JPS6011882B2 - Nematicide - Google Patents

Description

[Detailed Description of the Invention] In recent years, plant-parasitic nematodes have attracted attention as a major factor that inhibits production of agricultural crops, and in particular, the designated production area system for vegetables, etc.
Due to the increase in the variety of vegetables and continuous cultivation due to the promotion of horticultural crops,
Damage caused by nematodes is increasing year by year.

Furthermore, crop rotation is not possible for perennial crops such as orchards, tea gardens, and mulberry gardens, and nematodes are an important factor inhibiting production.
As a result of various studies in order to find a safe and effective nematicide from the above viewpoint, the present inventors found that the general formula of an acetylene derivative is R,1C...C-COR2 (in the formula, R,
represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkylcarbonyl group, a phenylcarbonyl group, a phenyl group which may be substituted with a halogen atom, a lower alkyl group or a lower alkoxy group, or a chenyl group, and R2 is A group of compounds represented by a hydrogen atom, a lower alkyl group, a lower alkynyl group, a phenyl group optionally substituted with a halogen atom or a lower alkoxy group, a chenyl group, an ethynylphenyl group, or an ethynylphenyl group substituted with a lower alkyl group. High effectiveness was found in a nematicidal test using the immersion method, and the present invention was completed.

Next, compounds according to the present invention are illustrated in Table 1.
The compounds illustrated in the table do not limit the types of acetylenes according to the present invention. The compounds according to the present invention are a group of known compounds that can generally be produced in the following manner.

The acetylene ketone according to the present invention can be easily synthesized by reacting a metal acetylide with an acid halide or an acid amide ester.

[R. B. Dav;s, D. Day. Schell, J.
Am. Chem. To Soc 7 & 1675 (1956)]
Furthermore, the acetylenaldehyde according to the present invention can be easily synthesized by reacting a metal acetylide with formic acid amide or orthoformic acid ester.

[E. R. Day. Tones et. al. , J. Che
m. Soc. , 3483 (1960)] Table 1 General formula R, -C=C-COR2 Production example 1 Preparation of compound No. 3 Anhydrous ether solution containing 0.3 holes of methylmagnesium iodide was cooled on ice, and 20.4 hols (0.3 hol) of an anhydrous ether solution containing 2-butinal (Compound No. 22) was added dropwise thereto.

After the dropwise addition, the mixture was refluxed for 2 hours, and then a saturated aqueous ammonium chloride solution was added little by little, followed by extraction with ether. The ether layer was washed with saturated brine and dried over anhydrous sodium sulfate. After carefully distilling off the ether, the remaining crude carbinol was dissolved in acetone, and Jones reagent was added dropwise under ice cooling until the solution took on a light green color. After stirring for 2 hours, excess oxidizing agent was decomposed with inpropyl alcohol, and sodium bicarbonate was added to neutralize the sulfuric acid.

Heat the precipitate in a furnace, carefully remove acetone from the furnace liquid,
A crude product was obtained. Distillation under reduced pressure yields the title compound 2.
4.6 ta was obtained. bp74-7500/96 rib Hg,
Yield 67%. Production Example 2 Preparation of Compound No. 4 27.2 moles (0.15 moles) of an anhydrous ether solution containing phenylmagnesium bromide was placed under ice, and 10.2 moles (0.15 moles) of 2- Anhydrous ether solution containing butinal is added dropwise.

After the addition, the mixture was refluxed for 3 hours. In a manner similar to that described in Preparation Example 1, crude carbinol was obtained, which was then oxidized with Jones reagent in acetone to obtain 21 units of the title compound. bp133/16 leg Hg, yield 63% Production example 3 Preparation of compound No. 5 Under a nitrogen stream, add 40 holes (0.35 holes) of phenylacetylene to an anhydrous ether solution.
．． A solution of 3 mole of ethylmagnesium bromide ether was added dropwise.

1. After refluxing for an hour, add acetaldehyde (0.3
mole) was added dropwise at -20 qo.

After praying for 2 hours, a saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate.

The layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude carbinol thus obtained was dissolved in acetone, and Jones reagent was added dropwise under ice cooling until the solution took on a tint green color. After stirring for 2 hours, excess oxidizing agent was decomposed with isopropyl alcohol, and sodium bicarbonate was added to neutralize the sulfuric acid.

The precipitate was removed and acetone was removed from the furnace solution to obtain a crude product. This was distilled under reduced pressure to obtain 1-phenyl-1-butyn-3-one of 28 g. bp12000/14 skin Hg
Production Example 4 Production of Compound No. 20 Phenyl acetylene 30 holes (0.29 holes), ethylmagnesium bromide 31.75 holes (0.24 mol)
e) and ``2-thiophene aldehyde 28 minutes (0.
24 mole) was subjected to Grignard reaction and Jones oxidation in the same manner as in Production Example 3 to obtain a crude product.

This was adsorbed on a silica gel column, and 39% of the target product was obtained from the io% ethyl acetate-n-hexane elution section (yield: 7
7%). mp57-5800 Production Example 5 Preparation of Compound No. 22 An ether solution of ethylmagnesium bromide [from 6 volumes of magnesium (0.25 gram atom), excess ethyl bromide, and 150 volumes of anhydrous ether] was heated under reflux. Inject excess propyne.

After allowing to reach room temperature, the Grignard solution was transferred to a dropping funnel. After cooling the solution of anhydrous ether 100 in DMF 55 (0.75 hoie) with ice and salt, the Grignard solution was added dropwise.After the addition, the Grignard solution was heated for 4 hours at 20 pm.The reaction solution was diluted with 5% sulfuric acid. The mixture was gradually added over one evening and incubated for one hour.The reaction solution was extracted three times with ether.The ether extracts were combined, washed with water, and dried over anhydrous sodium sulfate.The ether was carefully distilled off, and the remaining crude The aldehyde was distilled under reduced pressure. BP 4000/7 Hg, yield 8.3 yen (yield 43%) Production example 6 Preparation of compound No. 24 Ether solution of ethylmagnesium bromide [magnesium 6 yen (0.25 g A solution of 20.5 o.2 oles of 1-hexyne in 50 o. of anhydrous ether was added dropwise to the solution of 1-hexyne, excess ethyl bromide, and 150 o. of anhydrous ether.

The reaction was completed by refluxing for 1 hour and transferred to a dropping funnel.

DMF55 hole (0.78 hole) anhydrous ether 10
The Grignard solution was added dropwise to the 0.0 solution while stirring and cooling with an ice-salt cooling agent. After further stirring at 20 qo for 4 hours to terminate the reaction, the mixture was gradually added to 5% sulfuric acid with vigorous stirring for decomposition. After 1 hour, the mixture was extracted with ether, the extract was washed with water, and a short distillation tube was attached to remove the ether.

The remaining aldehyde was distilled under reduced pressure. Yield: 14.1 days (yield: 51%). bp54-55o0/16 Hg Active ingredient compounds of the composition of the present invention may include pentachlornitrobenzene (PCNB), bis(dimethylthiocarbamoyl)disulfide, tetrachloroisophthalonitrile,
3-Hydroxy-5-methylisoxazole, 5-ethoxy→, 3-trichloromethyl-1,2,4-thiadiazole, N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide, N-(1,1
・2,2-tetrachloroethylthio)-4-cyclohexene-1,2-dicarboximide, chloropicrin, etc., and 1,2-dibromoethane, 1,3-dichloropropane, and 1,2-dichlorohexene. Chlorproban, bis(2
- Nematicides such as chloro-1-methylethyl)-ether, bromomethane, sodium (ammonium) N-methyldithiocarbamate, organic nematicides, carbamate insecticides, chlorine insecticides, various herbicides, and fertilizers. It is also possible to mix it with or use it as a mixture.

Next, the effects of the nematocide of the present invention will be shown by test examples.

Test Example 1 The test nematodes were Pratyl nematodes, which were cultured indoors using alfalfa callus.
enchus Coffeeae).

Each drug was dissolved in methanol to a concentration of 1%, and this was diluted with a 0.1% EPAN420 (polyoxyethylene polypropylene glycol) aqueous solution to a predetermined concentration. Each diluted solution was dispensed in 10' portions into Syracuse watch glasses, 150 to 200 bran worms were placed in each watch glass, and growth was controlled for 4 hours at 25°C in the dark.

Thereafter, the nematocidal rate was determined by examining whether the animals were alive or dead under a binocular microscope.

The test was repeated five times. The results are shown in Table 2. Table 2 *Methomyl=S-methyl-N-(methylcarbamoyloxy)thioacetimidate Test Example 2 Similar to Test Example 1, female Pratylench nematode (Pratylench female Cof) was cultured indoors using alfalfa callus.
e) was used.

Each test drug was prepared into a 20% emulsion and used. The contents of the preparation are 2 parts by weight of each compound used in the present invention, 7 parts by weight of xylene.
0 parts by weight and 1 part by weight of polyoxyethylene nonylphenyl ether were mixed to prepare an emulsion. This formulation was diluted with water to the desired concentration. Dispense each dilution into 10 [dussyracian] watch glasses, and add 150 to 20 nematodes per watch glass.
0 head was added, and the growth was controlled for 4 hours at 25 ohms in the dark. Thereafter, the nematocidal rate was determined by examining whether the animals were alive or dead under a binocular microscope.

The test was repeated five times. The results are shown in Table 3. Table 3

Claims (1)

[Claims] 1 General formula R_1-C≡C-COR_2 (In the formula, when R_1 is a hydrogen atom, R_2 is a lower alkyl group, and when R_1 is a lower alkyl group, R_2 is a lower alkyl group.
_2 is a hydrogen atom, a lower alkyl group, a lower alkynyl group,
phenyl group or ethynyl phenyl group, when R_1 is a lower alkenyl group, R_2 is a hydrogen atom or a lower alkyl group, when R_1 is a lower alkylcarbonyl group, R_2 is a lower alkyl group,
When _1 is a phenylcarbonyl group, R_2 is a phenyl group, and when R_1 is a phenyl group, R_2
is a hydrogen atom, a lower alkyl group, a phenyl group, a halogen atom-substituted phenyl group, a lower alkoxy group-substituted phenyl group,
a thienyl group, an ethynyl phenyl group or a lower alkyl group-substituted ethynyl phenyl group, and when R_1 is a halogen atom-substituted phenyl group, R_2 is a pheny group;
When R_1 is a lower alkyl group-substituted phenyl group, R
_2 is a lower alkyl group or phenyl group, R_1
is a lower alkoxy group-substituted phenyl group, R_2
is a phenyl group or a thienyl group, and when R_1 is a thienyl group, R_2 is a phenyl group or a phenyl group substituted with a lower alkoxy group. A nematicide characterized by containing it as an ingredient.