JP2007099691A - Method for producing naphthalocyanine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a naphthalocyanine compound under a mild and easily attainable condition in high yield. <P>SOLUTION: A naphthalocyanine compound is produced by reacting a metal compound with a 2,3-naphthalenedicarboxylic acid derivative in the presence of a compound expressed by general formula (VII) (R<SP>71</SP>to R<SP>74</SP>are each H, an aliphatic group, an aromatic group or a heterocyclic group bonded through a carbon atom). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel method for producing naphthalocyanines useful for image forming materials, infrared thermosensitive recording materials, optical recording elements, optical film materials, and the like. More specifically, the present invention relates to a high yield under mild and simple conditions. The present invention relates to a method for producing a naphthalocyanine compound.

  Phthalocyanines are widely used as pigments, among which naphthalocyanines have been actively studied as near-infrared absorbing dyes.

  As a method for producing phthalocyanines, a method of heating phthalic anhydride or phthalimide at 200 to 300 ° C. in the presence of urea, a method of heating phthalonitrile together with ammonia or a catalyst at 150 to 250 ° C., etc. are widely known. (For example, refer nonpatent literature 1). In addition, attempts have been made to devise methods for adding raw materials and the like when producing phthalocyanines (for example, Patent Document 1 and Non-Patent Document 2). Furthermore, a method for efficiently synthesizing a 1-amino-3-iminoisoindolenine compound in which as many nitrogen atoms as possible are introduced into the raw material has been proposed (see, for example, Patent Document 2), and a specific reaction in the production of naphthalocyanine. Attempts have also been made to improve the yield of the solvent (for example, see Patent Documents 3, 4, and 5). However, the yield has not been sufficiently improved, and it has been desired to produce phthalocyanines with higher yield.

JP-A-6-228449 Japanese Patent Laid-Open No. 10-59974 JP-A-10-88017 Japanese Patent Laid-Open No. 10-158533 JP 11-349588 A Journal of Chemical Society, Parkin Transaction, I, pages 2453-2458 (issued in 1988) Journal of Organic Chemistry, 55, 2155-2159 (issued in 1990)

  An object of the present invention is to provide a production method for producing a naphthalocyanine compound in a high yield under mild and simple conditions.

  As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved by the following means.

(1) At least one 2,3-naphthalenedicarboxylic acid derivative selected from the group consisting of compounds represented by the following general formulas (II) to (VI) is represented by a metal compound and the following general formula (VII): The manufacturing method of the naphthalocyanine compound represented by the following general formula (I) characterized by including the process made to react in presence of the compound to be made.

In the general formula (I), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a substituent, and n11, n12, n13 and n14 each independently represent an integer of 0 to 6. M ¹ represents two atoms selected from the group consisting of a hydrogen atom and a monovalent metal atom, a divalent metal atom, or a divalent substituted metal atom including a trivalent or tetravalent metal atom.

In the general formulas (II) to (VI), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ each independently represent a substituent, and n21, n31, n41, n51 and n61 each independently represent 0 to 6 Represents an integer.

In the general formula (VII), R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group linked by a carbon atom. However, one of R ^{71 and} R ⁷² and one of R ^{73 and} R ⁷⁴ are not bonded to each other to form a 5-membered ring.

(2) The production method according to (1), wherein in the general formula (VII), R ⁷² and R ⁷³ are bonded to each other to form a 6-membered ring.
(3) The production method according to (1) or (2), wherein urea is further allowed to coexist during the reaction.
(4) The manufacturing method according to any one of (1) to (3), wherein the metal compound is a vanadium compound.
(5) The metal compound is vanadium (III) chloride, vanadium oxychloride (V), vanadium (III) acetylacetonate or vanadyl (IV) acetylacetonate, The manufacturing method of any one of Claims.
(6) The 2,3-naphthalenedicarboxylic acid derivative is at least one compound represented by the general formula (II), general formula (III) or general formula (VI) (1) The manufacturing method of any one of-(5).

  According to the production method of the present invention, a naphthalocyanine compound useful for an image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material and the like can be produced in a mild, simple and high yield.

  Hereinafter, the compound of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  In the present specification, the aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The alkyl group may have a branch and may form a ring (that is, a cycloalkyl group). The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 18 carbon atoms. The alkyl part of the substituted alkyl group is the same as the above alkyl group. The alkenyl group may have a branch, or may form a ring (that is, a cycloalkenyl group). The alkenyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. The alkynyl group may have a branch and may form a ring (that is, a cycloalkenyl group). The number of carbon atoms in the alkynyl group is preferably 2-20, and more preferably 2-18. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. The alkyl part of the aralkyl group and the substituted aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group and the substituted aralkyl group is the same as the following aryl group.

  Examples of the substituent of the alkyl part of the substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group include a halogen atom (for example, chlorine atom, bromine atom, iodine atom), alkyl group [straight chain, branched, cyclic Represents a substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl) group, Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [ 1.2.2] heptan-2-yl group, bicyclo [2.2.2] octane-3-yl) group, It is intended to encompass such tricyclo structure having many cyclic structures into. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group), a cycloalkenyl group (preferably a carbon number of 3 A substituted or unsubstituted cycloalkenyl group having ˜30, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as a 2-cyclopenten-1-yl group and 2-cyclohexene -1-yl group), a bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a hydrogen atom of a bicycloalkene having one double bond. For example, a bicyclo [2.2.1] hept-2-en-1-yl group, It is intended to include [2.2.2] oct-2-en-4-yl group). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, a trimethylsilylethynyl group, an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms). An aryl group such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or It is a monovalent group obtained by removing one hydrogen atom from a non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro, carboxy Group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group ), An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms such as phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2 -Tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group), heterocyclic oxy group (preferably having 2 carbon atoms) To 30 substituted or unsubstituted heterocyclic oxy groups, 1-phenyl te Razoru 5 group, 2-tetrahydropyranyloxy group),

Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy group, acetyloxy group , Pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethyl) Carbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group), alkoxycarbonyloxy group (preferably 2 carbon atoms 30 substituted or unsubstituted alkoxycarbonyloxy groups, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group), aryloxycarbonyloxy group (preferably having 7 to 7 carbon atoms) 30 substituted or unsubstituted aryloxycarbonyloxy groups, for example, phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group), amino group (preferably amino group, C1-C30 substituted or unsubstituted alkylamino group, C6-C30 substituted or unsubstituted anilino group, for example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino Group, Phenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formyl Amino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group), aminocarbonylamino group (preferably having 1 to 30 carbon atoms) A substituted or unsubstituted aminocarbonylamino group such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably having a carbon number) 2-30 Substituted or unsubstituted alkoxycarbonylamino group, for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group),

Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino Group), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, or an Nn group. -Octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, for example, , Methylsulfonyl Mino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably a C1-C30 substitution) Or an unsubstituted alkylthio group such as methylthio, ethylthio, n-hexadecylthio group, an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms such as a phenylthio group, a p-chlorophenylthio group, m- Methoxyphenylthio group), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), Sulfamoyl group (preferably substituted with 0 to 30 carbon atoms) Or an unsubstituted sulfamoyl group such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N- A benzoylsulfamoyl group, an N- (N′-phenylcarbamoyl) sulfamoyl) group, a sulfo group, an alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 30 A substituted or unsubstituted arylsulfinyl group, for example, a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted group having 1 to 30 carbon atoms) Alkylsulfonyl group of 6 to 3 0 substituted or unsubstituted arylsulfonyl group such as methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl group (preferably formyl group, substituted or unsubstituted group having 2 to 30 carbon atoms) A substituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to the carbonyl group at a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl Group, pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, 2-pyridylcarbonyl group, 2-furylcarbonyl) group, aryloxycarbonyl group (preferably, carbon number) 7-30 substituted or unsubstituted aryloxycarbo Group such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxycarbonyl group), alkoxycarbonyl group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) An alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, Carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group),

An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as a phenylazo group, a p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted or non-substituted having 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl group, dioctyl) Oxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy A group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group, a dioctyloxyphosphinyloxy group), a phosphinylamino group (preferably, A substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group, a silyl group (preferably a substituted or unsubstituted group having 3 to 30 carbon atoms). Substituted silyl groups such as trimethylsilyl group, tert-butyldimethylsilyl group, and phenyldimethylsilyl group).

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

  Examples of the substituent of the aryl moiety of the substituted aralkyl group include the substituents of the following substituted aryl group.

  In the present specification, the aromatic group means an aryl group and a substituted aryl group. These aromatic groups may be condensed with an aliphatic ring, another aromatic ring or a heterocyclic ring. 6-40 are preferable, as for the carbon atom number of an aromatic group, 6-30 are more preferable, and 6-20 are more preferable. Among them, the aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

  The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent of the substituted aryl group include the groups exemplified as the substituent of the alkyl moiety of the above-mentioned substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group.

  In the present specification, the heterocyclic group preferably contains a 5-membered or 6-membered saturated or unsaturated heterocyclic ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. As a ring-constituting hetero atom of the heterocyclic group, B, N, O, S, Se and Te are preferable, and N, O or S is more preferable. The heterocyclic group preferably has a valence (monovalent) in which the carbon atom is free (the heterocyclic group has a carbon atom at the bonding position and is bonded at the carbon atom). The number of carbon atoms of a preferable heterocyclic group is 1-40, More preferably, it is 1-30, More preferably, it is 1-20. Examples of the saturated heterocyclic ring in the heterocyclic group include a pyrrolidine ring, a morpholine ring, a 2-bora-1,3-dioxolane ring, and a 1,3-thiazolidine ring. Examples of the unsaturated heterocyclic ring in the heterocyclic group include imidazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzotriazole ring, benzoselenazole ring, pyridine ring, pyrimidine ring and quinoline ring. The heterocyclic group may have a substituent. Examples of such a substituent include those listed as examples of the substituent of the alkyl moiety of the aforementioned substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group.

Next, the compounds represented by the general formulas (I) to (VI) will be described.
In the general formula (I), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a substituent, and the substituent includes the alkyl part of the aforementioned substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group. The substituents mentioned as examples of the substituents are listed. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups , Heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino Group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or aryl Sulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, more preferably halogen atom, Alkyl group, aryl group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, aminocarbonylamino group , Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, A sulfo group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, a carbamoyl group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group, more preferably a halogen atom, Alkyl group, aryl group, hydroxyl group, alkoxy group, aryloxy group, amino group, mercapto group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, more preferred Is a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group, more preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number of 6 to An aryl group having 0, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an arylthio group having 6 to 20 carbon atoms, more preferably 1 carbon atom. -8 alkyl group, C6-C10 aryl group, C1-C8 alkoxy group, C6-C10 aryloxy group, C1-C8 alkylthio group, C6-C10 arylthio More preferably an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 8 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and an arylthio group having 6 to 8 carbon atoms.
When R ¹¹ there are a plurality, the plurality of R ¹¹ may be the being the same or different. A plurality of R ¹¹ may be bonded to each other to form a cyclic structure. The same applies to R ¹² , R ¹³ and R ¹⁴ .

  n11, n12, n13 and n14 each independently represents an integer of 0 to 6, preferably 0, 1 or 2, more preferably n11, n12, n13 and n14 are all the same number, 0, 1 or 2 More preferably, n11, n12, n13, and n14 are all the same number and 0.

M ¹ represents two atoms selected from a hydrogen atom or a monovalent metal atom, or represents a divalent substituted metal atom including a divalent metal atom, a trivalent or tetravalent metal atom.

Examples of the monovalent metal atom include alkali metal atoms (for example, Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ ).
When M ¹ means two atoms selected from a hydrogen atom or a monovalent metal atom, the two atoms may be the same or different, but it is preferable that two are the same atoms.

When M ¹ is a divalent metal atom, Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Ti ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^{2 +} , Ru ²⁺ , Rh ²⁺ , Pd ²⁺ , Pt ²⁺ , Ba ²⁺ , Cd ²⁺ , Hg ²⁺ , Pb ²⁺ , Sn ²⁺ .

When M ¹ represents a divalent substituted metal atom containing a trivalent or tetravalent metal atom, the trivalent or tetravalent metal atom includes Al, Ga, In, Tl, Mn, Fe, Ru, Cr, Si, Zr, Ge, Sn, Ti, Zr, and V are mentioned. The substitution in a substituted metal atom is a metal atom having an organic or inorganic ion, substituent or compound (including a ligand) bonded to the metal atom by an ionic bond, a covalent bond, or a coordinate bond. . Examples of such ions, substituents, and compounds include halogen atoms, hydroxyl groups, aliphatic oxy groups, aromatic oxy groups, aliphatic thio groups, aromatic thio groups, aliphatic groups, and aromatic groups. Examples of the substituent of the alkyl moiety of the substituted alkyl group, substituted alkenyl group, substituted alkynyl group, and substituted aralkyl group are as follows. Furthermore, a sulfonate ion, a carboxylate ion, a phosphate ion, an oxygen atom, a compound capable of coordination (a compound having an atom having a lone pair of electrons, and examples of the atom include an oxygen atom, a sulfur atom, and a nitrogen atom, Examples thereof include water, amine compounds, ether compounds, and thioether compounds).

M ¹ is preferably 2 hydrogen atoms, 2 Li ⁺ , 2 Na ⁺ , 2 K ⁺ , 2 Rb ⁺ , 2 Cs ⁺ , or 1 (hereinafter referred to as “1 Abbreviations) Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Ti ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ , Ru ²⁺ , Rh ²⁺ , Pd ²⁺ , Pt ²⁺ , Ba ²⁺ , Cd ²⁺ , Hg ²⁺ , Pb ²⁺ , Sn ²⁺ , Al-Cl, Al-Br, Al-F, Al-I , Ga-Cl, Ga-F, Ga-I, Ga-Br, In-Cl, In-Br, In-I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F, Mn -OH, Fe-Cl, Ru- Cl, CrCl 2, SiCl 2, SiBr 2, SiF 2, SiI 2, ZrCl 2, GeCl 2, GeBr 2, GeI 2, GeF 2, SnCl 2, SnBr 2, Sn I ₂ , SnF ₂ , TiCl ₂ , TiBr ₂ , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , SnR ₂ , GeR ₂ , Si (OR) ₂ , Sn (OR) ₂ , Ge (OR) ₂ , Ti (OR) ₂ , Cr (OR) ₂ , Sn (SR) ₂ , Ge (SR) ₂ [R represents an aliphatic group or an aromatic group], VO, MnO, TiO, more preferably 2 hydrogen atoms, 2 Li ⁺ , 2 Na ⁺ , 2 K ⁺ , Two Rb ⁺ , or Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Ti ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ²⁺ , Ru ²⁺ , Rh ²⁺ , Pd ²⁺ , Pt ²⁺ , Ba ²⁺ , Sn ²⁺ , Al—Cl, Al—Br, Ga—Cl, Ga—F, Ga—I, Ga—Br, In—Cl, In − r, Tl-Cl, Tl- Br, Mn-OH, Fe-Cl, Ru-Cl, CrCl 2, SiCl 2, SiBr 2, ZrCl 2, GeCl 2, GeBr 2, SnCl 2, SnBr 2, TiCl 2, TiBr ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , SnR ₂ , GeR ₂ , Si (OR ) ₂ , Sn (OR) ₂ , Ge (OR) ₂ , Ti (OR) ₂ , Cr (OR) ₂ , Sn (SR) ₂ , Ge (SR) ₂ [R represents an aliphatic group or an aromatic group. ], VO, MnO, TiO, more preferably 2 hydrogen atoms, 2 Li ⁺ , 2 Na ⁺ , 2 K ⁺ , or Be ²⁺ , Mg ²⁺ , Ca ²⁺ , ^{Ti 2+, Mn 2+, Fe 2+} , Co 2+, Ni 2+, Cu 2+, Zn 2+, Ru 2+, Rh 2+ ^{Pd 2+, Pt 2+, Ba 2+} , Sn 2+, Al-Cl, Ga-Cl, In-Cl, Tl-Cl, Mn-OH, Fe-Cl, Ru-Cl, CrCl 2, SiCl 2, ZrCl ₂ , GeCl ₂ , TiCl ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , GeR ₂ , Si (OR) ₂ , Ge (OR) ₂ , Ti (OR) ₂ , Cr (OR) ₂ [R represents an aliphatic group or an aromatic group], VO, MnO or TiO. Most preferred M ¹ is VO.

In the general formula (II), R ²¹ has the same meaning as R ¹¹ described above, and the preferred range is also the same. n21 is preferably 0, 1 or 2, and more preferably 0.

In the general formula (III), R ³¹ has the same meaning as R ¹¹ described above, and the preferred range is also the same. n31 is synonymous with n21, and its preferred range is also the same.

In the general formula (IV), R ⁴¹ has the same meaning as R ¹¹ described above, and the preferred range is also the same. n41 is synonymous with n21, and its preferred range is also the same.

In the general formula (V), R ⁵¹ has the same meaning as R ¹¹ described above, and the preferred range is also the same. n51 is synonymous with n21, and its preferred range is also the same.

In the general formula (VI), R ⁶¹ has the same meaning as R ¹¹ described above, and the preferred range is also the same. n61 is synonymous with n21, and its preferred range is also the same.

  Specific examples of the compound represented by the general formula (I) are shown below, but the compound of the general formula (I) that can be employed in the present invention is not limited thereto.

  Specific examples of the compounds represented by the general formulas (II) to (VI) include the respective compounds corresponding to the specific compound examples represented by the general formula (I).

Next, the manufacturing method of this invention is demonstrated.
In the production method of the present invention, at least one 2,3-naphthalenedicarboxylic acid derivative selected from the compounds represented by the general formulas (II) to (VI) is represented by a metal compound and the general formula (VII). The naphthalocyanine compound represented by the general formula (I) is produced by reacting in the presence of a compound.

  Among the 2,3-naphthalenedicarboxylic acid derivatives represented by the general formulas (II) to (VI) as raw materials, preferable ones are represented by the general formula (II), (III), (IV) or (VI). More preferably a compound represented by the general formula (II), (III) or (VI), more preferably a compound represented by the general formula (III) or (VI), A compound represented by the general formula (III) is preferable.

Below, the metal compound used by this invention is demonstrated.
The metal compound used in the present invention is an organic or inorganic compound containing a group 1 to 15 or lanthanoid metal. For metals, preferably Li, Na, Mg, Al, K, Ca, Si, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ga, Ru, Sn and Pb More preferably, Li, Na, Mg, Al, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, and more preferably Li, Na, Mg, K, Sc, Ti , V, Cr, Mn, Fe, Co, Ni, Cu and Zn, more preferably Li, V, Co, Ni, Cu and Zn, and most preferably V. Components other than the metal forming the metal salt are preferably halogen ions (for example, F ⁻ , Cl ⁻ , Br ⁻ ), CN ⁻ , SO ₄ ²⁻ , HO ⁻ , NO ₃ ⁻ , CO ₃ ²⁻ , carboxylate ions ( For example, acetate ion, oxalate ion), sulfonate ion (for example, methanesulfonate ion, benzenesulfonate ion), phosphate ion, alkoxy ion (for example, methoxy ion, ethoxy ion, isopropoxy ion, phenoxy ion, 4-oxo-2 -Pentene-2-oxy ion) and an oxygen atom (which forms a metal oxy form together with a metal). More preferred are Cl ⁻ , CN ⁻ , SO ₄ ²⁻ , HO ⁻ , CO ₃ ²⁻ , acetate ions, alkoxy ions and oxygen atoms, and more preferred are Cl ⁻ , CN ⁻ , SO ₄ ²⁻ , HO ⁻ , An acetate ion, an alkoxy ion and an oxygen atom, more preferably Cl ⁻ , CN ⁻ , an oxygen atom and a 4-oxo-2-pentene-2-oxy ion, and more preferably a Cl ⁻ , oxygen atom and 4-oxo-2- Pentene-2-oxy ion. Examples of the most preferred metal compounds include vanadium (III) chloride, vanadium oxychloride (V), vanadium (III) acetylacetonate and vanadyl (IV) acetylacetonate.

Next, the compound represented by formula (VII) will be described.
In the general formula (VII), R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group linked by a carbon atom. Preferred R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ are a hydrogen atom, an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms and a heterocycle having 3 to 20 carbon atoms connected by a carbon atom. More preferably a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms, and a heterocyclic group linked by a carbon atom having 3 to 10 carbon atoms, and more preferably Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Is an aryl group having ˜8, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In general formula (VII), R ⁷² and R ⁷³ are bonded to each other to form a 6-membered ring (preferably R ⁷² and R ⁷³ are bonded to each other to form an alkylene group having 3 to 5 carbon atoms. May optionally have a substituent), and in this case, a combination in which R ⁷¹ and R ⁷⁴ are the above preferred groups is more preferable.

In the general formula (VII), when R ⁷² and R ⁷³ are bonded to each other to form a 6-membered ring, more preferably R ⁷¹ and R ⁷⁴ are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and R ⁷² and And R ⁷³ is bonded to each other to form an alkylene having 3 to 5 carbon atoms, more preferably R ⁷¹ and R ⁷⁴ are a hydrogen atom or a methyl group, and R ⁷² and R ⁷³ are bonded to each other to form a carbon number of 3 Most preferably, R ⁷¹ and R ⁷⁴ are methyl groups and R ⁷² and R ⁷³ are combined to form a C 3 alkylene.

In the compound represented by the general formula (VII), either one of R ^{71 and} R ⁷² and one of R ^{73 and} R ⁷⁴ are not bonded to each other to form a 5-membered ring.

  Specific examples of the compound represented by the general formula (VII) include, for example, urea, N-methylurea, N, N-dimethylurea, N, N′-dimethylurea, N, N, N ′, N′-tetramethyl. Examples include urea, N, N-diethylurea, N, N, N ′, N′-tetraethylurea, trimethyleneurea, N, N′-dimethyltrimethyleneurea, and N, N′-diethyltrimethyleneurea.

  The ratio of the raw material used for the reaction is preferably 0.01 to 10 mol, more preferably 0.1 to 5 mol, relative to 1 mol of 2,3-naphthalenedicarboxylic acid derivative, More preferably, it is 0.15-2 mol, More preferably, it is 0.2-1 mol, More preferably, it is 0.22-0.4 mol. Moreover, the preferable amount of the compound represented by the general formula (VII) is 0.1 to 20 mol, more preferably 0.2 to 10 mol, more preferably 1 mol of 2,3-naphthalenedicarboxylic acid derivative. It is 0.5-6 mol, More preferably, it is 1-4 mol.

The compounds represented by the general formula (VII) may be used alone or in combination of two or more. Of these, it is particularly preferable to use urea in combination with a compound other than urea (NH ₂ CONH ₂ ).
The amount of urea (NH ₂ CONH ₂ ) to be added is preferably 0.5 to 10 mol, more preferably 1 to 6 mol, more preferably 2 to 4 mol, relative to 1 mol of 2,3-naphthalenedicarboxylic acid derivative. Yes, the whole amount may be added at the start of the reaction, or divided additions may be made as the reaction proceeds.

In the reaction, the compound represented by the general formula (VII) may be used as a solvent, or another solvent may be used in addition to this. Examples of the solvent used at this time include amide solvents (for example, N, N -Dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (eg sulfolane), sulfoxide solvents (eg dimethyl sulfoxide), ether solvents (eg dioxane, cyclopentyl methyl ether), ketones Solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene), halogen solvents (eg tetrachloroethane, chlorobenzene), alcohol solvents (eg 1-butanol, ethylene glycol, cyclohexanol), pyridine solvents ( For example, piligi , .Gamma.-picoline, 2,6-lutidine) is used alone or in combination. Preferred are amide solvents, sulfone solvents, ether solvents, halogen solvents, alcohol solvents, pyridine solvents, and more preferred are amide solvents, sulfone solvents, ether solvents, halogen solvents, alcohol solvents. More preferred are amide solvents and alcohol solvents, and more preferred solvents are amide solvents.
In the present invention, it is preferable to use a compound represented by the general formula (VII) as a solvent, and it is most preferable to use only a compound represented by the general formula (VII) as a solvent.

  The reaction temperature is 0 to 250 ° C., preferably 50 to 250 ° C., more preferably 80 to 230 ° C., particularly preferably 150 to 220 ° C., and the reaction temperature is changed during the reaction (for example, the first half 150 ° C., the second half 200 ° C.) is also preferable. The reaction time is usually in the range of 5 minutes to 30 hours.

  During the reaction, it is also preferable to remove by-product water out of the system, a method of distilling alone or with a solvent under reduced pressure or normal pressure, a method using an absorbent such as molecular sieve, a dehydrating condensing agent such as acetic anhydride. The method of using is preferably used. In addition, this reaction is also preferably performed in a closed system.

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Example 1 Synthesis of Compound (I-1)
Compound (I-1) was synthesized according to the following scheme.

60.0 g of compound (1), 100 g of compound (2), and 72 g of urea were placed in a three-necked flask, and 13.0 g of vanadium oxytrichloride was added dropwise at room temperature over 20 minutes. After the completion of dropping, the mixture was stirred as it was for 10 minutes, then immersed in an external oil bath at 200 ° C. and stirred for 9 hours.
At this time, the internal temperature reached 190 ° C. after 2 hours of immersion in the oil bath. To this was cooled to an internal temperature of 60 ° C., 100 ml of methanol was added dropwise over 10 minutes, and the mixture was further stirred for 10 minutes, followed by suction filtration and drying to obtain 56.1 g of the desired compound (I-1). (Yield 96%).
When the mass spectrum of this product was measured, it was M ⁺ = 779 (main peak). The spectral absorption spectrum using sulfuric acid as a solvent was λmax = 924 nm, and the Gram extinction coefficient was 1.1 × 10 ⁵ ml / g · cm.

(Example 2: Synthesis of compound (I-1))
The same procedure as in Example 1 was carried out except that 50 g of compound (2) and 50 g of 1-methyl-2-pyrrolidone were used instead of 100 g of compound (2) to obtain 53.2 g of target compound (I-1). (Yield 91%).

(Example 3: Synthesis of compound (I-1))
The same operation was performed except that 200 g of the compound (2) was used instead of 100 g of the compound (2) in Example 1, to obtain 51.5 g of the target compound (I-1) (yield 88%).

(Example 4: Synthesis of compound (I-1))
Compound (I-1) was synthesized according to the following scheme.

  Into a three-necked flask, 53.5 g of the compound (3), 100 g of the compound (2) and 36 g of urea were added, and 19.9 g of vanadyl (IV) acetylacetonate was added dropwise at room temperature over 20 minutes. After the completion of dropping, the mixture was stirred as it was for 10 minutes, then immersed in an external oil bath at 200 ° C. and stirred with heating for 10 hours. At this time, the internal temperature reached 190 ° C. after 2 hours of immersion in the oil bath. 100 ml of methanol was added dropwise to the place cooled to an internal temperature of 60 ° C. over 10 minutes, and the mixture was further stirred for 10 minutes, and then suction filtered and dried to obtain 55.6 g of the desired compound (I-1). (Yield 95%).

(Example 5: Synthesis of compound (I-1))
The same operation as in Example 4 was carried out except that 26.1 g of vanadium (III) acetylacetonate was used instead of 19.9 g of vanadyl (IV) acetylacetonate to obtain 53.8 g of the target compound (I-1). (Yield 92%).

Example 6 Synthesis of Compound (I-1)
The reaction was conducted in the same manner as in Example 1 except that 65.4 g of naphthalene-2,3-dicarboxylic acid was used instead of the compound (1) in Example 1, and 53.8 g of the target compound (I-1) was obtained. Obtained (yield 92%).

(Reference Example 1: Synthesis of compound (I-1), synthesis method described in JP-A-10-158533)
The target compound (I-1) was prepared in the same manner as in Example 1 except that 1,3-dimethyl-2-imidazolidinone (DMI) was used instead of the compound (2) in Example 1. 44.5 g was obtained (76% yield).
When the mass spectrum of this product was measured, it was M ⁺ = 779 (main peak). The spectral absorption spectrum using sulfuric acid as a solvent was λmax = 924 nm, and the Gram extinction coefficient was 1.1 × 10 ⁵ ml / g · cm.

  According to the production method of the present invention, a naphthalocyanine compound can be produced in a mild, simple and high yield. The naphthalocyanine compound produced by the production method of the present invention is useful for an image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material, and the like, and therefore has high industrial applicability. .

Claims (6)

At least one 2,3-naphthalenedicarboxylic acid derivative selected from the group consisting of compounds represented by the following general formulas (II) to (VI), a metal compound and a compound represented by the following general formula (VII) The manufacturing method of the naphthalocyanine compound represented by the following general formula (I) characterized by including the process made to react in presence of this.

[In General Formula (I), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a substituent, and n ¹¹ , n ¹² , n ¹³ and n ¹⁴ each independently represent an integer of 0 to 6. M ¹ represents two atoms selected from the group consisting of a hydrogen atom and a monovalent metal atom, a divalent metal atom, or a divalent substituted metal atom including a trivalent or tetravalent metal atom. ]

[In the general formulas (II) to (VI), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ each independently represent a substituent, and n21, n31, n41, n51 and n61 each independently represents 0 to Represents an integer of 6. ]

[In the general formula (VII), R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group linked by a carbon atom. However, one of R ^{71 and} R ⁷² and one of R ^{73 and} R ⁷⁴ are not bonded to each other to form a 5-membered ring. ] The process according to claim 1, wherein In the general formula (VII), characterized in that R ⁷² and R ⁷³ form a 6-membered ring bonded to each other.   The production method according to claim 1, wherein urea is further allowed to coexist during the reaction.   The said metal compound is a vanadium compound, The manufacturing method of any one of Claims 1-3 characterized by the above-mentioned.   5. The metal compound according to claim 1, wherein the metal compound is vanadium (III) chloride, vanadium oxychloride (V), vanadium (III) acetylacetonate or vanadyl (IV) acetylacetonate. The manufacturing method as described.    The 2,3-naphthalenedicarboxylic acid derivative is at least one compound represented by the general formula (II), the general formula (III), or the general formula (VI). The manufacturing method of any one of these.