JPH0794413B2 - Benzyl ether derivative and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is used as an intermediate in the production of 1,5-diphenyl-1H-1,2,4-triazole-3-carboxylic acid amide derivatives used as active ingredients of herbicides. And a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Rice, wheat, corn and the like are important crops, and the use of herbicides is indispensable in order to protect these crops from weed damage and increase their yield.

Conventionally, 1,5-diphenyl-1H-1,
The fact that the 2,4-triazole-3-carboxylic acid amide derivative has a herbicidal action is disclosed in JP-A-57-193406 and JP-A-
As described in No. 59-98004, the herbicidal effect and selectivity are not sufficient, the herbicidal activity is excellent, and the selectivity to kill only weeds without harming useful crops such as rice, wheat and corn. There has been a strong demand for the development of compounds having excellent herbicidal activity.

On the other hand, as a benzyl ether derivative,
2,6-Dimethyl-3- (methoxymethyl) -1-nitrobenzene, 6-ethyl-3- (propoxymethyl)-
1-nitrobenzene, 4-ethyl-3- (phenoxymethyl) -1-nitrobenzene, 2,6-dimethyl-3-
(Methoxymethyl) aniline, 6-ethyl-3- (propoxymethyl) aniline, 6-ethyl-3-[(1-methylethoxy) methyl] aniline, 4-ethyl-3-
(Phenoxymethylaniline) and the like are known, but none of them relate to an intermediate of a triazolecarboxylic acid amide derivative.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present inventors have conducted research to provide a compound that exhibits excellent herbicidal effects and does not harm useful crops such as rice, wheat, and corn. V)

[0006]

[Chemical 6]

1,5-diphenyl-1H-
The 1,2,4-triazole-3-carboxylic acid amide derivative was found to have an excellent selective herbicidal effect, and was further used as an intermediate for producing the triazolecarboxylic acid amide derivative represented by the formula (V). The present invention has been reached by finding a novel compound, a benzyl ether derivative.

[0008]

The benzyl ether derivative of the present invention is a novel compound represented by the following formula (I).

[0009]

[Chemical 7]

[Wherein R is a linear alkyl group having 4 to 10 carbon atoms, a branched alkyl group having 4 to 10 carbon atoms, and 3 to 3 carbon atoms]
Represents a cyclic alkyl group having 10 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with an alicyclic structure having 3 to 7 carbon atoms, a phenyl group or an aralkyl group having 7 to 9 carbon atoms, and X ¹ represents halogen; Alternatively, it represents an alkyl group having 1 to 3 carbon atoms,
X ² represents hydrogen, halogen or an alkyl group having 1 to 3 carbon atoms, and Z represents an NH ₂ group or a NO ₂ group.

However, when ^one of X ¹ or X ² is halogen at the 4 position of the benzene ring, the other one is 6
Except that it is a halogen at the position, or R is a phenyl group when X ¹ is an ethyl group at the 4 or 6 position and X ² is hydrogen. Or [in the formula, R is a fluorine-substituted, preferably 3 to 12, more preferably 3 to 7 fluorine-containing carbon atoms 2 to 2]
Substituted with 10 linear alkyl groups or fluorine,
It is preferably a branched alkyl group having 3 to 10 carbon atoms, which is substituted with 3 to 12, more preferably 3 to 7, fluorine, and X ¹ is halogen or an alkyl group having ¹ to 3 carbon atoms. X ² is hydrogen, halogen or 1 to 3
Represents an alkyl group of carbon atoms, and Z represents an NH ₂ group or a NO ₂ group. ] Particularly preferred benzyl ether derivatives are those in which R is a linear alkyl group having 2 to 4 carbon atoms substituted with 3 to 7 fluorine atoms, X ¹ is chlorine or a methyl group, and X ² is hydrogen. To be

In the present invention, the substitution position of the benzene ring of the formula (I) is such that the Z position is 1 in the benzene ring of the formula (I), and the other positions are respectively numbered clockwise. Therefore, the position of CH ₂ OR is 3.

The benzyl ether derivative of the present invention includes 4-chloro-3- (2,2,2-trifluoroethoxy) methyl-1-nitrobenzene 4-chloro-3- (2,2,3,3-). Tetrafluoropropoxy) methyl-1-nitrobenzene 4-chloro-3- (2,2,3,3,3-pentafluoropropoxy) methyl-1-nitrobenzene 4-chloro-3- (2,2,3,4,) 4,4-hexafluorobutoxy) methyl-1-nitrobenzene 4-chloro-3- (2,2,3,3,4,4,4-heptafluorobutoxy) methyl-1-nitrobenzene 3- (2,2,2 3,3,3-Pentafluoropropoxy)
Methyl-4-methyl-1-nitrobenzene 4-chloro-3- (2,2,2-trifluoroethoxy) methylaniline 4-chloro-3- (2,2,4,4-tetrafluoropropoxy) methylaniline 4-chloro-3- (2,2,3,3,3-pentafluoropropoxy) methylaniline 4-chloro-3- (2,2,3,4,4,4-hexafluorobutoxy) methylaniline 4- Chloro-3- (2,2,3,3,4,4,4-heptafluorobutoxy) methylaniline 3- (2,2,3,3,3-pentafluoropropoxy)
Methyl-4-methylaniline and the like are exemplified.

The benzyl ether derivative of the present invention has an excellent herbicidal action on grass weeds and broad-leaved plants, especially broad-leaved plants, while selective herbicides showing no phytotoxicity against crops such as rice, wheat and corn. 1,5-diphenyl-1H-1,2 represented by the general formula (V) having activity
It is useful as an intermediate of a 4-triazole-3-carboxylic acid amide derivative.

[0015]

[Chemical 8]

[Wherein R is a linear alkyl group having 4 to 10 carbon atoms, a branched alkyl group having 4 to 10 carbon atoms, and 3 carbon atoms]
10 amino cyclic alkyl group, the number 3-7 alicyclic structure substituted number 1-3 alkyl carbon atoms, a phenyl group or a number 7-9 or aralkyl group having a carbon, X ¹ is Halogen or an alkyl group having 1 to 3 carbon atoms, X ² represents hydrogen, halogen or an alkyl group having 1 to 3 carbon atoms, and Z represents an NH ₂ group or a NO ₂ group.

However, when ^one of X ¹ or X ² is halogen at the 4 position of the benzene ring, the other is 6
Except that it is a halogen at the position, or R is a phenyl group when X ¹ is an ethyl group at the 4 or 6 position and X ² is hydrogen. Or [in the formula, R is preferably a fluorine-substituted 3 to 12 carbon atoms, more preferably 3 to 7 fluorine-substituted carbon atoms 2 to 10]
Straight-chain alkyl groups or fluorine-substituted, preferably 3-12, more preferably 3-7 fluorine-substituted, branched alkyl groups having 3-10 carbon atoms, and X ¹ is halogen. Alternatively, it represents an alkyl group having 1 to 3 carbon atoms,
X ² represents hydrogen, halogen or an alkyl group having 1 to 3 carbon atoms, and Z represents an NH ₂ group or a NO ₂ group. The physicochemical properties of these triazole carboxamide derivatives are shown in Table 1.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

[Table 5]

[0023]

[Table 6]

[0024]

[Table 7]

[0025]

[Table 8]

[0026]

[Table 1]

[0027]

[Table 2]

The position numbers of the substituents in Table 1 are as shown in the following formula.

[0029]

[Chemical 9]

The results of elemental analysis of these triazole carboxamide derivatives are shown in Table 2.

[0031]

[Table 11]

[0032]

[Table 12]

Since each of these compounds has the selective herbicidal activity as described above, it can be widely used as a herbicide in paddy fields, upland fields and the like.

The benzyl ether derivative of the present invention can be obtained, for example, by the following method. (Reaction formula 1). That is, chloromethylnitrobenzene (IV) is etherified to synthesize nitrobenzyl ether (II), and this is reduced by a general method to obtain aminobenzyl ether (III). In etherification, it is common to react chloromethylnitrobenzene (IV) with alcohol ROH in the presence of a hydrochloric acid acceptor such as potassium hydroxide. In Reaction Scheme 1, R, X ¹ and X ² have the same meanings as in General Formula (I).

[0035]

[Chemical 10]

Next, the method for producing the azole derivative of formula (V) which is the final herbicide from the benzyl ether derivative of the present invention is as shown in the above reaction formulas 1 and (2).

When the aminobenzyl ether (III) obtained by the reaction formula (1) is reacted with nitrous acid to form a diazonium salt and then reacted with 2-phenyl-2-oxazoline-5-one, it is represented by the general formula (VI). The compound obtained is obtained. This 2-phenyl-4- (phenylhydrazono)-
Ammonia is added to the 2-oxazoline-5-one derivative in an organic solvent such as acetone or toluene at -10 to 150 ° C.
At 0.1 to 20 hours, then acidify the reaction mixture with hydrochloric acid, acetic acid, etc. and stir at 0 to 150 ° C. for 0.1 to 20 hours for dehydration ring closure to obtain a triazole derivative represented by the general formula (V) in a good yield. Can be obtained at.

In reaction formula 2, R, X ¹ , X ² , Y ¹ ,
Y ² has the same meaning as in formula (V).

[0039]

[Chemical 11]

1,5-diphenyl-1H of the general formula (V)
The -1,2,4-triazole-3-carboxylic acid amide derivative is used alone or with a wide range of carriers (diluents) and / or auxiliaries conventionally used for the preparation of agricultural chemicals. It can also be used as a composition such as a wettable powder, an emulsion, a granule and a powder.

1,5-diphenyl-1H- in the composition
The concentration of the 1,2,4-triazole-3-carboxylic acid amide derivative is preferably 0.1 to 50% by weight.

1,5-diphenyl-1H-1,2,
A 4-triazole-3-carboxylic acid amide derivative and a herbicide containing the compound as an active ingredient are applied to soils of paddy fields and uplands and / or foliage of plants by a conventionally known spraying method.
The amount of the compound sprayed per 10a is preferably 0.1 to 500 g
It is sprinkled to become.

The method for producing the novel benzyl ether derivative according to the present invention and its melting point or boiling point, and the method for producing the triazolecarboxylic acid amide derivative produced by using the benzyl ether derivative of the present invention as an intermediate and the derivative thereof are described below. Specific examples of the herbicide used as a component are shown below, but the present invention is not limited to the examples.

[0044]

[Example] Example 13- (2,2,3,3,3-pentafluoropropoxy
Si) Methyl-4-methyl-1-nitrobenzene [general formula
In _{(I), R = CH 2} CF 2 CF 3, X 1 = 4-
CH ₃ , X ² = H compound]

[0045]

[Chemical 12]

2-methyl-5-nitrobenzyl chloride
5.00 g (0.027 mol) and 2,2,3,3,3-pentafluoropropanol (21.3 g, 0.135 mol) were dissolved in 16.5 ml of dimethylformamide, 2.29 g (0.041 mol) of KOH pellets were added, and the mixture was stirred overnight. Dichloromethane was added, the salts were filtered off, the filtrate was made acidic, and the solvents were distilled off. The residue was dissolved in a mixed solvent of hexane / ethyl acetate = 9/1 (v / v), washed with diluted hydrochloric acid, water and saturated saline, and dried over magnesium sulfate. The oily substance obtained by distilling off the solvent was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 19/1, v / v) to obtain 7.71 g (95.5% yield) of 3-
(2,2,3,3,3-pentafluoropropoxy) methyl-4-methyl-1-nitrobenzene (mp 53.5-54.5
C) was obtained.

Example 23- (2,2,3,3,3-pentafluoropropoxy
Si) Methyl-4-methylaniline [odor of general formula (V)
And R = CH ₂ CF ₂ CF ₃ , X ¹ = 4-CH ₃ , X ²
= H compound]

[0048]

[Chemical 13]

7.30 g (0.02 g) of the nitro compound obtained in Example 1
44 mol) was dissolved in 40 ml of ethanol. 10% P to this
0.1 g of d-C and 3.66 g (0.073 mol) of hydrazine hydrate were added, and the mixture was refluxed for 1 hour on a water bath. After allowing to cool, the catalyst was separated by filtration through a Celite layer and washed with ethanol. The filtrate was concentrated, then dissolved in dichloromethane, washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous potassium carbonate. After distilling off the solvent, fractionation was carried out to obtain a fraction having a bp of 82 to 3 ° C. (0.18 mmHg) and 6.90 g (93% yield) of 3- (2,2,3,3,3).
3-Pentafluoropropoxy) methyl-4-methylaniline was obtained.

Reference Example 14-[[3-2,2,3,3,3-pentafluoropro
(Poxy) methyl-4-methylphenyl] hydrazono]-
2-phenyl-2-oxazolin-5-one [general formula
In _{(II), R = CH 2} CF 2 CF 3, X 1 = 4-
CH ₃ , X ² = Y ¹ = Y ² = H compound]

[0051]

[Chemical 14]

Aminobenzyl ether obtained in Example 2.
17 g (0.0101 mol) was added to 6.9 ml of acetic acid-1.8 ml of concentrated hydrochloric acid, and a solution of 0.729 g (0.0106 mol) of sodium nitrite / 2 ml of water was added dropwise at a temperature of 0 ° C or lower to prepare a diazonium salt solution. Separately, 2.08 g (0.0116 mol) of hippuric acid was added to 5.7 m of acetic anhydride.
l (0.0604 mol) and stirred at 80 ° C. for 10 minutes to obtain a solution of 2-phenyl-2-oxazolin-5-one. This solution was cooled to -20 ° C, 1.65 g of sodium acetate anhydride was added, and the above-mentioned diazonium salt solution was added with stirring to -20 to -10 ° C.
The mixture was stirred for 2 hours at room temperature and then for 5 hours at room temperature. Water was added, and the precipitated crystals were collected by filtration, washed thoroughly with water and dried to give 3.65 g (82.2
% Yield) of 4-[[3- (2,2,3,3,3-pentafluoropropoxy) methyl-4-methylphenyl] hydrazono] -2-phenyl-2-oxazolin-5-one. . Recrystallization from methylene chloride-hexane gave orange needle crystals (mp. 160-161 ° C).

Reference Example 2 1- [3- (2,2,3,3,3-pentafluoropro
Poxy) methyl-4-methyl] phenyl-5-phenyl
-1H-1,2,4-triazol-3-carboxylic acid
Synthesis of amide (Compound No. 26 in Table 1) 4-[[3- (2,2,3,3,3-pentafluoropropoxy) methyl-4-methylphenyl] obtained in Reference Example 1
Hydrazono] -2-phenyl-2-oxazoline-5-
3.30 g (7.5 mmol) of ON was suspended in 46 ml of acetone,
1.5 ml of concentrated ammonia water was added and stirred for 1 hour. Next, 1.6 ml of concentrated hydrochloric acid was added to make the mixture acidic, and the mixture was stirred at 40 to 50 ° C for 30 minutes. After the acetone was distilled off, the residue was extracted with benzene. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain a crude product. This was purified by silica gel chromatography (developing solvent: CH ₂ Cl ₂ / MeOH = 97/3, v / v) and further recrystallized to give 3.145 g (95.5% yield) of 1-.
[3- (2,2,3,3,3-pentafluoropropoxy) methyl-4-methyl] phenyl-5-phenyl-1
H-1,2,4-triazole-3-carboxylic acid amide (mp 127-129 ° C) was obtained.

Reference Example 31- [4-methyl-3-[(3-methylbutoxy) meth]
] Phenyl] -5-phenyl-1H-1,2,4-to
Riazole-3-carboxylic acid amide (Compound N in Table 1
o. 25) Synthesis Synthesized in the same manner as described in Examples 1 and 2 and Reference Example 1.
4-[[4-methyl-3- (3-methylbutoxy) meth]
Luphenyl] hydrazono] -2-phenyl-2-oxa
Zolin-5-one 1.668 g (4.4 mmol) was added to acetone 40
suspension in 1 ml, add 1.3 ml of concentrated aqueous ammonia, and add for 1 hour.
I mixed it. Next, add 1.5 ml of concentrated hydrochloric acid to make it acidic, and
Stir for 30 minutes at 50 ° C. Residue obtained by distilling off acetone
The residue was extracted with benzene. The organic layer is anhydrous sodium sulfate
After drying, the solvent was distilled off to obtain a crude product. Siri this
Kagel chromatography (Developing solvent: CH₂Cl₂/
MeOH = 97/3, v / v) and recrystallized to 1.4
98 g (90.0% yield) of 1- [4-methyl-3-[(3-me
Tylbutoxy) methyl] phenyl] -5-phenyl-1
H-1,2,4-triazol-3-carboxylic acid amide
(Mp83-85 ° C) was obtained.

Reference Example 4 1- (3-Butoxymethyl-4-chlorophenyl) -5
-Phenyl-1H-1,2,4-triazol-3-carb
Synthesis of ruvonic acid amide (Compound No. 1 in Table 1) 4-[(3-butoxymethyl-4-chlorophenyl) synthesized in the same manner as described in Examples 1 and 2 and Reference Example 1
Hydrazono] -2-phenyl-2-oxazoline-5-
1.157 g (3 mmol) of On was suspended in 10 ml of acetone,
0.6 ml of concentrated aqueous ammonia was added, and the mixture was stirred for 30 minutes at room temperature.
Next, 0.6 ml of concentrated hydrochloric acid was added to make the mixture acidic, and the mixture was stirred at 50 ° C. for 30 minutes. After removing the acetone by distillation, benzene and water were added for extraction, the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 1/2, v / v) and further recrystallized to give 1.0
87 g (94.2% yield) of 1- (3-butoxymethyl-4-
Chlorophenyl) -5-phenyl-1H-1,2,4-
Triazole-3-carboxylic acid amide (mp 96-98 ° C) was obtained.

Reference Example 51- [4-chloro-3-[(3-methylbutoxy) meth]
]] Phenyl] -5- (2-fluorophenyl) -1H
-1,2,4-triazole-3-carboxylic acid amide
(Synthesis of Compound No. 21 in Table 1 Similar to the method described in Examples 1 and 2 and Reference Example 1.
Synthesized 4- [4-chloro-3-[(3-methylbutoxy)
Si) methyl] phenylhydrazono] -2- (2-fluor
Rophenyl) -2-oxazolin-5-one 1.294 g (3
Suspension) in 10 ml of acetone and add concentrated aqueous ammonia.
 0.6 ml was added and stirred for 30 minutes at room temperature. Next, concentrated hydrochloric acid 0.6
After adding ml, the mixture was stirred at 50 ° C for 30 minutes. Distill off the acetone
Benzene and water are added to the residue to extract it, and the organic layer is saturated.
It was washed with Japanese salt water and dried over anhydrous sodium sulfate. solvent
The crude product obtained by distilling off the
Fee (developing solvent: hexane / ethyl acetate = 1/2, v /
v) and recrystallized from ethyl acetate-hexane.
1.062 g (82.3% yield) of 1- [4-chloro-3-
[(3-Methylbutoxy) methyl] phenyl] -5- (2
-Fluorophenyl) -1H-1,2,4-triazo
Le-3-carboxylic acid amide (mp113-115 ° C) was obtained.

Reference Example 6 Preparation of wettable powder Triazole carboxylic acid amide derivative (V): 50 parts Lignin sulfonate 5 parts Alkyl sulfonate 3 parts Diatomaceous earth 42 parts are mixed and pulverized to be a wettable powder and diluted with water. use.

Reference Example 7 Preparation of Emulsion Triazolecarboxylic acid amide derivative (V): 25 parts xylene 65 parts Polyoxyethylene alkylallyl ether 10 parts are uniformly mixed to prepare an emulsion, which is diluted with water and used.

Reference Example 8 Preparation of Granules Triazolecarboxylic acid amide derivative (V): 8 parts Bentonite 40 parts Clay 45 parts Lignin sulfonate 7 parts Uniformly mixed with water and further kneaded Granulated by an extrusion granulator It is processed and dried into granules.

Test examples are shown below to show the selective herbicidal activity of the compounds shown in Table 1.

The compounds shown as comparative examples in these test examples are compounds having the following formula disclosed in JP-A-59-98004 as an active ingredient.

[0062]

[Chemical 15]

Reference Test Example 1 Effect on Upland Weeds (Pre-emergence Soil Treatment) A planter (650 × 210 × 220 mm) was filled with sandy loam soil to form a field, and Aoyu, Kosendan, wild mustard, chickweed, Japanese perch, velvetleaf and edible millet , Seedgrass, wheat, and corn seeds were sown in fixed amounts and covered with soil, and then the wettable powder prepared in the same manner as in Reference Example 6 was diluted to a predetermined concentration with water and the spray gun sprayed the active ingredient at 200 g / 10a. The same amount was sprayed evenly on the soil surface, and then grown and controlled in a glass greenhouse.

On the 21st day after the above treatment, the herbicidal effect against each weed and the phytotoxicity against the crops were observed and evaluated according to the following criteria, and the results shown in Table 3 were obtained.

Evaluation criteria: 0 ... No effect 1 ... Less than 31% herbicidal effect 2 ... 31-50% herbicidal effect 3 ... 51-70% herbicidal effect 4 ... 71-90% Herbicidal effect of 5 …… 91 to 100% Herbicidal effect Level of phytotoxicity; A …… harmless, B …… slight harm, C …… moderate harm, D …… strong harm, E
...... Damage

[0066]

[Table 13]

[0067]

[Table 14]

[0068]

[Table 15]

Reference Test Example 2 Effect on Upland Weeds (Soil Treatment After Germination) According to the same procedure as described in Reference Test Example 1, seeds of various plants were sown, and each plant reached the 1-2 leaf stage. As in Reference Test Example 1, a wettable powder diluted with water was sprayed evenly on the foliage of each plant and the soil surface with a spray gun so that the amount of the active ingredient sprayed was 200 g / 10a. The cells were grown and managed in a greenhouse, and after 21 days from the treatment, the same criteria as those shown in Reference Test Example 1 were evaluated and the results shown in Table 4 were obtained.

[0070]

[Table 16]

[0071]

[Table 17]

[0072]

[Table 18]

Reference Test Example 3 Effects on Paddy Field Weeds and Chemical Injury Water was poured into a 1/2000 arel Wagner pot filled with paddy field soil to make it a submerged state, and seeds of Taenia cinerea, firefly, Hera modaka, eel, and velvet snail were sown. Planted a tuber. Furthermore, after transplanting two paddy rice seedlings (cultivar Sasanishiki) at the two-leaf stage, the pot was grown in a greenhouse for 3 days, and the emulsion prepared in the same manner as in Reference Example 7 was diluted to a predetermined concentration with water, and the amount of the active ingredient applied was changed. 200g / 10a
Was added dropwise to the water surface uniformly. Twenty-one days after the chemical treatment, the herbicidal effect and the degree of phytotoxicity of paddy rice were investigated on the basis of the same criteria as in Test Example 1, and the results shown in Table 5 were obtained.

[0074]

[Table 19]

[0075]

[Table 20]

[0076]

[Table 21]

[0077]

INDUSTRIAL APPLICABILITY The benzyl ether derivative represented by the general formula (I) of the present invention is a novel compound, exhibits excellent herbicidal activity and kills only weeds without damaging crops such as rice, wheat and corn. It is extremely useful as an intermediate for producing a triazolecarboxylic acid amide derivative represented by the formula (V), which is a herbicide having excellent selectivity.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoichi Kanda 5-6, Chuo 1-chome, Nishiki-cho, Iwaki-shi, Fukushima Prefecture (72) Inventor Jiro Akira Yamazaki 59-2, Kanayama, Joban Saigo-cho, Iwaki-shi, Fukushima Prefecture (72) Inventor Hirokawa Shinkawa 14 Suga, Nishiki-cho, Iwaki-shi, Fukushima (56) References “J. PRAKT. CHEM.”, Band 323, Heft 1, P. 129-132

Claims (6)

[Claims] 1. A compound represented by the general formula (I): (A) [wherein, R represents 4 to 10 linear alkyl group having a carbon number, number 4 to 10 branched alkyl group having a carbon carbon number 3-7
Represents an alkyl group having 1 to 3 carbon atoms, substituted with an alicyclic structure, a phenyl group or an aralkyl group having 7 to 9 carbon atoms, and X ¹ represents halogen or an alkyl group having 1 to 3 carbon atoms. , X ² is hydrogen or halogen and <br/> I Table, Z represents a ₂ group or an NO ₂ group NH. However, when ^one of X ¹ or X ² is halogen at the 4 position of the benzene ring, the other one is halogen at the 6 position, or X ¹ is an ethyl group at the 4 or 6 position. Except that when X ² is hydrogen, R is a phenyl group. ] Or (B) [in the formula, R is a fluorine-substituted carbon atom having 2 to 10 carbon atoms]
Number of carbon atoms substituted with a straight-chain alkyl group or fluorine
Represents 3 to 10 branched alkyl groups, X ¹ is halogen
Alternatively, it represents an alkyl group having 1 to 3 carbon atoms, and X ² is
Represents hydrogen or halogen, Z is NH ₂ group or
Represents a NO ₂ group. ] The benzyl ether derivative shown by these. 2. A straight-chain alkyl group having 2 to 10 carbon atoms, wherein R is substituted with 3 to 12 fluorine atoms, or a branched alkyl group having 3 to 10 carbon atoms, substituted with 3 to 12 fluorine atoms. benzyl ether derivative according to claim 1, wherein an alkyl group. Wherein R is three to seven carbon atoms which is substituted by fluorine 2-4 linear alkyl group, X ¹ is chlorine or a methyl group, according to claim 1, wherein X ² is hydrogen Benzyl ether derivative of. 4. 3- (2,2,3,3,3-pentafluoropropoxy) methyl-4-methyl-1-nitrobenzene or 3- (2,2,3,3,3-pentafluoropropoxy) methyl -4-methylaniline according to claim 1
The benzyl ether derivative described. 5. A compound represented by the general formula (II) : (A) [In the formula, R is a linear alkyl group having 4 to 10 carbon atoms.
Group, branched alkyl group having 4 to 10 carbon atoms, 3 to 7 carbon atoms
C 1-3 alkyl substituted with 4 alicyclic structures
Group, phenyl group or aralkyl group having 7 to 9 carbon atoms
X ¹ is halogen or an alkyl group having 1 to 3 carbon atoms.
Represents a alkyl group and X ² represents hydrogen or halogen.
You However, ^one of X ¹ or X ² is the 4-position of the benzene ring.
If the position is halogen, the other one is halo at position 6.
Except that it is Gen, or X ¹ is at the 4 or 6 position
Is an ethyl group, and R ² is hydrogen when X ² is hydrogen.
Except that it is a phenyl group. ] Or (B) [in the formula, R is a fluorine-substituted carbon atom having 2 to 10 carbon atoms]
Number of carbon atoms substituted with a straight-chain alkyl group or fluorine
Represents 3 to 10 branched alkyl groups, X ¹ is halogen
Alternatively, it represents an alkyl group having 1 to 3 carbon atoms, and X ² is
Represents hydrogen or halogen. ] The manufacturing method of the nitrobenzyl ether derivative shown by
Therefore, the general formula (IV) : [In the formula, X ¹ and X ² are as described above. ] In the presence of a hydrochloric acid acceptor in the form of alcohol ROH [formula
Inside, R is as above-mentioned. ] From reacting
How to do. 6. A compound represented by the general formula (III) : (A) [In the formula, R is a linear alkyl group having 4 to 10 carbon atoms.
Group, branched alkyl group having 4 to 10 carbon atoms, 3 to 7 carbon atoms
C 1-3 alkyl substituted with 4 alicyclic structures
Group, phenyl group or aralkyl group having 7 to 9 carbon atoms
X ¹ is halogen or an alkyl group having 1 to 3 carbon atoms.
Represents a alkyl group and X ² represents hydrogen or halogen.
You However, ^one of X ¹ or X ² is the 4-position of the benzene ring.
If the position is halogen, the other one is halo at position 6.
Except that it is Gen, or X ¹ is at the 4 or 6 position
Is an ethyl group, and R ² is hydrogen when X ² is hydrogen.
Except that it is a phenyl group. ] Or (B) [in the formula, R is a fluorine-substituted carbon atom having 2 to 10 carbon atoms]
Number of carbon atoms substituted with a straight-chain alkyl group or fluorine
Represents 3 to 10 branched alkyl groups, X ¹ is halogen
Alternatively, it represents an alkyl group having 1 to 3 carbon atoms, and X ² is
Represents hydrogen or halogen. ] The manufacturing method of the amino benzyl ether derivative shown by
Therefore, the general formula (II): [In the formula, R, X ¹ and X ² are as described above. ] The nitrobenzyl ether derivative represented by
The method consisting of and .