JPS60106859A - Metal complex salt compound - Google Patents

Abstract

NEW MATERIAL:A 2:1 metal complex salt compound of formula I , wherein R1 is H, a 1-10C alkyl, a 1-4C alkoxy, a 2-5C alkoxycarbonyl, a 2-5C acyl, aminocarbonyl, nitro, cyano, halogen, etc.; m is 1-4: R2 is H, halogen, cyano, nitro, methyl, ethyl, propyl; R3 is H, a 1-10C alkyl, (substd.) phenyl; R4 is H, a 1-4C alkyl, halogen; M is Cr, Co; X<-> is an anion. EXAMPLE:Compd. of formula II. USE:Production of an electrophotographic developing agent exhibiting stable charging characterisitcs. Dyeing or coloring natural and synthetic fibers and plastics brown with high fastness. PREPARATION:A diazo component of formula III (wherein R1, m are as defined above) is diazotized. The resulting diazo compd. is coupled with a coupling component of formula IV (wherein R2, R3, R4 are as defined above; Y<-> is an anion) to obtain a monoazo compd. of formula V (wherein R1, R2, R3, R4, m are as defined above; Z<-> is an anion). The monoazo compd. is treated with a Cr-imparting agent or a Co-imparting agent in water or an org. solvent.

Description

[Detailed description of the invention] The present invention relates to metal complex compounds.

More specifically, the present invention relates to the following general formula (1) (wherein R
1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 1 carbon number
-4 alkoxy group, C2-5 alkoxycarbonyl group, C2-5 acyl group, aminocarbonyl group, C2-5 alkyl abanocarbonyl group, C1-3 alkylsulfonyl group , aminosulfonyl i,
Represents an acylamino group, nitro group, cyano group, or halogen atom having 2 to 5 carbon atoms, m is an integer of 1 to 4, m
is two or more, R2 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a methyl group, an ethyl group, a propyl group, and R3 represents a hydrogen atom. , represents an alkyl group having 1 to 10 carbon atoms, or a phenyl group that may be substituted, R4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and M is a chromium atom or a cobalt atom. represents,
XO represents an anion. ) a new 2 represented by:
It is a fluorine metal complex salt compound.

The novel 7:c metal complex salt compound represented by the general formula (1) is useful in various uses, but it is particularly excellent in the charge control effect of electrophotographic developers, and contains the metal complex salt compound of the present invention. Electrophotographic developers exhibit extremely stable charging characteristics. In addition, the metal complex compound of the present invention has high fastness and is useful for dyeing natural delicates, synthetic fibers, and plastics.

The metal complex salt compound of the present invention has the following general formula (2) (wherein,
R1,m are as defined above. ) is diazotized by a conventional method, and this diazo compound is represented by the following general formula (6) (wherein s R2s R3,14 are as defined above, and YO represents an anion). °By coupling with the coupling component according to a conventional method,
A mono-1zo compound represented by the following general formula (4) (wherein, island, R,, R3, R4, and m are as defined in +tt+, and Z○ represents an anion) is synthesized, and then This 1,000-noazo compound can be obtained in high yield by treating it with a chromation-imparting agent or a cobaltation-imparting agent in water or an organic solvent by a conventional method.

Examples of the diazo component represented by the above general formula (2) used in the present invention include 3-chloro4-2-aminophenol, 4-chloro-2-7minophenol, 4-bromo-2-7minophenol, 5-promo-2-aminophenol, 4-iodo-2-aminophenol, 6,5-
dichloro-2-aminophenol, 4,6-dichloro-
2-aminophenol, 3,4.6-dolichloro 2-
Aminophenol, 4-di) o -2-aminoneenol, 5-nitro-2-aminophenol, 6-chloroμ
m4-nitro-2-aminophenol, 4-chloro-5
-2) o -2-aminoneenol, 4-chloro-
6-nitro-2-aminophenol, 6-promo-4-
Nitro-2-aminophenol, 4-methyl-2-aminophenol, 4-4-buty/I/-2-aminophenol, 4-4-octyl-2-aminophenol, 4.
5-dimethyl-2-7 minophenol, 4-methoxy-
2-7 Minophenol, 4-methyl-5-nitro 2-
Aminophenol, 4-bup-5-methyl-2-7minophenol, 4-cyano-2-aminophenol, 4
-acetyl-2-aminophenol, 4-methoxycarbonyl-2-aminophenol, 4-7minocarbonyl-2-aminophenol, 4-ethylaminocarbonyl-2-aminoenol, 4-aminosulfonyl-2
-aminophenol, 4-probylsulfonyl-2-aminephenol, etc.

Further, as the coupling component represented by the general formula (5), N-(2-oxo-6-hydroxy-1゜2-dihydropyridin-3-yl)pyridinium chloride, N-
(2-oxo4-methyl-6-hydroxy-1,2-
dihydropyridin-3-yl)pyridinium bromide, N-(1,4-dimethyl-2-oxo-6-hydroxy-1,2-cyhydropyridin-3-yl)pyridinium chloride, N-(2-oxy-4-ethyl -6-hydroxy-1,2-dihydropyridin-3-yl)pyridinium bromide, N-(2-oxy-4-cyano-
6-hydroxy-1,2-dihydropyridin-6-yl)pyridinium tetralide, N-(2-oxo-4-nitro-6-hydroμxy-1,2-dihydropyridine-3
-yl)pyridinium chloride, N-('-propyl-2-oxy-4-methyl-6-hydroxy-1,2
-dihydropyridin-3-yl)pyridinium chloride, N -(1-tt-butyl-2-oxy-4-methyl-6-dihydropyridin-3-yl)pyridinium-6-
yl)pyridinium prid, N-(1-octyl-
2-oxo-4-methyl-6-hydroxy-1,2-dihydropyridin-3-yl)pyridinium chloride,
N-[1-(2-chlorotetraphenyl)-2-oxo-4-
Methyl-6-hydro-1,2-dihydropyridine-
3-yl]pyridinium chloride, 4-methyl-N-
(2-oxo-4-methyl-6-hydroxy-1,2-
dihydropyridin-5-yl)pyridium bukimide,
3-poly(N-(2-oxo-4-methyl-6-hydroxy-1,2-dihydropyridin-5-yl)pyridinium) and the like are prepared.

Suitable solvents for forming a monoazo compound into a complex salt include water,
Single members such as ethylene glycol, methyl cellosolve, diethylene glycol, butanol, dimethylformamide, and triethanolamine may be used as a mixture. Examples of metallizing agents include sodium chromium salicylate, chromium formate, chromium acetate, chromium sulfate, chromium nitrate, Pupart acetate, cobalt chloride, and cobalt sulfate.

Hereinafter, the present invention will be explained in detail by way of examples.

In the examples, parts represent parts by weight.

Example 1 14.4 parts of 4-chloro-2-aminophenol was added to 26
The mixture was stirred with 100 parts of concentrated hydrochloric acid and 400 parts of water, cooled on ice to 0 to 5°C, 6.9 parts of sodium nitrite was added, and diazotized at the same temperature. This diazotide was mixed with 400 parts of water,
10 parts of sodium hydroxide and 3 parts of 2a
After performing a coupling reaction on a mixture of oxo-4-methyl-6-hydroxy-1,2-dihydrobiricin-3-yl)pyridinium chloride, a monoazo compound having the following structural formula was isolated. did.

Dissolve this monoazo compound in 150 parts of methyl cellosolve, add 17.4 parts of sodium chromium salicylate, stir at 90 to 95°C for 3 hours to perform chromation, cool to 30°C, add hydrochloric acid and Congo. Isolate the product as a red acid at room temperature and dry it under reduced pressure at 50 to 60°C to obtain chromium complex compound 3a as a reddish brown fine powder represented by the following formula.
Got 2 copies.

The maximum absorption wavelength of this complex salt compound in methanol solvent was 522 jII+. By using an electrophotographic developer comprising this complex salt compound, styrene-n-butyl methacrylate, and carbon black, extremely clear images could be obtained.

The coupling component used in this example can be synthesized by heating and stirring N-carbamoylmethylpyridinium chloride and ethyl a7toacetate in ethanol using sodium hydroxide as a catalyst.

Example 2 44.2 parts of a monoazo dye having the following structural formula obtained in the same manner as in Example 1 was dissolved in 140 parts of ethylene glycol, 17.4 parts of sodium chromium salicylate was added, and the mixture was stirred at 100 to 105°C for 3 hours. After shimming, the mixture was cooled to 20°C and treated in the same manner as in Example 1 to obtain 44 parts of brown powder represented by the following formula.

The maximum absorption wavelength of this chromium complex salt compound in dimethylformamide was measured to be 528 sm.

Examples S to 20 Complex salt compounds were obtained according to Example 1.2. The structural formula, maximum absorption wavelength, and appearance of this complex salt compound are summarized in the following table.

Claims (1)

[Scope of Claims] The following general formula (wherein R1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, or an alkoxycarbonyl group having 2 to 5 carbon atoms) 5 acyl group, aminocarbonyl group, alkylaminocarbonyl group having 2 to 5 carbon atoms, alkylsulfonyl group having 1 to 3 carbon atoms, aminosulfonyl group, azila ε) group having 2 to 5 carbon atoms, nitro group,
represents a cyano group, a halogen atom, m is an integer of 1 to 4, and when m is 2 or more, the islands can be different substituents; R2 represents a hydrogen atom, a halogen atom, a cyano group, Represents a nitro group, methyl group, ethyl group, or propyl group, R3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an optionally substituted phenyl group, and R4 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 4 represents an alkyl group or a halogen atom, ■ represents a chromium atom or a cobalt atom, and XO represents an anion. ) 2:
Type 1 metal complex compound.