JP2000281635A - Production of heptatrienedialdianil derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply obtain the subject derivative useful as an intermediate for a near infrared oxonol coloring matter or a cyanine coloring matter in a high yield by passing a specific hexadienal derivative through a formylating reaction. SOLUTION: (A) A hexadienal derivative represented by formula I [L is a (substituted)methyl; L1 to L4 are each a (substituted)methine] is formylated with (B) phosphorus oxychloride and (C) dimethylformamide and the resultant compound is then reacted with (D) an aniline derivative represented by formula II (R1 to R5 are each or a substituent group) to synthesize a derivative represented by formula III [L0 is a (substituted)methine]. Furthermore, in the above reaction, the component C is used in a molar amount of preferably 2-10 times based on the component A and the component B is used in a molar amount of preferably 1-5 times based on the component A. The component D is used in a molar amount of preferably 2-5 times based on the component A. A Vilsmeier reagent is preferably prepared from the component B and C in the system and the component A is then preferably added thereto and reacted at a reactional temperature of <=70 deg.C using an alcoholic solvent such as methanol as a reactional solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a heptatrienedial diannealed derivative, which is an important material as a near-infrared oxonol dye or a cyanine dye intermediate.

[0002]

2. Description of the Related Art Heptatrienedial diannealed derivatives are useful as intermediates and raw materials for near-infrared oxonol or cyanine dyes for photographic use, PDP use and the like. As a method for synthesizing 7-anilinohepta-2,4,6-trienalluphenylimine, which is one of the heptatrienedial diannealed derivatives, the following route is conventionally known. [Synthetic Route 1 (Zhurnal Organicheskoi Khimii, 6, 4
55 (1970))]

[0003]

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[Synthetic Route 2 (Zhurnal Organicheskoi
Khimii, 8, 674 (1972)]

[0005]

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However, the conventional synthesis route 1 requires a multi-step synthesis to obtain the desired product, and the synthesis route 2 requires the intermediate to be purified by distillation.
At present, there is a problem in terms of versatility and economy as an industrial production method for customarily using 7-anilinohepta-2,4,6-trienalluphenylimine as a synthesis condition.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned problems concerning the versatility and economical efficiency of the conventional method, and to provide a simple and high-yield heptatrienedial diannealed derivative. It is to provide a manufacturing method.

[0008]

The above object has been attained by the following items which specify the present invention. (1) A hexadienal derivative represented by the following general formula (I) is formylated with phosphorus oxychloride and dimethylformamide, and then reacted with an aniline derivative represented by the general formula (II) to obtain a compound represented by the general formula ( A method for producing a heptatrienedial diannealed derivative characterized by synthesizing a heptatrienedial diannealed derivative represented by III).

[0009]

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[In the formula, L represents a substituted or unsubstituted methyl group, and L ₁ , L ₂ , L ₃ and L ₄ each independently represent a substituted or unsubstituted methine group. ]

[0011]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a substituent. ]

[0013]

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[In the formula, L ₀ represents a substituted or unsubstituted methine group, and L ₁ , L ₂ , L ₃ , L ₄ , R ₁ , R ₂ , R ₃ , R ₄ ,
And R ₅ have the same meanings as in formulas (I) and (II). (2) wherein L represents an unsubstituted methyl group, L ₀ , L ₁ ,
The method for producing a heptatrienedial diannealed derivative according to the above (1), wherein L ₂ , L ₃ and L ₄ represent an unsubstituted methine group.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.
The gist of the present invention is that a heptatrienedial diannealed derivative is synthesized by formalizing a hexadienal derivative with phosphorus oxychloride and dimethylformamide and then treating with a aniline derivative. The hexadienal derivative is represented by the following general formula (I).

[0016]

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In the formula, L represents a methyl group which may have a substituent, and L ₁ , L ₂ , L ₃ and L ₄ each independently represent a methine group which may have a substituent. . Examples of the substituent of the methyl group represented by L or the substituent of the methine group represented by L ₁ , L ₂ , L ₃ and L ₄ include the following substituents. A substituted or unsubstituted alkyl group (for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, cyclohexyl, methoxyethyl, ethoxycarbonylethyl, cyanoethyl, diethylaminoethyl, hydroxyethyl,
Chloroethyl, acetoxyethyl, trifluoromethyl, etc.), an aralkyl group (eg, benzyl, etc.), an alkenyl group (eg, vinyl, etc.), an alkynyl group (eg, ethynyl, etc.), an aryl group (eg, phenyl,
4-methylphenyl, 4-methoxyphenyl, 4-carboxyphenyl, etc.), a heterocyclic group (eg, pyridyl, pyrimidyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, quinolyl, succinimide, phthalimide, maleimide, etc.), an acyl group (eg, acetyl, Propionyl, butanoyl, chloroacetyl, etc.), sulfonyl group (for example, methanesulfonyl, p-
Such as toluenesulfonyl), sulfinyl group (for example,
Methanesulfinyl, ethanesulfinyl, etc.), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl, 4-methoxyphenylcarbonyl, etc.), alkoxy group (eg, methoxy, ethoxy, n -Butoxy, methoxyethoxy, hydroxyethoxy, etc.), an aryloxy group (eg, phenoxy, 4-methoxyphenoxy, etc.), an alkylthio group (eg, methylthio, ethylthio, etc.), an arylthio group (eg, phenylthio, etc.), an acyloxy group (eg, , Acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, chloroacetyloxy, etc.), sulfonyloxy group (for example, methanesulfonyl Oxy), a carbamoyloxy group (eg, methylcarbamoyloxy, diethylcarbamoyloxy, etc.), an amino group (eg, unsubstituted amino, methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, morpholino, piperidino, Pyrrolidino, pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, ethylthiocarbonylamino, methylcarbamoylamino, phenylcarbamoylamino, methylsulfamoylamino, phenylsulfamoylamino, acetylamino, ethylcarbonylamino, ethylthiocarbonylamino, benzoyl Amino, chloroacetylamino, methanesulfonylamino, benzenesulfonylamino, etc.), carbamoyl group ( For example, unsubstituted carbamoyl, methylcarbamoyl, dimethylcarbamoyl, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.), halogen atom (eg, fluorine, chlorine, etc.), hydroxyl group, nitro group , A cyano group, a carboxy group, a sulfo group and the like. Preferred as the substituents for L and L _{1 to} L ₄ are a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and a 6 to 1 carbon atom.
An aryl group, a saturated or unsaturated heterocyclic group, and a halogen atom. Particularly preferably, L is an unsubstituted methyl group, and L ₁ , L ₂ , L ₃ and L ₄ are unsubstituted methine groups. The aniline derivative is represented by the following general formula (II).

[0018]

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In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a substituent. As the substituents represented by R _{1 to} R ₅ , those exemplified as the substituents of the methyl group represented by L or the substituents of the methine group represented by L _{1 to} L ₄ in the above general formula (I) Is the same as When R _{1 to} R ₅ have a substituent, each is connected to an unsaturated condensed ring (for example,
A naphthalene ring). Preferred substituents for R _{1 to} R ₅ are an alkyl group having 1 to 5 carbon atoms,
C6-10 aryl group, C2-5 acyl group, C1-5 sulfonyl group, C2-5 alkoxycarbonyl group, C1-5 alkoxy group, C6-6 An aryloxy group having 10 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, a carbamoyloxy group having 1 to 5 carbon atoms, an amino group having 0 to 5 carbon atoms, a carbamoyl group having 1 to 5 carbon atoms, and a sulfo group having 0 to 5 carbon atoms. A flufamoyl group, a halogen atom, a nitro group, a cyano group, and a saturated or unsaturated heterocyclic group. These substituents may further have the above-mentioned substituent (preferably a halogen atom). R _{1 to} R ₅
Is more preferably a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a substituted or unsubstituted alkoxy group or a halogen atom. The heptatrienedial diannealed derivative synthesized in the present invention is represented by the following general formula (III).

[0020]

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In the formula, L ₀ represents a methine group which may have a substituent, and L ₁ , L ₂ , L ₃ , L ₄ , R ₁ , R ₂ , R ₃ ,
R ₄ and R ₅ have the same meanings as in formulas (I) and (II). A preferred embodiment of L ₀ is L _{1 to} L _{4 of the} formula (I).
Is the same as Hereinafter, specific examples of the compounds represented by formulas (I) to (III) are shown, but the present invention is not limited thereto.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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The amount of dimethylformamide used in the formylation step is 2 to 2 with respect to the hexadienal derivative.
The molar ratio is preferably 10 times, more preferably 2 to 5 times. The amount of the phosphorus oxychloride to be used is preferably 1 to 5 times, more preferably 1 to 3 times the mole of the hexadienal derivative. The amount of the aniline derivative to be used is preferably 2 to 5 times, more preferably 2 to 4 times the mole of the hexadienal derivative.

With regard to the order of addition, a method is preferred in which the Vilsmeier reagent is adjusted in the system with dimethylformamide and phosphorus oxychloride, and then the hexadienal derivative is added. The temperature at the time of addition is not particularly limited as long as it is lower than the boiling point of the reaction solution, but is preferably 70 ° C. or lower. The reaction temperature is preferably between 20 ° C and 120 ° C, particularly preferably between 40 ° C and 90 ° C.

As a reaction solvent, toluene, xylene,
Hydrocarbon solvents such as hexane, amide solvents such as dimethylformamide, ether solvents such as tetrahydrofuran, alcohol solvents such as methanol and ethanol, nitrile solvents such as acetonitrile, ketone solvents such as acetone, and ethyl acetate solvents Ester solvents and the like can be used. Further, two or more organic solvents may be used in combination. Most preferably, it is an alcohol solvent.

[0031]

The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention.

Example 1 Synthesis of Compound (III-1) Phosphorus oxychloride 71 was added to a mixture of 89 ml (1.2 mol) of dimethylformamide and 8 ml of methanol under ice-cooling.
g (0.46 mol) was added dropwise. This reaction solution is heated to 70 ° C.
After warming to 25 ml of compound (I-1) (0.23
mol) was added dropwise at 80 ° C. or lower, and the mixture was stirred at 80 ° C. for 4 hours. After the reaction is completed, cool to room temperature
And extracted with 600 ml of methylene chloride. The extract of methylene chloride was dried over magnesium sulfate and filtered, 42 ml (0.46 mol) of aniline was added dropwise, and the mixture was stirred at room temperature for 4 hours. The resulting dark blue crystals were collected by filtration and washed with methylene chloride to obtain the desired product (III-1) 44
g was obtained. The yield was 70%. Analytical data: H-NMR (dmso-d 6): 11.85 (s, 1H), 8.55 (d, 2
H), 7.60 (dd, 2H), 7.2-7.5 (m, 10H), 6.60 (dd, 1H),
6.35 (dd, 2H) λmax: 590.0nm (in methanol)

Example 2 Synthesis of Compound (III-2) Phosphorus oxychloride 61 was added to a mixture of dimethylformamide (80 ml, 1.0 mol) and methanol (7 ml) under ice-cooling.
g (0.40 mol) was added dropwise. This reaction solution is heated to 70 ° C.
After heating to 19 g of compound (I-1) (0.20 m
ol) at 80 ° C. or lower, and the mixture was stirred at 80 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, poured into 500 ml of ice water, and extracted with 500 ml of methylene chloride. The extract of methylene chloride was dried over magnesium sulfate and filtered,
64 g (0.40 mol) of compound (II-2) was added dropwise,
Stirred at room temperature for 4 hours. The resulting dark blue crystals were collected by filtration and washed with methylene chloride to obtain the desired product (III-2) 30
g was obtained. Yield 36%. Analytical data: H-NMR (dmso-d 6): 12.40 (s, 1H), 8.70 (m, 3
H), 7.80 (s, 2H), 7.7 (m, 5H), 7.50 (m, 2H), 6.60 (d
d, 1H), 6.35 (dd, 2H) λmax: 584.5nm (in methanol)

From the above results, it can be understood that the synthesis method of the present invention provides a heptatrienedial diannealed derivative in a simple and high yield. Further, the present invention is advantageous in terms of economic efficiency as an industrial production method in that it can be synthesized using hexadienal which is easily available.

[0035]

According to the synthesis method of the present invention, a heptatrienedial diannealed derivative can be produced in a simple process with a high yield. In addition, since it can be easily synthesized from readily available hexadienal, it can be produced at lower cost than the conventional method.

Claims (2)

[Claims] 1. A hexadienal derivative represented by the following general formula (I) is formylated with phosphorus oxychloride and dimethylformamide, and then reacted with an aniline derivative represented by the general formula (II). A method for producing a heptatrienedial diannealed derivative characterized by synthesizing a heptatrienedial diannealed derivative represented by the formula (III). Embedded image Wherein L represents a substituted or unsubstituted methyl group;
L ₁ , L ₂ , L ₃ and L ₄ each independently represent a substituted or unsubstituted methine group. ] [Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or a substituent. ] [In the formula, L ₀ represents a substituted or unsubstituted methine group,
_{L 1, L 2, L 3} , L 4, R 1, R 2, R 3, R 4, and R ₅
Has the same meaning as in formulas (I) and (II). ] 2. The method according to claim 1, wherein L represents an unsubstituted methyl group,
_2. The method for producing a heptatrienedial diannealed derivative according to claim ₁ , wherein L ₀ , L ₁ , L ₂ , L ₃ and L ₄ represent an unsubstituted methine group.