CA1053250A - Water-insoluble azamethine compounds, process for their preparation and their use as dyeing agents - Google Patents

Abstract

Abstract of the Disclosure:
Condensing of 1-formyl-2-hydroxy-3-naphthalenecarboxylic acid arylamides with ammonia or aromatic amines yields novel azamethines which are useful as coloring matters, especially as pigments.

Description

1~53~SO

The present invention relates to new water-insoluble azamethine compounds of the general formula I

CH = N - A

X I ~ ~ ¦OH (I) CONH - Ar wherein X is hydragen, chlorine or bromine, Ar is phenyl or naphthyl which are unsubstituted or substituted by 1 to 3 substituents selected from the group consisting of halogen; lower alkyl; lower alkoxy; trifluoromethyl; nitro; cyano; carboxy; lower carbo-alkoxy; lower alkyl sulfonyl; carbamoyl; sulfamoyl, carboxylic or sulfonic acid mono- or di-(lower alkyl)-amide; carboxylic or sulfonic acid anilide which is unsubstituted in the phenyl nucleus or sub-stituted by halogen, lower alkyl, lower alkoxy, cyano, carbamoyl or sulfamoyl;
lower alkanoyl amino, phenyl sulfonyl or benzoyl amino which are unsubstituted in the phenyl nucleus or substituted by halogen, lower alkyl, lower alkoxy, cyano or nitro; or two substituents on Ar being phenyl together stand for a fused saturated 5- or 6-membered ring consisting of two adjacent carbon atoms I of the phenyl nucleus and further ring members selected from the group con-sisting of -CO-, -NH-, -O- and -S-; and A is hydrogen or has ~he meaning given for Ar.
J By "lower~ there are to be understood groups being or containing alkyl groups of 1 to 4 carbon atoms.
; 20 This invention moreover relates to a process for the preparation of these compounds of formula I or mixtures thereof, which comprises condensing 1 mol of one or more aldehydes of the general formula II

~ 2 : . :

~053250 ÇHO

OH (II) x 1~
~ CON~ - Ar in which Ar and X are defined as above, with 1 mol of one or more amines of the general formula III

: A - NH2 (III) in which A is defined as above, or a mixture of such compounds at a temperature of 20 to 200C.
-. As radicals Ar, there are mentioned, for example, phenylJ o-, m-, p-tolyl, o-, m-; p-methoxyphenyl, o-, m-, p-ethoxyphenyl, o-, m-, p-chlorophenyl, o-, m-, p-bromophenyl, o-, m-, p-nitrophenyl, 2,4-dimethylphenyl, 2,5-dimethoxy--; 10 phenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,4,5-trichlorophenyl, 2-chloro-3-methylphenyl, 2-chloro-4-methylphenyl, 2-chloro-5-methylphenyl, 3-chloro-2-methylphenyl, 4-chloro-2-methylphenyl, 2-methoxy-5-chlorophenyl, 2,5-dimethoxy-4-chlorophenyl, 2,4-dimethoxy-5-chlorophenyl, 2-methoxy-4-chloro-5-methylphenyl, 4-acetylaminophenyl, 4-benzoylaminophenyl, benzimidazolyl, phthalimidyl, tetrahydrodioxoquinoxaline, tetrahydrodioxoquinazolone or tetrahydrodioxo-phthalazine.
Preferred azamethine compounds are particularly those corresponding to the general formula IV

C~ = N ~ Yl _OH ~ 2 ~IV) CON~ - AT

2Q in ~hich X and Ax are defined as above, and Yl, Y2 and Y3 may be identical or diferent and stand for hydrogen or non ionic substituents.

11 ~

` ,~ -~os;~zso As non ionic substituents, there are mentioned, for example, halogen atoms, especially chlorine or bromine atoms; alkyl groups~ especially alkyl groups of 1 to 4 carbon atoms, preferably methyl or ethyl groups; alkoxy groups, especially having 1 to 4 carbon atoms, preferably methoxy and ethoxy groups;

3a-.

.
.
.

.:
. ` , ~ , : , . ~

nitro groups; alkyl- or arylsulfonyl groupq, especially alkyl-sulfonyl groups having 1 to 4 carbon ato~s in the alkyl moiety, phenyl, tolyl, sulfonam~do-phenyl, carbon,amidophenyl-9ulfonyl~
or the N-methyl- or N-ethyl-substituted radicals thereof, carboxylic acid ester groups~ optionally substituted qulfonic acid amide or carboxylic acid amide groupsJor acylamino groups.
Among the carboxylic acid esters groups, the carboxylic acid alkyl ester groups having 1 to 4 carbon atoms in the alkyl moiety are preferred, among optionally ~ubstituted sulfonic -~ 10 acid amide or carboxylic acid amide groups, those groups which carry one or two lower alkyl groups or a phenyl group which may agaîn be substituted by non-ionic substituents, such as lower alkyl, lower alkoxy, carbon~mide or sulfonami.de groups and/or chlori.ne atoms, are preferred.
Acylamino groups are, in particular, lower alkanoylamino groups, such as acetyl- or propionylamino groups, and benzoyl or phenyl~ulfonylamino groups which carry one or more of the above-cited non ionic substituents, among them preferably a radical of the formula : 20 R

. in which R stands for hydrogen, lower alkyl, lower alkoxy, a !.
sul~onamide or carbon~amide group or a chlorine atom.
..:
~: .25 Especially ~aluable properties are found in the new : . azamethine compounds, wherein at least one of the substituents Y1, Y2 or Y3 co~tains a grouping of the formula -CO-NH- or wherein Yl and Y2, taken together, stand for a grouping of ~29 the formula -NH-CO-NH-, ~CO-NH-CO-, -NH-CO-NH-CO-, ::~'{~
~ 4 _ . : - : ~: , ~ . .
. . . . . . . .
::- ~ .. . , -1053ZS~
-NH-CO-CO-NH- or -CO-NH-NH-CO-.
As a~omatic amines of formula III, there are especially mentioned amino-benzamides, amino-benzanilides, acylamino-anilines, amino-phenyl-sulfonamides, alkyl- or arylsulfonamino-anilines, amino-benzimidazoles, amino-benzoxazoles, amino-benzthinzoles, amino-phthalic acid imides, amino-quinazolinones, amino-quinoxalines, or amino-phthalazines, which are known and : are generally prepared by reduction of the corresponding nitro c ompounds .
The l-aldehydes of 2-hydroxy-naphthalene-3-carboxylic acid arylide~ of formula II, used as starting compounds, are obtained by reacting 2-hydroxy-naphthalene-3-carboxylic acid aryli.de~
with hexamethylene tetramine in the presence of a lower ali-phatic carboxylic acld with a mineral acid.
The condensation of one mol of an aldehyde of formula II
with one mol of an amine of formula III may be carried out both : in a neutral and acid, optionally aqueous medium, or in an organic solvent, such as an alcohol, for example methanol:, :
ethunol ~r butanol, in an aliphatic carboxylic acid, for example . 20 acetic acid, in dimethylformamide, xylene, chlorobenzene, di-chlorobenzene or nitrobenzene. It generally proceed rapidly :~ with quantitative yield at a temperature of 50 to 100 C;
1~:
.~ advantageou~ly there may be used a solvent or a mixture of solvents at an elevated temperature, for example from 130 to 170C or more, while water set free by the condensation reaction i8 separated by azeotropic distillation. In some cases, it may be advantageous to use the amines in the form of their salts l with mineral acids and to carry out the reaction by adding an .~ 29 at least eq~alent amou~t of ammonia, an ammonium salt or an ~ ; ~ 5 -.

, . . ...

::
- . : . . ..

.. ... , . .. , . ,; ,. . : . .: . . : ,: .:: . .: : .

aliphatic, aromatic or heterocyclic amine, for example tri-ethylamine, N,N-dimethylaniline or pyridine.
The conden~ation reaction may advantageously be carried out in the presence of surface-active compound~ or resin soaps or by adding these additives during or after the isolation of the dyestuff~, whereupon the disper~ibility, the degree of : glazing and/or the particle ~ize distribution, which is re-sponsible for a good gloss of the dyeings, ar~ positively influenced.
For obtaining optimum coloristic properties, it may some-times be advantageous to convert the final pigment into a finely divided form by heating the pigment in a ~lvent, . , optionally in the presence of water or salt solutions.
:~ As solven~ suitable for this purpose, there are mentioned those in wh~ich the dyestuffs are insoluble but promote a certain degree of superficial dissolving under the finishing ~, .
conditions, for example aliphatic alcohols, such as ethanol, isopropanol, iso- or n-butanol; chlorinated aromatic solvents, , 1, ~:~
1~ such as chlorobenzene. and chlorotoluene or dichlorobenzenes~
1~ .
as well as aprotic polar solvent , for example dimethylformamide, dimethylacetamide, dimethylsulfoxide, polyalkyl ureas and phosphoric acid amides.
In some cases, a finn dlvision~may also be brought about by grinding the pigments with salts or in solvents; the dry Zs~ grinding operation being preferably performed in vibrating mills wlth a sub~equent separation of the salt by dissolution in water, optionally ~ollowed by a wet grinding operation or a high-temperature treatment with solvents.
29~ As salt~, there~ are generally used the alkali metal or . .

~053Z5(~
alkaline earth metal ~alts of halohydric acids or of sulfuric acid, for example sodium or potassium chloride and sodium or magnesium sulfate.
The solvents used for the wet grinding operation are generally the same as mentioned above~ for example alcohols, acid amides or dimethylsulfoxide.
The new compounds are valuable dysing agents, especially valuable pigments suitable in particular for printing pastes and inks. They may, however, also be used for being in-corporated into high-molecular-weight organic materials, for example cellulose ethers and esters,such as ace$yl cellulose or nitro-cellulose, polyamides, polyurethanes or polyesters, natural or synthetic resins, for example aminoplasts, especially in urea- and melamine-formaldehyde resins, alkyd resin~, pheno-plasts, polycarbonates, poly-olefins, such a~ polyethylene or polypropylene, polyvinyl chloride, polyacrylonitrile, poly-acrylic acid esters, rubber, ca~ein, silicone and silicone resins~ as SUCIl or in mixture with one another. ~'or such an incorporation, it does not matter whether the abo~e-cited high-molecular-weight compounds are available as plastic ~asses, melts or spinning solutions, lacquers or printing pastes and inks. Depending on the intended purpose, it proved to be u~eful to incorporate the new pigments as toners or in the form of compositions.
The new pigments are distinguished by clear shades, high fastness to light, high tinctorial strength, high transpare~cy as well as an excellent stability on storage and rheological properties in printing varnishes.
- 29 They are therefore excellently suitable for use in multi-.

, ,'' ' ' ' ' ' ' '' - '."' ' ,: ,,~ " " ' ' "', '` : : ~ -. ,~ .: :
, ,. . , :. : ..
', - : :: . : . .
,. ~ . ' ' . .'. : :'' : ' . ' , :

HOE 74/~51_ lOS~2SO
color paper printing. Owing to their good fa~tness to sol~ents and migration, the pigments of the invention are advantageous also for the coloration of lacquers and plastic materials.
The following Examples illustrate the invention.

14.6 Grams of 2-hydroxynaphthalene-3-carboxylic acid anilide 1-aldehyde were heated at the boil in a mixture of 200 ml of ethanol and 200 ml of glacial acetic acid. Then a solùtion of 10.8 g of 3-amino-4-chloro-6-methyl-acetanilide in 100 ml of glacial acetic acid were added ts the above solution, whereupon an inten~ely yellow-colored product precipitated ~ within a short time. Stirring was continued for 1 hour at ; 95 C, the mixture was cooled and suction-filtered at room temperature. After washing with a small amount of methanol and water, 20.9 g of a yellow pigment of the for~ula "~ CH -- N ~CH3 ,~ HN-C O ~IH
~ C 0-CH3 were obtained.
, E X A M P L E 2:
29.2 Grams of 2-hydroxy-naphthalene-3_carboxylic acid anilide l-aldehyde were dissolved at 75C in 200 ml of dimethyl-formamide. ~t this temperature, a solution of 28.5 g of 3-amino-4-methoxy-benzoyl-amino-4'-ben~amide in 100 ml of dimethylformamide, S ml of glacial acetic acid and 50 ml of water was added dropwise, Stirring was continued for 3 hours 29 at 100 C, the product was suction-filtered, washed with water , :

- . ~ : . . . . .
..

, HOE 74!~ 051 2S() a~d dried. 46.4 Grams of a reddish yellow pigment of the formula OC~3 CH = N ~

- -HN-CO OH C0-~ ~ ol~2 - - .
were obtained.
E X A M P L E 3:
7.3 Grams of 2-hydroxy naphthalene-3-carboxylic acid anilide l-aldehyde were dissolved at the boil in 300 ml of ethanol. A ~olution of 4.4 g of 5-aminobenzimldazolone in 100 ml of glacial acetic acid was added at 80C, whereupon an intensely orange red colored pigment precipitated at onc0.
Stirr~ng was continued for 1 hour at 80C, the mixture wa~
allowed to cool to 20~, suction-filtered, washed with methanol and water and dried.
Yield: 10 g of a pigment of the formula ~--CH = N~

' ~ ~ 0 H
.
~ .
E X A M P L E 4:
19.3 Grams o~ 2-hydroxy naphthalene-3-carbo~ylic acid-2~, 5l-dimethoxy-4~-chloroanilide l-aldehyde were mixed in a high-speed ~tirrer with 200 ml of watar and 100 ml of glacial acetic acid. While stirring, a solution of 12.5 g of 3-amino-4-methoxy- -9 benz-anilide in 100 ml of dimethylformamide was added to this ,.~ _ 9 _ '::

, ' ' ' .

lOS3~:50 ~uspension. The temperature was maintained at 95 C for 10 hours, the product was then suction-filtered, washed with hot water and dried.
Yield: 23.7 g of a reddish yellow pigment of the formula ~3~ OCH3 OCH3 ~CH = N~
Cl~ -HN~O OH COI~

~3 '~ 10 Upon incorporation into polyvinyl chloride the pigment thus obtained yielded a reddish yellow coloration having a Yery good purity~ color ~ntensity and fastness to migration and light.
E X A M P~
38.6 Grams of Z-hydroxy naphthalene-3-carboxylic acid-2~, - g~-dimethox~-4~-chloroanilide l-aldehyde were dissol~ed at 120C in 500 ml of dimethylformamide. Then, a solution of 1~ g of 2-amino-4-acetylamino-anisole in 100 ml of water and 50 ml of glacial acetic acid were added dropwise. Stirring was con--` 20 tinued for 3 hours at 1OQC, the mixture w s suction-filtered when cooled to room temperature, washed with water and dried.

Yield: 42.2 g of a reddish yellow pigment of the formula OC~3 ~

Cl ~HN-CO OH . NH-cocH3 OCH

- 10 _ ::
-.: . , . .. :: : .. , ., : , .... . . . . :

: - .- . , . . . . .. , . . : .
.:

HOE 71~/F O';l ~S~ZSO
E X A M P L E ~-29.2 Grams of 2-hydroxy-naphthalene-3-carboxylic acid anilide 1-aldehyde were heated at the boil in 500 ml of ~lacial acetic acid and 500 ml of ethanol. To the hot suspension, a solution of 14 g of anthranilic acid in 50 ml of dimethyl-formamide was added, whereupon a clear solution was obtained, from which at once a reddish yellow pigment crystallized.
The product was refluxed for 5 hours, cooled and suction-filtered at room temperature. It was washed with methanol and water and ~ied.
Yield: 38.5 g of a pigment o~ the formula ~, COCH
CH = N~

~ C O o~

E x A M P L E 7:
7.7 Grams of 2-hydroxy naphthalene-3-carboxylic acid-2~-methylanilide-1-aldehyde were di~solved at 80C in 1000 ml of ethanol, and a ~olution of 4.6 g of 5 aminobenzimidazolone in 100 ml of glacial acetic acid was adrZed thereto. The mixture was then re~luxed for 2 hours. The orange-colored pigment was suction-filtered, washed with hot ethanol and water and dried.
. . .
Yield: 9.9 g of a pigment of the formula ~ H

CH = N~N~D :

CQ OH - -2g `~ C~3 :

: . . :
. : . :
. -...
."

53'~SO
E X A M P I, E 8:
A solution of 31.4 g of 5-amino-2-benzoylamino-1,4-di-methoxybenzene in 200 ml of glacial acetic acid, 400 ml of water and 10 ml of a 10 ~ solution of oxethylated ~tearyl alcohol was prepared. While stirring rapidly, a ~olution of 30.5 g of 2-hydroxy-3-carboxylic acid-2~-methylanilide-1-alde-hyde ~ in 200 ml of dimethylformamide was added dropwise.
Stirring was continued for 3 hours at 100C, the reaction mixture was cooled and the product suction-filtered at room temperature. After washing with methanol and water and sub-se~uent drying, 52.5 g of an intensely yellow colored pigment of the formula .

~ 3 ~ CH - N ~ CO~

~HN-CO OH .OCH3 were obtained.
E X A M P L E 9s_ 32.1 Grams of 2-hydroxy-3-carboxylic acid-2'-methoxy anilide 1-aldehyde were dissolved at 80C in 300 ml of glacial acetlc acid. This solution was combined with 10 ml of a 10 ~
aqueous solution of oxethylated stearyl alcohol, and 27.7 g of .
5-amino-2-ben7oylamino-3~methyl-6-methoxy-benzene in 200 ml of glacial acetic acid and 300 ml of water were added. Stirring wa~ continued for 3 hour~ at 100C and, after the usual woric-up, 50.1 g of an intensely orange colored pigment of the 29 f ormula ., .
_ 12 -.
, . : , : . . ' . . . :-, :. ~ . . .

HOE 74~F 051 1~5325(~

~ . OCH3 OCH3 ~ Cl~ = N-~ NH-CO

~HN- OH ~H3 were obtained.
E X A M P L E 10:
33.5 Grams of 2-hydroxy-3-carboxylic acid-2~-ethoxyanilide-1-aldehyde were dissolved at 70C in 250 ml of dimethyl-~
formamide. This solution was added dropwise within 20 minutes to a colution o~ 31.4 g o~ 5-amino-2-benzoylamino-1,4-dimethoxy-benzene in 200 ml of glacial acetic acid, 300 m~ of water and 10 ml o~ a 10 ~ aqueous solution of an oxethylated st0aryl alcohol. The mixture was heated to 95C and this temperature was maintained for 3 hours, the product was suction-filtered while hot, washed with hot water and dried. Yield: 51.2 g of a red azamethine pigment of the formula ~, OCH3 ` 20 . \~/
~CH = N ~ CO~

CO OH O~H3 i . .2H5 were obtained.
E X A M P_L E 11.
r t 33~2 Grams of 2-hydroxy naphthalene-3-carbo~ylic acid-4~-acetylamino-anilide-1-aldehyde were heated at the boil in Z9350 ml of ethanol. Then 4 g of a concentrated aqueous ammonia 1~
~ ~- 13 ~

: ,.

,. . .
. . ~

HOE 74/~ 051 lQS325~
solutiun in 30 ml of ethanol were added dropwise. Refluxing was continued for 60 minutes and, after the usual work-up, 32.7 g o~ a reddish yellow azamethine pigment of the formula ~
~C~
CH3-OC-HN ~ ~N-CO OH
were obtained.
: E X A M P L E S 12 - 26~
The following Table comprises further dyestuffs of the invention which can be prepared from amines of the formula III
(A-NH~) and 1-naphthaldehydes of the abovè formula II, acoording to the method disclosed in Examples 1 to 11:
T A B L E

Example A-NH2 1-naphthaldehyde(II) shade pro-duced with azamethine Ar X pigment .. ..... . .......
12 ~3 ~ Br yellow - . .
~ . COQGH~
~ ~2 . _ ~ ll reddish ..... ---- yellow ~ONH2 ' .
.

14 ~T~2 ~H H red , . cH3~ )2s~) ~C -- O
O~H3 H
.'' .
.
'' ' ' ' ' "

.. . .... " . , ~iu~ 1~ / r l(~S3ZSO
Example A-N~2 1-naphthaldehyde(II) shade pro-duced with azamethine Ar. X pigment _ .
H ~
~2 ~ ~ yellowish red O Cl ~' ~6 ~2Nf~c/ ~ reddish ` ^ Cl yellow . O

. l ~ H
1 ~ ll yellowlsh red O
~.

18 RzR~ R3 ~ yellowl~h red H2N~ ~CH~ H yellowish red ... ..
, Cl -- O -20 ~ N~2 ~0~t NH H orange 01~--CH3 0 r ~ 1 5 ,~

HOE 74/~ 051 l~S3ZSO
Example A-NH2 1-naphthaldehyde(II) shade pro-duc ed with azamethine ~r X pigment .

21 ~ OCH~ ~C=O H yellowi:~h red OCH3 .
~NH2 H
~ IN~ f~ ~
22 b~l OCH3 ~N~O I ~ red H

.. .. . . . . _, ,, 23 ~ N~2 _~-- Cl H yellow CONH-C~3 Cl 24 ~ 2 ~ 2~5 reddi ~h N~COCH3 H QC2~1S
*~ H2 ~ H yellowish , . H

26 0~< ~ 2 C1 h Yel owish ' : . . : . : . . . - :

.

,. ' "" ~ ~ '.

~1~53~:50 E X A M P L E - 27:
0.8 Gram of the pigment obtained according to Example 1,

2.4 ig of alumina hydrate and 4.8 g of a letter printing varnish were mixed on a three-roller mill, and the mixture was tri-turated to yield a letter printing ink having a pigment content of 10 ~ and producing yellow prints of high purity and color intensity.
Upon incorporation with a lacquer or a spinning solution, ; yellow colorations of good fastness to light and solvents were obtained.
E.X A M P L E 28:
67 Grams of polyvinyl chloride, 33 g of a platicizer composition consisting of a mixture of equal parts of dioctyl phthalate and dibutyl phthalate~ 0.1 g of the pigment obtained according to Example 3, and 0.5 g of titanium dioxide were mixed for 15 minutes at 150C in a roller mill to produce a foil with àn orange-red coloration, which was distinguished by a.high intensity, pure shade and good fa~tness to light and migration.
E X A M P L E 29:
4.5 Grams of the pigment obtained according to Example 5 were shaken for 45 minutes in a vibration ball mill with 25.5 g o~ a lacquer consi~ting of a 20 ~ solution of alkyd resin in xylene, then 60 g of a clear varnish consisting of 52.5 parts by weight of a 70 ~ alkyd resin solution in xylene~ 35 parts by weight o~ a 55 ~ melamine resin solution in butanol, 2.5 .
. parts by weight of butyl glycol, 5 parts by weight of butanol and 5 parts by weight of white spirit were added.
29 A reddish yellow colored full shade lacquer was obtained, i~ -~ 17 -.. . . .

105~Z~0 it was sprayed onto an aluminum sheet and stoved for 30 minutes at 140C. The reddish yellow coloration thus obtained had a satisfactory fastness to overlacquering and a g~od fastnes~
to light and weathering.
E X A M P L E 30:
0.~ Gram of the pigment obtained according to Example 7 were processed as in Example 27 to yield a letter printing ink which provided clear orange-colored prints of high color in-tens`ity and good fastness to light.

-~ .
_ 18 -. . . .

. .
. . . .. . . . . - ~ - : ... ~

- . . . ..

Claims (14)

I claim:

1. A compound of the formula wherein X is hydrogen, chlorine or bromine, Ar is phenyl or naphthyl which are unsubstituted or sub-stituted by 1 to 3 substituents selected from the group consisting of halogen; lower alkyl; lower alkoxy; tri-fluoromethyl; nitro; cyano; carboxy; lower carbo-alkoxy;
lower alkyl sulfonyl; carbamoyl; sulfamoyl; carboxylic or sulfonic acid mono- or di-(lower alkyl)-amide; carboxylic or sulfonic acid anilide which is unsubstituted in the phenyl nucleus or substituted by halogen, lower alkyl, lower alkoxy, cyano, carbamoyl or sulfamoyl; lower alkanoyl amino, phenyl sulfonyl or benzoyl amino which are unsub-stituted in the phenyl nucleus or substituted by halogen, lower alkyl, lower alkoxy, cyano or nitro; or two sub-stituents on Ar being phenyl together stand for a fused saturated 5- or 6-membered ring consisting of two adjacent carbon atoms of the phenyl nucleus and further ring members selected from the group consisting of -CO-, -NH-, -O- and -S-;
and A is hydrogen or has the meaning given for Ar.

2. A compound as defined in claim 1, wherein X is in peri-position to the hydroxy group, Ar is naphthyl; phenyl; phenyl substituted by 1 to 3 sub-stituents selected from the group consisting of chlorine, bromine, lower alkyl, lower alkoxy, trifluoromethyl, nitro, lower carboalkoxy, lower alkanoylamino, benzoyl-amino, carbamoyl, sulfamoyl, carboxylic or sulfonic acid mono- or di (lower alkyl)-amide, carboxylic or sulfonic acid anilide and carboxylic acid (carbamoyl phenyl)amide;
phthalimidyl, benzimidazolonyl, benzoxazolonyl, tetrahydro-dioxoquinazolone, tetrahydrodioxoquinoxaline or tetrahydro-dioxophthalazine; which heterocyclic radicals are unsub-stituted or substituted in the benzo nucleus by chlorine or nitro; and A is hydrogen or has the meanings given for Ar.

3. A compound as defined in claim 1, wherein X is hydrogen, Ar is phenyl substituted by 1 to 3 substituents selected from the group consisting of chlorine, methyl, methoxy and ethoxy; and A is phenyl substituted by carbamoyl, carboxylic acid anilide, acetamino or benzoyl-amino and additionally by 1 or 2 substituents selected from methoxy and ethoxy; benzimidazolone, nitrobenzimidazolone or phthalimidyl.

4. A compound as defined in claim 1, wherein X is hydrogen, Ar is chlorophenyl, dichlorophenyl, tolyl, anisyl, ethoxyphenyl or dimethoxy chlorophenyl and A is methoxybenzoic acid anilide, dimethoxy benzoylamino phenyl, benzimidazolonyl, nitrobenzimidazolonyl or phthalimidyl.

5. The compound as defined in claim 4, wherein A is benzimidazol-2-on-5-yl and Ar is 2-ethoxyphenyl.

6. The compound as defined in claim 4, wherein A is 6-nitro-5-benzimidazol-2-on-5-yl and Ar is 4-chlorophenyl.

7. The compound as defined in claim 4, wherein A is phthal-imide-5-yl and Ar is 2,4-dichlorophenyl.

8. The compound as defined in claim 4, wherein A is benz-imidazol-2-on-5-yl and A is 2-tolyl.

9. The compounds a defined in claim 4, wherein A is 2-methoxy -5-benzoic acid anilide and Ar is 2,5-dimethoxy-4-chloro-phenyl.

10. The compound as defined in claim 4, wherein A is 2,5 -di-methoxy-4-benzoylaminophenyl and Ar is 2-tolyl.

11. The compound as defined in claim 45 wherein A is 2,5-di-methoxy-4-benzoylaminophenyl and Ar is 2-anisyl.

12. A process for preparing a compound of the formula wherein X is hydrogen, chlorine or bromine, Ar is phenyl or naphthyl which are unsubstituted or sub-stituted by 1 to 3 substituents selected from the group consisting of halogen; lower alkyl; lower alkoxy; tri-fluoromethyl; nitro; cyano; carboxy; lower carbo-alkoxy;

lower alkyl sulfonyl; carbamoyl; sulfamoyl; carboxylic or sulfonic acid mono- or di-(lower alkyl)-amide; carboxylic or sulfonic acid anilide which is unsubstituted in the phenyl nucleus or substituted by halogen, lower alkyl, lower alkoxy, cyano, carbamoyl or sulfamoyl; lower alkanoyl amino, phenyl sulfonyl or benzoyl amino which are unsub-stituted in the phenyl nucleus or substituted by halogen, lower alkyl, lower alkoxy, cyano or nitro; of two sub-stituents on Ar being phenyl together stand for a fused saturated 5- or 6-membered ring consisting of two adjacent carbon atoms of the phenyl nucleus and further ring members selected from the group consisting of -CO-, -NR-, -O- and -S-;
and A is hydrogen or has the meaning given for Ar.

which comprises condensing 1 mol of a compound of the formula in which X and Ar are as defined above, or a mixture of such compounds, with 1 mol of a compound of the formula in which A is as defined above, or a mixture of such compounds at a temperature of 20 to 200°C.

13. A process as defined in claim 12, wherein the temperature is 50 to 100°C.

14. A process for pigmenting colorless substrates which com-prises contacting said substrates with a compound as defined in claim 1.