JPS6314763A - Novel n-(1-fluorinated alkoxy-2,2,2-trichloroethyl) substituted salicylamide derivative and agricultural and horticultural germicide and herbicide containing said derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X is H or Cl; R is hexafluoroisopropyl or heptafluoroethyl; R1 is H, acetyl, propionyl, me thoxyacetyl, etc.). EXAMPLE:N-[2,2,2-Trichloro-1-(2,2,3,3,4,4,4-heptafluorobutoxy)-ethyl]- 0-acetylsali cylamide. USE:An agricultural and horticultural germicide and herbicide, useful for downy mildew of cucumber, late blight of tomato, gray mold of kidney bean, etc., and capable of exhibiting a wide range of antimicrobial spectrum against various plant pathogenic germs and showing improved herbicidal activity against weeds in paddy field as well as upland field. PREPARATION:An N-(1,2,2,2-tetrachloroethyl)-0-acetyl-substituted salicylamide derivative expressed by formula II (R1 is COCH3), is reacted with a fluorinated alcohol in the presence of triethylamine in a solvent, e.g. benzene, etc., to afford the aimed compound expressed by formula I.

Description

[Detailed Description of the Invention] Industrial Benefits The present invention has excellent bactericidal properties that can be used to control various plant diseases, fungi, etc. on agricultural crops, etc. The present invention relates to a novel N-(l-fluorinated alkoxy-2,2,2-trichloroethyl)-substituted salicylamide derivative that exhibits herbicidal activity against various harmful weeds.

Compounds in which the substituent is an alkoxy group, a cycloalkoxy group, or a phenoxy group have been known as N-(1-substituted-2,2,2-)lichloroethyl) salicylamide derivatives. 1983-39040, JP-A-57-163354). Also, recently, Unexamined Japanese Patent Publication No. 61-6
No. 9751 discloses a salicylamide derivative having a trihalogenoalkoxy group as the above-mentioned substituent.

However, all of these known compounds have unsubstituted benzene rings. Incidentally, only a compound in which the fluorinated alkoxy group is a trifluoroethoxy group is disclosed as a compound in which the benzene ring is substituted (Japanese Patent Application Laid-open No. 69751/1983).

That is, the 0-acylated derivative of trifluoroethoxy group targeted by the present invention or the N-(1-fluorinated alkoxy-2,2°2-1-
(lichloroethyl)-substituted salicylamide derivatives are novel compounds that have not been described in any literature.

The present invention has a wide range of antibacterial spectra against various M (physical diseases) for the control of diseases such as small 7, agricultural 1, etc. The new N-(1-fluorinated alkoxy-2
, 2, 2, 1: ethyl)-substituted salicylamide derivatives.

The present invention will be explained in detail below.

N-(1-fluorinated alkoxy-2,2,
The 2-trichloroethyl)-substituted lilyamide derivative is characterized by being represented by the following general formula (1).

(In the formula, X represents a hydrogen atom or a chlorine atom, R represents a hexafluoroisoprobyl group, (or a heptafluorobutyl group, and ?1 represents a hydrogen atom, an acetyl group, a propionyl group, or a metho-1-cyano! Table 1 shows examples of the compound represented by the above general formula (1) and its physical and chemical properties.

- ``L↓ Scarcity'' with 1 eye J and 1-ru-muhikishi -
The compound according to the present invention represented by the general formula (1) is prepared as follows.

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

(In the formula, X, R, R,, have the same meanings as above.) That is, N-(1,2,
2,2-tetrachloroethyl)-〇-acetyl-substituted salicylamide derivative (R in formula (11), =C0CH3
Using 1 as a starting material, this is reacted in an organic solvent such as benzene in the presence of equimolar to slightly excess fluorinated alcohol and equimolar triethylamine at room temperature with stirring for 30 minutes to several hours. By doing this, we can easily formulate the general formula (
1) Target compound (R1=C0CI+31 in formula (1)
You can fl.

The target compound (1) obtained is separated and purified by silica gel color J, ri+:+-7l, etc. if it is in oily form, and recrystallized if it is in crystalline form. Purify by IU.

In addition, if a compound in which R1 in general formula (1) is a hydrogen atom is desired as the target compound, the acetylated product obtained by the method described in 1 above is heated under reflux with a small amount of concentrated hydrochloric acid in a solvent such as methanol for several hours. Further, if a compound in which R is an acyl derivative other than an acetyl group is desired, the above compound in which R is a hydrogen atom is added with acetonyl-II under cooling with ice water.
Add the desired acid chloride and 1-ethylamine in an organic solvent such as 3 molar to an molar excess of fvj,
Stir for 0 minutes to several hours to react-I! The desired acyl derivative can be easily prepared by using the following method.

Specific synthesis examples of the compounds according to the present invention are shown below.

[Synthesis Example 1] N-(1,2,2,2-tetrachloroethyl)-o-acetylsalicylamide5. Og (0,0145 mol) was dissolved in 100m it of benzene, and 1■, 1■-
Hebutafluorobutanol 3.47g (0,0174
mol) and then 1.70 g of triethylamine at room temperature.
(0,017 mol) was added and reacted with stirring for 1 hour.

Triethylamine hydrochloride was filtered from the resulting reaction solution, the benzene layer was washed with water, and dried over anhydrous sodium sulfate.
Benzene was distilled off under reduced pressure to obtain 7.0 g of a pale yellow oil.

Solidify this and add 45m of n-hexane 7! 3.9 g (yield: 53.4%) of compound No. 2 having a melting point of 82 to 4° C. was obtained as white crystals by recrystallization.

The physicochemical properties of the obtained compound are as follows.

IR(KBr,,cIll-'): 327
0 (Nll), 1750 (OCO), 1650 (C
ONI+) N M R” (CDCl2) δ (ppm) 2.
36 (3H,s: C0C1h), 4.33 (2+
1, tXt, J=211z, 1411z
: 0CHzCh), 6.10(III, d,
J=1011z: NIICH), 7.19-8.1
8 (511, m, benzene ring -〇+N1() [Synthesis Example 2] N-(2,2,2-) riff I:l I:]-1-(],
]i, 1.3,3.3-hexafluoroisopropoxyethyl)-o-acetylsalicylamide 3.2B(0,
00 (i7 mol) was dissolved in 30 ml of methanol, 0.2 mff 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 the precipitated white crystals were filtered off, thoroughly washed with water, and then dried.

Then, the dried product was converted into n-\,1-line:Hensen-5:I
Crystallized in a mixed solvent of 25 ta (!, melting point 142-4
2. Compound No. 5 having a temperature of 2.5°C as white crystals.
24 g (yield 77.2%) was obtained.

The physicochemical properties of the obtained compound are as follows.

IR (KBr, cm-'): 3270 (N
H), 1620 (CONH), NMR resource (CDCl
2) δ (ppm) 4.71 (1817 doublet, J = 6
Hz: OCH(CF3), 6.29(I
Hld, J=10Hz: NHCH), 6.8
8 to 7.84 (5■, -, benzene ring -H + N11),
11.12 (IH, s: benzene ring-01) [Synthesis example 3] 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 30 m 12 of methanol,
Add this to 0.2m7 of concentrated hydrochloric acid! was added and heated under reflux for 2.5 hours. After cooling, the reaction solution was poured into water, and the precipitated white crystals were filtered off, thoroughly washed with water, and then dried. Then, the dried product was
Recrystallized from 15III hexane, melting point 0:) ~ 5
1. Compound No. 8 having a temperature of 1.
115 g (yield 75.5%) was obtained.

The physicochemical rl'jt of the obtained compound is as follows.

IR (KBr, cm-'): 3240 (
Nll), 1630 (CONII) NMR Spicy (CI
ICI 3) δ (ppm) 4.34 (2111, L,
, J・-211z X141+2: 0CIlzCF
z), 6.09(III, d 8 J=H1lIz
: NIICII), 7.10 (Ill d
1. ■=・1OIIz: Benzene ring-1), 7.1
4(ill, d: J=lOllz: N-j
j), 7.43-7.70 (211, m, benzene ring-μ), 11.30111, S, benzene ring-0 river) [Synthesis Example 4] N-(2,2,2-trichloro-1 -(2, 2, 3, 3
,4,4,4-heptafluorobutoxy)ethyl]-5
-Chlorosalicylamide 1. Og (0,002 mol)
was dissolved in 20 tnl of acetonitrile, 0.26 g (0,0024 mol) of methoxyacetyl chloride was added thereto, and 0.2 g of triethylamine was added under cooling with ice water.
4 g (0,0024 mol) was added and reacted for 2 hours with stirring.

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

This was purified by silica gel column chromatography (developed with benzene:acetone 10:1), and n was 191.48.
0.74 g (yield: 64.9%) of compound number 11 having compound number 09 was obtained as a colorless oil.

The physicochemical properties of the obtained compound are as follows.

I R (NaC1, cm-'): 3270 (NH
), 1775 (OCO), 1665 (CONH) NMR” (CCI 4) δ (ppm)
: 3.49(3H,s,0CHa)4.21(
2+1, s: C0C4) 4.29 (2H1t,
L, J=211z, 1311z: 0ClhCF
z) 5.99 (III, d,, J-1011z:
NIICII) 7.20111, d: J=91
1z: benzene ring-1) 7.42 to 7.74 (21
1, m: benzene ring -H11) 7.90 (II
I, d,, J=311z: Benzene ring -I+ > [Synthesis Example 5] ■ Hill bottom N-(1,2,2,2-tetrachloryl)-o
-acety)le 5-chlorosalicylamyl' 3. h(
(1,01 mol) was dissolved in 100 mn of benzene, 2.02 g (0,012 mol) of 1.1,1,3.3.3-hexafluoro-2-propanol was added thereto, and the mixture was heated at room temperature. 1.2 g (0,012 mol) of triethylamine was added and reacted for 1 hour with JW stirring. From the obtained reaction solution, 1
- After separating the chloramine hydrochloride by filtration and washing the benzene layer with water, drying over anhydrous sodium sulfate, benzene was distilled off under reduced pressure to obtain 4.79 g of a slightly brown oil.

This was solidified and n-hexane 28% j! Compound No. 14 recrystallized from
3.58g of compound as white crystals (yield 70.2
%) was obtained.

The physicochemical properties of the obtained compound are as follows.

IR (KBr, cm-'): 3380 (N
H), 1780 (OCO), 1665 (CONH) N M R” (CDCl2) δ (ppm):
2.38 (3H,s, C0CHs), 4.83 (
IH, septet, J=6Hz: 0CH(Ch)t
), 6.28 (Ill, d, J=10Hz:
NHCH), 7.20 (IH, d, J-9Hz
: Benzene ring-1), 7.61 (IH, d, d
, J=3Hz, 9Hz: benzene ring-It)
, 7.81 (18, d, J=10Hz: NH)
, 7.99 (IH, d, J=3Hz: benzene ring -■) Mine The NMR data in each of the above synthesis examples are as follows.

s --- single line, d --- double line, t ---
---One triplet, fog---One--multiplet, J---
---Coupling constant Next, the effect of the compound according to the present invention on controlling diseases of agricultural crops caused by various plant pathogenic bacteria and the herbicidal effect on various weeds in fields and paddy fields will be explained.

Each of the compounds obtained as described above has a broad antibacterial spectrum against various plant pathogens, and is particularly effective against agricultural crops such as cucumber mildew, Phytophthora phytophthora, common bean gray mold, wheat powdery mildew, and rust. It exhibits an excellent bactericidal effect in controlling diseases, and also exhibits strong herbicidal properties against upland weeds such as wild mustard, 2L lentils, and green grass, as well as paddy weeds such as bulrushes and chinensis.

Examples of formulations of the compounds according to the present invention and their bactericidal effects against plant pathogens and herbicidal effects against weeds are shown below.

In addition, the compound according to the present invention can be formulated as a powder, wettable powder, granule, or mixed with a carrier (diluent).
It can be advantageously used as an agricultural and horticultural fungicide or herbicide in the form of an emulsion or liquid.

Furthermore, when using them, it is possible to ensure their effectiveness by appropriately adding auxiliary agents such as spreading agents, emulsifiers, wetting agents, and fixing agents as necessary.

Example 1 Formulation of powder: Parts by weight Compound of the present invention (Compound No. 1) 3 Clay
40 talc
57 was ground and mixed and used as powder.

Example 2 Formulation of wettable powder: Parts by weight Compound of the present invention (compound number 11) 50 Lignin sulfonate 5 Alkyl sulfonate 3 Diatomaceous earth
42 is pulverized and mixed to make a wettable powder, which is diluted with water and used.

Example 3 Preparation of granules: Parts by weight Compound of the present invention (compound number 9) 5 Bentonite 43 Clay 45 Lignosulfonate 7 were mixed uniformly, water was added, kneaded, and processed into granules using an extrusion granulator. Dry to make granules.

Example 4 Formulation of emulsion: Parts by weight Compound of the present invention (compound number + 4) 30 Polyoxyethylene ethylene gamma-ruyl ether
IO polyoxyethylene sorbitan monolaurate 3xylene
57 is uniformly mixed and dissolved to form an emulsion.

Example 5 Cucumber leaves and disease control effect test Cucumber leaves at the second true leaf stage (cultivar;
A wettable powder as in Example 2 was diluted and suspended in water to a predetermined concentration and sprayed at 5 mJ per pot (Sumo Hanshiro, 1 sown/pot, 3 pots/treated area used). After spraying leaves, a suspension of cucumber and disease fungus spores collected from diseased leaves was sprayed and inoculated.
It was kept under high humidity conditions of 20 to 22°C for 24 hours, and then left in a greenhouse. Five to seven days after inoculation, the disease severity was investigated according to the following investigation criteria.

(Survey group 1 disease severity: 0) No symptoms: 0.5: Lesion area ratio: less than 10%: 1: Lesion area ratio: 10% or more and less than 20%: 2: Lesion area ratio: 20% or more and less than 40% Item 3: Lesion area rate: 40%
Less than 160% 4 Lesion area rate 60% or more 8
Less than 0% 5 Lesion area ratio 80% or more The results are shown in Table 2-1.

Table 2 Example 6 Tomato seedlings (cultivar: Fukuju No. 2, 1 plant/pot, 3 pots/treatment area used) grown using unglazed ceramic bodies with a diameter of 10 cn+ A wettable powder as in Example 2 was diluted and suspended in water to a predetermined concentration and sprayed at 5 mJ per pot.After spraying, a suspension of tomato Phytophthora spores collected from blighted leaves was spray inoculated. , kept at 20-22℃ under high humidity conditions for 24 hours,
After that, it was left in the greenhouse. Five to seven days after inoculation, the disease severity was investigated according to the following investigation criteria.

(Survey criteria) Disease severity: 0 No symptoms: 0.5 Lesion area rate: less than 10% 1: Lesion area rate: 10% or more and less than 20% 2: Lesion area rate: 20% or more and less than 40% Item 3: Lesion area rate: 40%
60% or more 4 Lesion area rate 60% or more 8
Less than 0% 5 Lesion area ratio 80% or more The results are shown in Table 3.

Table 3 Example 7 Green bean gray mold control effect test diameter 10cn
Green bean leaves at the first leaf stage grown using + unglazed pottery (
A wettable powder as in Example 2 was diluted and suspended in water to a predetermined concentration, and sprayed at 5 ml per pot. After spraying the leaves, a circular section (diameter 4 mm) of agar agar containing botrytis, which had been cultured in advance at 20"C for 3 days on a sugar-added potato decoction agar medium, was placed directly on the center of the leaf (=J Se,
It was maintained at 20-22°C under high humidity conditions. 311 L after inoculation
Compare the lesion area in the untreated plot to the next survey), 5'
The degree of disease was investigated by ci&.

(Survey criteria) Disease severity: 0 No symptoms: 0.5 Diseases developed only directly under or around the inoculum agar 1: Lesion area ratio less than 20% 2: Lesion area ratio 20% or more but less than 40% thing 3
Lesion area ratio of 40% or more and less than 60% 4 Lesion area ratio of 60% or more and less than 80% 5 Lesion area ratio of 80% or more The results are shown in Table 4.

Table 4 Example 8 Wheat rust control test using a clay pot with a diameter of 10 cm! (Example 2 on young wheat (variety: Norin No. 64, tri tree/pot) at the second leaf stage of cultivation.
The wettable powder shown in 1 was diluted and suspended in water to a predetermined concentration and sprayed at a rate of 5 mL/pot. After spraying the leaves, the leaves were spray-inoculated with a suspension of summer spores of wheat rust, which were collected from rotten leaves, and kept under high humidity conditions at 20-23°C for 24 hours.

After that, it was left in a glass greenhouse, and 7 to 10 days after inoculation, the disease severity was investigated on 10 plants according to the following investigation criteria.
The average disease severity per leaf is shown.

(Survey criteria) Disease severity: 0.5 with no disease; 0.5 with a lesion area rate of less than 10%; ■ with a lesion area rate of 10% or more and less than 20%; 2 with a lesion area rate of 20% or more and less than 40%. Item 3: Lesion area rate: 40%
60% or more 4 Lesion area rate 60% or more 8
Less than 0% 5 Lesion area ratio 80% or more The results are shown in Table 5.

Table 5 Example 9 Wheat powdery mildew control effect test Using a clay pot with a diameter of 10 cm, young wheat seedlings of the second true leaf (cultivated) (variety;
A wettable powder as in Example 2 was diluted and suspended with water to a predetermined concentration in (Agricultural and Forestry 64 month, lfi tree/pot, 3 pots/treated area used) and 5+nj per pot! Spread. After spraying the leaves, the plants were inoculated by spraying with a suspension of powdery mildew spores collected from the rotten leaves, kept under high humidity conditions of 20-24°C for 24 hours, and then left in a greenhouse. The disease severity was investigated on the 9th to 11th day after inoculation according to the following investigation criteria.

(Survey criteria) Disease severity: 0 No symptoms: 0.5 Lesion area rate: less than 10% ■ Lesion area rate: 10% or more and less than 20% 2 Lesion area rate: 20% or more and less than 40% Item 3: Lesion area rate: 40%
60% or more 4 Lesion area rate 60% or more 8
Less than 0% 5 Lesion area ratio 80% or more The results are shown in Table 6.

Table 6 Example 10 Test of herbicidal effect by foliage treatment Growth in pots - I-grown blue beetle '11', Japanese sagebrush, wild mustard, Ebisu grass, Japanese brilliance, Japanese convolvulus, European bindweed, Japanese foxtail, edible violet, and blackberry (2000 for each test plant) A hydrating agent as in Example 2 was prepared and a chemical solution of the test compound adjusted to a predetermined concentration was applied to the stems and leaves of the leaves (at the time of 4 leaves).
An amount equivalent to 0g/10a was sprayed.

Fourteen days after spraying, the herbicidal effect was investigated using the following criteria.

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

Example 11 A 115,000a Wagner pot was filled with paddy soil, and each seed of Japanese grasshopper, firefly, Helaomodaka, Konagi, and Cyperus cyperus was mixed and sown in the soil surface layer ICl11, and 3rd seed transfer 1
A chemical solution (acetone solution) in an amount equivalent to 50 g/lOa was dropped with a pipette, and the degree of transplantation on the 14th day was investigated using the investigation criteria of Example 10. The results are shown in Table 8.

Claims (2)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(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)
2,2,2-trichloroethyl) substituted salicylamide derivatives. (2) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents a hydrogen atom or a chlorine atom, R represents a hexafluoroisopropyl group or a heptafluorobutyl group, R_1 represents a hydrogen atom, an acetyl group, a propionyl group, a methoxyacetyl group, or a cyclopropylcarbonyl group)
An agricultural and horticultural fungicide and herbicide containing a 2,2,2-trichloroethyl)-substituted salicylamide derivative.