CA1069905A - Isoindoles - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Novel 1-imino-3-(4-thioxo-5-thiazolidinylidene)-isoindolines of the formula

Description

~ 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 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~ ~ , 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~

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 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

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.

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~ ~ .

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.

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 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.

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.

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.

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.

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.

.; 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 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~

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~

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~

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, 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~

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.

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.

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 ~:' ." , :~ .. , .. . , , : :

Claims (6)

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

1. A compound of the formula in which R, R1, R2 and R3 are the same or different hydro-gen, alkyl having one to three carbon atoms, alkoxy having one to three carbon atoms, halo, trifluoromethyl, phenyl or phenyl substituted by alkyl having one to three carbon atoms, alkoxy having one to three carbon atoms or halogen; and Z is oxygen or sulfur.

2. A compound according to claim 1, wherein Z
is oxygen.

3. 1-Imino-3-(2-oxo-4-thioxo-5-thiazolidinylidene)-isoindoline according to claim 1.

4. 1-Imino-3-(2,4-dithioxo-5-thiazolidinylidene)-isoindoline according to claim 1,

5. 1-Imino-4,5,6,7-tetrachloro-3-(2-oxo-4-thioxo-5-thiazolidinylidene)isoindoline according to claim 1.

6. A prooesss for preparing a compound according to claim 1, which comprises interacting in approximately equimolecular proportion a compound of the formula and a compound of the formula .