V~ :
EX~PLE 40
__ _
A. Following a procedure similar to that described in
Example 36 but employing 3.1 g. of 2-[4-(diethylamino)-2-meth-
ylbenzoyl~benzoic acid and 3.0 g. of 4,4'-bis(dimethylamino)-
diphenylamine there was obtained 2.55 g. of 3-[4-(diethylamino)-
2-methylphenyl~-3-[N-(4-dimethylaminophenyl)-N-(4-dimethyl-
aminophenyl)amino~phthalide, m.p. 67-83.5C. A toluene solu-
tion of the product contacted with acidic clay or phenolic
resin eveloped 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(dimethyl-
amino)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 dis-
solved in 200 ml. of DMF and slowly added to 1-1/2 liter of
water containing 1 g of Dabco with vigorous stirring. The
air dried product was weighed S.0 g. and was essentially
identical to the product of part A above.
C. In a procedure similar to that descri~ed in Example
37, 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 60C. to obtain a clear
solution. When the solution had cooled to 40C., 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 60C. for one hour, cooled and stirred overnight at
0 room temperature. The tary material which separated was
-36-
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filtered, washed and dissolved in dimethylformamide. Addition
to an excess of water yielded 4.2 g. o~ a light grape-colored
solid which developed a bl2ck color on silica gel.
EXAMPLE 41
A. To a stirred mixture containing 36 g. of 4-(and 5-)-
carboxy-2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid (pre-
pared from trimellitic anhydride and 3-(diethylamino)phenol,
60 ml. of diethyl sulfate and 450 ml. of ace~tone at 35C. 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
96C. The reaction mixture was maintained at 96C. 0.5 hour
then stirred at room temperature overnight, diluted with 100
ml. of water and brought to pH 4.0 with 3N hydrochloric acid.
The resulting red precipitate was collected, washed with water
and air-dried to give 37 g. of 4-~and 5-)carboxy-2-t4-diethyl-
amino-2-ethoxybenzoyl)benzoic acid, m.p. 63-96C. 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-di-
methylamino-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 3N hydrochloric
acid. The resulting precipitate was collected, washed with
water and dried to give 4.8 g. of 5-(and 6-)carboxy-3-[4-(di-
-37-
:, ' ' , ' '.:'
.
.
~ 7 ~ 8
ethylamino)-2-ethoxyphenyl]-3-~N-(4-dimethylaminophenyl)-N-
(4-diethylaminophenyl)amino]phthalide, m.p. 167-173C.
C. To a mixture contalning 4.0 g. of the above acid,
4.0 g. of potassium carbonate and 100 ml. of N,N-dimethyl-
formamide was added 4.0 g. of dimethyl sulfate. After stirringfor 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-dimethylaminophenyl)-
N-(4-diethylaminophenyl)amino]phthalide, m.p. 87-93C. A
toluene 401ution of the product contacted with acidic clay
or phenolic resin developed a brown-black-colored image.
Following procedures similar to those of Examples
33 to 36 but employing the appropriate 2-[(4-disubstituted-
amino)benzoyl]benzoic acids of Formula II and the appropriate-
ly substituted diphenylamine of Formula III the phthalides of
Formula I wherein Z is
R8RgN
Examples 42 to 78, were obtained.
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EXAMPLE 79
The color formers of Examples 34 and 42 were micro-
encapsulated as follows. A solution containing 1 g. of the
color former in 49 g. of isopropylbiphenyl and a solution con-
taining 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 micro~cope. 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 follow-
ing the gradual addition of 670 ml. of water with heating
(at 50C.) 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 90C. and stirrçd 15 minutes.
After cooling to room temperature the mixture was added to
473 g. of the abova microcapsule dispersion and the resulting
emulsion stirred vigorously for 2 minutes, and then coated on
white typewritsr 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 34 produced an
orange image on both types of receiving sheets, and the color
former of Example 42 produced a red image on both types of
receiving sheets.
EXAMPLE 80
Polyvinyl alcohol dispersions of the color formers
~ "
, . .
~ '7~ 8
of Examples 34, 35 and 42 were prepared by shaking 1 hour on
a paint shaker a mixture containing 2.0 g. o 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 dis-
persion of Bisphenol A was prepared by shaking a mixture con-
taining 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 dis-
persion of Bisphenol A. The coating mixture was applied (at
thicknesses of 0.003 in. and 0.0015 in.) to white mimeo paper
qheets and the sheets were dried at room temperature. Con-
tacting the coated sheets with a heated stylus at a tempera- .
ture between 110C. and 150C. produced a dark orange image
on the sheet coated with the color former of Example 34, a ~;
dark red image on the sheet coated with the color former of
Example 35 and a dark purple image on the sheet coated with
the color former of Example 42.
EXAMPLE 81
Following a procedure similar to that described in
Example 79 but substituting kerosene for isopropylbiphenyl
the color former of Example 66 was microencapsulated and coat-
ed on a transfer sheet. The color former developed a red image
on both type~ of receiving sheets.
EXAMPLE 82
Following a procedure similar to that described in
Example 79 but omitting the addition of starch to the micro-
capsule dispersion, the color former of Example 40 was micro-
encapsulated and coated on a tran~fer sheet. The color former
-46-
... ~ . .
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developed a black image on both types of receiving sheets.
The image formPd 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 micro-
capsule dispersion, a mixture containing 0.876 g. of the
color former of Example 39 and 0.584 g. of crystal violet
lactone was microencapsulated and coated on a transfer sheet.
~he mixture of color formers developed a blue to black image
on resin-coated receiving sheets.
It is contemplated that by following procedures
similar to tho~e described in the foregoing Examples but
employing the appropriate 2-(3-indolyl) or [(4-disubstituted-
amino)benzoyl]benzoic acids of Formula II and appropriately
substituted diphenylamines of Formula III the phthalides of
Formula I wherein Z is
~'
Examples 84-117, or wherein Z is
~ .
R8RgN ~ R7
Examples 118-149, will be obtained.
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