CN101239942B

CN101239942B - Method for producing phthalocyanine compound and its intermediate, and intermediate compound for the same

Info

Publication number: CN101239942B
Application number: CN2008100048965A
Authority: CN
Inventors: 立石桂一; 矢吹嘉治
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2003-04-08
Filing date: 2004-04-08
Publication date: 2011-04-27
Anticipated expiration: 2024-04-08
Also published as: CN101239943B; CN1876627A; CN100378102C; CN101239943A; CN1539839A; CN101239935A; CN101239935B; CN101239942A

Abstract

The invention provides a method for producing a phthalocyanine compound which is a useful compound as a functional material, such as a dye, pigment, organic photo-conduction material, optical recording material, pharmaceutical and agrochemical, and its intermediate, and to provide the intermediate compound. This method for producing the phthalocyanine compound and its intermediate through specified reaction processes and the intermediate compound are provided, respectively.

Description

Phthalocyanine compound and intermediates preparation thereof and these midbody compounds

The application is dividing an application of the Chinese patent application No.200410033432.9 that submitted on April 8th, 2004.

Technical field

The present invention relates to the preparation method of the phthalocyanine compound shown in general formula (I) and the general formula (X) and as its intermediate, with the phthalimide compound shown in general formula (IV) and the logical formula V, with the phthalyl amine compound shown in the general formula (VI), and with the O-phthalic nitrile compound shown in general formula (VII) and the general formula (VIII).Phthalocyanine compound shown in compound shown in general formula (IV)～general formula (VIII) and general formula (I) and the general formula (X) and also is a kind of useful compound for the functional material of organic light-guide electric material, optical recording material, medical agricultural chemicals etc. not only aspect dyestuff, pigment.

Background technology

Phthalocyanine compound and various derivative, also have their preparation method all to be known by people.

As the method for preparation, for example open and put down in writing following method for making in the 2002-249677 communique the spy with the phthalocyanine compound shown in the general formula (I).

This method is used as synthetic intermediate with the 4-nitrophthalonitrile or the 3-nitrophthalonitrile of industry.But, use above-mentioned synthetic intermediate to need complex apparatus and operation steps for the industrial method for preparing phthalocyanine compound.

Therefore, the preparation method who is put down in writing above is when industrial production, in the problem that also exists needs to solve aspect productivity cost and the quality.

Inventor of the present invention develops as the synthetic route of synthesis material or synthetic intermediate not using nitrophthalonitrile, preparation method for the cheapness of target product phthalocyanine compound has carried out positive research, has drawn new preparation method of the present invention thus.And, preparation in accordance with the present invention, found that with the derivative shown in general formula (IV), (V), (VI), (VII), (VIII) these derivatives are the useful new compound of not putting down in writing, and have finished the present invention by above-mentioned discovery in aforesaid technical literature.

In order to solve aforementioned problems of the prior art, task of the present invention is to reach following purpose.

Summary of the invention

That is, first purpose of the present invention is that a kind of preparation method who does not use nitrophthalonitrile as the phthalocyanine compound of synthetic intermediate is provided.

Second purpose of the present invention is, a kind of method that can significantly improve the problem aspect its productivity cost and prepare the target product phthalocyanine compound at an easy rate when industrial production is provided.

The 3rd purpose of the present invention is, provides not only aspect dyestuff, pigment, and also is the new synthetic intermediate of useful compound for the functional material of organic light-guide electric material, optical recording material, medical agricultural chemicals etc.

Reaching aforementioned purpose is by following＜1〉to＜8 described in method.＜1 〉, it is characterized in that making this compound through following reaction (a)～(e) with the preparation method of the phthalocyanine compound shown in the general formula (I).

General formula (I)

In above-mentioned general formula (I), m represents 1～2 integer.N represents 1～4 integer.And m and n can be identical or different.M represents oxide compound, oxyhydroxide or the halogenide of hydrogen atom, atoms metal or atoms metal.R ₁, R ₂, R ₃, R ₄Can be identical or different, it represents to replace separately or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～20 are that cycloalkyl, replacement or unsubstituted the total number of carbon atoms of 3～20 are 2～20 thiazolinyl, replaces or unsubstituted the total number of carbon atoms is that alkynyl, replacement or unsubstituted the total number of carbon atoms of 2～12 are that aralkyl, replacement or unsubstituted the total number of carbon atoms of 7～20 are that 6～20 aryl or replacement or unsubstituted the total number of carbon atoms are 4～20 heterocyclic radical.

(a) will obtain phthalimide compound with the sulfhydryl compound shown in the following general formula (II) with the reaction of the phthalimide compound of the replacement shown in the following general formula (III) with the replacement shown in the following general formula (IV),

General formula (II) MS-R

In above-mentioned general formula (II), R represents to replace or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～20 are that cycloalkyl, replacement or unsubstituted the total number of carbon atoms of 3～20 are 2～20 thiazolinyl, replaces or unsubstituted the total number of carbon atoms is that alkynyl, replacement or unsubstituted the total number of carbon atoms of 2～12 are that aralkyl, replacement or unsubstituted the total number of carbon atoms of 7～20 are that 6～20 aryl or replacement or unsubstituted the total number of carbon atoms are 4～20 heterocyclic radical.

General formula (III)

In above-mentioned general formula (III), Y represents leavings group.N represents 1～4 integer.A represents hydrogen atom or atoms metal.

General formula (IV)

In above-mentioned general formula (IV), the implication of A is identical with A in the above-mentioned general formula (III).The implication of R is identical with R in the above-mentioned general formula (II).The implication of n is identical with n in the above-mentioned general formula (III).

(b) separate or do not separate this compound (IV), itself and oxidant reaction are obtained with the compound shown in the logical formula V,

(c) separate or do not separate this compound (V), make itself and ammonia react obtain phthalic diamide with the replacement shown in the general formula (VI),

(d) separate or do not separate this compound (VI), make itself and dewatering agent react the phthalonitrile that obtains with the replacement shown in the general formula (VII), if desired, separate or do not separate this compound (VII), perhaps substituting group is partly used the method for the substituting group conversion of chemistry, obtain with the like derivatives shown in the general formula (VIII)

Logical formula V

General formula (VI)

General formula (VII)

General formula (VIII)

The implication of middle R of above-mentioned logical formula V, general formula (VI) and general formula (VII) and n is identical with R and the n in the above-mentioned general formula (IV).The implication of A is identical with A in the above-mentioned general formula (III) in the logical formula V.

The implication of the middle m of above-mentioned logical formula V, general formula (VI), general formula (VII) and general formula (VIII) is identical with the m in the above-mentioned general formula (I).

In above-mentioned general formula (VIII), L represents to replace or unsubstituted the total number of carbon atoms is that alkylidene group, replacement or unsubstituted the total number of carbon atoms of 1～12 are that phenylene, replacement or unsubstituted the total number of carbon atoms of 6～18 are 10～20 naphthylidene, replaces or unsubstituted the total number of carbon atoms is the heterocyclic radical of 4～12 divalent.Z represents that hydrogen atom or substituting group, n represent 1～4 integer.

(e) phthalonitrile that will be selected from this at least a replacement in this compound (VII) and this compound (VIII) with the reaction of the metal derivative shown in the general formula (IX), obtain with the phthalocyanine compound shown in the general formula (I).

General formula (IX) M-(X) _d

In the above-mentioned general formula (IX), M represents oxide compound, oxyhydroxide and the halogenide of hydrogen atom, atoms metal or atoms metal.X represents 1 valency of halogen atom, acetate anion, acetylacetonate, oxygen etc. or the part of divalent.D represents 1～4 integer.

＜2〉as＜1〉preparation method of the phthalocyanine compound put down in writing, it is characterized in that M is Cu, Zn, Ni, Pb, Sn, Fe or Al in above-mentioned general formula (I).

＜3〉as＜1 〉～＜2〉phthalocyanine compound put down in writing preparation method, it is characterized in that R in above-mentioned general formula (I) ₁, R ₂, R ₃, R ₄Be to replace or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～12 are that 6～18 aryl or replacement or unsubstituted the total number of carbon atoms are 4～12 heterocyclic radical independently of one another.

＜4〉as＜1 〉～＜3 in the preparation method of the phthalocyanine compound put down in writing, it is characterized in that above-mentioned general formula (I) is with shown in the following general formula (X).

General formula (X)

R in the above-mentioned general formula (X) ₁, R ₂, R ₃, R ₄Can be identical or different, expression replaces or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～12 are that 6～18 aryl or replacement or unsubstituted the total number of carbon atoms are 4～12 heterocyclic radical, R ₁, R ₂, R ₃, R ₄Among at least one have ionic hydrophilic group as substituting group.M represents oxide compound, oxyhydroxide or the halogenide of hydrogen atom, atoms metal or atoms metal.

＜5〉as＜1 〉～＜4 in the preparation method of the phthalocyanine compound put down in writing, it is characterized in that the counter cation of the ionic hydrophilic group in the above-mentioned general formula (X) is a Li salt.

＜6〉as＜1 〉～＜5 in the preparation method of the phthalocyanine compound put down in writing, it is characterized in that the ionic hydrophilic group in the above-mentioned general formula (X) is sulfo group and/or carboxyl.

＜7〉as＜1〉preparation method of the phthalocyanine compound put down in writing, it is characterized in that oxygenant is hydrogen peroxide (H ₂O ₂).

＜8〉as＜1〉preparation method of the phthalocyanine compound put down in writing, it is characterized in that dewatering agent is Phosphorus Oxychloride (being also referred to as phosphoryl chloride).

In addition, as a part of the present invention, also synthesized following＜9〉to＜12 compound.

＜9〉with the phthalimide compound of the replacement shown in the general formula (IV), the represented group of R has ionic hydrophilic group as substituting group in the formula.

＜10〉to lead to the phthalimide compound of the replacement shown in the formula V.

＜11〉with the phthalyl amine compound of the replacement shown in the general formula (VI).

＜12〉with the O-phthalic nitrile compound of the replacement shown in general formula (VII) and/or the general formula (VIII).

Embodiment

Below the present invention is described in detail.

[preparation method of phthalocyanine compound, phthalimide compound, the phthalyl amine compound of replacement, the O-phthalic nitrile compound of replacement, the phthalocyanine compound of the replacement that obtains by this preparation method]

The preparation method of phthalocyanine compound of the present invention is, the at first synthetic phthalimide compound that has imported solvability group or its precursor in advance, after it being guided to the phthalyl amine compound that has imported solvability group or its precursor in advance again, then guide to the O-phthalic nitrile compound that has imported solvability group or its precursor in advance, make itself and metal derivative reaction with the preparation phthalocyanine compound.

In this preparation method, import solvability group or its precursor in advance to phthalic acid derivatives as raw material, like this in the structure of the phthalocyanine compound that obtains, for example on 4 phenyl ring, can not import solvability group or its precursor with omitting, thereby can only import desirable solvability group with specific number.

In more detail, by the solvability group (as the alkylsulfonyl that replaces) that imports electrophilic, can adjust phthalocyanine compound to higher oxidizing potential.Can provide thus a kind of as trichromatic pigment aspect color reprodubility, have the excellent absorption performance and also with respect to the reactive gas in light, heat, humidity and the atmosphere have enough resistivitys, phthalocyanine compound that solvability is good, and a kind of new preparation process that provides security countermeasure and cheap preparation in the preparation of taking into account.

Further, the preparation method of phthalocyanine compound of the present invention can also use with aforementioned solvability group or aforementioned precursor O-phthalic nitrile compounds different, more than 2 kinds and be prepared.

Obtained the distribution that ingredient proportion determined like this, formed the kind phthalocyanine compound different of solvability group, further improved solvability with the position by employed O-phthalic nitrile compound.Thus, the present invention also provides the deliquescent method of improvement phthalocyanine compound.

Also have under the situation of the precursor that R in general formula (the IV)～general formula (VII) of phthalocyanine compound intermediate of the present invention and/or the Z in the general formula (VIII) be the solvability group, after forming the phthalocyanine ring,, can synthesize of the present invention with the phthalocyanine compound shown in the following general formula (I) by it being transformed to the solvability group.

The solvability group is to pay the deliquescent substituting group of phthalocyanine compound.Paying by the solvability group under the water miscible situation of phthalocyanine compound, it represents hydrophilic radical.On the other hand, paying by the solvability group under the oil-soluble situation of phthalocyanine compound, it represents hydrophobic group.Phthalocyanine compound of the present invention can have water-soluble and oil soluble.

As hydrophilic radical, the substituting group that ionic hydrophilic radical is arranged or replaced that can enumerate by ionic hydrophilic radical.As ionic hydrophilic radical, can contain sulfo group, carboxyl, phosphono and quaternary ammonium group.Wherein preferred carboxyl, phosphono and sulfo group, preferred especially carboxyl, sulfo group.Carboxyl, phosphono and sulfo group can also be the forms of salt; gegenion as the form of salt for example can contain ammonium ion, alkalimetal ion (for example lithium ion, sodium ion, potassium ion) and organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl-phosphine ion).Preferred as alkali salt in the gegenion, wherein since lithium salts can to improve the solvability of dyestuff therefore preferred especially.

For the number of ionic hydrophilic radical, in 1 molecule phthalocyanine compound, preferably contain 2 at least, especially preferably contain sulfo group and/or carboxyl more than at least 2.

As hydrophobic group, carbonatoms is that 8 to 20 aliphatic group, carbonatoms are 8 to 20 aromatic group and the sulfamyl, alkylsulfonyl, sulfinyl, sulfenyl, formamyl, acyl group, ester group, alkoxyl group, aryloxy, amide group and the amino that are had on the one part-structure.Aliphatic group is represented alkynyl, the aralkyl of thiazolinyl, alkynyl, the replacement of alkyl, thiazolinyl, the replacement of alkyl, replacement, the aralkyl of replacement.Aliphatic group can have side chain, also can form ring.The aryl of aromatic group preferred aryl groups and replacement.As the preferred phenyl or naphthyl of aryl, preferred especially phenyl.

Also have, as the precursor of solvability group be illustrated in form the phthalocyanine ring after, can be the substituting group of solvability group by response transform.As this class substituting group, that can enumerate has hydroxyl, halogen atom, sulfydryl, amino, amide group, carbalkoxy, thiazolinyl, imino-isoreactivity substituting group or contains the substituting group of these substituted radicals.

Then to describing with the phthalocyanine compound shown in the following general formula (I).

General formula (I)

Of the present inventionly comprise this compound and its salt and their hydrate with the phthalocyanine compound shown in the aforementioned formula (I).

M in general formula (I) represents oxide compound, oxyhydroxide and the halogenide of hydrogen atom, atoms metal or atoms metal.Example as preferred L can be hydrogen atom, can be Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi etc. for atoms metal.

As oxide compound, can be VO, GeO etc.

As oxyhydroxide, can be Si (OH) ₂, Cr (OH) ₂, Sn (OH) ₂Deng.

As halogenide, can be AlCl, SiCl ₂, VCl, VCl ₂, VOCl, FeCl, GaCl, ZrCl etc.

Wherein for M, preferred Cu, Ni, Zn, Al etc., most preferably Cu.

M represents 1～2 integer.Preferred m is 2.

N represents 1～4 integer.Preferred n is 1～2 integer, is preferably 1 especially.

R ₁, R ₂, R ₃, R ₄Can be identical or different, it represents to replace separately or unsubstituted the total number of carbon atoms is 1～20 alkyl, replacement or unsubstituted the total number of carbon atoms are 3～20 cycloalkyl, replacement or unsubstituted the total number of carbon atoms are 2～20 thiazolinyl, replacement or unsubstituted the total number of carbon atoms are 2～12 alkynyl, replacement or unsubstituted the total number of carbon atoms are 7～20 aralkyl, replacement or unsubstituted the total number of carbon atoms are 6～20 aryl, perhaps replace or unsubstituted the total number of carbon atoms is 4～20 heterocyclic radical, wherein most preferably replace or unsubstituted the total number of carbon atoms is 1～12 alkyl, replacement or unsubstituted the total number of carbon atoms are 6～18 aryl, replacement or unsubstituted the total number of carbon atoms are 4～12 heterocyclic radical.

In addition, work as R ₁, R ₂, R ₃, R ₄Be can the situation of further substituted group under, can also further contain substituting group as described below.

Carbonatoms is that alkyl, the carbonatoms of 1～12 side chain or side chain is that aralkyl, the carbonatoms of 7～18 straight or branched is that thiazolinyl, the carbonatoms of 2～12 straight or branched is that alkynyl, the carbonatoms of 2～12 straight or branched is that cycloalkyl, the carbonatoms of 3～12 straight or branched is the cycloalkenyl group of 3～12 straight or branched; The group that contains side chain in above these groups can improve the solvability of dyestuff, and is therefore preferred, especially preferably contains the group of unsymmetrical carbon.What can enumerate is methyl; ethyl; propyl group; sec.-propyl; sec-butyl; the tertiary butyl; the 2-ethylhexyl; 2-methylsulfonyl ethyl; the 3-phenoxy propyl; trichloromethyl; cyclopentyl; halogen atom (chlorine atom for example; bromine atoms); aryl (phenyl for example; the 4-tert-butyl-phenyl; 2; the 4-di-tert-pentyl-phenyl); heterocyclic radical (imidazolyl for example; pyrazolyl; triazolyl; the 2-furyl; thienyl; pyrimidyl; benzothiazolyl); cyano group; hydroxyl; nitro; carboxyl; amino; alkoxyl group (methoxyl group for example; oxyethyl group; the 2-methoxy ethoxy; 2-methylsulfonyl oxyethyl group); aryloxy (phenoxy group for example; the 2-methylphenoxy; 4-tertiary butyl phenoxy group; the 3-nitro-phenoxy; 3-tert.-butoxy carbamyl phenoxyl; 3-methoxyl group formamyl); amido (ethanamide for example; benzamide; 4-(3-tertiary butyl-4-hydroxy phenoxy group) butyramide); alkylamino (methylamino-for example; fourth amino; diethylin; methyl fourth amino); anilino (phenylamino; the 2-chloroaniline); urea groups (phenylureido for example; the methylurea base; N; N-dibutyl urea groups); sulfamyl amino (N for example; N-dipropyl sulfamyl amino); alkyl sulfenyl (methylthio group; hot sulfenyl; 2-phenoxy group ethylmercapto group); phenyl sulfenyl (thiophenyl for example; 2-butoxy-uncle's 5-octyl group thiophenyl; 2-carboxyl thiophenyl); alkoxycarbonyl amino (for example methoxycarbonyl amino); sulfoamido (methylsulfonyl amido for example; benzene sulfonamido; the tolylsulfonyl amido); formamyl (N-ethylamino formyl radical for example; N; N-dibutylamino formyl radical); sulfamyl (N-ethyl sulfamyl for example; N; N-dipropyl sulfamyl; N-phenyl sulfamoyl base); alkylsulfonyl (methylsulfonyl; hot alkylsulfonyl; benzenesulfonyl; tosyl group); halogenation alkylsulfonyl (for example chlorosulfonyl); carbonyl halide (for example chlorination carbonyl); alkoxy carbonyl (methoxycarbonyl for example; butoxy carbonyl); oxa-cyclic group (1-phenyl-5-oxo tetrazyl for example; 2-oxo THP trtrahydropyranyl); azo-group (phenylazo-; 4-anisole azo-group; 4-valeryl amino-benzene azo-group; 2-hydroxyl-4-propionyl phenylazo-); acyloxy (for example acetoxyl group); carbamoyloxy (N-methylamino methanoyl for example; N-phenyl amino methanoyl); siloxy-(three siloxyies for example; the dibutyl siloxy-); aryloxycarbonyl amino (phenyloxycarbonyl amino); imido grpup (N-succimide base; the N phlhalimide base); thia cyclic group (2-thio phenyl benzothiazolyl for example; 2; 3-two phenoxy groups-6-sulfo--1; 3, the 5-triazolyl; 2-sulfo-pyridyl); sulfinyl (for example 3-phenoxy propyl sulfinyl); phosphono (phenoxy group phosphono for example; the octyloxy phosphono; the Phenylphosphine acyl group); acyl group (ethanoyl for example; 3-phenyl propionyl; benzoyl); ionic wetting ability group (carboxyl for example; sulfo group; phosphono and quaternary ammonium group) etc.

Wherein preferred halogen atom, heterocyclic radical, cyano group, carboxyl, amide group, sulfoamido, sulfamyl, formamyl, alkylsulfonyl, halosulfonyl groups, halo carboxyl, imino-, acyl group, sulfo group, quaternary ammonium group, more preferably cyano group, carboxyl, sulfamyl, formamyl, alkylsulfonyl, imino-, acyl group, sulfo group, quaternary ammonium group.

As R ₁, R ₂, R ₃, R ₄Shown replacement or unsubstituted alkyl, preferred carbonatoms are 1～20 alkyl.Wherein preferred especially carbonatoms is 1～12 alkyl.Particularly from deliquescent angle, preferred carbonatoms is 1～8 straight chained alkyl and/or branched-chain alkyl, especially preferably contains the alkyl of unsymmetrical carbon (use raceme).

As R ₁, R ₂, R ₃, R ₄Shown replacement or unsubstituted cycloalkyl, preferred carbonatoms are 3～20 cycloalkyl.Wherein preferred especially carbonatoms is 3～12 cycloalkyl.Particularly from deliquescent angle, preferred carbonatoms is 4～8 side chain cycloalkyl, especially preferably contains the cycloalkyl of unsymmetrical carbon (use raceme).

As R ₁, R ₂, R ₃, R ₄Shown replacement or unsubstituted thiazolinyl, preferred carbonatoms are 2～20 thiazolinyl.Wherein preferred especially carbonatoms is 2～12 thiazolinyl.Particularly from deliquescent angle, preferred carbonatoms is 3～12 branched-chain alkenyl, especially preferably contains the thiazolinyl of unsymmetrical carbon (use raceme).

As R ₁, R ₂, R ₃, R ₄Shown replacement or unsubstituted alkynyl, preferred carbonatoms are 2～20 alkynyl.Wherein preferred especially carbonatoms is 2～12 alkynyl.Particularly from deliquescent angle, preferred carbonatoms is an alkynyl group of 4～12, especially preferably contains the alkynyl of unsymmetrical carbon (use raceme).

As R ₁, R ₂, R ₃, R ₄Shown replacement or unsubstituted aralkyl, preferred carbonatoms are 7～20 aralkyl.Wherein preferred especially carbonatoms is 7～12 aralkyl.Particularly from deliquescent angle, preferred carbonatoms is 9～12 branched aralkyl groups, especially preferably contains the aralkyl of unsymmetrical carbon (use raceme).

As R ₁, R ₂, R ₃, R ₄Shown replacement or unsubstituted aryl, preferred carbonatoms are 6～20 aryl.Wherein preferred especially carbonatoms is 6～12 aryl.Particularly from deliquescent angle, preferred carbonatoms is 7～12 side chain aryl, especially preferably contains the alkyl of unsymmetrical carbon (use raceme).

As substituting group; preferred halogen atom, heterocyclic radical, cyano group, carboxyl, amide group, sulfoamido, sulfamyl, formamyl, alkylsulfonyl, imino-, acyl group, sulfo group, quaternary ammonium group, more preferably cyano group, carboxyl, sulfamyl, formamyl, alkylsulfonyl, imino-, acyl group, sulfo group, quaternary ammonium group.

As R ₁, R ₂, R ₃, R ₄Shown heterocyclic radical, preferred 5 yuan or 6 yuan of rings, also can be thick further and.Can also be aromatic heterocycle or nonaromatic heterocycles.

Following R ₁, R ₂, R ₃, R ₄Shown heterocyclic radical is an example of having omitted the heterocyclic radical type of its position of substitution, its position of substitution is not limited, and for example pyridyl can be at 2,3, and 4 replacements.It can be enumerated pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline 99.9, quinazoline, cinnoline, phthalazines, quinoxaline, pyrroles, indoles, furans, cumarone, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazoles, isoxazole, benzoisoxazole, tetramethyleneimine, piperidines, piperazine, imidazolone, thiazoline etc.

Optimization aromatic heterocyclic radical wherein, these preferred examples are to represent that with aforementioned same mode what it can be enumerated is pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazoles, imidazoles, benzoglyoxaline, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazoles etc.

Combination for the phthalocyanine compound preferred substituted shown in the general formula of the present invention (I), preferably having 1 in each substituting group is the compound of aforementioned preferred group, more preferably having more a plurality of in each substituting group is compounds of aforementioned preferred group, and most preferably whole substituting groups all is the compound of aforementioned preferred group.

For the most preferred combination of phthalocyanine compound shown in the aforementioned formula (I) be,

(A) R ₁, R ₂, R ₃And R ₄Shown can be identical or different, it can be to replace or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～20 are that cycloalkyl, replacement or unsubstituted the total number of carbon atoms of 3～20 are 2～20 thiazolinyl, replaces or unsubstituted the total number of carbon atoms is that alkynyl, replacement or unsubstituted the total number of carbon atoms of 2～12 are that aralkyl, replacement or unsubstituted the total number of carbon atoms of 7～20 are that 6～20 aryl or replacement or unsubstituted the total number of carbon atoms are 4～20 heterocyclic radical.Wherein preferred replace or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～12 are that aryl, replacement or unsubstituted the total number of carbon atoms of 6～18 are 4～12 heterocyclic radical.Wherein particularly from deliquescent angle, preferred carbonatoms is 1～8 straight chained alkyl and/or branched-chain alkyl, the alkyl that especially preferably contains unsymmetrical carbon (use raceme) further most preferably has ionic hydrophilic radical and/or hydroxyl as its substituent substituted alkyl.

(B) m is 1 or 2, most preferably 2.

(C) n represents R ₁, R ₂, R ₃And R ₄Substituent number, be 1～4 integer.Preferred n is 1 or 2, is more preferably 1.

(D) preferably Cu, Ni, Zn, Al, most preferably Cu of M.

(E) molecular weight of phthalocyanine compound is preferably in 750～2500 scope, more preferably in 995～2500 scope, wherein particularly preferably in 995～2000 scope, most preferably in 995～1800 scope.

1 molecule with the phthalocyanine compound shown in the aforementioned formula (I) in, preferably contain 1 ionic hydrophilic radical at least, particularly preferred ionic hydrophilic radical is a sulfo group, wherein has most choosing to contain sulfo group more than 2.

In the phthalocyanine compound shown in the aforementioned formula (I),, have good solvability in aqueous medium and dispersiveness because intramolecularly contains 1 ionic hydrophilic radical at least.

In phthalocyanine compound of the present invention shown in the aforementioned formula (I), more preferably has phthalocyanine compound with structure shown in the following general formula (X).

Phthalocyanine compound with structure shown in the following general formula (X) of the present invention comprises this compound and salt and their hydrate.

General formula (X)

M, R in the aforementioned formula (X) ₁, R ₂, R ₃And R ₄Independently of one another and aforementioned formula (I) in M, R ₁, R ₂, R ₃And R ₄Implication identical, its preferred example is also identical.

Combination for the phthalocyanine compound preferred substituted shown in the general formula of the present invention (X), preferably having 1 in each substituting group is the compound of aforementioned preferred group, more preferably having more a plurality of in each substituting group is compounds of aforementioned preferred group, and most preferably whole substituting groups all is the compound of aforementioned preferred group.

For the most preferred combination of phthalocyanine compound shown in the aforementioned formula (X) be,

(A) R ₁, R ₂, R ₃And R ₄Can be identical or different, preferably replace or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～12 are that 6～18 aryl or replacement or unsubstituted the total number of carbon atoms are 4～12 heterocyclic radical.Wherein particularly from deliquescent angle, preferred carbonatoms is 1～8 straight chained alkyl and/or branched-chain alkyl, the alkyl that especially preferably contains unsymmetrical carbon (use raceme) further most preferably has ionic hydrophilic radical and/or hydroxyl as its substituent substituted alkyl.

(B) preferably Cu, Ni, Zn, Al, most preferably Cu of M.

(C) molecular weight of phthalocyanine compound is preferably in 750～2500 scope, more preferably in 995～2500 scope, wherein particularly preferably in 995～2000 scope, most preferably in 995～1800 scope.

1 molecule with the phthalocyanine compound shown in the aforementioned formula (X) in, preferably contain 1 ionic hydrophilic radical at least, particularly preferred ionic hydrophilic radical is a sulfo group, wherein has most choosing to contain sulfo group more than 2.

In the phthalocyanine compound shown in the aforementioned formula (X),, have good solvability in aqueous medium and dispersiveness because intramolecularly contains 1 ionic hydrophilic radical at least.

As the object lesson with the phthalocyanine compound shown in general formula (I) or the general formula (X) can be for example special compound (particularly table 2～table 8) that the 2002-249677 communique is put down in writing of opening.

In the preparation method of phthalocyanine compound of the present invention, can use with the compound shown in the following general formula (III) as the phthalic imidine of raw material.State the phthalimide compound shown in the general formula (III) and describe following below.

General formula (III)

In above-mentioned general formula (III), Y represents leavings group.N is 1～4 integer.A represents hydrogen atom or atoms metal.

As preferred A, what can enumerate is hydrogen atom, Na atom, K atom, wherein preferred especially hydrogen atom.

As preferred leavings group Y, what can enumerate from the angle of easy acquisition raw material is nitro, halogen atom (for example chlorine atom, bromine atoms, iodine atom).

The present invention used with in the raw material phthalic imidine shown in the general formula (II), preferred especially 3-nitro phthalic imidine and 4-nitro phthalic imidine, most preferably 4-nitro phthalic imidine.

As the used sulfhydryl compound of the present invention, preferably with the compound shown in the following general formula (II).State the sulfhydryl compound shown in the general formula (III) and describe following below.

General formula (II) MS-R

In above-mentioned general formula (II), R can be identical or different, it preferably replaces or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～20 are that cycloalkyl, replacement or unsubstituted the total number of carbon atoms of 3～20 are 2～20 thiazolinyl, replaces or unsubstituted the total number of carbon atoms is that alkynyl, replacement or unsubstituted the total number of carbon atoms of 2～12 are that aralkyl, replacement or unsubstituted the total number of carbon atoms of 7～20 are that 6～20 aryl or replacement or unsubstituted the total number of carbon atoms are 4～20 heterocyclic radical.Wherein most preferably replace or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～12 are that aryl, replacement or unsubstituted the total number of carbon atoms of 6～18 are 4～12 heterocyclic radical.

In addition, when R be can the situation of further substituted group under, can also further have at aforementioned R ₁, R ₂, R ₃, R ₄Be can the situation of further substituted group under those mentioned substituting groups.

Wherein, preferred halogen atom, heterocyclic radical, cyano group, carboxyl, amide group, sulfoamido, sulfamyl, formamyl, alkylsulfonyl, halogenated alkylsulfonyl, halogenated carboxyl, imino-, acyl group, sulfo group, quaternary ammonium group, more preferably cyano group, carboxyl, sulfamyl, formamyl, alkylsulfonyl, imino-, acyl group, sulfo group, quaternary ammonium group.

In above-mentioned general formula (II), M represents hydrogen atom or atoms metal.

As preferred L, what can enumerate is hydrogen atom, Li atom, Na atom, K atom etc.Wherein preferred Na atom, K atom are particularly from the preferred Na atom of the angle of easy acquisition raw material.

Combination for the sulfhydryl compound preferred substituted shown in the aforementioned formula of the present invention (II), preferably having 1 in each substituting group is the compound of aforementioned preferred group, more preferably having more a plurality of in each substituting group is compounds of aforementioned preferred group, and most preferably whole substituting groups all is the compound of aforementioned preferred group.

For the most preferred combination of sulfhydryl compound shown in the aforementioned formula (II) be,

(A) R replaces or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～12 are that 6～18 aryl or replacement or unsubstituted the total number of carbon atoms are 4～12 heterocyclic radical.Wherein particularly from deliquescent angle, preferred carbonatoms is 1～8 straight chained alkyl and/or branched-chain alkyl, the alkyl that especially preferably contains unsymmetrical carbon (use raceme) further most preferably has ionic hydrophilic radical (sulfo group, carboxyl) and/or hydroxyl as its substituent substituted alkyl.

(B) the preferred Na atom of M, K atom, preferred especially Na atom.

Below the phthalimide compound with shown in the following general formula (IV) used among the present invention is described.

General formula (IV)

A, n in the above-mentioned general formula (IV) is identical with the implication of A, n in the aforementioned formula (III), and its preferred example is also identical.

R in the above-mentioned general formula (IV) is identical with the implication of R in the aforementioned formula (II), and its preferred example is also identical.

Combination for the phthalimide compound preferred substituted shown in the general formula of the present invention (IV), preferably having 1 in each substituting group is the compound of aforementioned preferred group, more preferably having more a plurality of in each substituting group is compounds of aforementioned preferred group, and most preferably whole substituting groups all is the compound of aforementioned preferred group.

For the most preferred combination of phthalimide compound shown in the aforementioned formula (IV) be,

(A) R replaces or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～12 are that 6～18 aryl or replacement or unsubstituted the total number of carbon atoms are 4～12 heterocyclic radical.Wherein particularly from deliquescent angle, preferred carbonatoms is 1～8 straight chained alkyl and/or branched-chain alkyl, particularly when containing unsymmetrical carbon (use raceme), further preferably have ionic hydrophilic radical (sulfo group, carboxyl) and/or hydroxyl as its substituent substituted alkyl, most preferably have sulfo group, carboxyl as its substituent substituted alkyl.

(B) preferably hydrogen atom, Na atom, K atom of A, preferred especially hydrogen atom.

(C) n preferably 1 or 2, are more preferably 1.

Be the object lesson of the phthalimide compound of the replacement shown in general formula of the present invention (IV) below, but the phthalimide compound of the replacement shown in the general formula of the present invention (IV) is not limited thereto.

Table 1

General formula (IV)

Below the phthalimide compound with shown in the following general formula (V) used among the present invention is described.

Logical formula V

A, n in the above-mentioned logical formula V is identical with the implication of A, n in the aforementioned formula (III), and its preferred example is also identical.

R in the above-mentioned logical formula V is identical with the implication of R in the aforementioned formula (IV), and its preferred example is also identical.

M represents 1～2 integer in the above-mentioned logical formula V, preferred especially 2.

Combination for the phthalimide compound preferred substituted shown in the logical formula V of the present invention, preferably having 1 in each substituting group is the compound of aforementioned preferred group, more preferably having more a plurality of in each substituting group is compounds of aforementioned preferred group, and most preferably whole substituting groups all is the compound of aforementioned preferred group.

For the most preferred combination of phthalimide compound shown in the aforementioned formula (V) be,

(C) n preferably 1 or 2, are more preferably 1.

Be the object lesson of the phthalimide compound of the replacement shown in the logical formula V of the present invention below, but the phthalimide compound of the replacement shown in the logical formula V of the present invention is not limited thereto.

Table 2

Logical formula V

Below the phthalyl amine compound with shown in the following general formula (VI) used among the present invention is described.

General formula (VI)

N in the above-mentioned general formula (VI) is identical with the implication of n in the aforementioned formula (III), and its preferred example is also identical.

R in the above-mentioned general formula (VI) is identical with the implication of R in the aforementioned formula (II), and its preferred example is also identical.

M represents 1～2 integer, preferred especially 2 in the above-mentioned general formula (VI).

Combination for the phthalyl amine compound preferred substituted shown in the general formula of the present invention (VI), preferably having 1 in each substituting group is the compound of aforementioned preferred group, more preferably having more a plurality of in each substituting group is compounds of aforementioned preferred group, and most preferably whole substituting groups all is the compound of aforementioned preferred group.

For the most preferred combination of phthalyl amine compound shown in the aforementioned formula (VI) be,

(B) n preferably 1 or 2, are more preferably 1.

(C) m preferably 1 or 2, are more preferably 2.

Be the object lesson of the phthalyl amine compound of the replacement shown in general formula of the present invention (VI) below, but the phthalyl amine compound of the replacement shown in the general formula of the present invention (VI) is not limited thereto.

Table 3

General formula (VI)

Below the O-phthalic nitrile compound with shown in the following general formula (VII) used among the present invention is described.

General formula (VII)

N in the above-mentioned general formula (VII) is identical with the implication of n in the aforementioned formula (III), and its preferred example is also identical.

R in the above-mentioned general formula (VII) is identical with the implication of R in the aforementioned formula (II); its preferred example is to replace or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～12 are that 6～18 aryl or replacement or unsubstituted the total number of carbon atoms are 4～12 heterocyclic radical; wherein especially this substituting group partly is transformed to the angle of similar derivative thing, preferred especially halogenation alkylsulfonyl (SO from the method for substituting group conversion that can be by chemistry ₂Cl) alkyl of Qu Daiing, the carbonyl halide (COCl) alkyl of Qu Daiing.

M represents 1～2 integer, preferred especially 2 in the above-mentioned general formula (VII).

Combination for the O-phthalic nitrile compound preferred substituted shown in the general formula of the present invention (VII), preferably at each substituent at least 1 be the compound of aforementioned preferred group, more preferably having more a plurality of in each substituting group is compounds of aforementioned preferred group, and most preferably whole substituting groups all is the compound of aforementioned preferred group.

For the most preferred combination of O-phthalic nitrile compound shown in the aforementioned formula (VII) be,

(A) R replaces or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～12 are that 6～18 aryl or replacement or unsubstituted the total number of carbon atoms are 4～12 heterocyclic radical.Wherein especially from the method for substituting group conversion that can be by chemistry angle, preferred especially halogenation alkylsulfonyl (SO with this substituting group part displacement similar derivative thing ₂Cl) alkyl of Qu Daiing, the carbonyl halide (COCl) alkyl of Qu Daiing.

(B) n preferably 1 or 2, are more preferably 1.

(C) m preferably 1 or 2, are more preferably 1.

Be the object lesson of the O-phthalic nitrile compound with the replacement shown in the general formula (VII) of the present invention below, but O-phthalic nitrile compound with the replacement shown in the general formula (VII) of the present invention is not limited thereto.

Table 4

General formula (VII)

Below the O-phthalic nitrile compound with shown in the following general formula (VIII) used among the present invention is described.

General formula (VIII)

O-phthalic nitrile compound shown in the above-mentioned general formula (VIII) is the method (R that the substituting group part (R) of the O-phthalic nitrile compound shown in the above-mentioned general formula (VII) is passed through the substituting group conversion of the chemistry from general formula (VII) to general formula (VIII) -the derivative that L-Z) obtains.

As concrete example, the substituting group part R of the O-phthalic nitrile compound shown in the above-mentioned general formula (VII) is halogenation alkylsulfonyl (SO for example ₂Cl) alkyl of Qu Daiing, halogenation alkylsulfonyl (SO ₂Cl) aryl of Qu Daiing, carbonyl halide (COCl) alkyl of Qu Daiing, carbonyl halide (COCl) aryl of Qu Daiing, in this case;

1. by adding water decomposition, can derive is the alkyl that sulfo group replaces, the aryl that sulfo group replaces, the alkyl of carboxyl substituted, the aryl that base replaces.Can also be the form of salt particularly as substituent sulfo group, carboxyl, as the salifiable gegenion of shape, for example can contain ammonium ion, alkalimetal ion (for example lithium ion, sodium ion, potassium ion) and organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl-phosphine ion).Preferred as alkali salt, particularly lithium salts (SO under the situation of sulfo group in these gegenions ₃Li) can improve solvability, therefore preferred especially.

During the crystallization of the salt of above-mentioned carboxyl, sulfo group after adding water decomposition, carry out the salify operation, it can be separated by using corresponding gegenion.

2. by amidation, can derive is sulfamyl (SO ₂NR ₁₁R ₁₂) alkyl, the sulfamyl (SO that replace ₂NR ₁₁R ₁₂) aryl, the formamyl (CONR that replace ₁₁R ₁₂) alkyl, the formamyl (CONR that replace ₁₁R ₁₂) aryl that replaces.(the R in the above-mentioned formula ₁₁, R ₁₂The substituting group of expression hydrogen atom or 1 valency)

L in the above-mentioned general formula (VIII) represents to replace or unsubstituted the total number of carbon atoms is that alkylidene group, replacement or unsubstituted the total number of carbon atoms of 1～12 are that phenylene, replacement or unsubstituted the total number of carbon atoms of 6～18 are that 10～20 naphthylidene or replacement or unsubstituted the total number of carbon atoms are the heterocyclic radical of 4～12 divalent.

Wherein preferred replace or unsubstituted the total number of carbon atoms is that alkylidene group, replacement or unsubstituted the total number of carbon atoms of 1～12 are 6～18 phenylene, preferred especially replace or unsubstituted the total number of carbon atoms is 1～12 alkylidene group.

In more detail, preferred the total number of carbon atoms be a straight or branched alkylidene group of 1～12 (for example under the situation of straight-chain alkyl-sub-,-(CH ₂) integer of n-:n=1～12), preferred especially the total number of carbon atoms is 1～8 straight or branched alkylidene group, wherein further preferred the total number of carbon atoms is a straight or branched alkylidene group of 2～6.

N in the above-mentioned general formula (VIII) is identical with the implication of n in the aforementioned formula (II), and its preferred example is also identical.

M represents 1～2 integer, preferred especially 2 in the above-mentioned general formula (VIII).

Z represents hydrogen atom or substituting group.

In addition, when Z be can the situation of further substituted group under, can also further have as the R in aforementioned formula (I) ₁～R ₄Be can the situation of further substituted group under mentioned those substituting groups (concrete example).

The example of preferred Z can be as the R in aforementioned formula (I) similarly ₁～R ₄Be can the situation of further substituted group under those mentioned substituting groups.

Wherein, preferred halogen atom, heterocyclic radical, cyano group, carboxyl, amide group, sulfoamido, sulfamyl, formamyl, alkylsulfonyl, imino-, acyl group, sulfo group, quaternary ammonium group; more preferably cyano group, carboxyl, sulfamyl, formamyl, alkylsulfonyl, imino-, acyl group, sulfo group, quaternary ammonium group, preferred especially sulfamyl, the formamyl of replacement, sulfo group, the carboxyl that replaces.

Combination for the O-phthalic nitrile compound preferred substituted shown in the general formula of the present invention (VIII), preferably having 1 in each substituting group is the compound of aforementioned preferred group, more preferably having more a plurality of in each substituting group is compounds of aforementioned preferred group, and most preferably whole substituting groups all is the compound of aforementioned preferred group.

For the particularly preferred combination of O-phthalic nitrile compound shown in the aforementioned formula (VIII) be,

(A) L replaces or unsubstituted the total number of carbon atoms is that alkylidene group, replacement or unsubstituted the total number of carbon atoms of 1～12 are that arylidene, replacement or unsubstituted the total number of carbon atoms of 6～18 are that 10～20 naphthylidene or replacement or unsubstituted the total number of carbon atoms are the heterocyclic radical of 4～12 divalent, wherein preferred replace or unsubstituted the total number of carbon atoms is that alkylidene group, replacement or unsubstituted the total number of carbon atoms of 1～12 are 6～18 phenylene, preferred especially replace or unsubstituted the total number of carbon atoms is 1～12 alkylidene group.In more detail, preferred the total number of carbon atoms is 1～12 straight or branched alkylidene group, and preferred especially the total number of carbon atoms is 1～8 straight or branched alkylidene group, and wherein further preferred the total number of carbon atoms is 2～6 straight or branched alkylidene group.

(B) the preferred hydrogen atom of Z, halogen atom, heterocyclic radical, cyano group, carboxyl, amide group, sulfoamido, sulfamyl, formamyl, alkylsulfonyl, imino-, acyl group, sulfo group, quaternary ammonium group; more preferably cyano group, carboxyl, sulfamyl, formamyl, alkylsulfonyl, imino-, acyl group, sulfo group, quaternary ammonium group, preferred especially sulfamyl, the formamyl of replacement, sulfo group, the carboxyl that replaces.

(C) n preferably 1 or 2, are more preferably 1.

(D) m preferably 1 or 2, are more preferably 2.

Be the object lesson of the O-phthalic nitrile compound with the replacement shown in the general formula (VIII) of the present invention below, but O-phthalic nitrile compound with the replacement shown in the general formula (VIII) of the present invention is not limited thereto.

Table 5

General formula (VIII)

Below the metal derivative with shown in the following general formula (IX) used among the present invention is described.

General formula (IX) M-(X) _d

M represents oxide compound, oxyhydroxide or the halogenide of hydrogen atom, atoms metal or atoms metal in above-mentioned general formula (IX).

As atoms metal, that can enumerate is Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi etc.

As oxide compound, can be VO, GeO etc.

As oxyhydroxide, can be Si (OH) ₂, Cr (OH) ₂, Sn (OH) ₂Deng.

As halogenide, can be AlCl, SiCl ₂, VCl, VCl ₂, VOCl, FeCl, GaCl, ZrCl etc.

Wherein for M, preferred Cu, Ni, Zn, Al etc., most preferably Cu.

In general formula (IX), Z represents the part of halogen atom, acetate anion, acetylacetonate, oxygen and so on 1 valency or divalent, and d represents 1～4 integer.

As the object lesson of metal derivative (metal derivative shown in the general formula (IX)), the halogenide that Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, Sn, Pt, Pb etc. are arranged, carboxylic acid derivative, vitriol, nitrate, carbonyl compound, oxide compound or the complex compound etc. that can enumerate.More particularly, cupric chloride, cupric bromide, cupric iodide, neutralized verdigris, nickelous chloride, nickelous bromide, nickel acetate, cobalt chloride, cobaltous bromide, Cobaltous diacetate, iron(ic) chloride, zinc chloride, zinc bromide, zinc iodide, zinc acetate, vanadium chloride, vanadylic chloride, Palladous chloride, palladium, aluminum chloride, Manganous chloride tetrahydrate, manganese acetate, acetopyruvic acid manganese, Manganous chloride tetrahydrate, lead chloride, plumbic acetate, indium chloride, titanium chloride, tin chloride etc.

Wherein preferred cupric chloride (CuCl ₂), neutralized verdigris, preferred especially cupric chloride (CuCl ₂).

About the preparation method of the phthalimide compound of the replacement shown in general formula of the present invention (IV), below the phthalimide compound shown in the mutual-through type (II) and the synthesis condition of the sulfhydryl compound shown in the general formula (III) be described in detail.

In the presence of basic cpd, to can make phthalimide compound corresponding to the metal-salt of alkyl sulfhydryl, aryl mercaptan or the heterocyclic radical mercaptan shown in the general formula (III) with the reaction of the phthalimide compound shown in the general formula (II) with the replacement shown in the general formula (IV).

As basic cpd, what can enumerate is basic metal classes such as metallic lithium, sodium Metal 99.5, potassium metal, oxyhydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, carbonate such as salt of wormwood, yellow soda ash, the acetate of sodium-acetate, Potassium ethanoate etc., the metal hydride class of lithium hydride, sodium hydride, potassium hydride KH etc., ammonobase classes such as Lithamide, sodium amide, potassium amide, perhaps alkoxyl group salt such as sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium.

In addition, these basic cpds also can mix use.With respect to 1 mole with the phthalimide compound shown in the general formula (II), the consumption of basic cpd is 0.5～20 times of mole, preferred 0.7～10 times of mole, especially most preferably 0.7～1.5 times of mole.

Preparation with the phthalimide compound of the replacement shown in the general formula (IV) is preferably carried out in organic solvent, used solvent should be the solvent that this reaction is not produced impairment, that can enumerate is N, dinethylformamide (DMF), N, N-dimethyl-imidazolinone (DMI), tetramethylene sulfone, N, N-dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMAc), toluene, dimethylbenzene, diethyl ether, tetrahydrofuran (THF) (THF), diox, diglyme etc.Also can carry out the self-dissolving reaction in addition by excessively using with alkyl sulfide alcohols, aryl mercaptan class or the heterocyclic radical thio-alcohol shown in the general formula (III).

Reaction with the phthalimide compound shown in the general formula (II), can be with the alkyl sulfhydryl for preparing, the metal-salt of aryl mercaptan or heterocyclic radical mercaptan joins in the solution or suspension liquid with the phthalimide compound shown in the general formula (II), also solution or the suspension liquid with the phthalimide compound shown in the general formula (II) can be joined in these metal-salts that prepare, further, can also be by will be with phthalimide compound and the alkyl sulfhydryl shown in the general formula (II), the metal-salt of aryl mercaptan or heterocyclic radical mercaptan coexists in solvent, and then the adding basic cpd, in preparing metal salt, react.

Temperature of reaction is according to the kind difference of its used reaction reagent, and its optimal temperature is also different, and preferred 0～150 ℃, further preferred 10～100 ℃, particularly most preferably 30～80 ℃.

Synthetic can take out by following method with the phthalimide compound of the replacement shown in the general formula (IV), can be used for following oxidizing reaction, can oxidizing reaction not be carried out in its taking-up like this, to prepare with the phthalimide compound shown in the logical formula V yet.

As removing method, according to the difference of the substituting group of correspondence, reaction solvent and difference after for example discharging, makes its crystallization with acid outs such as hydrochloric acid, sulfuric acid from water, obtain by filtration drying.After perhaps the reaction mixture filtered while hot being removed inorganics, the alcoholic solvent that injects methyl alcohol, ethanol, Virahol etc. makes its crystallization, obtains behind the filtration drying.

Preparation method about leading to the phthalimide compound of the replacement shown in the formula V as the present invention is elaborated to the phthalimide compound shown in general formula of the present invention (IV) and the synthesis condition of oxygenant below.

Can be with the phthalimide compound of the replacement shown in the logical formula V according to different situations, in the presence of catalyzer (for example lithium tungstate, sodium tungstate dihydrate), by preparing with oxidant reaction.

As preferred oxygenant, aquae hydrogenii dioxidi, mCPBA (a chloro perbenzoic acid), KMnO ₄And so on peracid, preferred especially aquae hydrogenii dioxidi.

Preparation with the phthalimide compound of the replacement shown in the logical formula V is preferably carried out in water or in the organic solvent, used solvent should be the solvent that oxidizing reaction is not had impairment, preferably water, acetic acid, propionic acid etc., the mixed solvent of special preferably water and acetic acid.

Temperature of reaction is according to the kind difference of its used reaction reagent, and its optimal temperature is also different, and preferred 0～80 ℃, further preferred 10～80 ℃, especially most preferably 30～75 ℃.

Synthetic can take out by following method with the phthalimide compound of the replacement shown in the logical formula V, can be used for following reaction, can oxidizing reaction not be carried out in its taking-up like this, to prepare with the phthalyl amine compound shown in the general formula (VI) yet.

As removing method, according to the difference of the substituting group of correspondence, reaction solvent and difference after for example discharging, makes its crystallization from water, obtain by filtration drying.The alcoholic solvent that perhaps can inject methyl alcohol, ethanol, Virahol etc. in reaction mixture makes its crystallization, obtains behind the filtration drying.

About the preparation method of the phthalyl amine compound of the replacement shown in general formula of the present invention (VI), below the phthalimide compound shown in the logical formula V of the present invention and the synthesis condition of ammonia are elaborated.

Phthalyl amine compound with the replacement shown in the general formula (VI) can make by making itself and ammonia react.

As the source of supply of preferred ammonia, ammoniacal liquor, ammonia (gas bottle), liquefied ammonia and as the ammonium salt (for example volatile salt, bicarbonate of ammonia, ammonium acetate) of ammonia precursor, the ammonium acetate under preferred especially ammonia, basic cpd exist wherein selects most ammonia.

Preparation with the phthalyl amine compound of the replacement shown in the general formula (VI) is preferably carried out in organic solvent, used solvent should be the solvent that this reaction is not produced impairment, that can enumerate is N, dinethylformamide (DMF), N, N-dimethyl-imidazolinone (DMI), tetramethylene sulfone, N, N-dimethyl sulfoxide (DMSO) (DMSO), N,N-dimethylacetamide (DMAc), toluene, dimethylbenzene, diethyl ether, tetrahydrofuran (THF) (THF), diox, diglyme, methyl alcohol, ethanol, Virahol, acetonitrile etc.Wherein preferred N, dinethylformamide (DMF), methyl alcohol, acetonitrile, N most preferably, dinethylformamide (DMF).

Temperature of reaction is according to the kind difference of its used reaction reagent, and its optimal temperature is also different, and preferred 0～80 ℃, further preferred 10～30 ℃, especially most preferably 15～20 ℃.

Synthetic can take out by following method with the phthalyl amine compound of the replacement shown in the general formula (VI), can be used for following reaction, can oxidizing reaction not be carried out in its taking-up like this, to prepare with the O-phthalic nitrile compound shown in the general formula (VII) yet.

As removing method, according to the difference of the substituting group of correspondence, reaction solvent and difference after for example discharging, makes its crystallization from water, obtain by filtration drying.

Its taking-up is not just being carried out under the situation of oxidizing reaction, reaction mixture is in heating up in a steamer under the room temperature reduced pressure and desolvating behind the contained ammonia, by obtaining with the O-phthalic nitrile compound shown in the general formula (VII) with the dewatering agent prepared in reaction.

Preparation method about the O-phthalic nitrile compound with the replacement shown in the general formula (VII) of the present invention is elaborated with the phthalimide compound shown in the general formula (VI) and the synthesis condition of dewatering agent to of the present invention below.

O-phthalic nitrile compound with the replacement shown in the general formula (VII) can make by making itself and dewatering agent reaction.

As preferred dewatering agent, what can enumerate is Phosphorus Oxychloride, thionyl chloride, special preferred oxygen phosphorus chloride.

Preparation with the O-phthalic nitrile compound of the replacement shown in the general formula (VII) is preferably carried out in organic solvent, and used solvent should be the solvent that this reaction is not produced impairment, and that preferably can enumerate is N, dinethylformamide (DMF), acetonitrile etc.The aspect of particularly never separating the phthalimide compound shown in the general formula (VI) and proceeding dehydration reaction considers, N most preferably, dinethylformamide (DMF).

Temperature of reaction is according to the kind difference of its used reaction reagent, and its optimal temperature is also different, and preferred 0～80 ℃, further preferred 10～50 ℃, especially most preferably 15～40 ℃.

Synthetic can take out by following method with the O-phthalic nitrile compound of the replacement shown in the general formula (VII), can be used for following reaction, can oxidizing reaction not be carried out in its taking-up like this, to prepare with the O-phthalic nitrile compound shown in the general formula (VII) yet.

As removing method, according to the difference of the substituting group of correspondence, reaction solvent and difference, the alcoholic solvent that for example can inject methyl alcohol, ethanol, Virahol etc. in reaction mixture makes its crystallization, obtains behind the filtration drying.

About the preparation method of the phthalocyanine compound (I) with the replacement shown in the general formula (I) of the present invention, be elaborated with the O-phthalic nitrile compound shown in general formula (VII) and/or the general formula (VIII) with the synthesis condition of the metal derivative shown in the general formula (IX) to of the present invention below.

The ratio of the consumption of O-phthalic nitrile compound and metal derivative is, and mol ratio (metal derivative: the O-phthalic nitrile compound) preferably at 1: 10～10: 1, particularly preferably in 1: 1～1: 5, wherein especially most preferably 1: 3～1: 4.

The reaction of O-phthalic nitrile compound and metal derivative is carried out in the presence of solvent usually.Use its boiling point more than 80 ℃ as solvent, preferred boiling point is at the organic solvent more than 130 ℃.For example Pentyl alcohol, n-hexyl alcohol, hexalin, 2-methyl-1-pentene alcohol, 1-amylalcohol, 2-amylalcohol, 1-octanol, 2-Ethylhexyl Alcohol, benzylalcohol, ethylene glycol, glycol ether, propylene glycol, ethoxy ethanol, propoxy-ethanol, dimethylaminoethanol, DEAE diethylaminoethanol, trichlorobenzene, chloronaphthalene, tetramethylene sulfone, oil of mirbane, quinoline, urea etc.1～100 quality that the consumption of solvent is preferably the O-phthalic nitrile compound doubly, more preferably 1～20 quality doubly, wherein especially most preferably 1～5 quality is doubly.

The reaction of O-phthalic nitrile compound and metal derivative can be carried out in the damping fluid by alkaline organic or formed alkaline inorganics of basic metal and acid.

The acid used as the present invention has no particular limits, so long as its dissociation constant pKa just can at organic compound below 7.0 or mineral compound in 25 ℃ the aqueous solution.

What PKa represented is the logarithmic value of the inverse of acid ionization constant, is the value of being tried to achieve under ionic strength is 0.1,25 ℃ condition.As the acid of this pKa between 0.0～7.0, can be the mineral acid of phosphoric acid etc., or organic acid such as acetic acid, propanedioic acid, citric acid, be the organic acid of pKa between 0.0～7.0 according to the effective acid of above-mentioned improvement.The organic acid that most preferably has carboxyl in this external organic acid.The organic acid of pKa between 0.0～7.0 can be the organic acid or the polybasic organic acid of monobasic.For the polybasic organic acid, can use metal-salt (for example sodium salt and sylvite) or the ammonium salt of its pKa between 0.0～7.0.The organic acid of pKa more than 2 kinds between 0.0～7.0 can also be mixed in addition and use.For the organic acid of used pKa between 0.0～7.0 among the present invention, the aliphatics monobasic organic acid that formic acid, acetic acid, monochloroacetic acid, monobromo acetic acid, oxyacetic acid, propionic acid, a chloropropionic acid, lactic acid, pyruvic acid, vinylformic acid, butyric acid, isopropylformic acid, trimethylacetic acid, aminobutyric acid, valeric acid, isovaleric acid etc. are arranged that it preferably can specifically be enumerated; Amino acidses such as l-asparagine, L-Ala, arginine, ethionine, glycine, glutamine, halfcystine, Serine, methionine(Met), leucine; Mono-substituted M-nitro benzoic acids such as M-nitro benzoic acid and chlorine, hydroxyl; The aromatic series monoprotic acid of nicotinic acid etc.; The binary aliphatic organic acid of oxalic acid, propanedioic acid, succsinic acid, tartrate, oxysuccinic acid, toxilic acid, fumaric acid, oxosuccinic acid, pentanedioic acid, hexanodioic acid etc.; The amino acids binary organic acid of aspartic acid, L-glutamic acid, pentanedioic acid, Gelucystine, xitix etc.; The various organic acids of ternary organic acid of citric acid and so on and so on.In these organic acids of the present invention, preferred aliphat monobasic organic acid, most preferably formic acid, acetic acid, propionic acid.

With respect to consumption with the compound shown in the general formula (I), these pKa are its 0.05～20 equivalent at the consumption of the compound below 7.0, preferred 0.1～10 times of equivalent, adding with such amount can be to playing restraining effect with the decomposition of the compound shown in the general formula (I).With respect to the consumption with the compound shown in the general formula (I), pKa can not fully suppress the decomposition with the compound shown in the general formula (I) when 0.05 times of equivalent of usefulness quantity not sufficient of the acid below 7.0.On the one hand, with respect to consumption, when pKa surpasses 20 times of equivalents at the consumption of the acid below 7.0, make reaction be difficult to carry out because the reaction system deflection is acid with the compound shown in the general formula (I).Excessively use alkali if also have when forming damping fluid, the formed salt of bronsted lowry acids and bases bronsted lowry can produce with the crystalline form.

The used alkali of the present invention is mineral alkali or organic bases.As mineral alkali, what can enumerate is the mineral alkali of Quilonum Retard, yellow soda ash, salt of wormwood, sodium bicarbonate, lithium hydroxide, potassium hydroxide etc., as organic bases, that can enumerate has triethylamine, Tributylamine, diisopropyl ethyl amine, pyridine, a Dimethylamino pyridine etc.Can also use the organic acid salt of Lithium Acetate, Potassium ethanoate, sodium oxalate, Calcium Disodium Versenate salt etc. in addition.These alkali dissolutions play the effect of buffered soln in reaction solvent, the alkali that preferred dissolution is high, for organic bases most preferably by the formed salt of alkalimetal ion.Preferred lithium ion, sodium ion, potassium ion in the alkalimetal ion, the wherein organic acid salt of lithium ion, sodium ion most preferably.With respect to the consumption with the compound shown in the general formula (I), the consumption of alkali is 0.05～30.0 equivalent, preferred 0.5～15.0 equivalent.

The reaction of O-phthalic nitrile compound and metal derivative is preferably carried out in 65～300 ℃ range of reaction temperature, more preferably at 70～250 ℃ range of reaction temperature, further preferably at 80～150 ℃ range of reaction temperature.Speed of response is very slow during 65 ℃ of this temperature of reaction less thaies, and the phthalocyanine derivates that obtains when surpassing 300 ℃ on the other hand may decompose.

Also has the reaction times preferably in 0.5～24 hour scope, more preferably in 1～10 hour scope, further preferably in 1～3 hour scope.This reaction times less than can make unreacting material exist in large quantities in 0.5 hour, and surpassing the phthalocyanine derivates that obtained in 24 hours on the other hand may decompose.

Among the preparation method of phthalocyanine compound of the present invention, after the product (phthalocyanine dye) that these reactions of process obtain can be handled by the postorder treatment process of common organic synthesis, be used for making with extra care or obtaining without making with extra care.

That is to say that the product that will dissociate out is without refining, perhaps by using for example column chromatography (example gel permeation chromatography (SEPHADEX alone or in combination from reaction system ^TMLH-20:Pharmacia production)) etc. purification operations is made with extra care, and obtains product.

Also have after reaction finishes, heat up in a steamer the dereaction solvent or it is not heated up in a steamer, pour in water or the ice, after carrying out or not neutralizing, the product that dissociates out without refining or by for example using the purification operations of recrystallization, column chromatography etc. to make with extra care alone or in combination, is obtained product.

In addition, can also be after reaction finishes, heat up in a steamer the dereaction solvent or it is not heated up in a steamer, pour in water or the ice, after carrying out or not neutralizing, the product that will extract from organic solvent/aqueous solution obtains product without refining or by for example using the purification operations of recrystallization, column chromatography etc. to make with extra care alone or in combination.

In an embodiment the preparation method of phthalocyanine compound of the present invention is described in detail below, but the present invention is not subjected to any restriction of these embodiment.

[embodiment]

(synthesis example)

Representational phthalocyanine compound of the present invention can synthesize by following synthetic route.According to the object lesson of synthesis example shown below, can also synthesize as the spy and open table 2 in the 2002-249677 communique～8 phthalocyanine compounds of being put down in writing.In following embodiment, λ max represents that maximum absorption wavelength, ε max represent the pairing molar absorptivity of maximum absorption wavelength.

Synthesis example 1: compound 1 synthetic

In nitrogen gas stream, the 4-nitro phthalic imidine (Tokyo changes into) of 288.2g is dissolved among the DMSO (dimethyl sulfoxide (DMSO)) of 1442mL, keep down for 20 ℃ stirring in interior temperature, add the 3-unithiols (85%) of 333g.Keep down for 50 ℃ stirring in interior temperature then, slowly add the 173.8g anhydrous sodium carbonate.Stirring reaction liquid Yi Bian be warming up to 70 ℃, keeps this temperature to stir 1 hour on one side.After being cooled to 40 ℃, reaction solution filters with cloth formula funnel, and filtrate is added to crystallization in the methyl alcohol of 2885mL, then at room temperature stirred 30 minutes, the 1442mL Virahol that reinjects, keep stirring make in temperature be cooled to 10 ℃.The coarse crystallization of separating out is filtered with cloth formula funnel, with the methanol cleaning of 962mL, and the dry then coarse crystallization that obtains 503.4g compound 1. ¹H-NMR (DMSO-d6), δ value TMS benchmark: 1.89～1.99 (2H, m); 2.51～2.65 (2H, t); 3.24～3.50 (2H, t); 7.64～7.76 (3H, m); 11.29～11.41 (1H, s)

Synthesis example 2: compound 2 synthetic

The compound 1 of 485.0g is added into 48.5mL acetic acid and 1500mL H ₂In the mixing solutions of O, keep down for 25 ℃ stirring, add 15g Na in interior temperature ₂WO ₄2H ₂Behind the O, 45 ℃ of dissolvings of temperature in being warming up to.Then while noticing that the heat release situation slowly drips the aquae hydrogenii dioxidi (30%) of 374mL.After 50 ℃ of interior temperature stir 60 minutes down, inwardly drip the aqueous solution of 88.2g/400mL S-WAT in warm 50 ℃ the reaction solution, behind Dropwise 5 32mL Virahol under this temperature, after being cooled to 10 ℃, then after stirring 30 minutes under this temperature, the crystallization of separating out is filtered with cloth formula funnel, obtain the compound 2 of 462.6g after the Virahol cleaning, drying with 525mL. ¹H-NMR (DMSO-d6), δ value TMS benchmark: 1.25～1.89 (2H, m); 2.48～2.52 (2H, t); 3.59～3.65 (2H, t); 8.04～8.11 (1H, d); 8.20 (1H, s); 8.29～8.33 (1H, d); 11.59～11.90 (1H, s)

Synthesis example 3-1: compound 3 synthetic

300g compound 2 is added among the DMF (dimethyl formamide) of 900mL, keeps down for 20 ℃ stirring, feed NH in interior temperature ₃Gas 90 minutes then stirred 3 hours under this temperature.Reaction solution (keeps under＜400mmHg) the condition stirring, heats up in a steamer the NH that remains in the solution in 20 ℃ of interior temperature, decompression then ₃Gas.(compound 2+NH ₃

The reaction solution of compound 3)

Synthesis example 3-2: compound 3 synthetic

300g compound 2 is added in the acetonitrile of 3000mL, keeps down for 20 ℃ stirring, feed NH in interior temperature ₃Gas 2 hours then after stirring 10 hours under this temperature, filters the crystallization of separating out with cloth formula funnel, obtain the compound 3 of 297.6g after the acetonitrile cleaning, drying with 30000mL. ¹H-NMR (DMSO-d6), δ value TMS benchmark: 1.77～1.88 (2H, m); 2.49～2.54 (2H, t); 3.49～3.54 (2H, t); 7.55 (1H, d); 7.69～7.71 (1H, d); 7.94～8.17 (3H, m)

Synthesis example 4-1: compound 4 synthetic

In 5 ℃ of DMF of interior temperature (dimethyl formamide), drip the POCl of 315.1mL to 600mL ₃, temperature is below 15 ℃ in keeping simultaneously.Then to POCl ₃In/DMF the solution, remain in interior temperature and to drip above-mentioned synthesis example 3-1 (compound 2+NH under the situation below 10 ℃ ₃=＞compound 3) reaction solution, temperature stirred 1 hour at 17 ℃ in keeping then.Then interior temperature is remained under 35 ℃ the situation H to 4500mL ₂Drip this reaction mixture among the O, compound 4 crystallizations are separated out.Then interior temperature is remained on 30 ℃ and stirred 30 minutes, the coarse crystallization of separating out is filtered with cloth formula funnel, use 4200mL H ₂After O cleaned, it was air-dry to clean the back with the Virahol of 2700mL again, obtained the compound of 234.6g. ¹H-NMR (DMSO-d6), δ value TMS benchmark: 1.81～1.91 (2H, m); 2.49～2.54 (2H, t); 3.62～3.74 (2H, t); 8.07～8.16 (1H, d); 8.36～8.49 (1H, d); 8.66～8.67 (2H, s)

Synthesis example 4-2: compound 4 synthetic

In 5 ℃ of DMF of interior temperature (dimethyl formamide), drip the POCl of 200mL to 860mL ₃, temperature is below 15 ℃ in keeping simultaneously.Then to POCl ₃In/DMF the solution, remain in interior temperature that segmentation drips the compound 3 that obtains among the 200g synthesis example 3-2 under the situation below 10 ℃, temperature stirred 1 hour at 20 ℃ in keeping then.Then remain under 35 ℃ the situation H to 2700mL in interior temperature ₂Drip this reaction mixture among the O, compound 4 crystallizations are separated out.Then interior temperature is remained on 30 ℃ and stirred 30 minutes, the coarse crystallization of separating out is filtered with cloth formula funnel, use 4200mL H ₂After O cleaned, it was air-dry to clean the back with the Virahol of 2700mL again, obtained the compound 4 of 153g.The crystallization of gained is same among crystallization that obtains and the above-mentioned synthesis example 4-1, and purity too.

Synthesis example 5: compound 5 synthetic

100g compound 4 is added under 35 ℃ of interior temperature in the acetone of 400mL and dissolves, then inject 45mL H ₂O is cooled to 20 ℃ while stir.Temperature surpasses the pyridine that drips 49mL under 40 ℃ the speed in not making then, then is warming up to 55 ℃, stirs 2 hours under this temperature.Under this temperature, drip the aqueous isopropanol of lithium chloride/750mL of 34g then, then after stirring 1 hour under this temperature, slowly cool to room temperature.The crystallization of separating out is filtered with cloth formula funnel, obtain the compound 5 of 86.5g after the Virahol cleaning, drying with 1000mL. ¹H-NMR (DMSO-d6), δ value TMS benchmark: 1.81～1.91 (2H, m); 2.29～2.54 (2H, t); 3.62～3.67 (2H, t); 8.07～8.16 (1H, d); 8.30～8.36 (1H, d); 8.66 (1H, s)

Synthesis example 6: compound 6 synthetic

100g compound 4 is added under 25 ℃ of interior temperature in the acetonitrile of 400mL after the dissolving,, then under this temperature, stirred 1 hour at 30 ℃ of Virahols that drip 45.1g down of interior temperature.After injecting the warm water (70 ℃) of 1200mL then in this temperature downhill reaction liquid, temperature reaches 70 ℃ in being warming up to, and stirs 1 hour under this temperature.After temperature slowly was cooled to 25 ℃ in stirring made on one side, the crystallization of separating out is filtered with cloth formula funnel, obtain the compound 6 of 91.4g after the water cleaning, drying with 1000mL. ¹H-NMR (DMSO-d6), δ value TMS benchmark: 1.01～1.03 (3H, d); 1.91～1.95 (2H, m); 2.79～2.83 (2H, t); 3.10～3.15 (2H, t); 3.62～3.86 (3H, m); 4.62～4.71 (1H, d); 7.12～7.16 (1H, t); 8.08～8.17 (1H, d); 8.37～8.47 (1H, d); 8.68 (1H, s)

Synthesis example 7: compound 7 synthetic

100g compound 4 is added under 25 ℃ of interior temperature in the acetonitrile of 400mL after the dissolving,, then under this temperature, stirred 1 hour at 30 ℃ of sec.-propyl propoxy-amine that drip 70.4g down of interior temperature.After injecting the warm water (70 ℃) of 1200mL then in this temperature downhill reaction liquid, heating up makes interior temperature reach 70 ℃, stirs 1 hour under this temperature.After temperature slowly was cooled to 25 ℃ in stirring made on one side, the crystallization of separating out is filtered with cloth formula funnel, obtain the compound 7 of 116.4g after the water cleaning, drying with 1000mL. ¹H-NMR (DMSO-d6), δ value TMS benchmark: 1.06～1.08 (6H, d); 1.58～1.63 (2H, t); 1.91～1.94 (2H, m); 2.91～2.93 (2H, dd); 3.07～3.09 (2H, t); 3.33～3.38 (2H, m); 3.47～3.49 (1H, m); 3.63～3.68 (2H, t); 7.12～7.16 (1H, t); 8.36～8.40 (1H, d); 8.43～8.47 (1H, d); 8.68～8.70 (1H, s)

Synthesis example 8: compound 101 synthetic

With 29.48g compound 5 in 2.6mL acetic acid and 35mL ethylene glycol mixture, form make behind the suspension liquid in temperature rise to 50 ℃, then add 6.04g Lithium Acetate, 3.24g cupric chloride (anhydrous), temperature rise to 85 ℃ in making.After stirring 3 hours under this temperature, temperature rise to 90 ℃ in making drips the concentrated hydrochloric acid of 19.7mL.After stirring 1 hour under this temperature, temperature is cooled to 60 ℃ in making then, adds the 4.49g lithium chloride, drips the 210mL Virahol and separate out crystallization under this temperature.After temperature is cooled to 30 ℃ in making then, crystallization precipitate is filtered, clean with the 200mL Virahol.After dried 28.77g coarse crystallization is dissolved in the ion exchanged water of 115mL, add 2.5N-LiOH aq, reach 10.5 until pH at 50 ℃.Then under this temperature, remove by filter the impurity in the aqueous solution, make the interior temperature rise to 90 ℃ of filtrate, after stirring 30 minutes under this temperature, drip the 330mL Virahol and separate out crystallization.After suspension liquid was cooled to room temperature, the suction strainer precipitate was cleaned with the 300mL Virahol, 80 ℃ of dryings 30 hours.Receipts amount 27.33g yield 85.5%.Discern in accordance with the following methods.Mass spectrometry: FAB-MS (NEGA 1343), ultimate analysis (measured value C, 36.69; H, 3.27; N, 7.79; For C ₄₄H ₃₆CuLi ₄N ₈O ₂₀S ₄5H ₂The calculated value C of O, 36.83; H, 3.23; N, 7.81), solution absorption: λ max=628.9nm, ε 71000 (H ₂O).

Synthesis example 9: compound 102 synthetic

30.52g compound 5 and 11.83g compound 6 are joined in 3.6mL acetic acid and the 100mL ethylene glycol mixtures, interior temperature in 110 ℃ makes its dissolving, after temperature is cooled to 50 ℃ in then making, add 8.34g Lithium Acetate, 4.47g cupric chloride (anhydrous), temperature rise to 85 ℃ in making.After stirring 3 hours under this temperature, temperature rise to 90 ℃ in making.Drip the concentrated hydrochloric acid of 27.8mL.After stirring 1 hour under this temperature, temperature is cooled to 60 ℃ in making then, adds the 6.2g lithium chloride, drips the 300mL Virahol and separate out crystallization under this temperature.After temperature is cooled to 30 ℃ in making then, crystallization precipitate is filtered, clean with the 300mL Virahol.After dried 35.29g coarse crystallization is dissolved in the ion exchanged water of 140mL, add 2.5N-LiOH aq, reach 10.5 until pH at 50 ℃.Then under this temperature, remove by filter the impurity in the aqueous solution, make the interior temperature rise to 90 ℃ of filtrate, after stirring 30 minutes under this temperature, drip the 400mL Virahol and separate out crystallization.After suspension liquid was cooled to room temperature, the suction strainer precipitate was cleaned with the 300mL Virahol, 80 ℃ of dryings 30 hours.Receipts amount 33.75g yield 76.5%.Discern in accordance with the following methods.Mass spectrometry: FAB-MS (NEGA 1395), ultimate analysis (measured value C, 39.02; H, 3.40; N, 8.72; For C ₄₇H ₄₄CuLi ₃N ₉O ₂₀S ₈3H ₂The calculated value C of O, 38.94; H, 3.48; N, 8.69), solution absorption: λ max=624.7nm, ε 57000 (H ₂O).

Synthesis example 10: compound 103 synthetic

With 41.35 compounds 7 in 2.86mL acetic acid and 165.4mL ethylene glycol mixture, form make behind the suspension liquid in temperature rise to 75 ℃, then add 3.30g Lithium Acetate, 3.36g cupric chloride (anhydrous), temperature rise to 95 ℃ in making.After stirring 3 hours under this temperature, temperature is cooled to 25 ℃ in making, and the 1N HCl that injects 165mL separates out crystallization.After stirring 30 minutes under this temperature, filter the crystallization of separating out, 400mL H then ₂O cleans.With dried 39.3g coarse crystallization in the acetonitrile of 240mL after 70 ℃ of dissolvings, then under this temperature, remove by filter the impurity in the aqueous solution, make the interior temperature of filtrate be cooled to 25 ℃, Dropwise 5 3mL Virahol and 160mL H ₂The mixed solution of O is separated out crystallization.The suction strainer precipitate is with 75mL Virahol and 75mL H ₂The mixed solvent of O was cleaned, 80 ℃ of dryings 30 hours.Receipts amount 38.13g yield 88.8%.Discern in accordance with the following methods.Mass spectrometry: FAB-MS (NEGA 1715), ultimate analysis (measured value C, 47.28; H, 5.48; N, 9.70; For C ₆₈H ₉₂CuN ₁₂O ₂₀S ₈1H ₂The calculated value C of O, 47.06; H, 5.46; N, 9.68), solution absorption: λ max=598.3nm, ε 36800 (vinyl acetic monomer)

The invention provides 1. a kind of preparation method who does not use nitrophthalonitrile as the phthalocyanine compound of synthetic intermediate; 2. a kind of method that when industrial production, can significantly improve the problem aspect its productivity cost and prepare the target product phthalocyanine compound at an easy rate.3. not only aspect dyestuff, pigment, and also be the new synthetic intermediate of useful compound for the functional material of organic light-guide electric material, optical recording material, medical agricultural chemicals etc.4. a kind of color reprodubility aspect about pigment have the excellent absorption performance and also with respect to the reactive gas in light, heat, humidity and the atmosphere have enough resistivitys, the good phthalocyanine compound of solvability and the preparation method of this compound.

Claims

1. with the phthalimide compound of the replacement shown in the logical formula V,

Logical formula V

In the formula, R represents to replace or unsubstituted the total number of carbon atoms is that alkyl, replacement or unsubstituted the total number of carbon atoms of 1～20 are that cycloalkyl, replacement or unsubstituted the total number of carbon atoms of 3～20 are 2～20 thiazolinyl, replaces or unsubstituted the total number of carbon atoms is that alkynyl, replacement or unsubstituted the total number of carbon atoms of 2～12 are that aralkyl, replacement or unsubstituted the total number of carbon atoms of 7～20 are that 6～20 aryl or replacement or unsubstituted the total number of carbon atoms are 4～20 heterocyclic radical; N represents 1～4 integer; M represents 1～2 integer; A represents hydrogen atom or atoms metal;

When R had substituting group, described substituting group was halogen atom, heterocyclic radical, cyano group, carboxyl, amide group, sulfoamido, sulfamyl, formamyl, alkylsulfonyl, halogenated alkylsulfonyl, halogenated carboxyl, imino-, acyl group, sulfo group or quaternary ammonium group;

Described atoms metal is Na atom or K atom.