JP3016104B2 - 1H-pyrrolo- [1,2-b] [1,2,4] triazole derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to 1H-pyrrolo- useful as synthetic intermediates and dyes for physiologically active substances such as medicines and agricultural chemicals.
[1,2-b] [1,2,4] triazole derivatives.

[0002]

2. Description of the Related Art 1H-pyrrolo- [1,2-b] [1,
[2,4] Triazole derivatives are useful as intermediates for synthesizing physiologically active substances such as pharmaceuticals and agricultural chemicals. In the field of photographic chemistry, it is known as a dye having a small number of coupler nuclei and side absorption (Abstracts of the Annual Meeting of the Society of Photographic Society of Japan, 1985). However, the conventionally known 1H-pyrrolo- [1,2-b] [1,2,4] triazole dye has a maximum absorption wavelength of less than 560 nm, and no dye having a maximum absorption wavelength of more than 600 nm has been known.

[0003]

In recent years, among the 1H-pyrrolo- [1,2-b] [1,2,4] triazole dyes, those having a maximum absorption wavelength exceeding 560 nm, especially 6
What exceeds 00 nm is desired. That is, there is a strong demand for a dye having a 1H-pyrrolo- [1,2-b] [1,2,4] triazole mother nucleus and having a small side absorption and a main absorption exceeding 600 nm.

An object of the present invention is to provide 1H-pyrrolo- [1,2
-B] A dye having a [1,2,4] triazole nucleus, having a small side absorption and a main absorption exceeding 600 nm, and a precursor thereof.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, the present invention has been achieved.
H-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 derivatives. (2) 1H-pyrrolo- [1, represented by the general formula [I]
2-b] [1,2,4] triazole derivatives.

[0006]

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(In the general formulas [I] and [II], X and Y each represent a cyano group or -COR.
Represents a hydrogen atom, an amino group, an alkoxy group, or an aryloxy group. Z represents a hydrogen atom, a halogen atom, an arylthio group, a heterocyclic thio group, an arylsulfinyl group or a nitroso group. Ar represents an aryl group. R
₁ , R ₂ represents a hydrogen atom or an alkyl group, and R ₃ represents a halogen atom or an alkyl group. n represents an integer of 0 to 4. )

Next, the compounds represented by the general formulas [I] and [II] will be described in detail. In the general formulas [I] and [II], X is preferably a cyano group and-
It has the following R in COR. That is, R
Is preferably a hydrogen atom, an amino group having 0 to 36 carbon atoms (hereinafter referred to as C number), a linear, branched or cyclic alkoxy having 1 to 36 (more preferably 1 to 24) C atoms. Represents an aryloxy group having 6 to 36 (more preferably 6 to 24) C atoms. The amino group, alkoxy group, and aryloxy group for R may be a substituent (for example, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an amino group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, An alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, 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).

X is preferably a cyano group and -CO
R has the following R. That is, R is preferably an unsubstituted, alkyl-substituted, aryl-substituted or heterocyclic-substituted amino group (an alkyl-substituted amino group, an aryl-substituted amino group, and a heterocyclic-substituted amino group are further substituted with a substituent group A). The alkyl in the alkyl-substituted amino group may be linear, branched or cyclic, for example, amino, ethylamino, n-dodecylamino, anilino, 2-chloroanilino, 2-naphthylamino, 2- Pyridyl-2-amino), linear, branched or cyclic unsubstituted or substituted groups (alkoxy, alkylthio, aryloxy, arylthio, alkylsulfonyl, arylsulfonyl, aryl, alkoxycarbonyl) , An epoxy group, a cyano group or a halogen atom-containing alkoxy group (for example, Carboxymethyl, ethoxy, isopropoxy, isobutoxy, n- octyloxy, n- decyloxy, n- dodecyloxy, n- hexadecyloxy, 2-ethylhexyl-oxy, 3,5,5-oxy,
2-ethyl-4-methylpentyloxy, 2-hexyldecyloxy, 2-heptylundecyloxy, 2-octyldodecyloxy, 2,4,6-trimethylheptyloxy, 2,4,6,8-tetramethylnonyl Oxy, benzyloxy, 2-phenethyloxy, 3- (t
-Octylphenoxy) propoxy, 3- (2,4-di-t-pentylphenoxy) propoxy, 2- (4-biphenylyloxy) ethoxy, 3-dodecyloxypropoxy, 2-dodecylthioethoxy, 9,10-epoxy Octadecyloxy, dodecyloxycarbonylmethoxy, 2- (2-naphthyloxy) ethoxy, 7,7-
Dimethyl-2- (3 ', 3'-dimethylbutyl) -5
Methyloctyloxy, 2-methyl-cyclohexyloxy, 2-hexyl-cyclohexyloxy), an unsubstituted or substituted aryloxy group (substituent group A) (for example, phenoxy, 2-t-amylphenoxy,
4-dodecyloxyphenoxy).

X represents R in the cyano group and -COR
Is particularly preferably a linear, branched or cyclic substituted alkoxy group and an unsubstituted or substituted aryloxy group.

In the general formula [I] or [II], Y has the same meaning as X. Y and X may be the same or different.

In the general formula [I] or [II], Z is preferably a hydrogen atom, a halogen atom, a C number of 6 to 36.
(More preferably 6 to 24) arylthio group, C number 1
An arylsulfinyl group of 1 to 36 (more preferably 1 to 24), a heterocyclic thio group or a nitroso group of 1 to 36 (more preferably 1 to 24), and an arylthio group, an arylsulfinyl group and a heterocyclic thio group are The substituent group A may be substituted.

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) phenylsulfenyl, 2- (phenoxycarbonylamino) phenylsulfenyl, 2- (phenoxycarbonyl) phenylsulfenyl, 2- (3,3-dimethylureido) phenylsulfenyl, pentafluoro Phenylsulfenyl, pentachlorophenylsulfenyl, 1,3,5-
Triisopropylphenylsulfenyl), unsubstituted or substituted groups (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 preferably a hydrogen atom, an arylthio group, or an arylsulfinyl group.

In the general formula [I], Ar is preferably C
An aryl group having the number of 6 to 36 (more preferably 6 to 30). Ar is preferably an unsubstituted or substituted aryl group (substituent group A) or an optionally fused aryl group (eg, phenyl, 3-nitrophenyl, 4-nitrophenyl, 4-cyanophenyl, 3,3 4-dicyanophenyl, 3,4-dimethoxycarbonylphenyl, 3-
(2-octyloxy-5-t-octyl) phenylsulfonylaminophenyl, 3,5-dichlorophenyl,
4- {1- (2,4-di-t-amylphenoxy) propanoylamino} phenyl, 4- (2-hexyldecyloxy) phenyl, 2- (2-hexyldecyloxy)
Phenyl, 3- (2,4-di-t-amylphenoxyacetylamino) phenyl).

In the general formula [II], R ₁ is preferably a hydrogen atom and a C number of 1 to 24 (more preferably 1 to 1).
Represents the alkyl group of 2). R ₁ 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 ₁ is particularly preferably the aforementioned alkyl group. In the general formula [II], R ₂ has the same meaning as R ₁ . R ₂ may be the same as R ₁ or may be different. R ₂ may form a ring together with R ₁ .

In the general formula [II], R ₃ is preferably a halogen atom, and C 1-24 (more preferably 1-12).
Represents an alkyl group. R ₃ 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 ₃ is particularly preferably a methyl group.

In the general formula [II], n is preferably an integer of 0 to 2, and particularly preferably 0 and 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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Specific examples of the compound to which the method of the present invention is applied are shown below, but the invention is not limited thereto. Specific examples of the compound represented by the general formula [I] are shown. In the following structural formula, (t) C ₅ H ₁₁ is -C (CH ₃ ) ₂ C ₂ H ₅ , and (t) C ₈ H ₁₇ is -C (C
H ₃ ) _{2 represents} CH ₂ C (CH ₃ ) ₃ ; M ⁺ is the value of the parent peak of the mass spectrum (M ⁺ ). λmax (nm) means the maximum absorption wavelength in the ethyl acetate solution when derived into the general formula [III]. General formula [III]

[0021]

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Further, for some, the melting point (mp) is described.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

[0027]

[Table 5]

[0028]

[Table 6]

[0029]

[Table 7]

[0030]

[Table 8]

[0031]

[Table 9]

[0032]

[Table 10]

[0033]

[Table 11]

Next, a typical synthetic route of the compound represented by the general formula [I] is shown below. When Y = COR ₁

[0035]

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When Y = CN

[0037]

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[0038]

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Here, the compound (i) can be synthesized by a known method. For example, JCS, 518 (1961)., JCS, 5
149 (1962)., Angew.Chem., 72, 956 (1960)., Berichte.,
97, 3436 (1964)., The literature cited therein, or a similar method.

Compound (iii) is a compound (i) of compound (i)
It is synthesized by a nucleophilic substitution reaction to i) followed by a ring closure reaction. At this time, it is preferable to use a base such as sodium hydride, triethylamine, diazabicycloundecene, potassium carbonate, and sodium carbonate. The reaction may be carried out without a solvent, but a solvent such as tetrahydrofuran, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N'-dimethylimidazolidone-2-one, acetone, and toluene are used. May be. The reaction temperature is generally -20C to 150C, preferably 0C to 100C.

Compound (v) is synthesized by a nucleophilic substitution reaction of compound (i) with compound (iv) and a subsequent ring-closure reaction in the same manner as in the method of synthesizing compound (iii).
Compound (vi) is induced by a dehydration reaction of compound (v). At this time, it is preferable to use phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride or the like. The reaction may be carried out without solvent or in toluene or chloroform. The reaction temperature is usually −10 to 250 ° C., preferably 20
C. to 200C.

The compound represented by the general formula [I] is a compound
It can be synthesized by a method known from (iii) or (vi). 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. 3,227,554.
The method described in (1), wherein aryl mercaptan, heterocyclic mercaptan and its corresponding disulfide are dissolved in a halogenated hydrocarbon solvent, converted into sulfenyl chloride with chlorine or sulfuryl chloride and dissolved in an aprotic polar solvent [ The compound can be synthesized by adding to the compound represented by formula [I]. Next, a typical synthetic route of the compound represented by the general formula [II] is shown below.

[0043]

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That is, the compound represented by the general formula [II]
It can be derived from the compound represented by the general formula [I] by a known method. For example, it can be induced by the method described in JP-A-63-145281. That is, it can be synthesized in the presence of the compound represented by the general formula [I], phenylenediamines, and an oxidizing agent.

This coupling reaction is described in “The Theory of the Photographic Process” edited by TH James (4th Edition).
As described in Chapter 12 of (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 in the general formula [I] is a hydrogen atom, 0.1 to 10 mol, preferably 0.5 to 2 mol of phenylenediamine coexists with 1 mol 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.

[0046]

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

[0047]

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Compound (a) (50.1 g, 0.1 mol)
To a solution of (b) (19.9 g, 0.11 mol) in tetrahydrofuran (300 ml) at 0 ° C. was added sodium hydride (12.0 g, 0.30 mol) little by little, taking care not to raise the reaction temperature. Add and stir for 1 hour. 1N diluted hydrochloric acid (200 ml) was added, and the mixture was extracted three times with ethyl acetate (300 ml). The organic layer is washed with water and saturated saline and dried over anhydrous sodium sulfate. The solvent is distilled off under reduced pressure, and the residue is purified by column chromatography (developing solvent; hexane: ethyl acetate = 3: 1) to give Exemplified Compound (I-1).
(7.57 g, 13%) was obtained.

Synthesis Example 2 Synthesis of Exemplified Compound (I-22) Exemplified compound (I-22) was synthesized by the following route.

[0050]

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From compound (c) (45.5 g, 50 mmol) and (d) (9.13 g, 55 mmol), compound (e) (3.90 g, 8%) was obtained in the same manner as in Synthesis Example 1.
Phosphorus oxychloride (1.47 g, 9.6 mmol) was added to compound (e) (3.90 g, 4.0 mmol), and the mixture was added at 100 ° C. for 1 hour.
Stir for hours. After cooling, water (10 cc) was added, and the mixture was extracted three times with ethyl acetate (30 cc). The organic layer is washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile (30 cc) to obtain Exemplified Compound (I-22) (3.22 g, 84%).

Synthesis Example 3 Synthesis of Exemplified Compound (I-20) Exemplified compound (I-20) was synthesized by the following route.

[0053]

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Exemplified compound (I-1) (2.91 g, 5 mm
ol) in methylene chloride (30 ml) was added dropwise sulfuryl chloride (0.74 g, 5.5 mmol) at 0 ° C. and stirred for 1 hour. Add water and extract three times with methylene chloride (30 cc). The organic layer is washed four times with water and once with saturated saline, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure and recrystallizing from acetonitrile, the exemplified compound (I-2) was obtained.
0) (2.83 g, 92%) was obtained.

Synthesis Example 4 Synthesis of Exemplified Compound (I-21) Exemplified compound (I-21) was synthesized by the following route.

[0056]

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Di-{(2-n-butoxy-5-t-octyl) phenyl} disulfide (3.53 g, 6 mmol)
To a methylene chloride (20 ml) solution at 0 ° C. was added with sulfuryl chloride (1.76 g, 13 mmol) and stirred for 1 hour.
Under reduced pressure, methylene chloride and sulfuryl chloride are removed. Methylene chloride (20 ml) was added to the residue, and this solution was added dropwise to a solution of Exemplified Compound (I-1) (2.91 g, 5 mmol) in N, N-dimethylformamide (10 ml) at 0 ° C. and stirred for 1 hour. I do. Add water and extract 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; hexane: ethyl acetate = 2: 1) to give Exemplified Compound (I-21).
(2.93 g, 67%) was obtained.

Synthesis Example 5 Synthesis Example of Dye of Exemplified Compound (I-20) Compound (I-20) (9.59 g, 10.0 mmol)
Of ethyl acetate-ethanol (1: 1) mixed solvent (100
ml) solution, an aqueous solution of sodium carbonate (9 g) (40 m
l) was added, followed by 4- [N-ethyl-N- (2-methanesulfonamidoethyl) amino] -2-methylaniline sulfate (6.38 g, 12.2 mmol) and 5 minutes at room temperature. Stir. Ammonium persulfate (4.5
An aqueous solution (20 ml) of g) was added dropwise, and the mixture was stirred for 1 hour, and then extracted three times with ethyl acetate. The organic layer is washed with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and column chromatography (developing solvent;
After purification with methylene chloride: methanol = 20: 1), recrystallization from methanol gave the dye of the exemplary compound (I-20) (10.2 g, 83%).

[0059]

Industrial Applicability 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. On the other hand, in the field of photographic chemistry, it is useful as a coupler. On the other hand, the compound represented by the general formula [II] is useful as a dye, has a small side absorption and a main absorption of 600.
It is excellent in that it is not less than nm.

Continued on the front page (72) Inventor Kazuyoshi Yamakawa 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Inside Fujisha Shin Film Co., Ltd. (72) Inventor Kozo Sato 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Examiner Fujisha Shin Film Co., Ltd. Naoko (58) Field surveyed (Int.Cl. ⁷ , DB name) C07D 487/04 139 C09B 44/10 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], X and Y each represent a cyano group or -COR. R represents a hydrogen atom, an amino group, an alkoxy group, or an aryloxy group. Ar
Represents an aryl group. R ₁ and R ₂ represent a hydrogen atom or an alkyl group, and R ₃ represents a halogen atom or an alkyl group. 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], X and Y each represent a cyano group or -COR. R represents a hydrogen atom, an amino group,
Represents an alkoxy group or an aryloxy group. Z represents a hydrogen atom, a haloken atom, an arylthio group, a heterocyclic thio group, an arylsulfinyl group or a nitroso group.
Ar represents an aryl group. )