JP2003128654A - Method for producing 4,4'-bipyridinium derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for simply producing a 4,4'-bipyridinium derivative in a high yield. SOLUTION: The 4,4'-bipyridinium derivative is synthesized by reacting N,N'- bis(heteroaryl)-4,4'-bipyridinium compound with amines or anilines.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a 4,4′-bipyridinium derivative that is an important material as a herbicide or an electrochromic display material. [0002] 4,4'-Bipyridinium derivatives have already been put into practical use as herbicides, and more recently have been studied as electrochromic display materials. 4,4'−
A method for producing a bipyridinium derivative includes a synthesis method called a Menstkin reaction, but this method cannot synthesize an aryl-substituted 4,4′-bipyridinium derivative. As a method for synthesizing an aryl-substituted 4,4′-bipyridinium derivative, a route as shown below has been conventionally known. [Synthetic route (Bull. Chem. Soc. Jpn., 64, 321 (19
(1991))] However, the conventional synthesis route requires the use of a nitro compound that has a risk of explosiveness, and the industrial production method currently has problems in terms of versatility and safety. is there. SUMMARY OF THE INVENTION The object of the present invention is to eliminate the above-mentioned problems relating to the versatility and safety of production in the conventional method, and to make 4,4'- simple and high yield. It is providing the manufacturing method of a bipyridinium derivative. The above object has been achieved by the following means. (1) N, N′-bis (heteroaryl)-represented by the following general formula (II) from 4,4′-bipyridine and a heteroaryl halogen compound represented by the following general formula (I)
A 4,4′-bipyridinium compound is synthesized, and then an amine represented by the following general formula (III) is reacted to synthesize a 4,4′-bipyridinium derivative represented by the following general formula (IV). A method for producing a 4,4′-bipyridinium derivative characterized by the above. [0007] [Wherein, R represents a heteroaryl group, R ₁ represents a substituent, and X represents a halogen atom. [2] The amount of the heteroaryl halogen compound used in the synthesis of the N, N′-bis (heteroaryl) -4,4′-bipyridinium compound is 2 to 10 times the mole of 4,4′-bipyridine. Yes, the reaction temperature is from 20 ° C to 20 ° C
The process for producing a 4,4′-bipyridinium derivative as described in (1), wherein the reaction time is between 0 ° C. and 1 to 100 hours. (3) The amount of amines used in the substitution reaction with amines is N, N′-bis (heteroaryl) -4,4′-.
2 to 10 moles relative to the bipyridinium compound,
The method for producing a 4,4′-bipyridinium derivative according to (1), wherein the reaction temperature is between 20 ° C. and 150 ° C., and the reaction time is 1 to 20 hours. (4) The amount of the heteroaryl halogen compound used in the synthesis of the N, N′-bis (heteroaryl) -4,4′-bipyridinium compound is 2 to 5 times the mole of 4,4′-bipyridine. The reaction temperature is from 80 ° C to 150 ° C.
The reaction time is 3 to 50 hours, and the amount of amines used in the substitution reaction with amines is N, N′-bis (heteroaryl) -4,4′-bipyridinium 4,4 ′ according to (1), characterized in that the amount is 2 to 3 times the mol of the compound, the reaction temperature is between 20 ° C. and 100 ° C., and the reaction time is 3 to 12 hours.
-Method for producing bipyridinium derivatives. DETAILED DESCRIPTION OF THE INVENTION Details of the present invention will be described below.
The main point of the present invention is that N, N′-bis (heteroaryl) is obtained from 4,4′-bipyridine and a heteroaryl halogen compound.
A 4,4′-bipyridinium compound is synthesized and then reacted with an amine to synthesize a 4,4′-bipyridinium derivative derivative. The heteroaryl halogen compound is represented by the following general formula (I). General formula (I) RX In the formula, R represents a heteroaryl group which may have a locating group. The heteroaryl group represented by R is preferably 0-20 carbon atoms, more preferably 3-3 carbon atoms.
10 containing a heteroatom such as N, O, S, and Se are preferable. Examples thereof include an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzimidazole ring, a pyridine ring, and a pyrimidine. Examples thereof include, but are not limited to, a ring, a pyrazine ring, a pyridazine ring, a furan ring, a thiophene ring, a pyrazole ring, a pyrrole ring, an isoxazole ring, and an indole ring. Examples of the substituent of the heteroaryl group represented by R 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.), aralkyl groups (eg benzyl etc.), alkenyl groups (eg vinyl etc.), alkynyl groups (eg ethynyl etc.), aryl groups (eg phenyl,
4-methylphenyl, 4-methoxyphenyl, 4-carboxyphenyl, etc.), heterocyclic groups (eg, pyridyl, pyrimidyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, quinolyl, succinimide, phthalimide, maleimide, etc.), acyl groups (eg, acetyl, Propionyl, butanoyl, chloroacetyl, etc.), sulfonyl groups (eg, methanesulfonyl, p-
Toluenesulfonyl, etc.), sulfinyl groups (e.g.,
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.), aryloxy groups (eg phenoxy, 4-methoxyphenoxy etc.), alkylthio groups (eg methylthio, ethylthio etc.), arylthio groups (eg phenylthio etc.), acyloxy groups (eg , Acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, chloroacetyloxy, etc.), sulfonyloxy groups (eg methanesulfonate Oxy, etc.), carbamoyloxy groups (eg, methylcarbamoyloxy, diethylcarbamoyloxy, etc.), amino groups (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 groups (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl etc.), halogen atoms (eg, fluorine, chlorine etc.), hydroxyl groups, nitro groups Cyano group, carboxy group, sulfo group and the like. R is preferably an oxazole ring,
Benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, particularly preferably oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, An imidazole ring, a benzimidazole ring, a pyridine ring, and a pyrimidine ring. X represents a halogen atom. As the halogen atom represented by X, a fluorine atom, a chlorine atom, a bromine atom,
It is an iodine atom. The N, N'-bis (heteroaryl) -4,4'-bipyridinium compound synthesized as an intermediate in the present invention is represented by the following general formula (II). Embedded image Wherein R and X are R and X in the general formula (I).
And the preferred embodiments are also the same. The amines used in the present invention are preferably compounds represented by the following general formula (III). General formula (III) R ₁ -NH _{2 In the} formula, R ₁ represents a substituent. Examples of the substituent represented by R ₁ include the same substituents as those exemplified as the substituent of the heteroaryl group represented by R in the general formula (I). R ₁ is preferably an alkyl group,
An aralkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group, particularly preferably an alkyl group,
An aryl group. The 4,4'-bipyridinium derivative synthesized by the present invention is represented by the following general formula (IV). Embedded image [0019] In the formula, R ₁ R ₁ and X are the general formula (III)
And X in the general formula (I) have the same meanings, and preferred embodiments thereof are also the same. Specific examples of the compounds represented by the general formulas (I) to (IV) are shown below, but the present invention is not limited thereto. Embedded image Embedded image Embedded image Embedded image 4, by heteroaryl halogen compounds
The amount of the heteroaryl halogen compound used in the quaternization of 4′-bipyridine is preferably 2 to 10 moles, more preferably 2 to 5 moles relative to 4,4′-bipyridine. The reaction temperature is preferably between 20 ° C. and 200 ° C., particularly preferably between 80 ° C. and 150 ° C. The reaction time is preferably 1 to 100 hours, more preferably 3 to 50 hours. As the reaction solvent, toluene, xylene,
Hydrocarbon solvents such as hexane, amide solvents such as dimethylformamide and dimethylimidazolidone, ether solvents such as tetrahydrofuran, alcohol solvents such as methanol, ethanol and butanol, nitrile solvents such as acetonitrile, and ketones such as acetone Solvents, ester solvents such as ethyl acetate, sulfolane, dimethyl sulfoxide, etc. can be used.
You may use together the organic solvent of a seed | species or more. Most preferred is an alcohol solvent. Moreover, you may use the heteroaryl halogen compound which is a quaternizing agent as a reaction solvent as it is. The amount of amine used in the substitution reaction with amines is N, N′-bis (heteroaryl) -4,4 ′.
-2-10 times mole is preferable with respect to a bipyridinium compound, More preferably, it is 2-3 times mole. The reaction temperature is preferably between 20 ° C. and 150 ° C., particularly preferably between 20 ° C. and 100 ° C. The reaction time is preferably 1 to 20 hours, more preferably 3 to 12 hours. The reaction system is a two-phase system of water-organic solvent,
Either a hydrous organic solvent or a homogeneous system of an organic solvent may be used. Examples of organic solvents include amide solvents such as dimethylformamide and dimethylimidazolidone, alcohol solvents such as methanol, ethanol, and butanol,
Sulfolane, dimethyl sulfoxide and the like can be used, and two or more organic solvents may be used in combination. Most preferred are amide solvents, alcohol solvents or water-containing solvents. The following examples are provided to illustrate the present invention in more detail but are not intended to limit the scope of the invention. [Example 1] Synthesis of Compound (II-2) 4,4'-Bipyridine (1.56 g, 0.010 mol)
And Compound (I-2) (4.07 g, 0.024 mol)
Was dissolved in butanol (20 mL), refluxed for 10 hours, filtered, and heated and washed with ethanol (50 mL) to obtain 3.72 g of compound (II-2) as a dark yellow powder. This corresponds to 75% of the theoretical yield. Analytical data: λmax: 355 nm (in methanol) MS (m / e): 424 (M ⁺ ) Synthesis of compound (IV-2) Compound (II-2) (1.98 g, 4.0 mmol) and Compound (III-2) (1.43 g, 9.6 mmol) was dissolved in DMF (25 mL), stirred at 90 ° C. for 6 hours, and then ethyl acetate (200 mL) was added. 2 at room temperature
After stirring for a period of time, the mixture was filtered and washed with ethyl acetate (50 mL) to obtain 1.14 g of a compound (IV-2) as a white yellow powder. This corresponds to 58% of the theoretical yield. Analytical data: ¹ H-NMR (D ₂ O): 9.6 (d, 4
H), 9.1 (d, 4H), 7.3-7.7 (m, 6
H), 2.3 (q, 8H), 1.1 (t, 12H) [Example 2] Synthesis of Compound (II-8) 4,4′-bipyridine (6.20 g, 0.040 mol)
And Compound (I-8) (36.4 g, 0.32 mol) was refluxed for 4 hours, and then DMF (100 mL) was added. After stirring at room temperature for 2 hours, the mixture was filtered and DMF (50 m
L) and 14.1 of the black powdered compound (II-8)
g was obtained. This corresponds to 92% of the theoretical yield. Analytical data: ¹ H-NMR (D ₂ O): 9.8 (d, 4
H), 8.9 (d, 4H), 8.8 (d, 2H), 8.
4 (dd, 2H), 8.2 (d, 2H), 7.9 (d
d, 2H) Synthesis of Compound (IV-4) Compound (II-8) (1.92 g, 5.0 mmol) and Compound (III-4) (2.22 g, 0.012 mol) were combined with DMF. (20 mL) and stirred at 100 ° C. for 6 hours. The resulting yellow precipitate was collected by filtration and DMF (50 m
L) and acetone (50 mL) were washed to obtain 0.75 g of yellow powdered compound (IV-4). This is 2 of the theoretical yield.
It corresponds to 7%. Analytical data: ¹ H-NMR (D ₂ O): 8.7-10.3
(Broad, 8H), 7.6 (d, 3H), 7.3-
7.5 (m, 5H) [Example 3] Synthesis of Compound (II-10) 4,4′-Bipyridine (5.0 g, 0.032 mol) and Compound (I-10) (9.1 g, 0.079 mol) were added to DMF (200 mL). Dissolved and stirred at 90 ° C. for 48 hours. The reaction solution was cooled to room temperature, filtered, and DMF
(50 mL) washed with yellow powder compound (II-10)
11.0g was obtained. This corresponds to 89% of the theoretical yield. Analytical data: ¹ H-NMR (D ₂ O): 10.4 (d, 4
H), 9.3 (d, 4H), 8.9 (d, 4H), 8.
0 (d, 2H) Synthesis of Compound (IV-10) Compound (II-10) (2.73 g, 7.1 mmol) and Compound (III-10) (2.4 g, 0.016 mol)
Was dissolved in DMF (40 mL). The mixture was stirred at room temperature for 6 hours, filtered, and washed with acetone (50 mL) to obtain 2.15 g of yellow powdered compound (IV-10). This corresponds to 61% of the theoretical yield. Analytical data: ¹ H-NMR (DMSO-d ₆ ): 9.5
(D, 4H), 8.7 (d, 4H), 2.4 (s, 18
H), 1.8 (s, 12H) From the above results, it can be seen that the synthesis method of the present invention provides a 4,4′-bipyridinium derivative with a simple and good yield. In addition, the present invention is advantageous in terms of economy and safety as an industrial production method in that it can be synthesized using various heteroaryl halogen compounds that are easily available without risk of explosiveness. According to the synthesis method of the present invention, a 4,4'-bipyridinium derivative can be produced in a simple process with a high yield. In addition, since it can be easily synthesized from a heteroaryl halogen compound, it can be produced more safely and cheaply than conventional methods.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4C055 AA01 AA05 AA06 AA10 BA01                       BA02 BA54 BB10 CA01 DA30                       DB03 DB04 DB08 EA01 EA03                       FA01                 4C063 AA05 BB02 CC29 CC62 DD12                       EE03

Claims (1)

What is claimed is: 1. N, N'- represented by the following general formula (II) from 4,4'-bipyridine and a heteroaryl halogen compound represented by the following general formula (I): A bis (heteroaryl) -4,4′-bipyridinium compound is synthesized,
Next, by reacting amines represented by the following general formula (III), 4, 4 represented by the following general formula (IV):
4. A method for producing a 4,4′-bipyridinium derivative, comprising synthesizing a 4′-bipyridinium derivative. [Chemical 1] [Wherein, R represents a heteroaryl group, R ₁ represents a substituent, and X represents a halogen atom. ]