JP3020188B2 - 1H-pyrrolo- [1,2-b] [1,2,4] triazole derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a synthetic intermediate for a physiologically active substance such as a medicine or an agricultural chemical, a chromogen for a dry analytical element, a dye for a thermal transfer dye-providing material, a filter dye for a solid-state image pickup tube or a color liquid crystal television. Useful 1H-pyrrolo- [1,2-
b] [1,2,4] triazole derivatives and their precursors.

[0002]

2. Description of the Related Art In general, dyes for thermal transfer dye donating materials, filter dyes for solid-state imaging tubes and color liquid crystal televisions, and ink dyes for electrostatic acceleration type ink jets are ethyl acetate,
It is used by dissolving it in organic solvents such as toluene, diethyl phthalate, methyl ethyl ketone, and cyclohexanone.
On the other hand, the 1H-pyrrolo- [1,2-b] [1,2,4] triazole derivative is manufactured by Ukrainskii Khimicheskii Zhurna.
l, Vol. 41, No. 2, PP. 181-185, 1975,
Khimiya Geterotsiklicheskikh Scedinenii, No. 2,
PP. 261-267, February, 1974, the reactivity of which is discussed, and Abstracts of the Annual Meeting of the Photographic Society of Japan 1985, JP-A-62-278552, JP-A-62-279.
339, JP-A-1-288835, U.S. Pat.
No. 10127, European Patent Publication No. 0491197 A1, US Pat.
No. 457 and No. 496202 as pharmaceuticals. However, these compounds have low solubility in organic solvents such as ethyl acetate, and have problems in operability in reactions and the like and in application to the above-mentioned applications.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel 1H-pyrrolo-soluble compound having high solubility in organic solvents.
[1,2-b] [1,2,4] triazole derivatives.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have achieved
-Pyrrolo- [1,2-b] [1,2,4] triazole derivatives have been found, and the invention has been made as follows. That is, (1) 1H-pyrrolo- represented by the general formula [II]
[1,2-b] [1,2,4] triazole derivative. (2) 1H-pyrrolo- [1, represented by the general formula [I]
2-b] [1,2,4] triazole derivative.

[0005]

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(In the general formulas [I] and [II], R represents an alkyl group having 4 to 36 carbon atoms or an aryl group having 8 to 40 carbon atoms. Z represents a hydrogen atom, a halogen atom, an arylthio group, a heterocyclic thio group. R ₁ represents an alkyl group, R represents an arylsulfinyl group or a nitroso group.
₂ , R ₃ represents a hydrogen atom or an alkyl group, and R ₄ represents a halogen atom or an alkyl group. n represents an integer of 0 to 4. )

Next, the compounds represented by formulas [I] and [II] will be described in detail. The compound represented by the general formula [II] is a cyan dye which is particularly useful as a dye or dye for various uses and has a main absorption exceeding 600 nm and a small side absorption, and has excellent light and heat fastness. The compound represented by the general formula [I] is useful as a precursor of the compound represented by the general formula [I].

In the general formulas (I) and (II), R represents a linear, branched or cyclic alkyl group having 4 to 36 carbon atoms or an aryl group having 8 to 40 carbon atoms, each of which is substituted. Groups (eg, halogen atoms, cyano groups,
Nitro group, alkyl group, alkenyl group, alkynyl group,
Aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group,
It may be substituted with a sulfamoyl group, a ureido group, an alkoxycarbonylamino group, a sulfamoylamino group, an alkoxysulfonyl group, an imide group or a heterocyclic group (hereinafter referred to as a substituent group A).

The alkyl group represented by R is, for example, n-butyl, isobutyl, n-octyl, n-decyl,
n-dodecyl, n-hexadecyl, 2-ethylhexyl, 3,5,5-trimethylhexyl, 2-ethyl-4
-Methylpentyl, 2-hexyldecyl, 2-heptylundecyl, 2-octyldodecyl, 2,4,6-trimethylheptyl, 2,4,6,8-tetramethylnonyl, benzyl, 2-phenethyl, 4- (2,6-dimethyl) heptyl, 4- (2-methyl-7-ethyl) undecyl, 3- (2,4-di-t-amylphenoxy) propyl, 2- (4-biphenyloxy) ethoxy, -Dodecyloxypropyl, 2-dodecylthioethyl, dodecyloxycarbonylmethyl, 7,7-dimethyl-2-
(3,3′-dimethylbutyl) -5-methyloctyl,
Examples include cyclohexyl, 2-methyl-cyclohexyl, and 2-cyclohexylcyclohexyl.

The aryl group represented by R is, for example, 2-t-amylphenyl, 2,4-di-t-amylphenyl, 2-t-butylphenyl, 2,6-diisopropylphenyl, 2,4,6- Merimethylphenyl, 2
-T-butyl-4- (1-ethoxycarbonyl) -tridecyloxyphenyl, 3-octanoylaminophenyl, 4-nonyloxyphenyl.

In the general formula [I] or [II], Z is preferably a hydrogen atom, a halogen atom, a carbon atom having 6 to 6 carbon atoms.
An arylthio group having 36 (more preferably 6 to 24), an arylsulfinyl group having 1 to 36 (more preferably 1 to 24) carbon atoms, and a heterocyclic thio group having 1 to 36 (more preferably 1 to 24) carbon atoms And an arylthio group, an arylsulfinyl group, and a heterocyclic thio group may be substituted with the substituent group A.

Z is preferably a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), an unsubstituted or substituted group (a halogen atom, an alkyl group, an alkoxy group, a cyano group, an aryloxycarbonyl group, an alkoxycarbonyl group). Arylthio group having a group, ureido group, alkoxycarbonylamino group, acylamino group, or carboxyl group (for example, 2- (n-butoxy)-
5- (t-octyloxy) phenylthio, 2- (t-
Amylcarbonylamino) phenylthio, 2- (phenoxycarbonylamino) phenylthio, 2- (phenoxycarbonyl) phenylthio, 2- (3,3-dimethylureido) phenylthio, pentafluorophenylthio, pentachlorophenylthio, 1,3 5-triisopropylphenylthio), an unsubstituted or substituted arylsulfinyl group having a substituent (halogen atom, alkyl group, alkoxy group, cyano group, alkoxycarbonyl group or carboxyl group) (for example, 2- (n-butoxy)
-5- (t-octyloxy) phenylsulfinyl,
2- (t-amylcarbonylamino) phenylsulfinyl, 2- (phenoxycarbonylamino) phenylsulfinyl, 2- (phenoxycarbonyl) phenylsulfinyl, 2- (3,3-dimethylureido) phenylsulfinyl, pentafluorophenylsulfinyl, Pantachlorophenylsulfinyl, 1,3,5-
Triisopropylphenylsulfinyl), unsubstituted or substituted (halogen atom, alkyl group, alkoxy group,
A heterocyclic thio group having a cyano group, an alkoxycarbonyl group, a carboxyl group, or a nitro group (for example, pyrazolylthio, 5-nitro-2-pyridylthio) or a nitroso group. Z is more preferably a hydrogen atom, a halogen atom, an arylthio group, or an arylsulfinyl group, and particularly preferably a hydrogen atom or a halogen atom.

In the general formula [I] or [II], R ₁ preferably has 1 to 36 carbon atoms (more preferably 1 to 2 carbon atoms).
And 4) a linear, branched or cyclic alkyl group.
Even if R ₁ is unsubstituted, a substituent (halogen atom, cyano group, nitro group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group , Acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoyl group, amino group, alkoxysulfonyl group, imide group Or a heterocyclic group).

R ₁ is, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a 1-ethylpentyl group,
Hexyloctyl group, cyclohexyl group, trifluoromethyl group, 3-chloropropyl group, cyanomethyl group, 3
-Nitropropyl group, 3- {4- (2-octyloxy-5-t-octyl) phenylsulfonylaminophenyl} propyl group, 3- (4-acetylamino) phenylpropyl group, 1- {1- (2 4-di-t-amylphenoxy) propanoylaminomethyldiethyl group, 1-acetylaminomethylethyl group, 1-phthalimidoylmethylethyl group, 1- (2-octyloxy-5-t-octyl) phenylsulfonylamino Methylethyl group, 1
A methanesulfonylaminomethylethyl group, 1- (2,
4-diamyl) phenoxypropyl group, 3-methoxypropyl group, ethoxycarbonylmethyl group, n-butoxycarbonylmethyl group, carboxylmethyl group, 2,4-
Di-t-amylphenoxycarbonylmethyl group, 2-acetyloxyethyl group, N, N-diethylaminocarbonylmethyl group, anilinocarbonylmethyl group, 2- (anilinocarbonylamino) ethyl group, 2- (ethoxycarbonylamino) And an ethyl group.

In the general formula [II], R ₂ is preferably a hydrogen atom or a group having 1 to 24 carbon atoms (more preferably 1 to 24 carbon atoms).
-12) represents an alkyl group. R ₂ is preferably a hydrogen atom, an unsubstituted or substituted alkyl group (eg, a halogen atom, a hydroxyl group, an alkoxy group, an alkanesulfonylamino group) (eg, methyl, ethyl, n-propyl, 2-hydroxyethyl, 2-hydroxyethyl). (Methanesulfonylamino) ethyl, 2-methoxyethyl, 2-ethoxyethyl). R ₂ is particularly preferably the aforementioned alkyl group. In the general formula [II], R ₃ has the same meaning as R ₂ . R ₃ may be the same as R ₂ or may be different. R ₃ may form a ring together with R ₂ .

In the general formula [II], R ₄ is preferably a halogen atom, having 1 to 24 carbon atoms (more preferably 1 to 24 carbon atoms).
12) represents an alkyl group. R ₄ is preferably a halogen atom (fluorine atom, chlorine atom), an unsubstituted or substituted alkyl group (eg, methyl, ethyl, 2-hydroxyethyl) such as a halogen atom, a hydroxyl group, an alkoxy group, or an alkanesulfonylamino group. ).
R ₄ is particularly preferably a methyl group.

In the general formula [II], n represents an integer of 0 to 4. (More preferably an integer of 0 to 2, particularly preferably 0 or 1.)

The compound represented by the general formula [I] is
Each compound in the following equilibrium state is also meant.

[0019]

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The compound represented by the general formula [I] can be synthesized by the following method. (Scheme I)

[0021]

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That is, the triazole (a) is alkylated to give 1-N-alkyl- [1,2,4] triazole (b), which is halogenated to give (c),
Thereafter, a ring-closing reaction is carried out to give 1H-pyrrolo- [1,2-b] [1,2,4] represented by the general formula (I) (Z = H).
Triazoles can be obtained. When Z is a group other than a hydrogen atom, for example, as a method for connecting an arylthio group or a heterocyclic thio group, a compound in which an aromatic mercapto or heterocyclic mercapto group is substituted at the 7-position is described in US Pat.
No. 7554, that is, a general formula in which an aryl mercaptan, a heterocyclic mercaptan and its corresponding disulfide are dissolved in a halogenated hydrocarbon solvent, and then converted into a sulfenyl chloride with chlorine or sulfuryl chloride and dissolved in an aprotic polar solvent. It can be synthesized by adding to the compound represented by [I] (Z = H).

The triazoles (a) can be synthesized by a known method, for example, JCS, 518 (1961)., JCS, 5149.
(1962)., Angew. Chem., 72.956 (196).
0)., Berichte., 97.3436 (1964). And the like, the literature cited therein, or a similar method. Next, examples of N-alkylating agents used in the alkylation of triazoles to 1-N-alkyl- [1,2,4] triazoles (b) (hereinafter referred to as Step 1) include α-chloroforms. Acrylonitrile, 1-cyano-1,2-dibromoethane and the like can be mentioned.

The base used in Step 1 includes
Inorganic bases, organic bases, organometallic bases and the like can be used. For example, sodium hydride, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), 1,5
-Diazabicyclo [4,3,0] -5-nonene (DB
N), triethylamine, 1,1,3,3-tetramethylguanidine, potassium carbonate, sodium carbonate, sodium ethoxide, trimethylbenzylammonium hydroxide, potassium hydride, potassium t-butoxide, sodium acetate, sodium methoxide, potassium Methoxide,
And the like. Among them, organic bases are preferable, and particularly preferable among these organic bases are organic amine bases. For example, DBU, DBN, 1,1,3,3
-Tetramethylguanidine, triethylamine, trimethylbenzylammonium hydroxide, and the like.

The N-alkylating agent in Step 1 is in a molar ratio to the azole (a) of 0.01 to 1000, preferably 0.05 to 20, more preferably 0.5 to 1
0 may be used. The molar ratio of the base to the triazoles (a) in Step 1 is 0.01 to 100, preferably 0.01 to 50, and more preferably 0.05 to 100.
2.0. As the solvent in Step 1, bases methylene, chloroform, 1,2-dichloroethane, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, dioxane, dimethoxyethane, diglyme, Benzene, toluene, ethyl acetate, acetone, xylene and the like are used, and methylene chloride, 1,2-dichloroethane, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, toluene and the like are particularly preferable.
The reaction temperature is -78 ° C to 250 ° C, preferably -10 ° C to
The temperature is 100 ° C, more preferably -5 ° C to 70 ° C, particularly preferably 5 ° C to 40 ° C. Reaction time is 30 seconds ~
72 hours, preferably 10 minutes to 48 hours, more preferably 20 minutes to 24 hours.

Next, the guidance from (b) to (c) (hereinafter referred to as
Step 2) will be described in detail. Examples of the halogenating agent used in the halogenation in Step 2 include chlorine, sulfuryl chloride, copper (II) chloride, N-chlorosuccinimide, N-bromocaprolactam, N-bromophthalimide, 1,3-dibromo-5. , 5-dimethylhydantoin, bromine, N-bromosuccinimide, copper (II) halide dioxane dibromide, phenyltrimethylammonium tribromide, pyridinium bromide perbromide, pyrrolidone hydrotribromide, and the like. Particularly, sulfuryl chloride, N-chlorosuccinimide,
Bromine, N-bromosuccinimide, pyridinium bromide perbromide and the like are preferred. The molar ratio of the halogenating agent to (b) in Step 2 is 0.01 to 100, preferably 0.5 to 10, and more preferably 1.
0 to 3.0. As the solvent in Step 2, the bases methylene, chloroform, 1,2-dichloroethane, acetonitrile, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide, dioxane, tetrahydrofuran, water, carbon tetrachloride, acetic acid,
Examples include methanol, ethanol, benzene, pyridine and the like, and particularly, methylene chloride, chloroform, N, N-
Preferred are dimethylformamide, N, N-dimethylacetamide, dioxane, tetrahydrofuran, water, carbon tetrachloride, acetic acid, methanol, ethanol, benzene, pyridine and the like.

The reaction temperature is -78 ° C to 150 ° C, preferably -20 ° C to 80 ° C, more preferably -10 ° C to 70 ° C.
° C, particularly preferably -10 ° C to 30 ° C. The reaction time is 1 minute to 72 hours, preferably 15 minutes to 48 hours, more preferably 30 minutes to 36 hours. next,
The derivation from Step (c) to the compound represented by Formula (I) (Z = H) (Step 3) will be described in detail. Step
In 3, in order to close the ring of (c), it is desirable to use a base. In the present invention, a ring closure reaction and an oxidation reaction are carried out in one step from (c) to obtain a compound of the general formula (I) wherein Z is a hydrogen atom.

Examples of the base used in Step 3 include sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydride, potassium tert-butoxide, 1,1 , 3,3-tetramethylguanidine, D
BU, DBN, sodium acetate, triethylamine, trimethylsilyloxypotassium, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide,
Sodium amide, n-butyllithium, n-methyllithium, t-butyllithium, i-propyllithium and the like can be mentioned, and particularly, sodium hydride, potassium t-butoxy, 1,1,3,3-tetramethylguanidine , DBU, DBN, triethylamine, sodium methoxide, sodium ethoxide, potassium methoxide, n-butyllithium and the like are preferable.

The molar ratio of the base to (c) in Step 3 is from 0.01 to 10, preferably from 0.5 to 5.
0, more preferably 1.0 to 4.0, and particularly preferably 2.8 to 4.0. As a solvent in Step 3, methylene chloride, chloroform, 1,2-dichloroethane, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran, dioxane, dimethoxyethane, diclime, benzene,
Toluene, methanol, ethanol, isopropanol, ethyl acetate, acetone, xylene, petroleum ether,
Examples thereof include diethyl ether and the like, and particularly, methylene chloride, chloroform, 1,2-dichloroethane, N, N-
Dimethylformamide, tetrahydrofuran, dioxane, diethyl ether and the like are preferred.

The reaction temperature varies depending on the system used, but is -100.
C. to 100 C., preferably -100 C. to 90 C., more preferably -78 C. to 60 C., particularly preferably -C.
50 ° C to 30 ° C. The addition of the base in Step 3
It is preferable to carry out the reaction slowly so that the reaction temperature in the system does not rise. In particular, it is preferable to carry out in a range of ± 2 ° C.
The reaction time is 30 seconds to 72 hours, preferably 5 minutes to 48 hours.
Time, more preferably 10 minutes to 12 hours. The product in each step can be separated from the reaction solution by a conventional method, but may be used as a starting material for a subsequent reaction without isolation as necessary. As an appropriate isolation procedure, a recrystallization method, a solvent extraction method, a filtration method, column chromatography, thin-layer chromatography, or the like is used alone or in an appropriate combination. Next, a typical synthetic route of the compound represented by the general formula [II] is shown below.

[0031]

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That is, the compound represented by the general formula [II]
The compound represented by the general formula [I] and the phenylenediamine (m) can be synthesized by a coupling reaction in the presence of an oxidizing agent.

This coupling reaction is described in "The Theory of the Photographic Process" edited by TH James.
(Macmillan. 1977), it is believed that nucleophilic attack of the coupler anion on quinone diimine formed by oxidation of phenylenediamine results in the formation of a leuco dye into an azomethine dye. Have been. The reaction preferably proceeds under basic conditions, and the reaction medium may be an organic solvent, an aqueous organic solvent or an aqueous solution. When reacting with a basic aqueous solution, the compound represented by the general formula [I] may be an oil-in-water dispersion, and the dispersion may be present in a hydrophilic colloid medium such as gelatin. . As the oxidizing agent, any oxidizing agent can be used as long as it has a potential capable of oxidizing phenylenediamine regardless of whether it is organic or inorganic, and this oxidizing agent may be dissolved or dispersed in the reaction medium. Is also good. When Z is a hydrogen atom in the general formula [I], 0.1 to 10 moles, preferably 0.5 to 2 moles of phenylenediamine coexist with 1 mole of the compound of the general formula [I], and oxidation is performed. The agent is used in at least 4 equivalents, preferably 4.4 to 20 equivalents. When Z is not a hydrogen atom, the compound of the general formula [II] can be synthesized in the same manner as above except that at least 2 equivalents, preferably 2.2 to 10 equivalents of the oxidizing agent are used. P for aqueous media
The coupling is preferably performed when H is 8 or more, preferably 10 to 12. As the oxidizing agent, silver halide,
Hydrogen peroxide, manganese dioxide, potassium persulfate, oxygen,
Other Compounds described in Organic Reagents by Fieser. Fieser can be used.

[0034]

Next, the present invention will be described in detail with reference to examples. Synthesis Example 1 Synthesis of Exemplified Compound (I-31) Exemplified compound (I-31) was synthesized by the following route.

[0035]

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Synthesis of Compound (3) Sodium methylate (28% in methanol) (67 g, 0.35 mol) was added at room temperature to a solution of imidate compound (2) (63.8 g, 0.33 mol) in ethanol (600 ml).
l) was added dropwise and stirred for 15 minutes. After filtering out the precipitated sodium chloride, the filtrate was added to the hydrazide compound (1) (99 g,
0.030 mol) and refluxed for 2 hours. After evaporating the ethanol under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/2) to obtain Compound (3) (55 g, 0.12).
mol, 37%).

Synthesis of Compound (4) 3.4 g (7.6 mmol) of Compound (3) was added at 115 ° C.
Stirred for 0 minutes. The residue was subjected to silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1 /
By purifying in 4), triazole (4) (2.7)
g, 6.3 mmol, 83%).

Synthesis of Compound (5) Triazole (4) (2.7 g, 6.3 mmol), octanol (5 g, 38 mmol) and tetraisopropoxytitanium (1 g, 3.5 mmol) were distilled at 150 ° C. with ethanol. The mixture was stirred for 4 hours while leaving. The residue was purified by silica gel chromatography (developing solvent: ethyl acetate / n-hexane = 1/20 → 1/5) to obtain triazole (5) (3.1 g, 6.0 mmol, 95%).

Synthesis of Compound (6) Triazole (5) (3.1 g, 6.0 mmol) and α
To a solution of chloroacrylonitrile (1 ml, 12 mmol) in tetrahydrofuran (THF) (25 ml) at room temperature was added tetramethylguanidine (TMG) (0.25 ml, 2.0 mmol).
l) was added dropwise. After stirring at room temperature for 2 hours, the reaction solution was poured into 1N aqueous hydrochloric acid (100 ml), and ethyl acetate (100 ml ×
Extracted in 2). The organic layer was washed with water (100 ml) and saturated saline (100 ml) and then dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1 /
The compound (6) (1.4 g,
2.3 mmol, 38%).

Synthesis of Exemplified Compound (I-31) Compound (6) (1.4 g, 2.3 mmol) in THF (20
Pyridinium bromide perpromide (0.8 ml)
(4 g, 2.65 mmol) and stirred at room temperature for 1 hour. An aqueous solution (10 g) of sodium thiosulfate (0.2 g) was added to the reaction solution.
0 ml) and extracted with ethyl acetate (100 ml × 2).
The organic layer was washed with water (100 ml) and saturated saline (100 ml).
And then dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, 50 ml of dichloromethane was added to the residue. After cooling the solution to 0 ° C., TMG (1.25 ml, 10 mmol)
Was added dropwise and stirred at room temperature for 1 hour. 1N hydrochloric acid 1
After adding 50 ml, the mixture was extracted with dichloromethane (75 ml × 2). The organic layer was washed with water (100 ml × 2) and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, silica gel column chromatography (developing solvent: ethyl acetate / n-
The compound (I-31) (0.59 g, 1.06 mmol, 46% fr.) Was purified by purification with hexane = 1/3.
m (2)) was obtained.

Synthesis Example 2 Synthesis of Exemplified Compounds (I-10) and (I-34)
34) was synthesized.

[0042]

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Synthesis of Compound (11) Sodium methylate (28% in methanol) (193 g, 1 mol) was added to a solution of imidate compound (8) (144 g, 0.95 mol) in ethanol (1.5 L) at room temperature.
l) was added dropwise and stirred at room temperature for 15 minutes. After filtering out the precipitated sodium chloride, the filtrate was added to the hydrazide compound (9) (9).
(4 g, 0.95 mol) and refluxed for 8 hours. Ethanol was distilled off under reduced pressure to obtain a crude triazole compound (11) (about 1).
00g) and used for the next step without further purification.

Synthesis of Compound (13) The crude triazole (11) obtained above (21 g, about 0.13
mol) and barium hydroxide octahydrate (21 g, about 0.06
(7 mol) was refluxed in water (40 ml) for 3 hours. The reaction solution was cooled to 10 ° C., and the precipitated crystals were collected by filtration and washed with ilopropanol to remove the barium salt (12) (13).
g, 0.052 mol). Barium salt (12) (10
g, 0.040 mol) and 2,4-di-t-octylphenol (9.35 g, 0.040 mol) in 100 ml of dichloromethane at 50C in 50 ml of trifluoroacetic anhydride.
Was added dropwise and stirred at room temperature for 1 hour. After distilling off the solvent and excess trifluoroacetic anhydride under reduced pressure, ethanol 1 was added.
00 ml was added and refluxed for 30 minutes. After ethanol was distilled off under reduced pressure, the residue was recrystallized from ethyl acetate / n-hexane to give the triazole compound (13) (10 g, 0.02
5 mol, 63%).

Synthesis of Compound (14) Triazole compound (13) (6.15 g, 15.4 mmol)
l) and α-chloroacrylonitrile (2.5 ml,
3.1 mmol) of dimethylformamide (DMF) (20
triethylamine (0.7 ml, 5 mmol) was added to a solution of (ml) / methanol (5 ml) at room temperature and stirred for 3 hours. 1N aqueous hydrochloric acid (100 ml) was added to the reaction mixture, and ethyl acetate (1 ml) was added.
00 ml × 2). The organic layer was washed with water (100 ml) and brine (100 ml) and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, silica gel column chromatography (developing solvent: ethyl acetate / n-hexane =
The compound (14) (3.4) was purified by 1/5).
g, 7.0 mmol, 45%).

Synthesis of Compound (I-10) Compound (14) (3.4 g, 7.0 mmol) in THF (30
ml) to pyridinium bromide perbromide (2.6 g,
8.0 mmol) and stirred at room temperature for 1 hour. An aqueous solution (200 ml) of sodium thiosulfate (0.5 g) was added to the reaction solution, and the mixture was extracted with ethyl acetate (150 ml × 2). The organic layer was washed with water (200 ml) and saturated saline (200 ml), and dried over anhydrous sodium sulfate. After the ethyl acetate was distilled off under reduced pressure, 100 ml of dichloromethane was added to obtain a crude (15) solution. After cooling this solution to 0 ° C., TMG (3.4 ml, 2
(7.2 mmol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After adding 200 ml of 1N hydrochloric acid to the reaction solution, dichloromethane (100
ml × 2). The organic layer was washed with water (100 ml × 2) and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by column chromatography (developing solvent: ethyl acetate / n-hexane = 1/5) to give Exemplified Compound (I-10) (1.5 g, 3.3 mmol, 48 mmol). % F
rom (14)).

Synthesis of Exemplified Compound (I-34) T of Exemplified Compound (I-10) (1.5 g, 3.3 mmol)
Sulfuryl chloride (0.45 g, 3.3 mmol) in HF solution
Was added and stirred at room temperature for 30 minutes. Water (100 ml) in the reaction solution
And extracted with ethyl acetate (100 ml × 2) and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/5) to give Exemplified Compound (I-34) (1.3 g, 2.7 mmol, 82) %)
I got

Synthesis Example 3 Synthesis of Exemplified Compound (I-18) Exemplified Compound (I-18) was synthesized in the same manner as in Synthesis Example 1, and Exemplified Compound (I-18) was synthesized by the following route.

[0049]

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Synthesis of Exemplified Compound (I-18) A solution of di-{(2-n-butoxy-5-t-octyl) phenyl} disulfide (3.53 g, 6 mmol) in methylene chloride (20 ml) was added at 0 ° C. Sulfuryl chloride (1.76
g, 13 mmol) and stirred for 1 hour. The methylene chloride and sulfuryl chloride were removed under reduced pressure, methylene chloride (20 ml) was added to the residue, and this solution was treated with the exemplified compound (I-5).
(2.4 g, 5.1 mmol) in DMF (10 ml).
C. and the mixture was stirred for 1 hour. Water is added and extracted twice with ethyl acetate (30 ml). The organic layer is washed with water and saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/5) to give Exemplified Compound (I-18) (2.6 g, 3.5).
mmol, 69%).

Synthesis Example 4 Synthesis of Dye (n) of Exemplary Compound (I-5) Dye (n) of Exemplary Compound (I-5) according to the following route
Was synthesized.

[0052]

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Synthesis of Dye (n) of Exemplified Compound (I-5) Sodium carbonate was added to a mixed solvent (100 ml) of Exemplified Compound (I-5) (4.7 g, 10 mmol) in ethyl acetate-ethanol (1: 1). (9 g) An aqueous solution (40 ml) was added, followed by 4- [N-ethyl-N- (2-methanesulfonamidoethyl) amino] -2-methylaniline sulfate (6.3).
8 g, 12.2 mmol) and stir at room temperature for 10 minutes. An aqueous solution of ammonium persulfate (4.5 g) (20 m
l) was added dropwise, and the mixture was stirred for 1 hour and extracted three times with ethyl acetate.
The organic layer is washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1)
/ 1) and then recrystallized from ethanol, dye (n) of Exemplified Compound (I-5) (5.1 g, 6.6 mmol, 6
6%).

Other compounds can be synthesized similarly. The specific examples of the compound of the present invention are shown below, but it should not be construed that the invention is limited thereto. M ⁺ is the value of the parent peak of the mass spectrum (M ⁺ ). λmax (nm) is represented by the general formula (III
] Means the maximum absorption wavelength in the ethyl acetate solution. General formula (III)

[0055]

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For some of them, the melting point (mp) is described.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

[Table 5]

[0062]

[Table 6]

[0063]

[Table 7]

[0064]

[Table 8]

Incidentally, all of the specific compound examples shown above showed high solubility (0.05 mol / l or more) in ethyl acetate.

[0066]

The derivative of the present invention represented by the general formula [I] is useful as an intermediate for synthesizing a physiologically active substance such as a medicine and an agricultural chemical. Further, it is useful as a coupler in the field of photographic chemistry. On the other hand, the compound represented by the general formula [II] is useful as a dye, and is excellent in that the side absorption is small and the main absorption is 600 nm or more. Furthermore, the compounds represented by the general formulas [I] and [II] both exhibit high solubility in organic solvents such as ethyl acetate.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 487/04 139 C09B 55/00 C09B 57/00

Claims (2)

(57) [Claims] 1. A 1H-pyrrolo- [1,2-b] [1,2,4] triazole derivative represented by the general formula [II]. Embedded image (In the general formula [II], R represents an alkyl group having 4 to 36 carbon atoms or an aryl group having 8 to 40 carbon atoms. R ₁ represents an alkyl group. R ₂ and R ₃ represent a hydrogen atom or alkyl. R ₄ represents a halogen atom or an alkyl group, and n represents an integer of 0 to _4. ) 2. A 1H-pyrrolo- [1,2-b] [1,2,4] triazole derivative represented by the general formula [I]. Embedded image (In the general formula [I], R represents an alkyl group having 4 to 36 carbon atoms or an aryl group having 8 to 40 carbon atoms. Z represents a hydrogen atom, a halogen atom, an arylthio group, a heterocyclic thio group, an arylsulfinyl. R ₁ represents an alkyl group or a nitroso group.)