Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
The present invention relates to new iminoisoindolin~ne pigments of
~he formula -
X2 ~ X2
X4 0
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~
:
.,., . ~ . :
~ .
-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
X3 COOR
,,`,, '. ~
; 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
. ,~ . . .
':'', `~': '~
~: `. , ;~
~:
:. :
- 8 -
'' ,
.'.. . . . . . . . .... . . .
.. . ..
~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 ::
~,.".,, , ~ ::
3 -
,.......................................................................... .
, :
;,
' ' :' ' ' , .' :' :'..... ' ~ ' . ' . . . : : .: .: ' . ': -,
~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 ~ : ` ~ ; :: : :: : ~ . . ` . ::: , . .. , . . .
