CA1037962A - Azamethine metal complex compounds - Google Patents

Abstract

AZAMETHINE METAL COMPLEX COMPOUNDS
Abstract of the Disclosure:
Azamethines which are obtainable by condensation of a 1-formyl-2-hydroxy-3-naphthoic acid arylamide with an ortho-hydroxy- or ortho-methoxy aniline form metal complexes with zinc, cadmium, cobalt, nickel or copper. These complexes are useful as pigments.

Description

~c -HOE 74lF 244 ~7 ~
The pr~sent invention provides new water-insoluble aza-methine metal complex pigments of the general formula I

X2 ~ X1 3 ~ ~ ~O
N _ h CH ¦ (I) Y ~ONH-Ar in which X1, X2 and X3 may be ~dent.ical or different~each re-presenting hydrogen or halogen atoms, alkyl, alkoxy, phenyl, ; tolyl, nitro, carbo-alkoxy, sul~onamide, mono- or dl- alkyl-. sulfonamide, carbona~ide9 mono~ or di-alkylcarbonamide, alkanoyl- :
amino groups or a group o~ the ~ormula ~;

wherein G is -NHCO-, -S02NH- or -CONH- and R is a hydrogen 20 or chlorine atom, an alkyl, alkoxy? sul~onamide or carbonamide ;~
group, X1 and X2 together can ~orm with the phenyl ring a benzimidazolone ring; Y i~ a hydrogen, chlorine or bromine atom;
Ar is the naphthyl group~ a phenyl group which can be sub-stituted by 1 to 3 alkyl, alkoxy, alkylsulfonyl, carbalkoxy9 trifluoromethyl, nitro, cyano~ alkanoylamino, benzoylamino~
~ carbonamide, mono or di-alkyl-carbonamide, sulfonamide, mono- ;
-- - or di~alkvlsulfonamide groups or by halogen atoms; or Ar is the benzimidazolone, chlorobenzimidazolone, quinazolindione, .

2~ quinoxQline, phthalimide or plithalazine group and M is a zinc, 2 ~

, .. , . . . ~ . ., ~

!- i ' . . ' . . : . .,; ' ` . , ' ` ' HOE _741F_ 244 ~7~
cadmium, cobalt, nickel or copper atom.
Particularly preferred are those pigments of the above formula I in which X1, X2 and X~ are identical or di~ferent, representing a hydrogen, chlorine or bromine'atom, an alkyl, 5 ~ikoxy, rlitr~, a~tyldmino, ~ zo-ylamill~, carbo~c~hox;, carbor.- ~
amide, alkylcarbonamide or phenylcarbonamide group, Y is a ~.:
hydrogen, chlorine or bromine atom9 Ar is a phenyl group, which may be substituted by 1 to 3 alkyl, alkoxy, alkylsulfonyl, carbalkoxy, tri~luoromethyl, nitro 9 cyano, alkanoyl-amino 9 :~
carbonamide, mono- or di-alkyl-carbonamide, sulfonamide, mono-or di-alkylsulfonamide groups, bromine or chlorine atomsOor Ar is the benzimidazolone or the chlorobenzimidazolone group and M represents a nickel, pre~erably a copper atom.
: The terms "alkyl", 'lalkoxy" and "alkanoyl" signify groups .
carrying 1 to 4 carbon atoms.
. As radicals Ar, there may be mentioned, for example9 pher:i.yl-, o-, m-, p-tolyl- 9 O- p m-~ p-methox~phenyl-, o-, m-~
p-e~hoxyphenyl-, o-, m-, p-chlorophenyl-p o-, m-~ p~bromophenyl-, o-, m-trifluoromethylphenyl, o-~ m-, p-nitrophenyl-, 2,4-di-. 20 methyl-, 2,5-dimethoxyphenyl-, 294-dichlorophenyl-, 2,5-di-- chlorophenyl--p 2,5-dichlorophenyl-, 2,4,5-trichlorophenyl, 2-chloro-3-methylphenyl-,.2-chloro-4-methylphenyl- 9 2-chloro-.
.5~methylphenyl~, 3-chloro-2-methylphenyl-~ 4-chloro--2-me~hyl~
phenyl-, 2-methoxy-5-chloro- phenyl-, 2,5 dimethoxy-4-chloro~
phenyl-, 2,4 dimethoxy-5-chloro- phenyl-, 2-methoxy-4-chloro_ 5-methylpheny~-, 4-acetylamino- phenyl-p 4-benæoylaminophenyl-p ~ -benzimidazolyl_, phthalimi~yl-, qu~noxalyl_, quinazolyl_ or phthalazinyl groups.
The inventi.on moreover provides a process ~or the pre- i:
: paration of the compounds o~ ~he ~ormula I 9 in which azamethines .

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

HOE 74/F 244_ ~ Q379~2 of the general ~ormula II
.. ... .

X,3 ~

Y - CON~-Ar in which X1, X2, X3, Y and Ar are de~ined as above, Z stands ~:
for hydrogen or a methyl group, are treated with a metal~
releasing salt o~ copper, nickel~ zinc, cadmium or cobalt.
: The metallization is preferably effected~ in the usual way, - with salts of the bivalent copper, cobalt or nickel, : ~.
15 . for example, with their chlorides or sul~ates, but preferably :
witll their acetates, formates or stearates, in polar organic ~ ~;
sol-rents. Such sol~ents are, for example~ glycolmonomethyl ether,- formamide, dimethylformamide, N-methylpyrrolidone, . glacial acetic acid, alcohols or mixtures of such solve~ts, 20 optionally in admixture with water. The metallization process is preferably e~fe~ted in 2 - 6 hours at temperatures varying between 70 and 180C; if Z stands for hydrogen, the preferred temperature is up to 150C.
~ In the case of metallization o~ compounds o~ the formula II ~
- 25 with Z = CH3, a desalkylation takes place at the same time~ :
The desalkylating metallization is preferably ef~ected at elevated temperatures in a polar organic solvent, preferably :~
at temperatures between 100 and 180C. Suitable solvents are~
29 for example 7 glycolmonomethyl- and monoethyl ethers~ dipolar ~ _ 4 . . :~
.. ' ' :

~ LQ3~9b;~
aprotic solvents such as dimethylformamide, dimethylsulfoxide, -~
` tetramethylene sulfone or N-methylpyrrolidone.
The metal complexes can be ~solated ~rom these solvents by filtration.
For cbtainin~ ~p~mwm tinc-torial prope~t~e~ wi-~h the pigments of the invention, it rnay sometimes be advantageous to convert the final pigment into a solvent, optionally in the presence of water or a salt solution~
As solvents suitable for this purpose, there may be mentio-- 10 ned those in which the pigments are insoluble but promote a certain degree of superficial dissolving under the finishing conditions, for examile aliphatic alcohols, for example ethanol, isopropanol, i50- or n-butanol; chlorinated aromatic solvents, ~or example chlorobenzene and chlorotoluenes or dichloro-1~ benzenes, as well as dipolar aprotic solvents, for example di-meth~rlformamide, dimethylacetamide, dimethylsulphoxide, poly-alky; ureas and phosphoric acid tris-(dimethylamide).
[n some cases, a state o~ fine division may also be ~rought about by grinding the pigments with salts or in solvents, the dry grinding operation being preferably performed in a vibrating ;~
mill with subsequent separation o~ the salt by dissolution in -wa~er, optionally followed by a wet grinding operation or a high-temperature treatment with solvents. ;~
As salts, there are generally used the alkali metal or alkaline earth metal salts of halohydric acids or of sulphuric acid, for example sodium or potassium chloride and sodium or magnesium sulphate.
The solvents used for the wet grinding operation are 29 generally the same as mentioned above, for example alcohols, . .

1(337~
acid amides or dimethyl~ulphoxide.
The non-metallized azamethines of the general formula II
can be obtained according to German O~fenlegungsschrfit No. 2 408 291 by condensation of one mol of an aldehyde o~
~h~ general lOf~uia Ill CHO
¦ OH

- Y CONH-Ar (III) with one mol of an o-aminophenole or o-aminophenol ether of the general formula IV

- X~ X 1 . X3 ~ Oz (I~) ~H2 ~~

in k~own manner.
.~s examples for the aldehydes of the formula III there can be mentioned:
1-formyl-2-hydroxy-3-naphthoic acid-anilide " -2'-chloroanilide n -4'-chloroanilide " -2', 4'-dichloroanilide " -2', 5'-dichloroanilide " -2'-methylanilide ; " -4'-methylanilide " -2t-methoxyanilid~
1-formyl-2-hydroxy-3-naphthoic acid-2' ethoxyanilide 29 " 4'-methoxyanilide : - 6 -. . ;- ~. . - . . ,- . .. . - -, , . , :
~. . :.. . , ! . .
:, ,, ' . , '' ' . . ": '' , ~ :, , ' : ' ' '' ' . ' ' ' . ' ' ' '' ~ ' ' ' ~' , ' ' ' ~ ' ' ' , /~L~ 2l~_ `
10~7 9 6'~
1-formyl-2-hydroxy-3-naphthoic acid-4'-ethoxyanilide -2~, 4'-dimethylanilide "-2'-methyl-3'-chloroanilide "2'-methyl-4~-chloroanilide ~ ii~2:, 5l-di~ sl~xy~lllif1~
-2~, 5'-dimethoxy-4'-chloro~ ~:
anilide -2'~ 4~-dimethoxy-5l-chloro- ~
anilide :
" -4'-acetylaminoanilide ?
. n -4~-benzoylaminoanilide .:~
"-3'-trifluoromethylanilide `:~
2'-nitroanilide 1_formyl_2_hydroxy-~-bromo-3-naphthoic acid anilide 1-formyl-2-h~droxy-3-naphthoyl-5'-aminobenzimidazolone " -5'-amino-7'-chlorobenzimida- -zolone ~i - -6'-aminoquinazolindione " .7'-aminoquinazolinidone ~
" -6~-aminoquinoxaline ~ ; :
" -4'-aminophthalimide n -6'-aminophthalazine As examples ~or 2-hydroxy or 2-alkoxyamines of the general formula IV there can be mentioned 2-aminophenol7 2-amino-4- ~:
chlorophenol, 2-amino-5-chlorophenol, 2-amino-6-chlorophenol, 2-amino-4-bromophenol, 1-amino-2-naphthol~ 2-amino-4-nitro-phenol, 2-amino-5-nitrophenol, 2-methoxy-5-acetylaminoaniline~ :
- 2-methoxy-5-methyl-4-benzoylaminoaniline, 5-amino 4-~ydroxy~ :
29 1,2-xylene, 5-amino-4-hydro.xy-1J3 xylene, 6-chloro-4-amino`~
- 7 - :~

HOE 741~ 2l44 103 ~

3-hydroxy-toluene, 4,6-dichloro~2-aminophenol, 3,4,6 trichloro-2-aminophenol~ 3,4,6-tetrachloro-2-aminophenol~ 5~nitro-3-amino-2-hydroxytoluene, 5-nitro-3-amino-4-hydroxytoluene, 496-dinitro-2-aminophenol, 6-chloro-4-nitro-2-aminophenol, 4-chloro-5-ni-tro-2~aminophenol 4-chloro-6-ni~ro_2-~m~n~nh~nol; 5-chl nrn_~_aminn_ anisol, 6-chloro-2-aminoanisol, 4-nitro-2-aminoanisol, 5-nitro-- 2-aminoanisol, 3,5-dinitro-2-aminoanisol, 4-chloro-5-nitro-2-am.inoanisol, 2-amino-1,4 dimethoxybenzene9 2-amino-4-acet--aminoanisol, 3-amino-4-hydroxybenzoic acid methyl ester, 3-amino-4-methoxybenzoic acid amide, 3-amino-4-methoxybenzoic .. acid anilide, 3-amino-4-methoxy-benzoic acid-3'-chloro~2'-methylanilide, 3-amino-4 methoxybenzoic acid-2' 9 5'-dichloro anilide, 5-amino-6-hydroxybenzimidazolone-2 or 5-amino-6-hy~roxy-7-chlorobenzimidazolone-2.
The new compounds are ~aluable pigments suitable i~ par ticular ~or printing pastes and inks, for disperse dyes~
lacquers and for incorporation into high-molecular-weight . organic materials, for example cellulose ethers and -esters such as cellulose acetate or nitrate, polyamides, polyurethanes .: 20 or polyesters such as polyethylene glycol terephthalate, natural or synthetic resins, for example aminoplasts, especially urea-and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines, for example polyethylene or polypropylene, polyvinyl chloride, polyacrylonitrile, poly-acrylic acid esters, rubber, ~asein resins, sili¢~nes a~d : silicone resi~s, as such or in admixture with one another.
For such an incorporation, it is im~aterial whether the above~
msntioned high-molecular-weight compounds are in the form o~
29 plastic masse~J melts or spinning solutions, lacquers or .
' ` ` ' ' ' ' " ' ' ~ ' ~' ' ' '``'~ ' - . ~ , .

~ HOE ?4/F 244 ~037~

printing pastes or inks. Depending on th~e intended purpose, it is useful to incorporate th~ new pigments aS toners or in the form of preparations.
The new pigments excell particularly by their high tinctorial ``
strength and transparency, their good fastness to overlacquering and their excellent fastness to light. They are therefore excellently suitable for the pigmentation of metal-effect lacquers.
- ~he following examples illustrate the inventionO
Temperatures are indicated in C.
E X A M P L E 1: `
29.2 g of 1-formyl-2-hydroxy-3-naphthoic acid anilide were added to 200 ml of ethanol and 200 ml of water and vigourously stirred ~or 15 minutes. Afterwards, 11.4 g of 2-aminophenol were added, ~igourously stirring was continued for one hour whil~ covering the reaction vessel with nitrogen. The r~action mixt~re was then heated and maintained at 60 during 90 minutes~
afterwards it was cooled, the crystals were suction-filtered~
washed with water and dried at 60.
The yield of the ~ellow azamethine was almost quantitative (38 g)~
19.1 g o~ the so obtained azamethine were dissol~ed in -~
100 ml of dimethylformamide and 10 g of copper(II)acetate in 100 ml of glycol-dimethyl ether were added. The mixture was ~5 stirred ~or 4 hours at 105, then it was cooled and the pre-cipita~e was suction-filtered at room temperature. The filter ~` ~
residue was washed with dimethylformamide and afterwards with ~ -water and then dried. 18.3 g of the deep-yellow colored aza~
2~ methine copper-complex of the formula g ~

~` :
HOE 74/~ 4 ~, .
~37~6Z

HC
` ~o--~uo ,,, , , CON}I--W
- were obtained.
. E X_A M P L E S 2.- 42: . :
It is possible to obtain other azamethine complexes (I), . 10 when azamethines of the general formula II 9 obtained by con-densation o~ aldehydes of the formula III as indicated in example 1l~ith amines ~ the ~ormu].a IV, react with metal salts - as demonstrated in example 1~

.. . .
:` 15 X X2 . ~ X3 oæ CH
~ ~ Xl ~ + M ~+ ~ ~
Y ONH-Ar 3 . Y CONH~Ar Xz . .
III IV

- Example¦ Ar Y Xl X2 X3 Z M +~ Shade in the :~
~- .... . . lacquer ~ , . .. ~ - . .
2 ¦ ¦ 4-C H H H ~ C~l ¦ reddi~h 3 ~ H H H H Cu . . ` ;- .

.. . . .

~V;~75~;2 Example Ar Y X1 . . }~2 . X3 Z~ Shade in -the .. _ ~ - . ,

4 ~3C H 4 OCH3 H H H CU
~C1 ~ H H H H CU ~e11OW-Orange 3C FH3 .
:
6 1 ~1 H 15- C6 5 H ~I H I CU eddi8h yell ow 7 ~~93 4 COOCH3 H H H CU
8 ~ 5 H H H H CU reddi~h . . . yellow ~ ~
~4 NHCOCH3 H H CH3 CU ;;

11 ~02 4_CON~ H H H CU 1 12 1~;O2CH3 14 co H-C6~5 H H CH3 ~CU I 1 13 ¦~ H ¦5-NH 0 C6H5 4-CH3 H CH3 ¦CU ¦ Ye~1OW--Ir~9C
14 ¦ ~ Br¦5-Cl H H H ¦CU I n :.-:- . --: . ~ .. - :. ... , : ~ .. . : .
. :-. :: . '. . . : . ~ . . :

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

Example¦ Ar Y ¦ X1 X2 X Z 1 ~S ~ ¦Shade in th~
. . J . 3laoquer ~ `
~ . __ ~
~ 6-C1 H nn Izn 1 yellow 16 ~ H 4-Br H H H Cu¦ reddish Cl . . yellow.
17 ~ 4-Cl 5-CH3 H H Cu ~ellow .": 1 . ....
:' . . . .

18 ~ Cl H 4-C1 6-Cl H H r~i ., :
. -~3 . . ~ . 19 H 5-N02 6-CH3 H H Cu 20 ~ ICOC~3 H 5-Cl ~ H C}~3 Cu redd sh CH3 O . ... ~ .
2;1 ~ 4, 5-NH- d -NH H . H Cu ..
. .

-22 ~ NH n 4~Cl H H H Cuyellow . . -: 2 ~ ~ H 3-C1 4~C1 6-Cl H Cu g eenish - ~Hj . ~ . ~ . ...... ~

2 4 ~ ON~2 H H H H Cue ish S02NHCH3 . .
g ~ H H H H Cull . ..
,- _....... .. _ _ , - .~ . , _ 26 ~NHCOC6H5 H 4-CoNHc6H5 H H H Cu edd sh :: ;

HOE_74/F 24 7~iZ
Example¦ A~ , X1 ` X2 X Z ¦ ~ ~+ IShade in the , 3 lac~uer `
__. _ ., _ . ... ~. _ . . ` ... ,. _ k_~C02CH3 H H H H HCu Ivel l ow . .
.`
28 ~3 H ~1 H H H Cu. Il `
~ .
CN .
29 ~3 H 4-Br H H H Cun ~ H H H H H Cu n Br :.:
CH S~ .
3 ~ 3~> . H . ~ . . H Cu ddi h 32 ~ H 4-C1 5-No 2 H H Gu n 33 CH3 ~3 H 4-CooCH3 H H H Cu n tl . .
. CH3 .
34 ~ H 4-CH3 X H H Cu l- . tl .: - . . 3 ~~_ .
~ Br 4-CooCH3 H H ~ H Cu oran~
Cl~ ' _ . .
36 ~ H 4-CoocH H H H Cu reddish . 3 . yellow ~1 . .
~\
37 ~ H . 4~CoocH3 ~ ~ ~i C~t ye~ ow ,: Cl .
~ .
., .
.. 13 .

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

i~7~9~Z

Example ¦ Ar y Z ~ + Shade in the 38 ¦ Cll N ¦ N ¦ ~ ¦ H I ~i I Cu orallg~, ~ ~ ~ H H H ~I H H yellow 40 ~ o X ¦ N ~ N ¦ Cu orallg~

41 ¦ 1~` ?;~ N 1 4 Ol ¦ H ¦ N N ¦ Cu yellow 42 ~ H ¦_Cl ~ b ~

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

,~ ;, : ' :

~, ' - , . ~.

.' .
.. . .. . .. ... . .

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula wherein X1, X2 and X3, which are identical or different, are hydrogen, halogen, lower alkyl, lower alkoxy, phenyl, tolyl, nitro, lower carboalkoxy, sulfonamide, lower mono- or dialkyl sulfonamide, carbamoyl, lower mono- or di-alkyl carbamoyl, lower alkanoyl or a group of the formula wherein G is -NHCO-, -SO2NH- or -CONH- and R is hydrogen, chlorine, lower alkyl, lower alkoxy, sulfonamide or carbamoyl, or X1 and X2 together with the benzene ring to which they are linked stand for benzimidazole; Y is hydrogen, chlorine or bromine; Ar is benzimidazolonyl, chlorobenzimidazolonyl, quinazolin-dionyl, quinoxazolinyl phthalimidyl, phthalazinyl, naphthyl, phenyl or phenyl substituted by 1 to 3 equal or different substituents selected from lower alkyl, lower alkoxy, lower alkylsulfonyl, lower carboalkoxy, trifluoromethyl, nitro, cyane, lower alkanoylamino, benzoylamino, carbamoyl, lower mono- or dialkyl carbamoyl, sulfonamide, lower mono- or dialkyl sulfonamide and halogen;
and M is zinc, cadmium, cobalt, nickel or copper.

2. A compound as claimed in claim 1, wherein X1, X2 and X3 are hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, nitro, acetamino, carbomethoxy, carbamoyl, lower alkyl carbamoyl, phenylcarbamoyl; Y is hydrogen, chlorine or bromine; Ar is benzimidazolyl, chlorobenzimidazolyl, phenyl or phenyl substituted by 1 to 3 substituents selected from lower alkyl, lower alkoxy, lower alkyl-sulfonyl, lower carboalkoxy, trifluoromethyl, nitro, cyano, lower alkanoylamino, benzoylamino, carbamoyl, lower mono- or dialkyl carbamoyl, sulfonamide, lower mono- or dialkylsulfonamide, bromo and chloro;
and M is nickel or copper.

3. A compound as claimed in claim 1 having the formula wherein Y is hydrogen or bromine, X1 is hydrogen, chlorine or lower carboal-koxy, X2 is hydrogen or nitro, R1 is hydrogen, lower alkyl or lower alkoxy;
R2 is hydrogen or chlorine and R3 is hydrogen or lower alkoxy.

4. The compound as claimed in claim 3, wherein Y, X1 and X2 are hydrogen, R1 and R3 are methoxy and R2 is chlorine.

5. The compound as claimed in claim 3, wherein Y, X1, R2 and R3 are hydrogen and R1 is ethoxy.

6. The compound as claimed in claim 3, wherein Y, X1, X2, R2 and R3 are hydrogen and R1 is methoxy.

7. The compound as claimed in claim 3, wherein Y, R1, R2 and R3 are hydrogen, X1 is chlorine and X2 is nitro.

8. The compound as claimed in claim 3, wherein Y, X2, R2 and R3 are hydrogen, X1 is carbomethoxy and R1 is methyl.

9. The compound as claimed in claim 3, wherein X2, R2 and R3 are hydrogen, Y is bromine, X1 is carbomethoxy and R1 is methoxy.

10. A process for the preparation of a compound as claimed in claim 1, which comprises reacting a compound of the formula in which X1, X2, X3, Ar and Y have the meanings given in claim 1 and Z is hydrogen or methyl, with a salt having M as cation in a polar organic solvent at a temperature of 70 to 180°C.

11. A process as claimed in claim 10, wherein M is copper, nickel or cobalt.

12. A process as claimed in claims 10 and 119 wherein M is copper.

13. A process as claimed in claim 10, wherein Z is hydrogen and the temperature is 70 to 150°C.

14. A process as claimed in claim 10, wherein Z is methyl and the temperature is 100 to 180°C.

15. A process for coloring colourless articles which comprises contacting said article with a compound as claimed in

claim 1.