JPH11140080A - Production of quinoline derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce the subject compound and its tautomer suitable for use in a luminous layer of a fluorescent flaw detecting agent or an electroluminescent element by reacting a zinc complex having a specific structure in an aqueous solution of a mineral acid at a specified concentration. SOLUTION: (A) A zinc complex represented by formula I (Y<1> to Y<20> are each independently H, a halogen, nitro, cyano, hydroxyl, amino, an alkyl, an aryl, an alkoxy or the like) is reacted in (B) a mineral acid at >=8 wt.% concentration (preferably hydrochloric acid at 8-35 wt.% concentration or sulfuric acid at 8-50 wt.% concentration) to afford (C) a quinoline compound represented by formula II (R<1> to R<10> are each independently H, a halogen, nitro, cyano, hydroxyl, amino, an alkyl, an aryl, an alkoxy or the like) and its tautomer. For example, a zinc complex represented by formula III can be obtained by heating phthalimide with quinaldine, zinc chloride and N,N-dimethylaniline, further adding pyridine thereto and heating the resultant mixture as the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a quinoline compound suitable for use in a fluorescent flaw detector or a light emitting layer of an electroluminescent device.

[0002]

2. Description of the Related Art A dye having a fluorescent property has long been represented by the following formula (3).

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[0003] The quinoline compound represented by
gs Ann. Chem. , Vol. 315, p. 30
3 (1901) and Chem. Ber. , Vol. 1
00, p. 2261-2273 (1967). JP-A-56-147784 describes a method in which phthalimide and quinaldine are dehydrated and condensed with zinc chloride in the presence of pyridine or quinoline. However, this prior art is complicated in operation, the yield of the obtained quinoline compound of the formula (3) is low,
It is hard to say that it is an industrial manufacturing method. Further, the luminance in a solid state is low.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the following general formula (1)

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[In the formula (1), Y ¹ , Y ² , Y ³ , Y ⁴ ,
Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ , Y ¹² , Y ¹³ ,
Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ , Y ¹⁸ , Y ¹⁹ , and Y ²⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted alkyl group Substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted N-alkylamino group, substituted or unsubstituted N, N-dialkylamino group, substituted or unsubstituted N -Represents an arylamino group, a substituted or unsubstituted N, N-diarylamino group, or a substituted or unsubstituted N-alkyl-N-arylamino group. By reacting the zinc complex represented by the formula (1) with a specific concentration of a mineral acid to obtain a high-quality general formula (2) that cannot be achieved by the prior art.

[0006]

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In the formula (2), R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted alkyl group, Unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted N-alkylamino group, substituted or unsubstituted N, N-
Represents a dialkylamino group, a substituted or unsubstituted N-arylamino group, a substituted or unsubstituted N, N-diarylamino group, or a substituted or unsubstituted N-alkyl-N-arylamino group. ] And a technique capable of producing the quinoline compound and a tautomer thereof.

That is, the present invention is a method for producing a quinoline compound suitable for use in a fluorescent flaw detector or a light emitting layer of an electroluminescence device.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
According to a specific embodiment of the present invention, a quinoline compound represented by the general formula (2) and a tautomer thereof are obtained by reacting a zinc complex represented by the general formula (1) with a mineral acid aqueous solution having a specific concentration. Can be obtained.

[0010] Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , represented as a substituent of the compounds (1) and (2) of the present invention,
Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , Y ¹⁵ ,
Y ¹⁶ , Y ¹⁷ , Y ¹⁸ , Y ¹⁹ , Y ²⁰ , R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted alkyl group, Unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted N-alkylamino group, substituted or unsubstituted N, N-
Represents a dialkylamino group, a substituted or unsubstituted N-arylamino group, a substituted or unsubstituted N, N-diarylamino group, or a substituted or unsubstituted N-alkyl-N-arylamino group.

As a specific example, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the substituted or unsubstituted alkyl group include straight-chain, branched or cyclic hydrocarbon groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl and iso-propyl. Group, n-butyl group, iso-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, tert-pentyl group, sec-pentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group,
1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2
-Trimethylpropyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, methylcyclopentyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group,
3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 1,2
-Dimethylpentyl group, 1,3-dimethylpentyl group,
1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethylpentyl group, 1- Ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,1,2-trimethylbutyl group, 1,1,3-trimethylbutyl group,
1,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 1,3,3-trimethylbutyl group, 2,
3,3-trimethylbutyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3- Methylbutyl group, 1-n-propylbutyl group, 1-iso-propylbutyl group 1-i
so-propyl-2-methylpropyl group, methylcyclohexyl group, n-octyl group, 1-methylheptyl group,
2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3- Dimethylhexyl group, 1,4
-Dimethylhexyl group, 1,5-dimethylhexyl group,
2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3, 5-dimethylhexyl group, 4,
4-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3
-Ethylhexyl group 4-ethylhexyl group, 1-n-
Propylpentyl group, 2-n-propylpentyl group, 1
-Iso-propylpentyl group, 2-iso-propylpentyl group, 1-ethyl-1-methylpentyl group, 1-
Ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group, 2
-Ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group,
2-ethyl-4-methylpentyl group, 3-ethyl-1-
Methylpentyl group, 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-
4-methylpentyl group, 1,1,2-trimethylpentyl group, 1,1,3-trimethylpentyl group, 1,1,4
-Trimethylpentyl, 1,2,2-trimethylpentyl, 1,2,3-trimethylpentyl, 1,2,2
4-trimethylpentyl group, 1,3,4-trimethylpentyl group, 2,2,3-trimethylpentyl group, 2,
2,4-trimethylpentyl group, 2,3,4-trimethylpentyl group, 1,3,3-trimethylpentyl group,
2,3,3-trimethylpentyl group, 3,3,4-trimethylpentyl group, 1,4,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 3,4,4-
Trimethylpentyl group, 1-n-butylbutyl group, 1-
iso-butylbutyl group, 1-sec-butylbutyl group, 1-tert-butylbutyl group, 2-tert-butylbutyl group, 1-n-propyl-1-methylbutyl group, 1-n-propyl-2-methylbutyl group, 1- n-
Propyl-3-methylbutyl group, 1-iso-propyl-1-methylbutyl group, 1-iso-propyl-2-methylbutyl group, 1-iso-propyl-3-methylbutyl group, 1,1-diethylbutyl group, 2-diethylbutyl group, 1-ethyl-1,2-dimethylbutyl group, 1-
Ethyl-1,3-dimethylbutyl group, 1-ethyl-2,
3-dimethylbutyl group, 2-ethyl-1,1-dimethylbutyl group, 2-ethyl-1,2-dimethylbutyl group, 2
-Ethyl-1,3-dimethylbutyl group, 2-ethyl-
2,3-dimethylbutyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4
-A dimethylcyclohexyl group, an ethylcyclohexyl group, an n-nonyl group, a 3,5,5-trimethylhexyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as an n-decyl group, a fluoromethyl group, Trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoroethyl group, chloroethyl group,
Bromoethyl group, trifluoroethyl group, pentafluoroethyl group, tetrachloroethyl group, hexafluoro-
a straight-chain, branched or cyclic alkyl halide group having 1 to 10 carbon atoms in which 1 to 21 halogen atoms such as an isopropyl group are substituted, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a pen Toxicmethyl group, hexyloxymethyl group, cyclohexyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentoxyethyl group, hexyloxyethyl group, cyclohexyloxyethyl group, methoxyethoxyethyl group, A methoxypropyl group, an ethoxypropyl group, a propoxypropyl group, a butoxypropyl group, a pentoxypropyl group, a hexyloxypropyl group, a cyclohexyloxypropyl group, a methoxyethoxypropyl group, etc. Al Alkoxyalkyl group group is substituted, methylthiomethyl group, ethylthiomethyl group, propyl thio methyl group, butylthiomethyl group, pentylthio methyl group,
Hexylthiomethyl group, cyclohexylthiomethyl group,
Methylthioethyl, ethylthioethyl, propylthioethyl, butylthioethyl, pentylthioethyl, hexylthioethyl, cyclohexylthioethyl, methoxyethylthioethyl, methylthiopropyl, ethylthiopropyl, propyl Thiopropyl group,
Butylthiopropyl group, pentylthiopropyl group, hexylthiopropyl group, cyclohexylthiopropyl group,
An alkyl group substituted by a linear, branched or cyclic alkylthio group having 1 to 10 carbon atoms such as methoxyethylthiopropyl group, N-methylaminomethyl group, N, N-dimethylaminomethyl group, N-ethylaminomethyl group , N, N-diethylaminomethyl group, N-propylaminomethyl group,
N, N-dipropylaminomethyl group, N-methyl-N-
An ethylaminomethyl group, an N-methylaminoethyl group,
N, N-dimethylaminoethyl group, N-ethylaminoethyl group, N, N-diethylaminoethyl group, N-propylaminoethyl group, N, N-dipropylaminoethyl group, N-methyl-N-ethylaminoethyl Group, N-methylaminopropyl group, N, N-dimethylaminopropyl group, N-ethylaminopropyl group, N, N-diethylaminopropyl group, N-propylaminopropyl group, N,
Examples thereof include a linear, branched or cyclic alkylamino group having 1 to 10 carbon atoms such as an N-dipropylaminopropyl group and an N-ethyl-N-butylaminopropyl group, or an alkyl group substituted with a dialkylamino group.

Examples of the substituted or unsubstituted aryl group include phenyl, naphthyl, anthranyl, 2-methylphenyl, and 3-methylphenyl, 4-methylphenyl, and 2,3-dimethylphenyl. , 2,4-
Dimethylphenyl group, 2,5-dimethylphenyl group,
2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,
3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group,
2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2-ethylphenyl group, propylphenyl group, butylphenyl group, hexylphenyl group, cyclohexylphenyl group, octylphenyl group, 2-methyl- 1-naphthyl group, 3-methyl-1-naphthyl group,
4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-
Naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-
Methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, 2-ethyl-
An aryl group substituted by a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as 1-naphthyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,3-dimethoxyphenyl group, 2,4 -Dimethoxyphenyl group, 2,5
-Dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,6-dimethoxyphenyl group, 2,
3,4-trimethoxyphenyl group, 2,3,5-trimethoxyphenyl group, 2,3,6-trimethoxyphenyl group, 2,4,5-trimethoxyphenyl group, 2,4,6
-Trimethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 2-ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, octyloxyphenyl group, 2-methoxy- 1-naphthyl group, 3-methoxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 5-methoxy-1-naphthyl group, 6-methoxy-1
-Naphthyl group, 7-methoxy-1-naphthyl group, 8-methoxy-1-naphthyl group, 1-methoxy-2-naphthyl group, 3-methoxy-2-naphthyl group, 4-methoxy-2
-Naphthyl group, 5-methoxy-2-naphthyl group, 6-methoxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 8-methoxy-2-naphthyl group, 2-ethoxy-1
An aryl group substituted by a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms such as a naphthyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, dibromophenyl group, iodophenyl group, fluorophenyl An aryl group substituted with a halogen atom such as a trifluoromethylphenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group or a pentafluorophenyl group; an aryl group substituted with a halogenated alkyl group such as a trifluoromethylphenyl group; -Dimethylaminophenyl group, N, N-diethylaminophenyl group,
N-monosubstituted amino substitution such as N-phenyl-N-methylaminophenyl group, N-tolyl-N-ethylaminophenyl group, N-chlorophenyl-N-cyclohexylaminophenyl group, N, N-ditolylaminophenyl group Aryl groups, N, N-disubstituted aminoaryl groups,
Other examples include an alkylthioaryl group such as a methylthiophenyl group, an ethylthiophenyl group, a methylthionaphthyl group, and a phenylthiophenyl group, and an arylthioaryl group.

Examples of substituted or unsubstituted alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1,1 -Dimethylbutoxy group, 1,2-dimethylbutoxy group, 2,2-dimethylbutoxy group, 1-ethylpropoxy group, 2-ethylpropoxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, methylcyclohexyloxy group, Octyloxy, ethylcyclohexyl, dimethylcyclohexyloxy, nonyloxy, 2-
A linear, branched or cyclic C1-C10 alkoxy group such as ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, decyloxy group, fluoromethoxy group, trifluoromethoxy group, fluoroethoxy group, trifluoro Straight chain in which 1 to 21 halogen atoms such as ethoxy group, hexafluoroethoxy group, fluoropropoxy group, trifluoropropoxy group, hexafluoropropoxy group, chloromethoxy group, trichloromethoxy group, chloroethoxy group and trichloroethoxy group are substituted A branched or cyclic halogenated alkoxy group having 1 to 10 carbon atoms,
Methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, butoxymethoxy group, cyclohexyloxymethoxy group, methoxymethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, cyclohexyloxyethoxy group, methoxyethoxyethoxy Group, ethoxyethoxyethoxy group, propoxyethoxyethoxy group, butoxyethoxyethoxy group, methoxymethylethoxy group, ethoxymethylethoxy group, propoxymethylethoxy group,
Butoxymethylethoxy, cyclohexyloxymethylethoxy, methoxyethoxymethylethoxy, ethoxyethoxymethylethoxy, propoxyethoxymethylethoxy, butoxyethoxymethylethoxy, 2-[(2′-methoxy) propoxy] propoxy, methoxy A linear, branched or cyclic C1-C10 alkoxyalkoxy group such as a propoxy group, an ethoxypropoxy group and an ethoxypropoxy group, an alkoxyalkoxyalkoxy group, an N-methylaminomethoxy group, N,
N-dimethylaminomethoxy group, N-ethylaminomethoxy group, N, N-diethylaminomethoxy group, N-methylaminoethoxy group, N, N-dimethylaminoethoxy group, N-ethylaminoethoxy group, N, N-diethylamino Ethoxy, N-methylaminopropoxy, N,
N-dibutylaminopropoxy group, linear, branched or cyclic alkylaminoalkoxy group having 1 to 10 carbon atoms such as N-methylaminobutoxy group, methylthiomethoxy group,
Straight-chain, branched or cyclic C1-C1 groups such as ethylthiomethoxy, propylthiomethoxy, methylthioethoxy, ethylthioethoxy, and propylthioethoxy;
And an aryloxyalkoxy group such as an alkylthioalkoxy group, a phenoxyethoxy group, a naphthyloxyethoxy group, a tolyloxyethoxy group, and an ethylphenoxyethoxy group.

Examples of substituted or unsubstituted aryloxy groups include phenyloxy, naphthyloxy, anthranyloxy, 2-methylphenyloxy, and 3-
Methylphenyloxy group, 4-methylphenyloxy group, 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3, 4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 3,6-dimethylphenyloxy group, 2,3
4-trimethylphenyloxy group, 2,3,5-trimethylphenyloxy group, 2,3,6-trimethylphenyloxy group, 2,4,5-trimethylphenyloxy group, 2,4,6-trimethylphenyloxy group , 3,
4,5-trimethylphenyloxy group, 2-ethylphenyloxy group, propylphenyloxy group, butylphenyloxy group, hexylphenyloxy group, cyclohexylphenyloxy group, octylphenyloxy group, 2
-Methyl-1-naphthyloxy group, 3-methyl-1-naphthyloxy group, 4-methyl-1-naphthyloxy group,
5-methyl-1-naphthyloxy group, 6-methyl-1-
Naphthyloxy group, 7-methyl-1-naphthyloxy group, 8-methyl-1-naphthyloxy group, 1-methyl-
2-naphthyloxy group, 3-methyl-2-naphthyloxy group, 4-methyl-2-naphthyloxy group, 5-methyl-2-naphthyloxy group, 6-methyl-2-naphthyloxy group, 7-methyl- An aryloxy group substituted with a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as a 2-naphthyloxy group, an 8-methyl-2-naphthyloxy group, and a 2-ethyl-1-naphthyloxy group. And a 3-methoxyphenyloxy group, a 4-methoxyphenyloxy group, a 2,3-dimethoxyphenyloxy group,
2,4-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 2,6-dimethoxyphenyloxy group, 3,4-dimethoxyphenyloxy group, 3,5
-Dimethoxyphenyloxy group, 3,6-dimethoxyphenyloxy group, 2,3,4-trimethoxyphenyloxy group, 2,3,5-trimethoxyphenyloxy group,
2,3,6-trimethoxyphenyloxy group, 2,4
5-trimethoxyphenyloxy group, 2,4,6-trimethoxyphenyloxy group, 3,4,5-trimethoxyphenyloxy group, 2-ethoxyphenyloxy group, propoxyphenyloxy group, butoxyphenyloxy group, hexyl Oxyphenyloxy group, cyclohexyloxyphenyloxy group, octyloxyphenyloxy group, 2-methoxy-1-naphthyloxy group, 3-methoxy-1-naphthyloxy group, 4-methoxy-1-naphthyloxy group, 5-methoxy -1-naphthyloxy group,
6-methoxy-1-naphthyloxy group, 7-methoxy-
1-naphthyloxy group, 8-methoxy-1-naphthyloxy group, 1-methoxy-2-naphthyloxy group, 3-methoxy-2-naphthyloxy group, 4-methoxy-2-naphthyloxy group, 5-methoxy- Carbon number 1 such as 2-naphthyloxy group, 6-methoxy-2-naphthyloxy group, 7-methoxy-2-naphthyloxy group, 8-methoxy-2-naphthyloxy group, 2-ethoxy-1-naphthyloxy group, etc. And aryloxy groups substituted with a linear, branched or cyclic alkoxy group of 10 to 10, such as chlorophenyloxy, dichlorophenyloxy, trichlorophenyloxy, bromophenyloxy, dibromophenyloxy, and iodophenyloxy. , Fluorophenyloxy group, difluorophenyloxy group, trifluorophenyloxy An aryloxy group substituted with a halogen atom such as a trifluoromethylphenyloxy group, a trifluoromethylphenyloxy group, or the like; -Dimethylaminophenyloxy group, N, N-diethylaminophenyloxy group, N-phenyl-N-methylaminophenyloxy group, N-tolyl-N-ethylaminophenyloxy group, N-chlorophenyl-N-cyclohexylaminophenyloxy N-monosubstituted aminoaryloxy group such as N, N-ditolylaminophenyloxy group, N, N
An alkylthioaryloxy group such as a methylthiophenyloxy group, an ethylthiophenyloxy group, a methylthionaphthyloxy group, a cyclohexylthiophenyloxy group, a phenylthiophenyloxy group, a naphthylthiophenyloxy group; And an arylthioaryloxy group such as a phenylthionaphthyloxy group.

Examples of the substituted or unsubstituted N-alkylamino groups include methylamino, ethylamino, n-propylamino, iso-propylamino, n-butylamino, iso-butylamino, sec- -Butylamino group, n-pentylamino group, 1-methylbutylamino group, 2-methylbutylamino group, 3-methylbutylamino group, 1,1-dimethylbutylamino group, 1,2-dimethylbutylamino group, 2,2-dimethylbutylamino group, 1-ethylpropylamino group, 2-ethylpropylamino group, n-hexylamino group, cyclohexylamino group, n-heptylamino group, methylcyclohexylamino group, n-octylamino group, 2-ethylhexylamino group, ethylcyclohexylamino group, dimethylcyclohexylamino , N- nonylamino group, 3,5,5
A straight-chain, branched or cyclic alkylamino group having 1 to 10 carbon atoms such as a trimethylhexylamino group, an n-decylamino group, a methoxymethylamino group, an ethoxymethylamino group, a methoxyethylamino group, an ethoxyethylamino group, n -Propoxyethylamino group, iso-propoxyethylamino group, n-butoxyethylamino group, is
o-butoxyethylamino group, tert-butoxyethylamino group, n-hexyloxy-ethylamino group, cyclohexyloxyethylamino group, 2-methoxypropylamino group, methoxy-iso-propylamino group,
C1-C1 such as 2-ethoxypropylamino group, ethoxy-iso-propylamino group, 2-propoxypropylamino group, propoxy-iso-propylamino group, etc.
0 linear, branched or cyclic alkoxyalkylamino group, methylthiomethylamino group, ethylthiomethylamino group, methylthioethylamino group, ethylthioethylamino group, n-propylthioethylamino group, iso-propylthioethylamino Group, n-butylthioethylamino group, iso-butylthioethylamino group, tert-
Butylthioethylamino group, n-hexylthioethylamino group, cyclohexylthioethylamino group, 2-methylthiopropylamino group, methylthio-iso-propylamino group, 2-ethylthiopropylamino group, ethylthio-iso-propylamino group A straight chain having 1 to 10 carbon atoms such as a 2-propylthiopropylamino group, a propylthio-iso-propylamino group, a methylthioethoxyethylamino group, an ethylthioethylthioethylamino group,
A branched or cyclic alkylthioalkylamino group, N-
Methylaminomethylamino group, N-methylaminoethylamino group, N-ethylaminomethylamino group, N-ethylaminoethylamino group, N, N-dimethylaminomethylamino group, N, N-diethylaminomethylamino group,
A linear chain having 1 to 10 carbon atoms such as an N, N-dimethylaminoethylamino group, an N, N-diethylaminoethylamino group,
Examples thereof include a branched or cyclic N-alkylaminoalkylamino group and an N, N-dialkylaminoalkylamino group.

Examples of the substituted or unsubstituted N, N-dialkylamino group include N, N-dimethylamino group,
N, N-diethylamino group, N, N-di (n-propyl) amino group, N, N-di (iso-propyl) amino group, N, N-di (n-butyl) amino group, N, N- Di (iso-butyl) amino group, N, N-di (sec-butyl) amino group, N, N-di (n-pentyl) amino group, N, N-di (1-methylbutyl) amino group, N, N
-Di (2-methylbutyl) amino group, N, N-di (3-
Methylbutyl) amino group, N, N-di (1,1-dimethylbutyl) amino group, N, N-di (1,2-dimethylbutyl) amino group, N, N-di (2,2-dimethylbutyl) An amino group, an N, N-di (1-ethylpropyl) amino group, an N, N-di (2-ethylpropyl) amino group,
N, N-di (n-hexyl) amino group, N, N-di (cyclohexyl) amino group, N, N-di (n-heptyl)
Amino group, N, N-di (methylcyclohexyl) amino group, N, N-di (n-octyl) amino group, N, N-di (2-ethylhexyl) amino group, N, N-di (dimethylcyclohexyl) Amino group, N, N-di (n-nonyl) amino group, N, N-di (3,5,5-trimethylhexyl) amino group, N, N-di (n-decyl) amino group, N-methyl -N-ethylamino group, N-propyl-
C1-C10 linear, branched or branched such as N-ethylamino group, N-hexyl-N-ethylamino group, N-octyl-N-ethylamino group, N- (cyclohexyl) -N-ethylamino group, etc. A cyclic alkyldisubstituted amino group, N,
N-di (methoxymethyl) amino group, N, N-di (ethoxymethyl) amino group, N, N-di (methoxyethyl)
Amino group, N, N-di (ethoxyethyl) amino group,
N, N-di (n-propoxyethyl) amino group, N, N
-Di (iso-propoxyethyl) amino group, N, N-
Di (n-butoxyethyl) amino group, N, N-di (is
o-butoxyethyl) amino group, N, N-di (tert
-Butoxyethyl) amino group, N, N-di (n-hexyloxyethyl) amino group, N, N-di (cyclohexyloxyethyl) amino group, N, N-di (2-methoxypropyl) amino group, N , N-di (methoxy-iso-
Propyl) amino group, N, N-di (2-ethoxypropyl) amino group, N, N-di (ethoxy-iso-propyl) amino group, N, N-di (2-propoxypropyl)
Amino group, N, N-di (propoxy-iso-propyl) amino group, N, N-di (methoxyethoxyethyl)
Amino group, N, N-di (ethoxyethoxyethyl) amino group, N-methyl-N- (methoxyethyl) amino group,
An N- (propyloxyethyl) -N-ethylamino group,
N-hexyloxyethyl-N-ethylamino group, N-
(Ethoxyethoxyethyl) -N-ethylamino group, N
A dialkylamino group substituted with a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms such as-(cyclohexyloxyethyl) -N-ethylamino group, an N, N-di (methylthiomethyl) amino group, N , N-di (ethylthiomethyl) amino group, N, N-di (methylthioethyl)
An amino group, an N, N-di (ethylthioethyl) amino group,
An N, N-di (n-propylthioethyl) amino group,
N-di (iso-propylthioethyl) amino group, N,
N-di (n-butylthioethyl) amino group, N, N-di (iso-butylthioethyl) amino group, N, N-di (tert-butylthioethyl) amino group, N, N-di (n -Hexylthioethyl) amino group, N, N-di (cyclohexylthioethyl) amino group, N, N-di (2-
Methylthiopropyl) amino group, N, N-di (methylthio-iso-propyl) amino group, N, N-di (2-ethylthiopropyl) amino group, N, N-di (ethylthio-iso-propyl) amino group N, N-di (2-propylthiopropyl) amino group, N, N-di (propylthio-iso-propyl) amino group, N, N-di (methylthioethoxyethyl) amino group, N, N-di ( N, N substituted with a linear, branched or cyclic alkylthio group having 1 to 10 carbon atoms such as an ethylthioethylthioethyl) amino group
-Dialkylthioalkylamino group, N, N-di (N-
Methylaminomethyl) amino group, N, N-di (N-methylaminoethyl) amino group, N, N-di (N-ethylaminomethyl) amino group, N, N-di (N-ethylaminoethyl) amino Group, N, N-di (N, N-dimethylaminomethyl) amino group, N, N-di (N, N-diethylaminomethyl) amino group, N, N-di (N, N-dimethylaminoethyl) amino A linear group having 1 to 10 carbon atoms such as a group, N, N-di (N, N-diethylaminoethyl) amino group,
Examples thereof include a branched or cyclic N, N-di (N-alkylaminoalkyl) amino group and an N, N-di (N, N-dialkylaminoalkyl) amino group.

Examples of the substituted or unsubstituted N-arylamino group include N-phenylamino group, N-tolylamino group, N-chlorophenylamino group, N-trifluorophenylamino group, N-naphthylamino group, -Methylnaphthylamino group, N-chloronaphthylamino group and the like.

Examples of the substituted or unsubstituted N, N-diarylamino group include N, N-diphenylamino group, N, N
-Ditolylamino group, N, N-dichlorophenylamino group, N, N-ditrifluorophenylamino group, N, N
-Dinaphthylamino group, N, N-dimethylnaphthylamino group, N, N-dichloronaphthylamino group and the like.

Examples of the substituted or unsubstituted N-alkyl-N-arylamino group include N-methyl-N-phenylamino group, N-ethyl-N-tolylamino group, N-methoxyethyl-N-chlorophenylamino group. , N-ethyl-
N-trifluorophenylamino group, N-cyclohexyl-N-naphthylamino group, N-ethyl-N-naphthylamino group, N-2-ethylhexyl-N-methylnaphthylamino group, N-methyl-N-chloronaphthylamino And the like.

Preferred examples of the substituents of Y ^{1 to} Y ²⁰ and R ^{1 to} R ¹⁰ include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a trifluoromethyl group, a phenyl group, and an amino group. And nitro groups.

In the method of the present invention, the zinc complex represented by the general formula (1) is represented by the following general formula (4)

Embedded image

[In the formula (4), Y ²¹ , Y ²² , Y ²³ , Y ²⁴ ,
Y ²⁵ and Y ²⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, A substituted or unsubstituted aryloxy group, a substituted or unsubstituted N-alkylamino group, a substituted or unsubstituted N, N-dialkylamino group,
Substituted or unsubstituted N-arylamino group, substituted or unsubstituted N, N-diarylamino group, substituted or unsubstituted N
-Represents an alkyl-N-arylamino group. And a quinoline derivative represented by the following general formula (5):

[0024]

Embedded image [In the formula (5), Y ²⁷ , Y ²⁸ , Y ²⁹ and Y ³⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted alkyl group,
Substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted N-alkylamino group, substituted or unsubstituted N,
Represents an N-dialkylamino group, a substituted or unsubstituted N-arylamino group, a substituted or unsubstituted N, N-diarylamino group, or a substituted or unsubstituted N-alkyl-N-arylamino group. Is reacted with a zinc halide in an organic solvent, and then heat-treated with an organic basic compound such as pyridine to obtain a corresponding zinc complex of the general formula (1).

In the method of the present invention, specific examples of the mineral acid used are hydrochloric acid, hydrobromic acid, sulfuric acid and phosphoric acid. Preferably, hydrochloric acid and sulfuric acid are used.

In the method of the present invention, the concentration of the mineral acid to be used depends on the kind of the mineral acid, but is not less than 8% by weight. Preferably, a mineral acid exceeding 10% by weight is good.
When the mineral acid is hydrochloric acid, its concentration is from 8 to 35% by weight, preferably more than 10% by weight and up to 30% by weight. When the mineral acid is sulfuric acid, it is 8 to 50% by weight, preferably more than 10% by weight and up to 40% by weight. The amount used is 5 to the zinc complex of the general formula (1).
The molar ratio is from 200 to 200, preferably from 7 to 50. When a basic compound that forms a salt with a mineral acid is present in the reaction system, it is necessary to use an excess of the basic compound to form the salt.
Further, in order to improve operability such as stirring, the weight of the aqueous solution of the mineral acid having a predetermined concentration is used in an amount of 3 to 100 parts by weight based on 1 part of the zinc complex of the general formula (1).

In the method of the present invention, the reaction temperature is 20
-100 ° C, preferably 80-98 ° C. The reaction time is usually 0.1 to 10 hours.

As a treatment after completion of the reaction, the precipitated solid is directly collected by filtration, washed and dried. When the luminance is low, the luminance may be increased by performing thermal sludgeging again with a mineral acid, filtering the precipitated solid as it is, washing and drying.

The X-ray diffraction spectrum (Cu-Kα) of the quinoline compound of the formula (3) obtained by the method of the present invention shows a Bragg angle (2θ) of 1
2.8 °, 15.2 ° 18.3 °, 22.5 °, 25
° and 28.4 ° as crystals having at least peaks. In particular, 1 for the peak at 15.2 °.
Crystals having a peak intensity ratio of 2.8 ° of 0.7 or less are:
Against Lumogen Brilliant Yellow
It is a compound having an excellent light-emitting property with a luminance of 180% or more in a solid state.

A method for producing an electroluminescent display device from the obtained compound of the formula (3) is disclosed in
JP-A-8-194393; Appl. Phys. L
ett. , 51 (12), 913 (1987); A
ppl. Phys. , 65 (9) 3610 (198
9); Japan Journal of Apply
eds Physics vol 27 No. 2 L2
69 (1988), vol27 No. 4 L713
(1988) can be used.

[0031]

EXAMPLES The present invention will be described in further detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention.

Synthesis Example (Synthesis Example of Zinc Complex) 15 g (0.102 mol) of phthalimide, quinaldine 2
9.4 g (0.204 mol), zinc chloride 29.2 g
(0.214 mol) and N, N-dimethylaniline 150
g was placed in the reactor at room temperature. 2 at 150 ° C under nitrogen aeration
After heating at 180 ° C. for 8 hours, and then cooling to 50 ° C. The crystal part was collected by filtration, washed with methanol and then with water. Further, 600 g of pyridine was added and
Heated at 115 ° C. for 8 hours. After cooling, the crystal part is collected by filtration,
Washing was performed thoroughly. The crystals are dried in a drier and the following formula (6)

[0033]

Embedded image 27.6 g of a zinc complex was obtained. The yield based on phthalimide was 89%.

Example 1 (Synthesis example 1 of quinoline compound of formula (3)) 15.2 g (0.0249 mol) of the zinc complex obtained in the synthesis example
And 300 g (1.23 mol) of a 15% hydrochloric acid aqueous solution were charged into the reactor and treated at 95 ° C. for 1 hour. After cooling to 50 ° C,
It was filtered and washed with water. Take out the filter cake, dry it, and use formula (3)
12.4 g of the quinoline compound was obtained. Purity was 99%. The purity conversion yield was 90% based on the zinc complex. The crystals were measured in a solid state with a fluorometer (UM-2S, manufactured by Hexa Scientific). Lumogen Brillia
The luminance was 211% with respect to nt Yellow.

Example 2 A zinc complex of the formula (6) 15.2 obtained by the same operation as in the synthesis example.
g (0.0249 mol) in 300 g of a 30% aqueous sulfuric acid solution
(0.918 mol) and the reactor were treated at 80 ° C. for 1 hour. After cooling to 50 ° C., the mixture was filtered and washed with water. 10. The filter cake is taken out and dried, and the quinoline compound of the formula (3) is obtained.
3 g were obtained. Purity was 99%. The purity conversion yield was 82% based on quinaldine. The crystals were measured in a solid state with a fluorometer (UM-2S, manufactured by Hexa Scientific). The luminance with respect to the luminogen Brilliant Yellow was 204%.

Example 3 A zinc complex of the formula (6) 15.2 obtained by the same operation as in the synthesis example.
g (0.0249 mol) in 500 g of a 20% aqueous sulfuric acid solution
(1.02 mol) and the reactor were treated at 80 ° C. for 1 hour. After cooling to 50 ° C., the mixture was filtered and washed with water. The filter cake was taken out and dried, and the quinoline compound of the formula (3) was added in an amount of 11.8.
g was obtained. Purity was 100%. The purity conversion yield was 87% based on quinaldine. The crystals were measured in a solid state with a fluorometer (UM-2S, manufactured by Hexa Scientific). The luminance with respect to the luminogen Brilliant Yellow was 196%.

Comparative Example (Additional Examination of JP-A-56-147784) 135 g (0.918 mol) of phthalimide, 132 g (0.922 mol) of quinaldine, 191 g of zinc chloride (1.
40 mol), 73 g of pyridine and 9 of o-dichlorobenzene 9
80 g was placed in a reactor and heated at 175-180 ° C. for 7 hours. After cooling to room temperature, add 1000 g of methanol,
After the crystals were sufficiently loosened, the crystal part was collected by filtration and washed with methanol. The obtained yellow-brown crystal cake was discharged and dispersed in 2 kg (3.29 mol) of a 6% aqueous hydrochloric acid solution,
For 1 hour. After cooling to 50 ° C., the mixture was filtered and washed with water. The filter cake is dried, and the quinoline compound of the formula (4) is added to 13
7.5 g were obtained. Purity was 98%. The yield in terms of purity based on phthalimide was 54%. When this crystal was measured in a solid state with a fluorometer (UM-2S type manufactured by Hexa Scientific Co., Ltd.), it was found that the luminogen Brilliant Yellow was used.
The luminance with respect to w was 150%.

[0038]

According to the present invention, a high quality dye of the general formula (2) can be produced from the zinc complex of the general formula (1). That is, the present invention provides a useful production method for producing a dye excellent as a flaw detector material or an EL material.

Claims (3)

[Claims] [Claim 1] The following general formula (1) [In the formula (1), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ ,
Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , Y ¹⁵ ,
Y ¹⁶ , Y ¹⁷ , Y ¹⁸ , Y ¹⁹ and Y ²⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl Group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted N-alkylamino group, substituted or unsubstituted N, N-
Represents a dialkylamino group, a substituted or unsubstituted N-arylamino group, a substituted or unsubstituted N, N-diarylamino group, or a substituted or unsubstituted N-alkyl-N-arylamino group. Wherein the zinc complex represented by the following general formula (2) is reacted with a mineral acid having a concentration of 8% by weight or more. [In the formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group,
Substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted N-alkylamino group, substituted or unsubstituted N, N-dialkylamino A substituted or unsubstituted N-arylamino group, a substituted or unsubstituted N, N-diarylamino group, or a substituted or unsubstituted N-alkyl-N-arylamino group. ] And a method for producing the tautomer thereof. 2. Mineral acid at a concentration of 8% by weight or more is 8-35% by weight.
2. The method according to claim 1, wherein the hydrochloric acid is weight percent. 3. Mineral acid at a concentration of 8% by weight or more is from 8 to 50%.
The method of claim 1 wherein the weight percent is sulfuric acid.