CA1054607A - Iminoisoindolinone pigments - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Iminoisoindolinone pigments of the formula

Description

The present invention relates to new iminoisoindolin~ne pigments of ~he formula -X2 ~ X2 wherein Xl, X2, X3 and X4 each denote H atoms or halogen atoms~ one of the sub-stituents Xl and X4 representing a halogen atom and not more than one of the -substituents X2 and X3 denoti~ng a halogen atom, with the proviso that X3 must not be a chlorine atom if Xl denotes a H atom; or wherein X2 denotes a cyano or carboxylic acid ester group, and Xl, X3 and X4 all denote H atoms, and Yl ;
and Y2 denote H atoms or chlorine atoms or alkyl or alkoxy groups containing `:
1 - 4 C atoms.
Pigments of particular interest are those of the formula ~I) wherein the substituents Xl - X4 denote H atoms or chlorine atoms, and one of the sub-stituents Xl and X4 represents a chlorine atom a~d not more than one of the sub- ~ -i stituents X2 and X3 denotes a chlo~ine atom, and X3 must not be a chlorine atom if Xl represents a H atom.
Particularl~ preferred p~gments are those of the formula (I) wherein Xl - X4 have the meaning indicated above~ and Yl and Y2 denote H atoms.~-~
The new iminoisoindolinone pigments are obtained if an isoindolinone of the formula Xl ;~
X3 ~ ~ NH (111) X~, O .. :, ', wherein V denotes a group of the formula :~ ' :''' ,. . ,- , . :
.;

1 1054~()7 ~< J4 :, ~ .
: wherein Y4 represents an imino or thio group and Y3 denotes a halogen atom, :
an alkoxy group or a tertiary amino group, is eondensed, in a molar ratio of - ~

2:1, with a diamine of the formula .~ ~-., Yl ' ~ ~ ' "' ' H2N --Y~ NH2 (V) ; 2 : ~:
The starting material is pre~erably an isoindolinone of the formula (III~ wherein the substituents Xl X4 denote H atoms or chlorine atoms, and 'A'` ~' ~''' one of the substituents Xl and X4 represents a chlorine atom and not more than `.
one of the substituents X2 and X3 denotes a halogen atom and X3 denotes a H . -:10 atom if Xl represents a H atom. . ;~
The isoindolinones which are used as the starting .
.~ . : . ~ . ...
,.~ ~ '' ,` ~'.

:,

3~

:
.,., . ~ . :

~ .

,:. ~ , , , , , , , ~ . ..

~ S~ 7 ma-ter.ial, co~ n, :n the 2-posi-tion, an imino or th.io group, 2 halogen atoms, 2 tertiary amino groups, for example piperidino or morpholino groups, or, par-ticularly, 2 alkoxy groups contai~ing 1 - 4 C atoms, preferably methoxy groups.
The isoindolinones therefore preferably correspond to . .
the formula :.. , ~ .
RO OR

1 (VI) ~ ;

. . 4 ~ wherein Xl - X4 have the meaning indicated above and R denotes : an alkyl radical having 1 - 4 C a~toms, preferably a methyl . ~ ;
;., group. "; .
:~ , The 3,3-dialkoxyisoindolinones are obtained by a known process by reacting the corresponding o-cyano-benzoic acid ; `
; alkyl es-ter of ~he formula '' i Xl ' ,, .~ X2~,CN .
3 ~ COOAlky~ (VII) f ~
: ~ :
with an alkali metal alcoholate solution in a lo~er alcohol.
As a rule it is not necessary to isolate the isoindolinone .
thus obtained3 in most cases it can be employed directly for -i the reaction ~ith the diamine The 3-iminoisoindolinones are obtained by a known ~ 4 ~
:1 .
:1 . . . ' process by reacting the corresponding o-cyano-benzoic acid alkyl ester wi~h ammonia.
The o-cyanobenzoic acid esters of the for~ula (VII) ~ .;
are obtained, in turn, from ~he anthranilic acid es~ers of the .~ formula , :.
.-:. v ::

2 ~ N 2 ,,`,, '. ~
; X4 ~`~
by ~he Sandmeyer reaetion, by diazotisation and reaction with ~
potassium cyanide. ~.--~ The following may be mentioned as examples of o-cyano- ~ `~
:;, benzoic acid esters: 6-chloro-2-cyano-benzoic acid methyl ~ ~ 10 ester, 4-chloro-2-cyano-benzoic acid methyl ester, 6-fluoro~
,.3 2-cyano_benzoic acid m~thyl ester, 5-iodo-2-cyano-benzoic ;~ acid methyl estar, 3,4-dichloro-2-cyano-benzoic acid methyl .~ ester, 3,5-dichloro-2 cyano-benzoic acid me~hyl ester, 4,6-dichloro-2-cyano-benzoic acid me~hyl ester, 2,4-dicyano-benzoic acid methyl ester and 2-cyano-terephthalic acid dimethyl ester. . ~:
".,, '~'~
`', ~ ~ , .'.'.' ~ ~ .

"
', `"':"

~ ~5- ~ .

~.~S~7 ::

~ p-Phenyl~nediamine is a particularly preferred diamin~
:~ starting material.
`` ~e following diamines may be mentioned as examples:
1,4-diaminobenzene, 1,3-diaminobenzene, 1,3-diamino-4-mqthyl-: henzene~ 1,3-diamino-4-me~hoxybenzene, 1,3-cliamino-2-methyl-benzene~ 1,3-diamino-2JS-dichlorobenzene, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2,5-dimethylbenzene~ 1j4-diamino-2-methoxybenzene, 1,4- -~
diamino-2,5-dimethoxybenzene, 1,4-diamino-2-chloro-5-methyl- ~ `
benzene, 1,4-diamino-2-chloro-5-methoxybenzene, 1,4-diamino ~ : ;
"'~", 2-chloro-5-~thoxybenzene~ 1~4-diamino-2~5-diethoxybenzene~
,~ 4,4'-cliamino-diphenyl sulphide, 4,4'-diamino-benzoylanlline, ~ -.
~:i 4,4i-diamino-2-ethoxy-benzoylanilîne, 3,3'-diamino-2,2'- .
; dimethoxy-benzoylaniline, 4,4'-diamino-diphenylurea, 4,4'-~ ", . .
diamino-3,3'-dimethoxy-diphenylurea, 4,4'-diaminostilbene, . 4,4'-diamino-azobenzene, 2-methyl-4,4'-diaminoazobenzene, 2~methoxy-4,4'-diaminoazobenzene, 2,5-dimethyl-4,4'-diamino-azobenzene, 2,5,2'-trimethyl-4,4'-diaminoazobenzene, 3- . ;
:
., 20 methyl-2'-methoxy-4,4'-cliaminoazobenzene, 3-chloro-2'-methyl-., ` .~ ~ .
~:j 4,4'-diaminoa%obenzene, 4-chloro-3,4'-diaminoazobenzene, 2- . ~: ~

"-,: ,;~ , , ~ :

~,:
... ,; ~- ., ,- ., ::: - 6 -37 ~ ~
- . ., ~;~ chloro-4,3'-diaminoazobanzene, 2-methyl-4,3'-diaminoazoben-zene, 2-methoxy-4,3'-diaminoazobenzene, 2,4-diaminoazobenzene, 5-methoxy-2,4-diaminoazobenzene, 2,4-diamino-3',5'-dimethyl-.... . .
~` 4'~acetylaminoazobenzene, 2,4-diamino-5-methoxy-3',5'-di- ~
,~ .
~ chloro-4'-acetyla~inoazobenzene, 4,4'-diamino-phenyl-1-azo- ~
". ~ I
~...... i naphthalene-l', 4,4'-diaminobenzophenone, 4,4'-diaminodi-phenyl ether, 4,4'-diaminodiphenylmethane, 2,Z'-diaminodi- ;
benzyl, 1,4-diaminonaphthalene and 1,5-dia~inonaphthalene. -~
s The condensation takes place in part even in the cold, but if appropriate by warming the intimately mixed reac-~ tants, and particularly advantageously in ~he presence of -~i inert organic solvsnts, that is to say organic solvents which -~`~lj do not take part in the reaction.
~'~'b~ If 3-imino-isoindolin-1-ones, 3-thio-isoindolin-1-onesr or 3,3-bis-~er~.-amino-isoindolin-1-ones or alkali metal sal~s of 3,3-dialkoxyisoindol m l-ones are used as starting ~i ~aterials, it is adva~tageous to use water-miscible org2nic `~ ~ solvents, for example lower aliphatic alcohols, such as lower ~i alkanols, for exampla methanol, isopropanol or butanol, lower " 1 :: . ~ .
~: 20 cyclic ethers, such as dioxane or e~hylene glycol monomethyl ether, or lower aliphatic ketones, such as acetone. The ;l condensation takes placs in this case even at relativelylow temperatures. It is advantageous to carry ouS the reac~ion in ~he presence of base-binding agents; examples of these which should be ~entioned are lower fatty acids, which then simultaneously act as the solvent, particularly acetic acid.

. - 7 - ~ -.

~S~7 If 313-dihalogeno-isoindolin-l-ones are used, organic -~
solvents whioh are free from hydroxyl ~roupsJ such as hydro-carbons, for example aromatic hydrocarbons, such as benzene, toluene, xylene, tetrahydronaphthalene or diphenyl, or cyclo aliphatic hydrocarbons, for example cyclohexane, and also ~-halogena~ed hydrocarbons, such as aliphatic halogenated hydro-carbons, for example carbon ~etrachloride or tetrachloro ~ i ethylene, or aromatic halogenated hydrocarbons, such as ~-chlorobenzene or dichlorobenzenes and trichlorobenzenes, and 0 al50 aromatic nitro-hydrocarbons~ such as nitroben~sne, ethers, in particular aliphatic e~hers, such as dibutyl ether, aroma-~-1 tic ethers, such as diphenyl ether, or cyclic ethers, such as dioxane, and also ketones, such as acetone, or esters, particularly esters of lower fatty acids with lower alkanols, -~
such as ethyl aceta~e, in the presencle of acid-binding agents, ~; ;
are preferred. ~ ~
~ ~ , The new pigment is precipitlated from the reaction medium directly after its formation. It can be used direct, as a raw pigmentJ for csrtain purposes; it is advantageous, 1 20 however, be~ore its application, to condi*ion it by methods ,:i which are in themselves known, for example by extraction with organîc solvents or by grinding with grinding auxiliaries which can aterwards be removed, for example salts or, in ;~ particular, hexachloroethane, or by alkaline reprecipitation. o~
The purity, tinctorial strength and ~ransparency can be ~urther improved in this manner.
The new colorants are valuable pigments whieh can be . ,~ . . .

':'', `~': '~
~: `. , ;~
~:
:. :

'' , .'.. . . . . . . . .... . . .
.. . ..

~q~5~7 .
.. . .
used in a finely divided for~ for pigmenting high-molecular organic material, for exa~ple cellulose ethers and cellulose .: . .
esters, such as ethylcellulose, acetylcellulose or nitro-- cellulose, polyamides, polyurethanes or polyesters, natural resins or synthetic resins, for example aminoplasts, particularly ther~oplastic and ~hermosetting acrylic resins, ~ urea-formaldehyde and melamine-for~aldehyde resins, and also ; alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride, polyethylene, poly-,,, :
~ 10 propylene, polyacrylonitrile and polyacrylic acid ssters, ,. ~
rubber, cas~in, silicone and silicone resins, individually or as mixtures. It is immaterial here whether ~he high-mole-~ ...... , cular compo~nds ~entioned are present as plastic compositions or as melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending Olt the end use, it `
proves advantageous to use the new pil~ents as toners or in ., the fornt of preparations. The new pi~tents are distinguished ~ ir `i by their high level of fastness, and particularly by out-,-~ standing ~astness to light, migration and wea~hering. The ;^~
iminoisoindolinones derived fro~ p-phenyl~nediamin~ are distinguished by valuable medium yellow shades which have ~1~ hitherto only been obtained with iminoisoindolinones formed from complicated diamines.
,.~ .::
Example 1 5.1 g of 6-chloro-2-cyanobenzoic acid methyl ester are ~ introduced into a solution of 1.35 g of sodiu~ methylate in ; 40 ml of methanol. The mixture is stirred for 30 minutes at , :, :

. - ' ', '' ' ' ', .. ' ~ ,: , '. : ' ~
. .

:; `
~05~
room temperatuJ~e~ a clear solution ~eing formed. 1.35 g of p-phenylenediamine are now added and the mixture is stirred ^ for a further 15 hours a-t room temperature. The yellow sodium salt of the colorant separa-tes ou-t. The mixture is diluted with 100 m] ol o-dichlorobenzene and acidified ~ri-th 5 ml of glacial ace-tic acid. The reaction mixture is now - warmed to 150C, whilst stirring well and distilling o~f the ` methanol. The temperature i5 kept at 150Gfor 2 hours; the ;~ mixture is -then allowed to cool to 100Cand is filtered.
, The moist pigment is washed well with methanol, acetone and water and is dried at 100C in a vacuum oven. This gives ,'` 1, .

4.8 g of a yellow pigment which corresponds to the formula The pigment can be employed for colouring lacquers ~ ;
and plastics, direct or in a comminuted form, for example `~
after grinding with a grinding auxiliary which can afterwards . .
-s~ be removed, such as, for example, sodium ch]oride. Fairly `~
deep colourings in pure, yellow colour shades which are `
distinguished by good fastness to light and migra-tion 7 are ,~ achieved in this way. ;
;~ 6-Chloro-2-cyanobenzoic acid me-thyl ester can be pre-pared, for example, from 6-chloroanthranilic acid methyl ester by the Sandmeyer reactio-n by diazotisation and reaction with ~; - 10 ~
. ~ . , , :

:. :..... .. , . ,,: ~. - . :: . . ,, ; , . ., . ~ : . .

`
~l:)S~6 po-tassi~lm cya1~i.,^J.e. A.~-ter recrys-talllsation ~rom isopropano]., the pure compoulld has a melting poin-t oI 76-77C.
~ les 2 - 9 ., The Table which follows lis-ts fur-ther pigmen-ts of the '` formula : .
, X~X2 ~ ~i ,, x~, o 1~ X4, wherein the substituents Xl - X4 have the meaning indicated in the columns~ which are obtained if 2 mols of the o-cyano-:1 benzoic acid ester listed in column II are condensed, in ,,~ accordance with the instructions of Example 1, wi-th 1 mol o~
; p-phenylenediamine. Column III glves the melting point o~
the o--cyanobenzolc acid ester used and column VIII gi~2S t'ne shade of P~ contalning 0.2% of the resulting pigment.
.,,.'1 '~,` ~
~3 3 ~
~: ". ~ .

. 3~ ~ :

:s~ '~

'", ~' .:
~i . .j,, 1~5~
q~blc~

Ex. o cyanobenzoic meltine Xl X2 X X4 Shads . aci.d es-ter point 3 _ ~____.~ _.__ _ ~ ~
2 4-chloro-2-cyanobenzoic -117~18C HCl HH medi.um :.~ acid methyl es-ter yellol,r ~ ~ 2-cyano-tereph-thalic 115-16C H o~3 H H .
.~ acid dimethyl ester :~: 4 294-dicyanobenzoic acid 168-6~C H CN H H n :' . methyl ester I 5 5-iodo-2-cyanobenzoic 107-08C H H I H . "
acid methyI es-ter .
~ 6 6-fluoro-2-cyanobenzoic 74-75C H H H F n :~
:. acid methyl ester .
:.~ 7 4,6~dichloro-2-cyano- 70-71C H Cl H Cl ~j benzoic acid methyl .
ester ^.-:
8 3,5-dichloro-2-cyano- 102-03C Cl H Cl H ll . .
~enzoic acid methyl ., es-ter .~., 9 3,4-dichloro 2-cyano- 120C Cl Cl H H n .

.' /, ' __ ,, ..... . _ _ _ _ _ . _ .~ As indicatèd in Example 1, the cyanobenzoi.c acid ~.~ methyl esters used can be obtained from the corresponding '~ . anthranilic acid methyl esters.
' Fxamples l _ 8 `;, Pigments having similarly good propertieis are obtained ;
.
-t~ if the cyanobenzoic acid esters listed in column II of the -table below are condensed with the diamine indicated in .
.~ column III, in accordance wi-th the instructions of Example 1, ;', in a molar ratio of 2:1. Column IV gi~es the colour shade of :.-i - 1.2 _ :
,, :`?
", ~ :

~ ~ ~0~ 7 a PVC sheet ~rhich c~ntainc3 0.2~ o~ the colorant.
Table II
, :~
: ~ ~x.
11 3,5-dichloro-2-cyano- 1,5~naphthylene- orange benzoic acid methyl diamine eister . - :., . ~
.~ 12 " 2,5~dime~thyl-1,4- yellowish~
phenylenediamine tinged :~
orange 13 ~1 2-methyl-5-chloro-.~ . 1,4-phenylenediamine yell.ow ~ 14 3,4-dichloro-2-cyano- " yellow :- benzoic acid methyl : ester .`~ 15 " 1,5-naphthylene- orange `.-:; diamine . ~ .
. 16 2~cyano-tereph-thalic " orange `ij acid dime-thyl ester 17 2,5-dimethyl~1,4- yellow .. phenylenediamine ~:
~:' 18 " 2-chloro-5-methyl yellow : 1,4--phenylenediamine .~
~ 19 6-chloro~2~cyano- 2_ehloro-5 methoxy- yellow :::
.. :.¦ ben~.oic acid methyl 1,4--phenylenediamine .::~
:3 ester .:
. .,:1 ~, ;.~':: 20 6-chloro-2-cyano- 2,5-diethoxy~1,4- reddish- ~
I-i benzoie aeid methyl phenylenediamine tinged : :
.~ ester yellow --~ 21 ~,4-dichloro-2-cyano- 2,5-dichloro-174 yellow benzoie acid methyl phenylenediamine :` ester . . -~
. :~. .. ..

65 parts of stabilised polyvinyl chloride, 35 parts ,:, of dioctyl phthalate and 0.2 part of the colorant obtained . in aeeordanee with Example 1 are stirred together and the ::

~,.".,, , ~ ::

,.......................................................................... .

, :
;, ' ' :' ' ' , .' :' :'..... ' ~ ' . ' . . . : : .: .: ' . ': -, ~S46~7 mixture i..5 th~ orl;ed on a twin-roll calender ~or 7 minutes at 140C. This gives a yellow~coloured sheet with very good fastness to ligh-t and migra-tion.
Exa~lple 23 10 g of ti-taniu~ dio~ide and 2 g of the pigment prepared in accordance wi-th ~xample 1 are ground in a ball mill for 48 hours together wi-th 88 g of a mixture of 26.4 g of coconut alkyd resin, 24.0 g of melamine--formaldehyde resin ~
(50% solids con-tent), 8.8 g of ethylene glycol monomethyl ~ ~;
ether and 28.8 g o:~ xylene.
, ~ , I~ this lacquer is sprayed onto an aluminium foi], pre-dried ~or ~0 minutes at room ternperature and then stoved ;1 for 30 minutes at 120C, a yellow lacquering is ob-tained which - ~
~ is distinguished by a good depth of colour and very good fast~ ``
;, ness to overlacquering, ligh-t and weathering. ~ ~

~ , :`. 1 ` , ;. ~., ~ -: ................................ . . . .
.`,' j ~; ,:~
. ~.~ , ..
l,fj , , ,. l ~

i ~ : ` ~ ; :: : :: : ~ . . ` . ::: , . .. , . . .

Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Iminoisoindolinone pigments of the formula (I) wherein X1, X2, X3 and X4 each denote H atoms or halogen atoms, one of the sub-stituents X1 and X4 representing a halogen atom and not more than one of the substituents X2 and X3 denoting a halogen atom, with the proviso that X3 must not be a chlorine atom if X1 denotes a H atom; or wherein X2 denotes a cyano or carboxylic acid ester group, and X1, X3 and X4 all denote H atoms, and Y1 and Y2 denote H atoms or chlorine atoms or alkyl or alkoxy groups containing 1 - 4 C atoms.

2. Iminoisoindolinone pigments according to claim 1, wherein the sub-stituents X1 - X4 denote H atoms or chlorine atoms, and one of the substituents X1 and X4 represents a chlorine atom and not more than one of the substituents X2 and X3 denotes a chlorine atom and X3 denotes a H atom, if X1 represents a H atom.

3. Iminoisoindolinone pigment according to claim 1 or 2, wherein Y1 and Y2 denote H atoms.

4. A pigment of the formula .

5. A pigment of the formula

6. A pigment of the formula

7. A pigment of the formula

8. A pigment of the formula