New bis-2-azomethine pigments, process for their manufacture and their use
United States Patent 1 1 LEplattenier et al.  
 [451 Apr. 1, 1975 NEW BIS-Z-AZOMETHINE PIGMENTS,  
 PROCESS FOR THEIR MANUFACTURE AND THEIR USE [75] Inventors: Francois LEplattenier, Therwil;  
 Andre Pugin, Riehen; Laurent Vuitel, Therwil, all of Switzerland [73] Assignee: Ciba-Geigy Corp., Ardslgy, NY.  
 [22] Filed: June 13, 1973 [21] Appl. No.: 369,671  
 [30] Foreign Application Priority Data June 19, 1972 Switzerland 9190/72 [52] US. Cl...... 260/439 R, 260/429 R, 260/429 C, 260/429.9, 260/438.1, 260/465 D, 260/465 F, 260/465 E, 260/469 260/471 H, 260/473 R, 260/515 P, 260/518 R, 260/519, 260/520, 260/556 B, 260/565 S, 260/558 R, 260/559 [51] Int. Cl C07f 15/04, C07f 3/08, C07f 1/08 [58] Field of Search 260/439 R, 429 R, 429 C, 260/438.l, 429.9; 106/288 Q [56] References Cited UNITED STATES PATENTS 2,993,065 7/1961 Kumins et al. 260/439 R 3,393,178 7/1968 Lynch ct a1 260/40 3,398,170 8/1968 Cyba ct a1 260/439 R 3,440,254 4/1969 Lenoir ct a1. 260/249 R 3,441,578 4/1969 Dimroth 260/249 R 3,457,301 7/1969 Lenoir ct al. 106/288 Q 3,472,876 10/1969 Klein 260/439 R 3,687,991 8/1972 Gacng ct a1 260/429.9  
 Primary Examiner-Arthur P. Demers Attorney. Agent, or Firm-Vincent .1. Cavalieri [57] ABSTRACT Bis-azomethine pigments of the formula 3 Claims, No Drawings 1 NEW BIS-Z-AZOMETHINE PIGMENTS, PROCESS FOR THEIR MANUFACTURE AND THEIR USE A It has been found that new,&#39;valuable bis-azomethine pigments of the formula wherein X denotes an aromatic radical on which the imino groups are in the o-position, Y denotes a hydroxyl, alkoxy, cycloalkoxy, aralkoxy or aryloxy, amino, alkylamino or arylamino group and Z denotes a H or halogen atom or an alkoxy, nitro or nitrile group, the radical X having to be free of nitro groups if Y denotes an arylamino group and Z denotes a H atom, as well as metal complexes of these azomethines are obtained if an aldehyde of the formula is condensed in the molar ratio of 2:1 with an appropriate diamine of the formula and the resulting bis-azomethine is metallised if desired.  
  Dyestuffs of particular interest are those of the formula OH OH Z COY YO C -Z wherein R and R denote H or halogen atoms, lower alky, alkoxy, alkoxycarbonyl, alkylsulphonyl or alkanoylamino groups, trifluoromethyl or nitro groups or phenoxy or phenylmercapto groups which are optionally substituted by halogen atoms or lower alkyl or alkoxy groups, or wherein the radicals R and R together form a fused benzene ring and R is a H or halogen atom or a lower alkyl group.  
  Possible starting substances are the l-formyl-Z- hydroxynaphthalene-3-carboxylic acids, their esters, especially with lower aliphatic, araliphatic or alicyclic alcohols or with phenols, their amides, alkylamides or arylamides, especially those of the formula HCO I OH R3 wherein Z has the indicated meaning, R and R denote H or halogen atoms, lower alkyl, alkoxy, alkoxycarbonyl, alkylsulphonyl or alkanoylamino groups, trifluoromethyl or nitro groups or phenoxy or phenylmercapto groups which are optionally substituted by halogen atoms or lower alkyl or alkoxy groups, or the radicals R and R, together form a fused benzene ring, and R is a H or halogen atom or a lower alkyl group.  
  The aldehydes which serve as starting substances are in most cases unknown compounds. As examples there may be mentioned: l-formyl-2- hydroxynaphthalene-3-carboxylic acid, l-formyl-6- bromo-2-hydroxynaphthalene-3-carboxylic acid, I- formyl-6-methoxy-2-hydroxynaphthalene-3-carboxylic acid, l-formyl-2-hydroxynaphthalene-3-carboxylic acid methyl ester, l-formyl-2-hydroxynaphthalene-3- carboxylic acid ethyl ester, l-formyl-Z- hydroxynaphthalene-3-carboxylic acid propyl ester, 1- formyl-2-hydroxynaphthalene-3-carboxylic acid butyl ester, l-formyl-2-hydroxynapthalene-3-carboxylic acid ,B-ethoxyethyl ester, l-formyl-2-hydroxynaphthalene- 3-carboxylic acid phenyl ester, l-formyl-2- .hydroxynaphthalene-3-carboxylic acid benzyl ester, 1-  
 formyl-2-hydroxynaphthalene-3carboxylic acid 2 methoxyphenylamide, l-formyl-Z- I hydroxynaphthalene-3carboxylic acid 4- methoxyphenylamide, 1-formyl-2- hydroxynaphthalene-3-carboxylic acid 2&#39;- ethoxyphenylamide, 1formyl-2-hydroxynaphthalene- 3-carboxylic acid 4&#39;-ethoxyphenylamide, l-formyl-2- hydroxynaphthalene-3-carboxylic acid 2,5-dimethoxyphenylamide, l-formyl-Z- hydroxynaphthalene-3-carboxylic acid 2 methoxy-5&#39;- chlorophenylamide, 1-formyl-2-hydroxynaphthalene- 3-carboxylic acid 2,4&#39;-dimethoxy-5- chlorophenylamide, lformyl-Z-hydroxynaphthalene- 3-carboxylic acid 2&#39;,5-dimethoxy-4- chlorophenylamide, l-formyl-6-bromo-2- hydroxynaphthalene-3-carboxylic acid phenylamide and lformyl-2-hydroxynaphthalene-3carboxylic acid a-naphthylamide.  
  lFormyl-Z-hydroxynaphthalene-3-carboxylic acid is a known compound which is obtained by formylation of 2,3-hydroxynaphthalene carboxylic acid.  
  The 1formyl-2-hydroxynaphthalene-3-carboxylic acid esters are new and can be obtained by reaction of lformyl-2-hydroxynaphthalene-3-carboxylic acid with thionyl chloride to give l-formyl-2- hydroxynaphthalene-3carboxylic acid chloride andreaction of the latter with an alcohol or phenol.  
  The lfoimyl-Z-hydroxynaphthalene-3-carboxylic acid anilides are partly known and can be obtained by reaction of l-formyl-2,3-hydroxynaphthalic acid with thionyl chloride to give the acid chloride, condensation of the latter with an aminobenzene to give the anil of the lformyl-Z,3-hydroxynaphthalene carboxylic acid anilide and hydrolysis of the latter to give the l-formyl- 2,3-hydroxynaphthalene carboxylic acid anilide.  
  The new lformyl-2,3-hydroxynapthalene carboxylic acid alkylamides can be obtained analogously.  
  Possible aromatic diamines are both carbocyclic and heterocyclic aromatic 1,2-diamines, preferably phenylenediamines and especially those of the formula phenylenediamine, 4-methoxy-l,Z-phenylenediamine,  
 4-phenoxy-1,2-phenylendiamine, 4-methylsulphonyl- LZ-PhenyIenediamine, 4-ethylsulphonyl- 1 ,2- phenylenediamine, 4-carboxy-l,2-phenylenediamine,  
 4-methoxycarbonyll ,Z-phenylenediamine, 4- ethoxycarbonyll ,Z-phenylenediamine, 4- butoxycarbonyl-l ,2-phenylenediamine, 4- hexyloxycarbonyl-l ,Z-phenylenediamine, 4-  
 octyloxycarbonyll ,Z-phenylenediamine, 4-cyano-1 ,2- phenylenediamine, 4-acetylaminol ,2- phenylenediamine, 4-benzoylaminol ,2-  
 phenylenediamine; 3,4-diaminodiphenyl, 1,2- diaminonaphthalene, 2,3-diaminonaphthalene, 1,2- diamino-S,6,7,S-tetrahydronaphthalene, 2,3-diamino- 5 ,6,&#39;7,S-tetrahydronaphthalene, 1,2- diaminoanthraquinone, 2,3-diaminoanthraquinone, 9, l O-diaminophenanthrene, 5 ,6- diaminoacenaphthene, 3,4-diaminopyridine, 2,3-  
 diaminodiphenylene oxide, 2,3-diaminoquinoxaline and 2-methyl-5,6-diaminobenzimidazole.  
  The condensation of the aldehyde with the diamine is appropriately carried out in water or in organic solvent at elevated temperature, preferably between 50C and the boiling point of the solvent used. As examples of solvents there may be mentioned: water, alcohol, glacial acetic acid, dioxane, dimethylformamide, N- methylpyrroiidone, butyrolactone, glycol monomethyl ether, xylene, chlorobenzene, o-dichlorobenzene, nitrobenzene or mixtures thereof. Since the bis-azomethines obtained are sparingly soluble in&#39;the solvents mentioned, they can easily be isolated by filtration. Any impurities can be removed by elution.  
  For conversion into the metal complexes, the resulting bis-azomethines are treated with agents which release divalent metals, for example with salts of zinc or cadmium, but especially of copper and above all of nickel. Preferably, the formates, acetates or stearates of these metals are used. The metallisation is appropriately carried out in one of, or in a mixture of, the abovementioned solvents.  
  The metallisation can be also be carried out simultaneously with the condensation by condensing the aldehyde together with the diamine in one of the abovementioned solvents in the presence of metal salts.  
  The metal complexes obtained preferably correspond to the formula COY YOC Z Z \/5 COY YO W wherein M denotes a nickel or copper atom and R R Y and Z have the abovementioned meaning.  
  The new dyestuffs represent valuable pigments which can be used in a finely divided form for pigmenting high molecular organic material, for example cellulose ethers and cellulose esters, such asethylcellulose, cellulose acetate, cellulose butyrate, natural resins or synthetic resins, such as polymerisation resins or polycondensation resins, for example aminoplasts. especially urea-formaldehyde and melamine-formaldehyde&#34; resins, alkyd resins, phenoplasts, polycarbonates, polyesters, polyamides or polyurethanes, polyolefines. such as polyethylene or polypropylene, polyvinyl chloride, polystyrene, polyacrylonitrile, polyacrylic acid esters, rubber, casein, silicones and silicone resins, individually or as mixtures.  
  lt is immaterial whether the high molecular compounds mentioned are in the form of plastic masses or melts or in the form of spinning solutions, lacquers, paints or printing inks. It proves advantageous to use the new pigments as toners or in the form of preparations, depending on the application.  
  In addition to the pure pigment the preparations can, for example, additionally contain natural resins, such as abietic acid or its esters, ethylcellulose, cellulose acetobutyrate, alkaline earth metal salts of higher fatty acids, fatty amines, such as stearylamine or rosin amine, vinyl chloride vinyl acetate copolymers, polyacrylonitrile or polyterpene resins or water-soluble dyestuffs, for example dyestuff-sulphonic acids or their alkaline earth metal salts. 1  
  In the examples which follow the parts denote parts by weight, unless otherwise stated.  
 EXAMPLE 1 3.50 g (0.012 mol) of l-formyl-2-hydroxy-3- naphthoic acid anilide are suspended in 60 ml of alcohol or glacial acetic acid and a solution of0.64 g (0.006 mol) of o-phenylenediamine in ml of alcohol or glacial acetic acid is added. After refluxing for 3 hours, the orange suspension is filtered hot. The filter residue is boiled in 50 ml of methylcellosolve for 1 hour at 100C. After cooling to 20C, the mixture is filtered and the residue is washed with water, alcohol and acetone. 3.45  
 g (88% of theory) of an orange pigment of the formula wherein X, and X H, are obtained.  
  l-Formyl-2-hydroxy-3-naphthoic acid anilide used in Example 1 can be obtained as follows:  
 &#39; 32.4 g (0.150 mol) of l-formyl-2-hydroxy-3- naphthoic acid in 375 ml of chloroform are carefully treated with 150 ml of thionyl chloride and the mixture is warmed to the boil. After one hour, the reaction mixture is evaporated on a rotary evaporator, the residue is taken up in 300 ml of petroleum ether, the mixture is stirred for 5 minutes and the product is filtered off. The acid chloride thus obtained is well washed with petroleum ether and redissolved in 350 ml of chloroform. After adding 41.0 ml (0.450 mol) of aniline dissolved in ml of chloroform, the reaction mixture is stirred for 15 minutes and evaporated in vacuo, and the residue is stirred in water. It is then filtered off and the filter residue is well washed with water and dissolved in 1.5 litres of ethylcellosolve. 50 ml of concentrated hydrochloric acid are added dropwise to this solution and the mixture is then heated for 10 minutes under reflux. After cooling, the amide which has crystallised out is filtered off, washed with alcohol and dried. 24.5 g (56.2% of theory) of a yellowish analytically pure substance are obtained (melting point 217C).  
  The aldehydes used in Examples 2, 3, 4 and 5 (Table 1) can be obtained analogously.  
 EXAMPLES 2-6 If the procedure indicated in Example 1 is followed but using, instead of 0.012 mol of l-formyl-Z-hydroxy- 3-naphthoic acid anilide, the amounts of aldehyde indicated in the table which follows, similar pigments are obtained, with the colour and yield indicated in Table l.  
 TABLE 1&#39; l i iii ri r Aldehyde ald e l 1 3 r X1 X; pzr c e iit i l 2 CHO 0.014 H H 05 Yellow.  
 -o ONHC1 a 3H0 I 0.020 H n 83 D0.  
 /-\OH ()CHs v i -ooNfl-@-oom 4 0110 0.020 -o1 -c1 91 Do.  
  O OH TABLE I- Continued Example number Aldehyde Mols of aldehyde Yield, Shade in X1 X2 percent PVC (IJHO OH CHO  l-Formyl-2-hydroxy-3-naphthoic acid methyl ester, used in Example 6, is obtainable as follows: 64.8 g (0.30 mol) of l-formyl-23-naphthoic acid are suspended in 200 ml of methylene chloride and 29ml of thionyl chloride are added. After refluxing for 2 hours the reaction mixture is evaporated on a rotary evap0ra-. tor. The acid chloride thus obtained is well washed with petroleum ether and taken up in 300 ml of methylene chloride. After addition of 100 ml (2.48 mols) of methanol and 24 ml of pyridine (0.30 mol), the reaction mixture is stirred for 1 hour under reflux and then evaporated in a rotary evaporator. The residue is well washed with water and recrystallised from n-butanol. 42.6 g (61.8% of theory) of a yellow analytically pure substance are obtained (melting point l40-l4lC).  
 EXAMPLE 7 1.50 g (0.002 mol) of the azomethine from Example 2 are dissolved in 50 ml of dimethylformamide and the solution is warmed with 0.50 g (0.002 mol) of nickel-ll acetate tetrahydrate for 2 hours to 70C. After cooling, the red-brown precipitate is filtered off and washed with dimethylformamide, alcohol, water and acetone. 1.15 g (72% of theory) of a red-brown pigment of the formula are obtained.  
  EXAMPLES 8 44 wherein X Y and Z have the meaning indicated in Columns 2 to 4 of Table II which follows, are metallised, in the molar amount indicated in Column 6, with the metal indicated in Column 5, in accordance with the instructions of Example 4. Column 7 indicates the yield and Column 8 the shade of the resulting colouration in polyvinyl chloride.  
 TABLE II Yield,  
 Example N 0. X; Y Z M+ Mol percent Shade in PVC 8 -OH H Ni 0.005 88 Red-brown.  
 9 Sameasabove OH H Cu 0.005 88 Yellow-brown- 10 .do OH H Zn 0.005 Yellow.  
 11 OH; OH H Ni 0.003 69 Orange.  
 12 Sameasabove OH H Cu 0.003 92 Yellow-brown.  
 Yield,  
 Example N0. X1 Y Z M M01 percent Shade in PVC 13 (|.OOH OH 11 Ni 0.003 80 Orange.  
 14 Same as above OH H Cu 0.003 90 Brown.  
 15- (|)C2H5 OH H Ni 0. 003 85 Red-brown.  
 OH H Cu 0.003 65 D0.  
  Sameasabove OH H Zn 0.003 87 Yellow.  
 OH H Ni 0.003 91 Orange.  
 19 Sameasabove OH 11 Cu 0.003 94 D0.  
 20 OH H Ni 0.003 89 Brown.  
 I O l 21 Sameasabove OH H Cu 0.003 88 Yellow.  
 22 0H NO2 Ni 0.004 95 Do.  
 23 Sameasabove OH Br Ni 0.0025 87 Orange.  
 Br Zn 0.0025 86 Yellow.  
 H Ni 0.005 91 Red.  
 H Cu 0.005 95 Yellow-brown.  
 H Zn 0.003 89 Yellow.  
 28 Sameasslbove H Ni 0.002 99 Red 29 do Same as above H Cu 0.0035 76 Brown.  
 Zn 0. 0035 71 Orange.  
 Cu 0.0025 92 Do.  
 32 CH3 CH3 d0 11 Ni 0.004 71 DO.  
 33 C1 C1 10 H Ni 0.004 83 Do.  
 34 Same as above II Ni 0.002 93 Red.  
 -NH- CHa 35 .do H Ni 0.002 04 Orange.  
 Yield, Example No. X1 Y Z M M01 percent Shade in PVC 36 Same as above CH II Cu 0.0025 79 Brown.  
 NH Cl 37 do Same asabove II Zn 0.002 06 Yellow.  
 38 do do H Cd 0. 0013 100 D0.  
 39 .do CH |O II Ni 0. 002 68 D0. NH @-oom 40. CH O H Cu 0.002 67 Brown.  
 | -NH -OCH 41 Same as above Same as above H Zn 0.002 76 Yellow.  
 42 do -OOH H Ni 0.003 95 Orange. 43 do 0CH H Cu 0.003 95 Yellow-brown.  
 44 Cl (&#39;11 0CH H Ni 0.004 76 Brown.  
 The metal complexes which are mentioned in Exam- R1 R2 ples 7 to 44 can be manufactured in one step by reacting the l-formyl-2-hydroxy-3-naphth0ic acid or 1- formyl-Z-hydroxy-3-naphthoic acid arylides and l-formyl-2-hydroxynaphthoic acid methyl ester with the diamine in the presence of the metal ion and in a solvent such as alcohol, methylcellosolve, dioxane, glacial acetic acid or dimethylformamide.  
 EXAMPLE 45 4.32 g (0.02 mol) of l-formyl-2-hydroxy-3-naphthoic acid, L08 g (0.01 mol) of o-phenylenediamine and 2.50 g (0.01 mol) of nickel(ll) acetate tetrahydrate are suspended in 100 ml of glacial acetic acid and the mixture is boiled for minutes under reflux. A thick orange precipitate forms. Ater cooling, the product is filtered off and washed with glacial acetic acid, alcohol, water and acetone. 4.20 g (75% of theory) of a redbrown pigment, which is identical with the product of Example 8, are obtained.  
 EXAMPLE 46 65 parts of stablised polyvinyl chloride, parts of dioctyl phthalate and 0.2 part of the dyestuff obtained according to Example 1 are stirred together and then milled for 7 minutes at 140C on a two-roll calender. An orange-coloured sheet of good fastness to light and to migration is obtained.  
 We claim:  
 I. A bis-azomethine pigment of the formula k, z-[iklcoy YOC Z 2. A bis-azomethine pigment according to claim 1 wherein Y is wherein R, and R, are hydrogen, halogen, lower alkyl, lower alkoxy, trifluoromethyl or phenoxy, or R and R together form a fused benzene ring, and R is hydrogen,  
 halogen or lower alkyl.  
 3. The compound according to claim 1 of the formula i ONH HNO oi N: CH