JPH0768196B2 - Novel N- (1-fluorinated alkoxy-2,2,2-trichloroethyl) -substituted salicylamide derivative and agricultural / horticultural fungicide and herbicide containing the derivative - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel N which has excellent bactericidal properties and is used for controlling diseases such as agricultural crops caused by various plant pathogens, and has a herbicidal action against various harmful weeds. And a (1-fluorinated alkoxy-2,2,2-trichloroethyl) -substituted salicylamide derivative.

2. Description of the Related Art Conventionally, as N- (1-substituted-2,2,2-trichloroethyl) salicylamide derivatives, compounds in which the substituent is an alkoxy group, a cycloalkoxy group or a phenoxy group have been known (JP-A-54). -39040, JP-A-57-163354
issue). Further, recently, Japanese Patent Application Laid-Open No. 61-69751 discloses a salicylamide derivative having a trihalogenoalkoxy group as the above substituent.

However, the benzene rings of these known compounds are all unsubstituted. It should be noted that only compounds in which the fluorinated alkoxy group is a trifluoroethoxy group are disclosed as those in which the benzene ring has been substituted (Japanese Patent Laid-Open No. Sho 61-187).
61-69751).

That is, an O-acylated derivative of a trifluoroethoxy group or an N- (1-fluorinated alkoxy-2,2,2-trichloroethyl) -substituted salicylamide derivative having a substituent introduced into a benzene ring, which is the object of the present invention, Is a novel compound that has not been published in the literature.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention exhibits a broad spectrum antibacterial spectrum against various plant pathogens, exhibits an excellent bactericidal effect in controlling diseases such as agricultural crops, and exerts a strong weeding effect also on weeds in fields. Novel N- (1-fluorinated alkoxy-2,2,2-
An object is to provide a trichloroethyl) -substituted salicylamide derivative.

The present invention will be described in detail below.

Composition of the invention N- (1-fluorinated alkoxy-2,2,2-
The trichloroethyl) -substituted salicylamide derivative is characterized by being represented by the following general formula (I).

(In the formula, X represents a hydrogen atom or a chlorine atom, R represents a hexafluoroisopropyl group or a heptafluorobutyl group, and R ₁ represents a hydrogen atom, an acetyl group, a propionyl group, a methoxyacetyl group or a cyclopropylcarbonyl group. The compounds represented by the above general formula (I) and their physicochemical properties are shown in Table 1.

Means for Solving the Problems The compound of the present invention represented by the above general formula (I) is prepared by the following.

The outline of the reaction formula for synthesizing this compound is as follows.

(In the formula, X, R, and R ₁ have the same meanings as described above.) That is, N- (1,2,2,2-tetrachloroethyl) -o-acetyl-substituted represented by the above formula (II). A salicylamide derivative (R ₁ = COCH ₃ in the formula (II)) is used as a starting material, and this is used in an organic solvent such as benzene with an equimolar amount or a molar excess of fluorinated alcohols and triethylamine. By reacting in the presence of the compound at room temperature for 30 minutes to several hours with stirring, the target compound of the general formula (I) {R ₁ ═COCH ₃ in the formula (I)} can be easily obtained.

When the obtained target compound (I) is in an oily form, it can be separated and purified by silica gel column chromatography or the like, and when it is in a crystalline form, it can be purified by recrystallization or the like.

When a compound of the general formula (I) in which R ₁ is a hydrogen atom is desired as the target compound, the acetylated product obtained by the above method is heated under reflux with a small amount of concentrated hydrochloric acid for several hours in a solvent such as methanol. Well, further, when a compound in which R ₁ is an acyl derivative other than an acetyl group is desired, the above compound in which R ₁ is a hydrogen atom is cooled in ice water in an organic solvent such as acetonitrile, in an equimolar amount or in excess thereof. The desired acyl derivative can be easily obtained by adding moles of the desired acid chloride and triethylamine, and stirring and reacting for 30 minutes to several hours.

Specific synthetic examples of the compound according to the present invention are shown below.

[Synthesis Example 1] N- [2,2,2-trichloro-1- (2,2,3,3,4,4,4-heptafluorobutoxy) -ethyl] -o-acetylsalicylamide (in Table 1 Synthesis of compound No. 2): N- (1,2,2,2-tetrachloroethyl) -o-acetylsalicylamide 5.0 g (0.0145 mol) was dissolved in 100 ml of benzene, and 1H, 1H-heptafluorobutanol 3.47 was dissolved therein. g
(0.0174 mol) and then triethylamine 1.
70 g (0.017 mol) was added and reacted for 1 hour with stirring. Triethylamine hydrochloride was filtered off from the resulting reaction solution, the benzene layer was washed with water, dried over anhydrous sodium sulfate, and benzene was distilled off under reduced pressure to obtain 7.0 g of a slightly yellow oily substance.

This was solidified and recrystallized from 45 ml of n-hexane to give a melting point of 82.
Compound No. 2 having a temperature of ~ 4 ° C as white crystals
3.9 g (yield 53.4%) was obtained.

The physicochemical properties of the obtained compound are as follows.

IR (KBr, cm ^-1 ): 3270 (NH), 1750 (OCO), 1650 (CON
H) NMR ^* (CDCl ₃ ) δ (ppm) 2.36 (3H, s: COC H ₃ ), 4.33 (2H, t, t, J = 2Hz, 14Hz: OC H ₂ CF ₂ ), 6.10 (1H, d, J = 10 Hz: NHC H ), 7.19 to 8.18 (5H, m, benzene ring- H + NH ) [Synthesis example 2] N- [2,2,2-trichloro-1- (1,1,1,3, Synthesis of 3,3-hexafluoroisopropoxy) ethyl] salicylamide (Compound No. 5 in Table 1) N- [2,2,2-trichloro-1- (1,1,1,3,3,3-hexa 3.2 g (0.0067 mol) of fluoroisopropoxy) ethyl] -o-acetylsalicylamide was dissolved in 30 ml of methanol, 0.2 ml of concentrated hydrochloric acid was added thereto, and the mixture was heated under reflux for 2 hours.
After cooling, the reaction solution was poured into water, and white crystals that precipitated were separated by filtration, washed well with water, and then dried. Then, the dried product was recrystallized with 25 ml of a mixed solvent of n-hexane: benzene = 5: 1, and the melting point was 142.
Compound No. 5 having a temperature of ~ 4 ° C as white crystals
2.24 g (yield 77.2%) was obtained.

The physicochemical properties of the obtained compound are as follows.

IR (KBr, cm ⁻¹ ): 3270 (NH), 1620 (OCNH), NMR ^* (CDCl ₃ ) δ (ppm) 4.71 (1H, 7-fold line, J = 6Hz: OC H (CF ₃ ) ₂ ), 6.29 (1H, d, J = 10Hz: NHC H), 6.88~7.84 (5H, m, benzene ring - H + N H), 11.12 (1H, s: benzene ring -O H) synthesis example 3 N- [ Synthesis of 2,2,2-trichloro-1- (2,2,3,3,4,4,4-heptafluorobutoxy) ethyl] -5-chlorosalicylamide (Compound No. 8 in Table 1) N- [ 2,2,2-trichloro-1- (2,2,3,3,4,4,4-heptafluorobutoxy) ethyl] -o-acetyl-5-chlorosalicylamide 2.66 g (0.0049 mol) in methanol 3
It was dissolved in 0 ml, 0.2 ml of concentrated hydrochloric acid was added thereto, and the mixture was heated under reflux for 2.5 hours. After cooling, the reaction solution was poured into water, and white crystals that precipitated were separated by filtration, washed well with water, and then dried. Then, the dried product was recrystallized from 15 ml of n-hexane to give 1.85 g of a compound of Compound No. 8 having a melting point of 93 to 5 ° C as white crystals (yield: 75.
5%).

The physicochemical properties of the obtained compound are as follows.

IR (KBr, cm ⁻¹ ): 3240 (NH), 1630 (CONH) NMR ^* (CDCl ₃ ) δ (ppm) 4.34 (2H, t, t, J = 2 Hz, 14 Hz: OC H ₂ CF ₂ ), 6.09 (1H, d, J = 10Hz: NHC H ), 7.10 (1H, d, J = 10Hz: benzene ring- H ), 7.14 (1H, d: J = 10HZ: NH ), 7.43 to 7.70 (2H, m) , benzene ring - H), 11.31 (1H, s, benzene ring -O H) synthesis example 4] N- [2,2,2-trichloro-1- (2,2,3,3,4,4, Synthesis of 4-heptafluorobutoxy) ethyl] -o-methoxyacetyl-5-chlorosalicylamide (Compound No. 11 in Table 1) N- [2,2,2-trichloro-1- (2,2,3,3 , 4,4,4-Heptafluorobutoxy) ethyl] -5-chlorosalicylamide (1.0 g, 0.002 mol) was dissolved in 20 ml of acetonitrile, and methoxyacetyl chloride (0.26 g, 0.0024 mol) was added thereto.
Mol), and triethylamine (0.
24 g (0.0024 mol) was added and reacted for 2 hours with stirring.

The resulting reaction solution was poured into ice water, and the oily substance that precipitated was extracted with chloroform. The chloroform layer was separated, dried over anhydrous sodium sulfate and concentrated to give a colorless oil.

This was purified by silica gel column chromatography (developing benzene: acetone 10: 1), and 0.74 g of a compound of Compound No. 11 having n _D ¹⁹ 1.4809 as a colorless oil (yield 64.
9%).

The physicochemical properties of the obtained compound are as follows.

IR (NaCl, cm ^-1 ): 3270 (NH), 1775 (OCO), 1665 (CO
NH) NMR ^* (CCl ₄ ) δ (ppm): 3.49 (3H, s, OC H ₃ ) 4.21 (2H, s: COC H ₂ ) 4.29 (2H, t, t, J = 2Hz, 13Hz: OC H _{2 CF 2) 5.99 (1H, d} , J = 10Hz: NHC H) 7.21 (1H, d: J = 9Hz: benzene ring - H) 7.42~7.74 (2H, m : benzene ring - H + N H) 7.90 ( 1H, d, J = 3 Hz: benzene ring- H ) [Synthesis example 5] N- [2,2,2-trichloro-1- (1,1,1,3,3,3-hexafluoroisopropoxy) ethyl]- o-acetyl-5
-Synthesis of chlorosalicylamide (Compound No. 14 in Table 1) N- (1,2,2,2-tetrachloroethyl) -o-acetyl-5-chlorosalicylamide 3.8 g (0.01 mol) was dissolved in 100 ml of benzene. Then, 2.01 g (0.012 mol) of 1,1,1,3,3,3-hexafluoro-2-propanol was added thereto, and then 1.2 g (0.012 mol) of triethylamine was added at room temperature and the reaction was continued for 1 hour with stirring. Let Triethylamine hydrochloride was filtered off from the obtained reaction solution, the benzene layer was washed with water, dried over anhydrous sodium sulfate, and benzene was distilled off under reduced pressure to obtain 4.79 g of a slightly brown oily substance.

This was solidified and recrystallized from 28 ml of n-hexane, melting point
The compound No. 14 having a temperature of 109 to 111 ° C. was obtained as white crystals (3.58 g, yield 70.2%).

The physicochemical properties of the obtained compound are as follows.

IR (KBr, cm ^-1 ): 3880 (NH), 1780 (OCO), 1665 (CON
H) NMR _* (CDCl ₃ ) δ (ppm): 2.38 (3H, s, COC
H ₃ ), 4.83 (1H, 7 lines, J = 6Hz: OC H (CF ₃ ) ₂ ), 6.28 (1H, d, J = 10Hz: NHC H ), 7.20 (1H, d, J = 9Hz: benzene Ring- H ), 7.61 (1H, d, d, J = 3Hz, 9Hz: benzene Ring- H ), 7.81 (1H, d, J = 10Hz: NH ), 7.99 (1H, d, J = 3Hz: Benzene Ring- H ) _* The NMR-related data in each of the above synthesis examples are shown below.

s ... single line, d ... double line, t ... triple line, m ... multiple line, J ... Coupling constant Next, the compound according to the present invention is used for controlling disease and field of agricultural crops by various plant pathogens. Explain the herbicidal effect against various weeds in paddy fields.

Each compound obtained as described above has a broad antibacterial spectrum against various plant pathogenic fungi, especially for the control of diseases of agricultural products such as citrus radish disease, tomato blight, kidney bean mildew, wheat powdery mildew and red rust. It shows an excellent bactericidal effect, and shows strong herbicidal activity against field mustard weeds such as wild mustard, Kosendan grass, Aoyu and paddy field weeds such as firefly and eel.

Hereinafter, formulation examples of the compound according to the present invention, and bactericidal effect against phytopathogenic fungi and herbicidal effect against weeds are shown by examples.

Incidentally, the formulation ratio of the compound according to the present invention, the compound as it is, or mixed with a carrier (diluent) in the form of powder, wettable powder, granules, emulsions or liquids as an agricultural and horticultural fungicide or herbicide. It can be used to advantage.

In addition, in using them, it is possible to ensure certain effects by appropriately adding auxiliary agents such as a spreading agent, an emulsifying agent, a wetting agent, and a fixing agent, if necessary.

Example 1 Formulation of powder: Part by weight The compound of the present invention (Compound No. 1) 3 Clay 40 Talc 57 is pulverized and mixed and used as a powder.

Example 2 Formulation of wettable powder: Part by weight Compound of the present invention (Compound No. 11) 50 Lignin sulfonate 5 Alkyl sulfonate 3 Diatomaceous earth 42 is ground and mixed to obtain a wettable powder, which is diluted with water before use.

Example 3 Formulation of granules: parts by weight Compound of the present invention (Compound No. 9) 5 Bentonite 43 Clay 45 Lignin sulfonate 7 is uniformly mixed and further kneaded by adding water, and processed into granules by an extrusion granulator. Dry to make granules.

Example 4 Formulation of emulsion: parts by weight Compound of the present invention (Compound No. 14) 30 Polyoxyethylene alkyl allyl ether 10 Polyoxyethylene sorbitan monolaurate 3 Xylene 57 is uniformly mixed and dissolved to prepare an emulsion.

Example 5 Kyu-ribe and disease control effect test Example of Kyuri leaf (cultivar; Sagamihanjiro, 1 sowing / pot, 3 pots / treatment group used) such as the second true leaf cultivated in a biscuit pot with a diameter of 10 cm A wettable powder form such as No. 2 was diluted and suspended in water to a predetermined concentration and sprayed in an amount of 5 ml per pot. After air drying the sprayed leaves,
A suspension of spores of Fusarium cinerea downy mildew collected from the diseased leaves was spray-inoculated, kept under high humidity conditions at 20 to 22 ° C for 24 hours, and then left in a greenhouse. On the 5th to 7th day after the inoculation, the post-sickness was investigated according to the following investigation criteria.

(Survey Criteria) Post-risk degree of disease 0 No disease 0.5 Disease area ratio less than 10% 1 Disease area ratio 10% to less than 20% 2 Disease area ratio 20% to less than 40% 3 Lesion area ratio 40% or more and less than 60% 4 Lesion area ratio 60% or more and less than 80% 5 Lesion area ratio 80% or more The results are shown in Table 2.

Example 6 Tomato late blight control effect test Tomato seedlings at the third true leaf stage cultivated in a biscuit pot with a diameter of 10 cm (cultivar; Shouju No. 2, 1 planting / pot, 3 pots / using treatment zone)
The water-dispersible powder as in Example 2 was diluted and suspended in water to a predetermined concentration and sprayed in an amount of 5 ml per pot. After air-drying the sprayed leaves, a suspension of tomato blight spores collected from scab was spray-inoculated, kept under high humidity conditions at 20-22 ° C for 24 hours, and then left in a greenhouse. On the 5th to 7th day after the inoculation, the sickness was investigated according to the following investigation criteria.

(Survey Criteria) Post-risk degree of disease 0 No disease 0.5 Disease area ratio less than 10% 1 Disease area ratio 10% to less than 20% 2 Disease area ratio 20% to less than 40% 3 Lesion area ratio 40% or more and less than 60% 4 Lesion area ratio 60% or more and less than 80% 5 Lesion area ratio 80% or more The results are shown in Table 3.

Example 7 Test for controlling green mold disease of kidney bean A predetermined concentration of the wettable powder form as in Example 2 was applied to the kidney bean leaves (variety: Honkin) at the time of the first true leaf cultivated in a clay pot with a diameter of 10 cm. Was diluted and suspended with water and sprayed in an amount of 5 ml per pot.
After air-drying the sprayed leaves, a circular slice (diameter 4 mm) of gray mold fungus-containing agar, which had been cultivated in advance for 30 days at 20 ° C using sugar-added potato decoction agar, was directly attached to the center of the leaf. 22 ° C
It was kept under high humidity conditions. On the third day after the inoculation, the lesion area was compared with the lesion area of the untreated plot, and the sickness was examined according to the following examination criteria.

(Survey Criteria) Post-sickness degree of disease 0 No disease 0.5 Diseased only under or near the agar containing inoculum 1 Disease area ratio less than 20% 2 Disease area ratio 20% or more and less than 40% 3 Lesion area ratio 40% or more and less than 60% 4 Lesion area ratio 60% or more and less than 80% 5 Lesion area ratio 80% or more The results are shown in Table 4.

Example 8 Wheat leaf rust control test A seedling wheat (variety: Norin 64, 16 / pot) seedlings at the time of the second true leaf grown in a biscuit pot with a diameter of 10 cm was prepared in the wettable powder form shown in Example 2. Dilute and suspend the product to the specified concentration with water and spray 5 ml /
It was sprayed in the proportion of pots. After air-drying the sprayed leaves, spray inoculate a suspension of wheat red rust fungal spores collected from scab leaves and inoculate for 20-23
It was kept under high humidity conditions at 24 ° C for 24 hours. Then, leave it in a glass greenhouse, and 7-10 days after inoculation, 10
The sickness of the book was investigated and the average sickness per leaf was shown.

(Survey Criteria) Post-risk degree of disease 0 No disease 0.5 Disease area ratio less than 10% 1 Disease area ratio 10% to less than 20% 2 Disease area ratio 20% to less than 40% 3 Lesion area ratio 40% or more and less than 60% 4 Lesion area ratio 60% or more and less than 80% 5 Lesion area ratio 80% or more The results are shown in Table 5.

Example 9 Wheat powdery mildew control effect test Example of seedling wheat in the second true leaf stage (cultivar; Norin 64, 16 / pot, 3 pots / treatment group used) cultivated in a biscuit pot with a diameter of 10 cm A wettable powder form such as No. 2 was diluted and suspended in water to a predetermined concentration and sprayed in an amount of 5 ml per pot. After air-drying the sprayed leaves, a suspension of wheat powdery mildew spores collected from the diseased leaves was spray-inoculated, kept under high humidity conditions at 20 to 24 ° C for 24 hours, and then left in a greenhouse. On the 9th to 11th day after the inoculation, the sickness was examined according to the following criteria.

(Survey Criteria) Post-risk degree of disease 0 No disease 0.5 Disease area ratio less than 10% 1 Disease area ratio 10% to less than 20% 2 Disease area ratio 20% to less than 40% 3 Lesion area ratio 40% or more and less than 60% 4 Lesion area ratio 60% or more and less than 80% 5 Lesion area ratio 80% or more The results are shown in Table 6.

Example 10 Test of herbicidal effect by foliar treatment Leaf mallow, Kosendangsa, wild mustard, Ebisugusa, Acacia catechu, Periwinkle, Bindweed, Enocorogusa, edible millet, and Japanese cedar (2 to 4 leaves for each test plant) ), The wettable powder as in Example 2 was prepared, and the drug solution of the test compound adjusted to a predetermined concentration was prepared.
The amount equivalent to 100g / 10a was sprayed.

14 days after spraying, weed effect was investigated according to the following criteria.

Survey criteria 0: No effect 1: 30% or less herbicidal effect 2: 31% to 50% herbicidal effect 3: 51% to 70% herbicidal effect 4: 71% to 90% herbicidal effect 5: 91% to 100 The results of the herbicidal effect of% are shown in Table 7.

Example 11 Wagner pots of 1 / 5000a filled with paddy soil, Novier,
Seedlings of firefly, herring mold, eel, and pearl oyster were mixed and sown in 1 cm of the soil surface layer, and after 3 days, 150 g / 10a equivalent amount of chemical solution (acetone solution) was added dropwise with a pipette and 14 days later. investigated. The results are shown in Table 8.

Claims (2)

[Claims] 1. A general formula (I) (In the formula, X represents a hydrogen atom or a chlorine atom, R represents a hexafluoroisopropyl group or a heptafluorobutyl group, and R ₁ represents a hydrogen atom, an acetyl group, a propionyl group, a methoxyacetyl group or a cyclopropylcarbonyl group. ) N- (1-fluorinated alkoxy-2,2,
2-Trichloroethyl) -substituted salicylamide derivative. 2. General formula (I) (In the formula, X represents a hydrogen atom or a chlorine atom, R represents a hexafluoroisopropyl group or a heptafluorobutyl group, and R ₁ represents a hydrogen atom, an acetyl group, a propionyl group, a methoxyacetyl group or a cyclopropylcarbonyl group. ) N- (1-fluorinated alkoxy-2,2,
Agricultural and horticultural fungicides and herbicides containing a 2-trichloroethyl) -substituted salicylamide derivative.