JPS6368503A - Agricultural and horticultural germicide containing fluorine - Google Patents

Abstract

PURPOSE:The titled germicide, containing a trifluoroacetaldehyde phenylhydrazone derivative as an active ingredient, having high antimicrobial activity against phycomycetes, ascomycetes, basidiomycetes, etc., without phytotoxicity to crops and capable of exhibiting effects even on resistant germs. CONSTITUTION:An agricultural and horticultural germicide containing a compound expressed by the formula (R1-R5 are H, lower alkyl, halogen, nitro or lower alkoxy). The germicide is capable of protecting crops from blights caused by molds and usable in various forms of wettable powder, emulsion, dust, granule, suspension pharmaceuticals, etc. The application amount thereof expressed in terms of the active ingredient is preferably 50-200g/10a in the case of a foliar spraying agent or 500-2,000g/10a in the case of soil treatment and the germicide is used by adjusting the active ingredient content to 1-50wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a complete set of agents for protecting crops from diseases caused by filamentous fungi, which are a widespread problem in agriculture and horticulture.

(Problems to be Solved by the Invention) Today's agriculture ensures high productivity through fertilizers, pesticides, and various agricultural materials. On the other hand, the emergence of resistant bacteria due to the continuous use of pesticides and soil diseases caused by the repeated cultivation of a single crop in an area are becoming major problems. Under these circumstances, the development of novel and highly safe drugs is strongly desired, and the present invention provides one means for achieving this.

(Means for Solving the Problems) The fungicide according to the present invention has a growth inhibiting effect and a bactericidal effect on algae, ascomycetes, and basidiomycetes.

The trichloroacetaldehyde phenylhydrazone derivative according to the present invention can be easily synthesized by a dehydration reaction or dealcoholization reaction between a known aldehyde or aldehyde derivative such as hemiacetal and unsubstituted or substituted phenylhydrazine.

Synthesis example (compound 8) 3.5-dichlorophenylhydrazine hydrochloride 2.1f (
α01-) and trifluoroacetaldehyde hemiacetal 2.9F (102moz) '1t ethanol2
0 sd, and concentrated hydrochloric acid (Li2-) was added dropwise. After flowing rapidly for 2 hours, it was cooled to room temperature, poured into 200 ml of water, and the precipitated oil was extracted with 100 ml of toluene.

Next, the solvent was distilled off from the organic layer dried over anhydrous sodium sulfate, and oily trifluoroacetaldehyde was obtained.
．． 2.32 of 5-dichlorophenylhydrazone was obtained.

Engineering R (Neat): 3300.1590110-N
MR (OD(24): TM8 standard (pPm) 0-1
: 144.3 (!1) a-2, O-6: 111B ((1) 0-3, C-5: 135.6 (13) 0-4: 121.7 ((1) 0-7
: 12 (15(d), 125.3(d), 125.8(
(1) 12a5(d) 0-8:957(8), 11t7(8), 129.6c
8>, 147.7<8) Reference value: Jc, -269,8- Cholera, trifluorophenylhydrazone derivatives are novel compounds and have high antibacterial activity.

Typical compounds according to the present invention are shown in Table 1 below.

Table 1 Compounds Structural formula Melting point ■ Engineering J, (c, -
1) 10F, (H=NNH@Oll 5
300 1600 112020F, 0H-Nu pass'
Ol, 3340141゜1,3゜3 0F, OH eyes NNH Dr oil 3510 1600
112540F, CH,, NN heart O1l 33201
59011205 C! F, 0H=NNHhaO1l 5
300159011256 (!F'3(!IZ=
NNH((Σ)-ot J3-45 5510
1590 1125 (nujol) 70F, 0H=NH
To H0115310160011209 0B', 0
H-NNshi(〉OHs 81-63 3280 1
+510 1150 (nujol)10 C! FsC
H-NNH Two No. 22 City Q06 3230 1580
1130(nujol)11 0FsOH-NNt(
)-QC! H18248! +300 1610 112
0 (nuJOl) When using the compound according to the present invention as a fungicide, the compound is mixed with various carriers using common agrochemical formulation techniques to form an aquarium, emulsion, powder, etc.
It can be used in various forms such as granules and suspension preparations. Among the carriers, a common organic solvent is used as a liquid carrier, and a common clay mineral, pumice, etc. are used as a solid carrier. Additionally, a surfactant can be added to impart emulsifying properties, dispersibility, spreading properties, etc. during formulation. Furthermore, it can also be used in combination with agricultural chemicals such as fertilizers, insecticides, and fungicides.

In order to use it as a fungicide, it is necessary to apply it sufficiently to achieve the desired effect due to its active ingredients. In the case of a foliar spray, the application rate is within the range of 10 to 1000 r/10a, but generally 50 to 200 F7
10a is appropriate, 500-200 for soil treatment
02/10a is suitable. The content of active ingredients is 1 to 5.
It is used in the form of an aqueous solution, an emulsion, a powder, a granule, or a suspension preparation.

To make an emulsion, the active ingredient (z ff14) is dissolved in a commercially acceptable organic solvent and a solvent-soluble emulsion is added. Suitable solvents include xylene, 0-chlorotoluene, cyclohexanone, isophorone, dimethylformamide, dimethyl sulfoxide. Or a mixture of these.

The surfactant used as an emulsifier accounts for 1 to 20% by weight of the emulsion and may be anionic, cationic, or nonionic. Examples of anionic surfactants include alkyl sulfate esters, alkyldiphenyl ether disulfonates, naphthalene methanesulfonates, lignosulfonates, alkylsulfosuccinates [1], alkylbenzenesulfonates, and alkyl phosphates.

Examples of cationic surfactants include alkylamine salts and quaternary ammonium salts. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, nrubitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester,
Examples include polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, and polyoxyethylene fatty acid ester. The concentration of the active ingredient is suitably in the range of 10 to 70% by weight, preferably 25 to 50% by weight.

Aqueous preparations are formulated by adding the active ingredient to an inert finely divided solid carrier and a surfactant. Generally, the active ingredient is mixed in an amount of 10 to 70% by weight, and the surfactant is mixed in an amount of 1 to 20% by weight.

Solid carriers commonly used for formulating the active ingredients are naturally occurring clays, silicates, silicas, and alkaline earth metal carbonates. Typical examples of these are kaolin, dicrite, talc, diatomaceous earth, magnesium carbonate, calcium carbonate, dolomite, and the like. Generally used emulsifiers, spreading agents, and dispersants include anionic surfactants, nonionic surfactants, or mixtures of these.
The surfactants used are the same as those listed above for use in emulsions.

Powders are prepared by combining the active ingredient with inert carriers customary for the manufacture of powders, such as Merck, micronized clay, phyllite, diatomaceous earth, magnesium carbonate, and the like. The concentration of the active ingredient is preferably 0.5 to 20% by weight, particularly 2 to 10% by weight.

Granules are produced in a granulator by mixing the active ingredient with an inert finely divided carrier, such as bentonite, kaolin clay, diatomaceous earth or Merck, and kneading with water. Alternatively, if the active ingredient is in the form of an oil, use a granular carrier that has been granulated in advance and has a particle size range of, for example, 15 to 30 mesh, or a granular mineral that has been crushed with natural pumice, acid clay, or zeolite and has an adjusted particle size range. Or attach it together with a dispersant. If the active ingredient is solid, it can be prepared by adhering it in a state dissolved in an organic solvent or in a state in which a spreading agent or a dispersing agent is further added. The active ingredient of such granules is (L5 to 20% by weight, preferably 2 to 10% by weight).

Suspended formulations are mainly used when the active ingredient is solid, and are prepared by pulverizing the active ingredient and mixing it with a surfactant and water. The surfactants used here include any of the anionic surfactants, cationic surfactants, and nonionic surfactants mentioned above for use in emulsions, either alone or in combination. The amount used is generally 1 to 20% in the mixture. Active ingredient Fi10~
A range of 70% i lid part, preferably 25 to 50% weight f part is suitable.

Emulsifiers, wettable powders, and saponifying agents are mainly used as foliage sprays and soil irrigation agents, and powders and granules are mainly used as soil admixtures.

(Example) Specific examples regarding the preparation of the present invention agent are shown below.
Note that "section" means "heavy IT section."

Example 1 (Emulsion) Compound vlJ4 2 30 parts xylene 55 parts cyclohexanone 10 parts Lupol 800
(Trademark of Toho Chemical Co., Ltd.) 5 parts or more were uniformly mixed and dissolved to obtain an emulsion of the present invention.

Example 2 (Irrigation agent) Compound/% 6 50 parts Kaolin clay 42 parts Tsurupol 50
59 Part 5 Crane Pole 5060
At least 5 parts were mixed and ground to obtain an irrigation agent of the present invention.

Example 3 (Powder) 5 parts of Compound 43 and 95 parts or more of kaolin clay were mixed to obtain a powder of the present invention.

Example 4 (Granules) Compound 4 8 10 parts Granular acid clay 90 parts An active ingredient was adhered to granular acid clay to obtain granules of the present invention.

Example 5 (suspended formulation) Compound/1610 20 parts ethylene glycol 5 parts Tsurpol 5
078 (Toho Chemical Trademark) 5th part Tsurupol 7512 (Toho Chemical Trademark) α
5 parts water
69.5 parts or more were uniformly mixed and ground to obtain a suspended preparation of the present invention.

The growth-inhibiting effect and disease-preventing effect of the drug of the present invention on typical filamentous fungi and bacteria will be shown below using test examples.

Test Example 1 Direct Antibacterial Power A potato dextrose agar medium (PDM medium) and a dimethyl sulfoxide solution of the compound were mixed in a Petri dish with a diameter of 9 am, and a plate was prepared at a predetermined concentration. On this agar, punch out mycelial masses that had been grown in PD medium in advance into 4-diameter pieces.
m) for 2 days, and 7 for Pusarium oxysporum (Pusarium oxysporum) for 5 days.
Rhizoctonia solani (Rh1zoatonia 1)
olani) was cultured at 25° C. for 3 days, and the colony diameter was compared with the colony diameter without the addition of the drug to calculate the growth inhibition rate. The average of the results is shown in Table 2.

Table 2 Bacterial species Bicillum 7 Zalium Rhizoctonia concentration (I) pm) 100 10 5 100
10 5 100 10 5 Compound 1 Free rot test example 2 Drug-resistant gray mold (Botrytis ci
According to Direct Antibacterial Activity Test Example 1 against Streptococcus nerea), a benzimidazole fungicide-resistant strain (R strain), a benzimidazole-based fungicide-resistant strain (RR strain), and a susceptible strain were grown in PDA medium according to Example 1. Antibacterial activity against strains (8 strains) was examined. The culture conditions were a PDmu medium for 25C1s days, and the colony diameter was compared with that without any drug added, and the growth inhibition rate was calculated. The average of the results is shown in Table 3. Note that a control drug was also tested in the same manner.

Rumors Hero
A-~ Rent B
hu”+ ao c
o w o.

To 0+ To
Dude! q+ts Saltwater Rumor - Test Example 3 Control of Botrytis Botrytis A 150-meter resin container with a depth of 7 tx was filled with 500 m of field soil, and cucumber (fork No. 1) seeds were sown in bottlings. When the cotyledons developed, a 2000-fold diluted solution of each compound water agent according to Example 2 was sprayed 5 times per pot. After the spray solution on the leaves had dried, a suspension of spores of Botrytis spp. was attached to a piece of circular paper with a diameter of 8 square centimeters, and the paper was stretched with the attached side facing down. The mice were placed in a biotron at 25° C. and 80% humidity, and the onset of disease was investigated after 5 days. The test was performed in two replicates. The results are shown in Table 4.

, Table 4 Compound layer Number of diseased strains Drug damage 2 0/6 o15 &gmezu 5
': V6 0/6 Not approved 5 V60
/6 Not approved 6 V6O13g rare 7 V60/6 Not approved 8'
Ps O/s gmezu9 1/6 a
/6 Not recognized 1o V6 '/6
g Mezu untreated V65/l Not recognized (Effect of the invention) As described above, the compound according to the present invention has high antibacterial activity against algae, ascomycetes, and basidiomycetes, and is resistant to existing fungicides. It is equally effective against sensitive bacterial strains as it is against sensitive bacterial strains. At the same time, it has excellent bactericidal activity with almost no phytotoxicity to crops.

Hodogaya Chemical Industry Co., Ltd.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1, R_2, R_3, R_4, and R_5 represent hydrogen, lower alkyl, halogen, nitro, or lower alkoxy group.) An agricultural and horticultural fungicide containing a trifluoroacetaldehyde phenylhydrazone derivative represented by the following as an active ingredient.