JPS63264449A - Agricultural and horticultural germicide - Google Patents

Abstract

PURPOSE:To obtain an agricultural and horticultural germicide, containing an iodopropargylcarbamate derivative as an active ingredient and capable of exhibiting excellent effects on phycomycetes, such as downy mildew or late blight, and other various blights. CONSTITUTION:A carbamate derivative expressed by the formula (n is 1-5; X is H, halogen or lower alkyl; R<1> and R<2> are H or methyl) is mixed with a normally used carrier and converted into a pharmaceutical by a conventional method to afford the aimed substance. The content of the compound which is the active ingredient in the pharmaceutical is preferably 1-90% and can be prepared in the form of wettable powder, suspension, dust, liquid formulation, etc. The application amount is normally preferably 1-100g per are and used in farmland, paddy field, orchard, tea garden, pasture, lawn, etc. The compound expressed by the formula is obtained by reacting a phenyl isocyanate derivative with an iodopropargyl alcohol derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application in the Pharmaceutical Industry The present invention relates to a fungicide for agricultural use containing an iodopropargyl carbamate derivative as an active ingredient.

<Prior art> Up until now, dithiocarbamate compounds such as mancozeb and maneb, and phthalide compounds such as cabtan and difortan have been well known as agricultural and horticultural fungicides having a wide range of antibacterial activity. Although it is described that it has activity against algae, there is no mention of its bactericidal activity for agricultural and horticultural purposes.

<Problems to be solved by the invention> However, although agricultural and horticultural fungicides such as mancozeb, maneb, cabtan, and difortan have a wide range of antifungal activity, they do not have practical control effects against all diseases. In addition, the amount used is 1 to 2 kg of raw material.
/ A3 cannot be expected to be sufficiently effective unless a very large amount is used, so it cannot be said that it is necessarily fully satisfactory as a fungicide for agriculture and horticulture.

<Means for Solving the Problems> In view of the above circumstances, the present inventors sought to develop an excellent agricultural and horticultural fungicide.As a result of various studies, the iodopropargyl carbamate derivative described in the present invention , with few problems as mentioned above [where n represents an integer from 1 to 5,
X's are the same or different and represent a hydrogen atom, a halogen atom or a lower alkyl group, and R1 and R1 are the same or different and represent a hydrogen atom or a methyl group. ] The present invention provides an agricultural and horticultural fungicide characterized by containing a carbamate derivative represented by the following as an active ingredient.

Next, the present invention will be explained in more detail. General formula [! The carbamate derivative represented by, for example, the general formula [where n represents an integer of 1 to 5, and X's are the same or different and represent a hydrogen atom, a halogen atom, or a lower alkyl group. ] By reacting the phenyl isocyanate derivative shown with the toiodopropargyl alcohol derivative,
can be manufactured. This reaction can be carried out using, for example, toluene,
In #I medium such as aromatic hydrocarbons such as benzene, ethers such as diethyl ether and tetrahydrofuran, and halogenated hydrocarbons such as chloroform and dichloromethane,
It can be carried out at room temperature to 100'C, + Shun hours for 12 hours.

Moreover, the reaction can also be carried out using an octagrade amine such as pyridine or triethylamine as a reaction catalyst.

Plant diseases that can be controlled by the fungicide of the present invention include downy mildew (Peronos) of canola and radish crops.
pora brassicae), downy mildew of spinach (Peronospora 5pinacae)
, tobacco mildew (Peronospora tab
acina), cucumber downy mildew (Pseudop
eronospora cubensis), grape downy mildew (Plasmopara vi ticola)
), downy mildew of Apiaceae plants (Plasmoparan
Phytophthora cacto-rum), apple, strawberry, and ginseng blight (Phytophthora cacto-rum)
, gray late blight of tomatoes and cucumbers (Phytoph-t
hora capsici), pineapple blight (
Phytophthora cinnamomi)
, late blight of potatoes, tomatoes, and eggplants (Phytopht
hora 1nfestans), tobacco, fava beans,
Late blight of green onion (Phytophthoranicotia)
nae Var, n1cotianae), spinach damping-off (Pythium sp, ) cucumber seedling damping-off (Pythium aphaniderma)
tum), :I Wheat brown snow rot (Pythium
sp, ), tobacco seedling damping-off (Pythiumd sp.
ebaryanum), soybean Pythium R
ot (Pythiumaphanidermatum
%P, debaryanum, P, irreg
ul-are 1P, myriotylum, P,
ultimum ) Rice blast disease (Pyric
u! aria oryzae), sesame leaf blight (Co
chl 1obolus mlyabeanus)
, apple scab (Venturia 1naequa)
lis), leaf rot (Valsamali), leaf spot (Alternaria mali), black spot of pear (Alternaria Kikuchiana)
, Venturia nashicola
, citrus black spot (Diaporthe citr)
i), green mold (Penicillium digi)
tatum), blue mold (Penicillium
itali-cum), Phomopsis”pl of peach, anthracnose of oyster (Glo
eosporium <aki).

Leaf fall disease (Cercospora kaki, Myc
osphaerella nawae), grape late rot (Glomerella cingula-ta), gray mold (Botrytis cinerea),
Spotted leaf disease of wheat (Helminthosporium g.
ramineum), naked smut (Ustilago
nuda), leaf blight (Septoriatritic
i), Leptosphaeria nod
orum), Pseudocercospo
Rella herpotrichoides), powdery mildew (Er, ysiphe graminis)
, Rust (Puccinia graminis, P
, striiformis, P. reco-ndi
ta), anthracnose disease of cucurbits (Colletotrichu
mlagenarium), vine blight (Mycos
phaerella me-1onis), powdery mildew (Sphaerotheca fuliginea)
).

Tomato ring spot disease (Alternaria 5olani)
), Tobacco Akaboshi (Alternaria lo)
ngipes), anthracnose (Colletotrich
um tabacum), brown spot of sugar beet (Ce
rcospora beticola), summer blight of potatoes (Alternaria 5olani),
Groundnut brown spot (Cercospora arac)
hidicola), soybean brown spot disease (Sept.
ria glycines), black spot (Diapor
the phaseolum), anthracnose (Coll
etotrichum sp, ), purpura (Cer
cospora kilkhii).

Although the agricultural and horticultural fungicides of the present invention can be used as active ingredients alone, they are usually mixed with solid carriers, limb carriers, surfactants, and other formulation auxiliaries to form emulsions, wettable powders, and suspensions. , powder, ff agent, etc. In this case, the active ingredient content of the active ingredient compound in the formulation is 0.1 to 99.
9 inches, preferably 1 to 90 inches.

The solid carrier mentioned above is kaolin clay.

attapulgite clay, bentonite, acid clay,
Examples include fine powders or granules such as pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide.
Examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile, Examples include water. Emulsification.

Surfactants used for dispersion, wet carbon, etc.
Anionic surfactants such as alkyl sulfate salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, phosphoryoxyethylene alkylaryl ether phosphate salts, naphthalene sulfonic acid formalin combinations, and polyoxyethylene alkyl ethers.

Examples include nonionic surfactants such as polyoxyethylene polyoxybrobylene block copolymer 1, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Formulation auxiliaries include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, and CMC (carboxymethyl cellulose).

Examples include PAP (isopropyl acid phosphate).

Examples of methods for applying the agricultural and horticultural fungicide of the present invention include:
Examples include spraying on grass, soil treatment, seed disinfection, etc., but any application method commonly used by those skilled in the art will be sufficiently effective. The application amount of the active ingredient of the agricultural and horticultural fungicide of the present invention varies depending on the target crop, target disease, degree of disease occurrence, formulation form, application method, application time, weather conditions, etc., but is usually 0.5 per are. ~200, preferably 1-100
y, and when applying emulsions, wettable powders, suspensions, solutions, etc. diluted with water, the application concentration is 0.005 to 0.5.
11 is preferably 0.01 to 0.2%, and powders, granules, etc. are applied as they are without any dilution.

Furthermore, the agricultural and horticultural fungicide of the present invention can be used in fields, paddy fields, orchards, tea gardens, pastures, lawns, etc., and can be used in combination with other plant disease control agents to enhance bactericidal efficacy. You can also expect

Furthermore, it can also be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth regulators, and fertilizers.

<Effects of the Invention> The compound of the present invention not only has excellent effects against plant diseases caused by algae and fungi such as downy mildew and late blight, but also has excellent effects against various diseases. It can be used in many applications as a very useful agricultural and horticultural fungicide.

<Example> Next, the present invention will be explained in more detail with reference to production examples, formulation examples, and test examples.

Production Example 3 - Phenyl isocyanate 1.2S' (10 mmol) was added to a dry tetrahydrofuran solution (80 txl) containing drops of iodopropargyl alcohol 1.81i (10 mmol) and triethylamine, and the mixture was stirred at room temperature for 12 hours. . The solvent was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate to give 3-iodopropargyl N-
1.5y of phenyl carbamate was obtained.

mp145-146°C Some of the compounds that can be produced by such a production method are shown in Table 1.

Table 1 general formula Examples of formulations are shown below. Note that parts represent parts by weight.

Formulation Example 1 50 parts each of compounds (1) to (c), 8 parts of calcium lignin sulfonate, sodium lauryl sulfate sulfur, 2 parts of acid, and 46 parts of synthetic hydrous silicon oxide were thoroughly ground and mixed to form hydrated compounds of the present invention. get the agent.

Formulation Example 2 Compounds (25 parts each of υ~■, 3 parts of polyoxyethylene sorbicun monooleate 3CMC, and 69 parts of water were mixed and wet-pulverized until the particle size of the active ingredient became 5 microns or less. to obtain a suspension of

Formulation Example 8 2 parts of each of Compounds (1) to 88 parts of kaolin clay and 10 parts of talc are thoroughly ground and combined for 8 f to obtain each powder of the present invention.

Formulation Example 4 Compounds (1) to @2 each (1,<, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 60 parts of xylene)
These are mixed to obtain each emulsion of the present invention.

Formulation Example 6 2 parts each of compounds (1) to (c), synthetic hydrated silicon oxide ti
, 2 parts of tJ calcium geninsulfonate, 80 parts of night and 65 parts of kaolin clay were thoroughly ground and mixed,
After adding water and kneading well, the mixture is powdered and dried to obtain each powder of the present invention.

Test example> Next, a test example of the agricultural and horticultural fungicide of the present invention will be shown.

The test compounds are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 Control efficacy is determined by visual observation of the disease state of the test plants during oral inspection, i.e., the degree of bacterial flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, it is rated "5". , if about 10 pieces are recognized, it will be 4J, if about 80 pieces are recognized, it will be r8J, if about 50 pieces are recognized, it will be (-24, 70 copies, if about 6 pieces are recognized, it will be 1
'', and if there is no difference from the disease onset state when no compound is tested, it is evaluated as ``0'' and evaluated on a 6-level scale, each marked as 5, 4, 8, 2, and 1°0. - Test Example 1 - Potato Phytophthora Phytophthora prevention test (preventive effect) A plastic pot was filled with sandy loam, potatoes (Danshaku) were heated to +i4, and grown in a greenhouse for 20 days. after that,
A test drug made into a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed on foliage so as to sufficiently adhere to the leaf surface. After spraying, a spore suspension of Potato Phytophthora was sprayed and inoculated. After growing in one apparatus at 20° C. and high humidity, the plants were grown for 5 days under lighting, and the pesticidal efficacy was investigated. The results are shown in Table 3.

@Table 3 Test Example 2 Grape vine disease control test (preventive effect) A plastic pot was filled with sandy loam, grapes were sown, and grown in a greenhouse for 50 days. The test drug prepared as a hydrating powder according to Formulation Example 1 is diluted with water to a specified concentration, and sprayed on the foliage of grape seedlings that have developed their 5th to 6th true leaves, making sure to sufficiently adhere to the leaf surface. did. After spraying, a spore suspension of grapevine and diseased bacteria was sprayed and inoculated. After electrode application, the plants were kept at 20° C. and high humidity for 10 days, and then kept alive for 8 days under lighting to evaluate their pesticidal efficacy.

The results are shown in Table 4.

Test Example 8 Wheat eye spot disease control test (preventive effect) Plastic pots were filled with sandy loam soil, wheat (Norin No. 78) was sown, and wheat seedlings were grown for 10 days in a greenhouse. The test chemical was made into a wettable powder, diluted with water to a predetermined concentration, and sprayed on the foliage to ensure sufficient adhesion to the leaf surface. After spraying, the plants were air-dried and then sprayed and inoculated with a spore suspension of Eyespot Disease. After inoculation, incubate at 15°C in the dark and humid environment for 4 days.
After being exposed to the apparatus for 4 days, the insects were left to survive for 4 days under light and high humidity to investigate their pesticidal efficacy. The results are shown in Table 5.

Table 5 Test Example 4 Apple Scotch Disease Control Test (Preventive Effect) Plastic pots were filled with sandy loam, apples were sown, and grown in a greenhouse for 20 days. A test drug prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined eL degree on a young apple seedling that had developed its 4th to 6th true leaves, and the mixture was applied to the stems and leaves so that it fully adhered to the leaf surface. Spread. After spraying, a spore suspension of apple scab fungus was injected and inoculated. After inoculation, the seeds were grown for 4 times at 15° C. under high humidity, and then grown for 15 days under light to investigate the pesticidal efficacy. The results are shown in Table 6.

\, Table 6 Test Example 5 Wheat leaf blight control test (preventive effect) A plastic pot was filled with sandy loam, and wheat (Norin No. 78) was sown and grown in a greenhouse for 8 days. A test chemical prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and sprayed on the foliage of wheat seedlings so as to sufficiently adhere to the leaf surface. After spraying, spray and inoculate the leaf blight fungus, and after inoculation, keep the temperature at 15°C.
The plants were grown for 8 days in the dark and humid, and then grown for 15 days under illumination at 15° C., and their pesticidal efficacy was investigated. The results are shown in Table 7.

Table 7

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. 1 and R^
2 are the same or different and represent a hydrogen atom or a methyl group. ] An agricultural and horticultural fungicide characterized by containing a carbamate derivative represented by the following as an active ingredient. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. 1 and R^
2 are the same or different and represent a hydrogen atom or a methyl group. Here, when R^1 and R^2 simultaneously represent a hydrogen atom, Xn is a hydrogen atom, a 3-chloro atom, a 4
- Not a chloro atom, a 3-methyl group, or a 2,4-dichloro atom. ] A carbamate derivative represented by