Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 6~95
~,~
The present application is a divisional o~
Application 233033 ~iled August 7, 1975.
The invention de~cribed herein relatas to 1~ ~ :
imino-3-~4-thioxo-5-thi~zolidinylidene)isoindolinec and
to processes for obtaining ~hem.
Ou~ above:applicatlon relate~ to novel metal ~
: chelate pi~meh~ of the ~ormula ~ .
R2 ~ R R ~ ~ 2
R3 ~ ~ ~ ~ 3
Nt
S~--C-~ S f~ S ~ ~
~ ~ lH ~ ~ Formula I
in whiah R, Rl, R2 and R3 are the~ same or di~ferent hydro ~:~
gen, alkyl having one to three carbon atoms, alkoxy :`
: havin~ one to three carbon atoms,~halo, trifluoromethyl~ : :
phenyl or phenyl substituted ~y alkyl having one to three
: carbon atoms:, alko~y~having one to three c~r~on atoms~
; : or~halogen; Me ~i5 copper, cobalt or nickel~ and Z is : .
~ Qxygen or ~ul~ur. Particularly preferred compound~are :
: those of Formu~à ~, wherein Me is nickel and Z i~ oxy~en~
: : The~compou~ds~of Formula I:, which are metal
chelate~ o~ l-imino-3-(4-thiox~-5-thiaëolidinylidene)-
i~indolines~ are water~insoluble plgments, generally
: ~ 20 ~ brown to green in shade.~ The~ are use~u~ ~or coloring
~atural ~iber~,::synthetic fiber-forming material~and .:~
: cellul~ic materlal such as threads~ sheetsr ~iber~,
.
., ; '~ .
.:
`' '''' , ' ',, " ~ ' , `', '`.','. ' `' ': :',' , ' ", " .,. ' ',; ' ', ' . :',' :
'~ ` ` ' , `, " ' ' .. ',' ';, ' ' . ','. ' ,. ' ' , `' ' :.' ', ' .,, ' '' `'~.' ' '. ' .' '
', ' .'` ' ' ', ' . . . ' ' ' ' ` ~, ." ,, ' ": ': :: ".: ' ` , ' ' ` ' ' ,; ' `, ,' '' ' " . ' .' ' ',
-2-
fllaments, textile fabrics and the liker as well a~ in
the manufacture of paper, varnishe~, inks, coatings and
plastics~ Becauqe the pigment~ of this invention have
good to excellent light-fastne~s, they are par~icularly
suitable for the prepar~tion of ccatings that are
designed for outdoor expo~ure such a~ automotive finishe~.
The present inventlon r~lates to novel-l-lmlno-
3-(4-thioxo-5-thlazolidinylldene)isolndolines represented
by the ~ormula NH
R2 r " Formula II
~3 S'~ ~ C=S
~C _ NH
"'
wherein R, Rl, R2 and R3 are the same or different hydrogen,
alkyl havlng one to three carbon at~ms r alkoxy having one
to three car~on atom~ halo, tri~luoromethyl~ phenyl or
phenyl substitu~ed by alkyl having one to three carbon
atom~; alkoxy having one to three car~on ~toms or halogen:
and Z i~ O or S~ Par~icularly prlsferred embodiment~ are
the l-imino~3-(2-oxo~4~thioxo~5~thiazolidinylldene)iso~
indolines~ that is, wherein Z i8 ~
~t will t ~ course, be understood by those
~killed in the art t~at b~th the compounds o~ th~s ~`~
lnvention (Formula ~I) and the ~inal product3 (Formula ~
may exi~t and may ~e repre~ented ln any one of se~eral `!
tautomeric ~orms~' Howe~er t ~tructural determinatibns
lead to the conclusion that the f~rms deplcted ~y the ~:
struc~ur~ rmula~ and a3 named are the most likely
under ordinary condi~ions.
The compounds of Formula ~ are chemical
intermediates u~eful for preparing c~mpounds of Formula
~ by lnteractiny appr~ximataly tw~ molecular equlvalent3
o~ a compound o~ the Formula ~I with approximately one
molecular equivalent of a sal~ of a divalent met~l~
:
, . ~ . - .. .. : ; , - ., , ,., . . .. . ~ .
699~5
--3--
Me, wherein R, Rl, R2; R3 and Z each have the same respec-
tive meaning~ given in relation to Formula I and Formula
~I above~
One can prepare the novel l imino-3-(4-thioxo-
5-thlazolidinylidene)isolndoles of Formula ~I by interactlng
in approxima~ely e~ulmolecular proportions a compound of
the formula ~ ~H
1 ~ ~ K - Formula I~I
R2~ ~ ,
R3 H
and a compound of the formula
f ~2-l=S
~ NH Formula ~V
whereln R, Rl, R2, R3 and Z each have the same re~pectlve
meanings given ln relation to Formula II above~
As u~ed throughoutr the term "halogen" includes
chlorlne r bromine, ~luorine and iodine,
As used herein, the term "alkyl having one to
thxee carbon atoms" includes saturated straight- or
branched-chaln aliphatic radicals ~epresented by methyl~
ethyl, propyl, and isopropyl,
Similarly, the term ~alkoxy having one ~o
three carbon atoms'~ include~ straighk- or branched-chain
aliphatic groups attached to the oxygen atom. Included
- in this term are methoxy, ethoxy~ propoxy and isopropoxy~
~ n the proce~s ~or preparing the l-imino-
3-~4-thioxo-5-thiazolldlnylldenP)isoindolines repre~ented
by Formula II~ one condenses the appropriate 1~3-dilmino-
isoindollne ~Formula ~I) through ~ne of the imino
m~leties with the loss of ammonia at the site o~ the
active methylene molety o~ the appropriate 4-thioxo~
thiazolidine (Fo~mula I~)~ The reaction proceeds ~mo~thly
at re~lux in a lower-aliphatic alcohol such as methanol
: 3
; ` : `;, ` ` `. , ~. :: .. `., ` . :
- . .. , ,`, .. ` . .. ... .... . . .. ..
` -`. . ... . .
,. . . ; .,: . ~ , ` . ~ , . .. . `. ` .
~ . ... . . . . , `.. . . . ``.
~L~699~D~
--4--
and is preferably carried out under an a~mosphere of
nitrogen.
Th~ 4-thioxothiazolidilles represented by
Formula IV, whlch are re~uire~ ~or ~he above reaction,
are gener~lly known in the art and are conviently prepared
by employing known chemical procedures, For example,
the known 2-oxo-4-thioxothiazolidlne (Formula IV where
z is o is obtained by the treatment of 2,4-dioxothiazol-
idine with phosphorous pentasulfide. The starting
material 2,4-dithioxothla201idlne (Formula IV where Z
is S) is prepared by interacting commercially available
4-oxo-2-thloxothia~olldlne wlth pho~phorous pentasulfide,
The 1 r 3-diiminol90indolineg 0~ Formul~ XI~ are
a known clas~ of c~mpounds readily o~t~ined ~y procedure.~
well--known in the prior art. For example, an appropriate
phthalonitrile is interacted wlth ammonia or with a
su~stance which gives off ammonia undex the reaction con-
ditions, ~or in~tance urea, to produce the correspondlng
1,3-diiminoisoindoline. For example, the following
1,3-diiminol~oindolines of Formula ~II are u~eful ~tarting
materials for preparing the l-imino-3-(4-thioxo-5-thia-
aolidinylidene)i~oindollnes represented by Formula II
above~
1,3-Dlminoisoindoline
5-Methyl-1,3-diiminolsoindoline
4,5-Dlmethyl-1,3-diiminoisoindoline
4~5~6,7-Tetxaethyl-1~3-diiminoisQindoline
4,5,7-Trimethyl-1,3-diimlnoisolndollne
4-Isopropyl-7-methyl-1,3-dilminolsolndoline
4 r 7-Dimethoxy~l r 3-diiminoisoindoline
4,5-Dipropyl-7-ethoxy-1~3-diiminoisoindoline
5~Ethoxy-1~3-diimlnoisolndoline
4,5,7-Trimethoxy-1,3-diiminoisoindoline
4,7-Diethoxy-1,3-diiminoisoindoline
4-Chloro-1,3-dliminoisoindoline
5-Bromo-1,3-dliminolsoindol~ne
5,6-Dichloro-1,3-dliminoisoindoline
., , ~
,: : ,,. ; ;, .
,, :, ~" ' :, ,. : , . . ' . ' ;
99~5
--5--
4,5,6,7-Tetrachloro-1,3-diiminoisoindoline
5,6-Dibromo-4,7-di~luoro~1,3-diimlnoisoindoline
5-Chloro-4,~,7-tri~luoro-1,3-diiminoisoindoline
5,6-Diiodo-4,7-dimethoxy-1,3-diimlnoisoindoline
4,7-Di~luoro-1,3-diiminol~oindoline
4,5,6,7-Tetrabromo-1,3-diiminoisoindollne
4-Phenyl-1,3-diiminolsoindoline
4-Methyl-5~6,7-triphenyl-1,3-diiminoisoindoline
7-Ethoxy-4-methyl-5-phenyl-1,3-diiminoisoindoline
4,5,6,7-Tetraphenyl-1,3-diimlnolsolndoline
5-(2,4,5-Trimethylphenyl~-1,3-diiminoisolndoline
4-(3,4-Dimethoxyphenylj-1,3-dllminoisoindoline
4~p-Chlorophenyl~ 3-diiminoisoindoline
4 ~ Brom~phenyl ~ -7-phenyl-1,3-diiminoisolndoldne
4,5~7~Trlphenyl-I,3-dliminolsoindoline
The structure~ of the compounds of this
invention were established~by the m~des o~ ~ynthesls~
elementary analysls o~ represent~ti~e samples and ~y
ultr~iolet, in~rared, nuclear magnetic re~onance and ~ass
spectral analyses. The cour~e of t~e reaction~ ~or the ~ -
preparation of the intermediates was ~ollowed ~y the use
o~ thin layer chromatography. -
The invention is illustrated by the following
examples, without howe~er, being limited thereto~ Melting
point9 are uncorrected unle~s otherwi~e lndicated, In
the follow~ng example~, the term "parts~ is in each
inskance used to indica~e part~ by weight and the
relationship of parts by weight to parts ~y volume is
the same as that o~ the kilogram to the liter.
30 ~ ~ EX~MPLE 1
To a stirred 301ution of 49~7 part~ of 2-oxo~
4-thioxothiazolidine~in 9~0 parts of methanol there wa~
added at 40~C. and under an atmo~phere of nitrogen
54.3 parts of powdered 1,3-diiminoisoindoline, ~nitially, ;;
35~ a thick slurry resulted. The reaction mixture was
stirred at room temperature ~or two hours during which
time tha mlxture ~radually thlnned. The mlxture was then
. .
, ~.
:' :
~LQ69~)5
heated at reflux for approxlmately two hours and after
cooling to 25C,, was filtered. ~he oollected solid
was washed with fresh methanol and dried in ~acuo at
50C~, to obtain l-lmino-3-(2-oxo-4-thioxo-5-thiazolidinyl-
5 idene)isoindoline as an orange powder melting at 267~8C.
(dec.)~
Anal.
Cal d for CllH7N3OS2: C, 50.56; H, 2,70: N, 16,08; ;
S, 24,54
Found: Cr 50.36; H~ 2~53~ N~ 16,25
S, 2~.38
This compound, which corresponds to Formula ~I wherein
R, Rl, R2 and ~3 are each hydrogen, was found on testing
in vitro by standard serlal dllution procedures to ba
bacterlostatic versus: Staphylococcus aureus Smith at a
minimal concentration of 62.5 parts per million:
Esherichia coli Vogel at 125 parts per million; Klebslella
pneumoniae 39645 at 125 parts per million: Proteus
mirabilis MGH-l at 125 parts per million: Pseudomonas
aeru ~nosa MGH-2 at 125 parts per m11ion. The compound
was also found to be fungistatic versus~ Trico~hyton
menta~rophytes 9129 at 62.5 parts per million:
Aspergillis ~ 16404 at 125 parts per million and
Candida alblcans 10231 at 125 parts per milllonO
EXAMPLE 2
A solution of 7.2 parts of 1,3-dilminoisoindoline
in 100 parts of methanol wa~ added to a solution o~ 7.2
parts of 2,4-dithioxo-thiazolidine in 75 parts o~ methanol
~nder an atmosphere of nitrogen. ~he mixture was stirred
a~ room temperature ~or 24 hours and the solid which
separated was collected by flltratlon, washed with
a small volume of fre~h methanol and drled in~~a6ùo at
sO~C~, to obtain l-imino-3-(2,4-dithioxo-5-thiazolidinyl-
idene)isoindoline as a red orange crystalline solid
which sintered at 268-270C~
Anal.
Cal'd or CllH7N3S3: C, 47.62; H, 2.55: N~ 15.15: 5, 34,66
`'',
, .. ;,,, , .. ~ .. ..
., , . . . ~
, . , , ~ ., . ,, ~, .
~@~6~
Found: C, 47.60; H, 2.58; N, 14.91; S, 34.64
This compound, which corresponds to Formula II wherein
R, Rl, R2 and R3 are each hydrogen and Z is sulfur; was
found on testing in vitro by standard serial dilution :-
procedures to be bacteriostatic versus~ hi~
a reus Smith at a minimal concentration of 125 parts
per million; Escherichla coli Vogel at greater than
125 parts per million; Klebsiella pneumoniae 39645 at 125
parts per million; P~oteu~ mirabilis MGH-l at greater
than 125 parts per million; Pseudomonas aeruginosa MGH-2
at g~eater than 125 parts per million, The compound
was also found to be fungistatic versus: Trlcophyton
mentagrophytes 9129 at greater than 250 parts per million;
Aspergillls ~ 16404 at greater than 125 parts per
million and Candida albicans 10231 at greater than 125
parts ~er million.
EXAMPLE 3
Proceeding ln a manner similar to that des-
cribed above in Example 1 but ~ubst~tuting an equivalent
am~unt of 5-methyl-1,3-dllmlnols~indoline for the 1~3
diiminolsoindoline used in that ~-xamplep there is obtained
l-imino-5-methyl-3-(2-oxo-4-thio:Ko-5-thiazolidinylidene)-
isoindoline~ ~ .
EXAMPLE 4
Using a procedure similar to that described in
Example 2 but sub~ituting 4,5-dimethyl-1,3-dliminoiso- :
indoline for the 1,3-diiminolsolndoline used in that
example, there i9 obtained as the product 1-imino-4,5
dlmethyl-3-(2,4-dithl~xo-5-thiazolldinylidene~isoindoline.
EXAMPLE 5
When an e~uivalent amount of 4,5,6,7-tetraethyl-
1,3-diiminoi30indoline i8 ~ubskituted for the 1,3-dlimino- :
isoindoline in the procedure descri~ed in Example 1, `~
there ls obtained as the product 1-imino-4,5,6,7-tetra-
et~yl-3-(2-oxo-4-thi~xo-5-thlazolidinylidene)isolndollne~
~ . . .. .. . .
~)699~5
--8--
EXAMPLE ~
Following the procedure described in Example
2, but using equivalent amounts of 4,5,7-trimethyl~1,3-
diiminoisoindoline in place of 1,3-diiminolsoindoline, :~
there is obtained as the product, 1-imino-4,5,7-~rl-
methyl 3-(2,4-dithioxo-5-thiazolidinylidene)isoindoline~
EXAM ~-~
Proceeding in a manner similar to that de~cribed
above, in Example 2, but substituting an equlvalent amount
of 4-isopr~pyl-7-methyl-1,3-diiminoisoindoline for the
1,3-diiminols~indoline used ln that example, there 1~ i
obtained l-imino-4-is~propyl-7-methyl-3-(2,4-dithioxo-
5-thia~olidinylidene)i~oindoline.
EXAMPLE 8
Usin~ a procedure simllar to that described in ~:
Example 2, but substitutlng 4,7-dimethoxy-1,3-diiminoi~o~
indoline ~or 1,3-diimlnolsoindoline, there i3 o~tained
a~ the product l-imino-4,7-dimethoxy-3-~2,4-dithioxo-5-
thiazolidinylidene)isoindoline,
EXAMPLE ~
When an equivalent amount of 4,5-dipropyl-7- :
ethoxy~l,3-diiminois~indoline i~ substituted f~r 1 r 3
dilmlnoisoindoline in the procedure descri~ed in Example
1, there ls obtained as ~he product 1-lmin~-4,5-dipropyl-
7-ethoxy-3-(2-oxo-4-thloxo-5-thiazolidinylidene)i~oindoline.
EXAMPLE 10
Foll~wing the proc~dure descxibed in Example 2,
but using an equivalent amount of 5-eth~xy-1,3-diiminoiso~ ;
indoline in place of 1,3-diimlnoisoindoline, there is
obtalned as the product l-lmino 5 ethoxy-3-(2,4~1thioxo-
5 thlazolindlnylidene)lsoindoline.
EXAMPLE 11
Proceeding ln a manner similar to that descrlbed :~
above ln Example 1, but substituting an e~ui~alent amount
of 4,5~7-trimethoxy-1~3-dilminoisoindo}ine for the
1,3-diimlnolsoindoline u~ed ln that example~ there i~ :
obtained l-imino-4,5,7-trimethoxy-3-(2-oxo-4-thioxo-5-
.. . . ~ ., . -.
..... . . . .
~699~
g
thiazolidinylidene)isoindollne.
EXAMPLE 12
Using a procedure similar to that de~cribed in :~
Example 2, but ~ubstituting 4,7-diethoxy-1,3-diiminoi~o- :
indoline for ~,3-diiminoisoindoline, there is obtained
as the product l-imino~4,7-diethoxy-3-(2,4-dithioxo-5-
thiazolidinylidene)l~oindollne~
EXAMP~E 13
Proceedlng in a manner similar to that dewribed
above in Example 1, but ~ubstituting an equivalent amount
of 4~chl~ro-1,3-d1imlnoisolndoline ~or the 1,3-dilmino-
isoindoline used in that example, there is obtained 1-
imino-4-chloro~3-~2-oxo-4-thioxo-4-thiazolidinylidene)-
isoindoline.
XAMPLE 14
.; When an equivalent amount of 5-bromo-1 r3~
diiminoisolndoline is ~ub3tituted for 1,3-diiminolæoindoline
in the procedure ~escribed ln Example 2, there is obtained
a~ the product l-~mino~5-~romo-3-~2,4~dithioxo-5~thlazol-
idinylidene]lsoindoline~
EXAMP~E~15
Followlng the procedure! described in Example 1,
but us~ng an equiualeht amount o~ 5,6-dichloro~1,3-diimino~
isoindollne in place of 1 t 3-dlimlnoisolndoline fi there 1~
obtained a~ the produck 1-iminG-5,6-dichloro-3-~2-oxo- ;
4-thloxo-5-thlazolidinylidene)i~oindoline.
E~AMPLE 16
Proceeding in a manner similar to that de~crlbed
above in Example 2, but sub~tituting an equivalent amount
o~ 4,5,6,7-tetrachloro-1,3-diiminolsoindoline for 1,3-
diiminol~indoline used in that example, there is obtained
l-imino~4,5,6 r 7~ketrachloro-3-t2,4-dithioxo-5-thiazol-
idinylidene)l~oindoline
EXAMPLE 17
3S U~ing a procedure ~imilar to that de~crl~ed
in Example 1, but su~stitutl~y 5,6-di~romo-4~7-dlfluoro
1,3~diiminoi~oind~1ine ~or 1,3-diimlnolsoindollne~ there
9 .
, . .
, . ,. ~ ,, , , ,, . ., , . .,.. . , .. ,. ~ , ...... . . . . .
-, . , ,.. ", . , .. . , .... ,.. ' .. .
:' . :'' ' ',. : ',' ',' ': : .:: . ::,, . .. '': :~, ': ! :': ' '
1~6~
--10--
is obtained as the product l-lmino-5,6-dibromo-4,7-di-
~luoro-3-(2-oxo-4-thi~xo-5-thiazolidinylidene)isoindoline~
EX~MPLE 18
When an equivalent amount of 5-chloro-4,6,7-
trlfluoro-1,3-diiminoisoindoline is substituted for :~
1,3-diiminolso~ndollne in the procedure described in
Examp~e 1, there i8 obtained as the product l~imino-~-
~hloro-4,6,7-trifluoro-3-(2-oxo-4-thioxo-5-thiazolidinyl-
iden~ soindoline.
EX~MPLE 19
-
Following the procedure described in Example
2, but using equivalent amounts of 5,6-diiodo-4,7-
dimethoxy-1,3-diiminoisoindoline ln place of 1,3-diimino-
isoindoline, there i~ obtained as the product l-imino-
5,6-dii~.d~-4,7 dimethoxy-3-(2,4-dithioxo-5-thiazolindinyl
iden~i~soi~doi~ne~
E~MPhE 20 :
_
Proceeding in a manner similar to that described ::
above in Example 2, ~ut substituting ah e~ui~alent amount
of 4,7-di~luoro-1,3~dllminoisolndoline ~or 1,3-diiminoiso~
indoline ~sed in that example, there is obtained l~imlno- ::
4,7-difluoro-3-(2,4-dithioxo-5-thiazollndinylidene)isoln- ~;
d~line~
EXAMPLE 21
Using a procedure similar to that de~cribed in
Example 1, but substitutlng 4,5,6,7-tetrabromo-1~3-di- ~:
iminoisoindoline f~ 1 r 3-diimln~isoindoline~ there is
obtained as the prod~ct l-imlno~4,5,6,7-tetrabromo-3-(2- ::
oxo~4-thiaxo~ th~azolidinylidene)isoindoline~
EXAMPLE 22
When an equ~valent am~unt of 4-phenyl-1,3-
di~minQiSQlIldOline i9 sub~tltuted for 1,3-dllminoisoindoline
in the proce~ure described in Example 1~ there is obtalned
a~ the product l-imino-4 phenyl~3-(2-oxo-4-thioxo-5-
thiazolidinylidene)isoindoline,
EXAMPLE 23
Followdng the procedure described in Example 2,
~ Q
6~39~5
but using equivalent amounts of 4-methyl~5,6,7-triphenyl-
1,3-diimlnoisoindollne in place ~ 1,3-diiminoisoindoline,
there is obtained as the product l-imino-4-methyl-5,6,7-
triphenyl~3-(2,4-dithl~xo-5~thiazolindinylidene)isoindoline.
EX~MPLE 24'
Proceeding in a manner similar to that described
abo~e in Example 1, but substltuting an e~uivalent amoun~
o 7-ethoxy-4-methyl-5-phenyl-1,3-diiminoisoindoline for
1,3-diiminoisoindoline used in that example r t here is
o~tained 1-imino-7~ethoxy-4~methyl-S-~henyl-3-(2-oxo-4-
thioxo-5-thiazoli~inylidene)isoindoline.
EX~MPLE 25
Using a pr~cedure similar to that descrlbe~ in
Example 1, but substituting 4,5 r 6 r 7-tetraphenyl-1,3-
diiminoi~oindoline ~or 1,3-dllminois~indol~ne, t~erë i~
obtained as the proi~c~ l-imlno-4,5,6~7-tetraphenyl-3-
(2~ 4-thio~5-thiazQlldinylidane)isoindoline~
EXAMPLF 26
When an equl~alent amount ~f 5-(2,4,5-trimethyl~
phenyl)-1,3-dliminoisoindoline is sub~tituted ~or I,3-di~
iminoi~oindaline in the procedure descrlbed in Example
1, there is obtained a~ the product l~imino-5-(2,4,5-
trimethylphenyl)-3-(2-oxo-4-thi~xo-5-thiazolidlnylidene~-
isoindGline.
EXAMPLE 27
Following the pr~cedure descrlbed in Example
2, but using an equi~alent amount o~ 4-(3,4-dimethoxy-
phenyl)-1,3-dilmin~i~oindoline in place o~ 1,3-diimlni-
isoindoline, th~ is obtalned as the product l-lmino-
4-(3,4-dimethoxyphenyl~-3-(2,4-dithioxo-5~ azolldlnyl_
idene~ nd~line~
EXAMPLE_28
Using a pr~cedure similar to tha~ described
in Example 2, but substituting 4-(p-chlorophenyl)_1,3-
diiminoi~olnd~lin~ ~or 1j3-diimin~isoind~line, there is
obtalned a3 the product l~imino-4-(p-chl~rophenyl)-3-
~2,4-dithiox~-5-thla~olidinylidene)isoindoline,
.
1~6~
-12~
~EXAMPLE 29
-
Proceeding in a manner slmilar to that des-
cri~ed above in Example 1, but substituting an equivalent
amount of 4-(p-bromophenyl)-7-phenyl-1,3-dilminoisoindoline
for 1,3-diiminoisoindoline use~ in that example,:there
is obtained l-imino-4-(p~bromophenyl)~7-phenyl-3-(2-oxo-
4-thioxo-5-thiazolidlnylidene)isolndoline.
EXAMPLE 30
Following the procedure described in Example 2,
but using an equivalent amount of 4,5,7-trlphenyl-1~3-
dilminoisoindoline in place o~ 1,3-diiminoi~oindoline,
there is ohtained as the product l-imino-4~5~7-triphenyl-
3-(2,4-dithioxo-5-thiazolidlnylidene)isoindoline.
EXAMP~E 31
To a mixture of 14,1 parts of 4,5,6,7-tetra- -
chloro-1,3-diiminoi~oindoline, 6~7 parts of 2-oxo-4- ;
thl~x~thiazolldlne and 10~0 parts o~ ~re~hly prepared,
grou~d anhydrous sodium acetate, there wa~ added 157
parts o~ glacial acetlc acid~ ~he resulting slurry :-
was heated at re~lux under a continuous ~low of nitrogen
for approximately one hour. The reaction solution was
cooled to room temperature r sealled under an atmo~phere
of nitrogen and set aside for about sixty hour~ The i:
sol~d which separated on standlng was collected by
~iltratl~n at rQOm temperature, ~ashed fi~e tlmes, each
with 21.0 parts glacial acetic acid and then a total
o~ ei~ht times, each with 20~0 parts distilled water~
The water-wet pulp wa~ stlrred with 90~0 parts o~ 28
: per cent aqueou~ ammonia, ~lltered to remove any in-
~olubl~s and the product reprecipitated by adjusting
the pH of the solution t~ 6.0 by the addition of 99.2
parts of 6N hydrochloric acid qolution. The solld
was collected by ~iltratlon, washed with 3,000 part~ ~f
water and a~r dried at 60C., to obtaln l-imlno~4r5r6~7~
tetrachloro~3-(2-oxo~4-thioxo-5-thiazolldinylidene~iso- ~:
indoline as a brown powder ~hich did not melt up to 340C.
~2
~:'
." , :~ .. , .. . , , : :
