JPS5953907B2 - Phthalimide derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention is based on the general formula X, OR, When an atom
X2 represents a methyl group, or when X is a methyl group, X2 represents a hydrogen atom.

) relates to a novel phthalimide derivative represented by Examples of the novel phthalimide derivatives of the present invention include the following. (1) N-(2,6-diethylphenyl)2-methylphthalimide (2) N-(236-diisopropylphenyl)2-methylphthalimide (3) N
-(2,6-diethylphenyl)3-methylphthalimide(4)N-(236-diisopropylphenyl)3-
Methylphthalimide The novel compound (I) according to the present invention can be produced by the method shown in the following formula.

X, 0 , , Xl and X2 have the same meanings as described above.

) In the above reaction, the compound having formula (l) is used in equimolar to slightly excess amount relative to the compound having formula (), and both are heated in the presence or absence of a solvent, preferably in an inert solvent. This makes it easier to implement.

The solvent used is not particularly limited as long as it does not participate in this reaction, and the starting compounds of formula () and formula 1),
and solvents capable of dissolving intermediate (5), such as lower fatty acids such as acetic acid; lower alcohols such as ethanol or n-butanol; ethers such as tetrahydrofuran or dioxane; methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone Ketones such as or these solvents and benzene or xylene′! ．． ′:,Go=2:=Niri:Noka weight::τku[■■
The use of ketones such as alcohols, methyl isobutyl ketone, and cyclohexanone is particularly advantageous for suitably carrying out this reaction.

The reaction temperature is not particularly limited, but it is selected from the temperature at which the intermediate phthalamic acid (5) melts when the reaction is carried out without a solvent, and from the range of 60°C to 160°C when a solvent is used. The time required for the reaction is usually 1 to 3 hours. For reactions in low-boiling solvents such as methanol or ethanol, it is advantageous to have a suitable amount of a dehydrating agent such as sulfuric acid or p-toluenesulfonic acid present.

After the reaction is completed, the target compound is collected from the reaction mixture by a conventional method.

For example, it can be obtained by cooling the reaction mixture and collecting any crystals that precipitate. Alternatively, it can be obtained by distilling off the solvent used in the reaction to precipitate crystals. The crude crystals thus obtained are
If necessary, it can be purified by conventional methods such as recrystallization from a suitable solvent such as methanol. When the reaction is carried out in a solvent that can be dehydrated by azeotropy, such as methyl isobutyl ketone or n-butanol, the mother liquor from which precipitated crystals have been collected after cooling can be used as a reaction solvent to carry out the same reaction. It is also possible to repeat.

The method for producing the novel phthalimide derivative (1) of the present invention will be explained in more detail with reference to Examples.

Example 1 N-(2,6-diethylphenyl)2-methylphthalimide 2-methylphthalic anhydride 16.29 and 2,6-
After adding 16.49 g of diethylaniline into 50 d of ethanol and stirring for 30 minutes, 0.59 g of p-toluenesulfonic acid was added and the mixture was heated under reflux for 2 hours.

After the reaction was completed, the solvent was distilled off from the reaction mixture and the residue was washed with methanol to obtain the target compound 24.59 having a melting point of 100.5-101.5°C. The following compounds were produced according to the above method.

Exemplary compound corrosion Melting point (0C) 2166.5-167.
5 Example 2 N-(2,6-diethylphenyl)3-methylphthalimide (a) Methyl isobutyl ketone 3759 and 3-methylphthalic anhydride 28 in a reactor equipped with a water separator
1.3 g was added and heated to slowly reflux.

Next, 2,6-diethylaniline 3009 was added dropwise over 1.5 hours, and the mixture was further heated under reflux for 1 hour to remove 32 ml of separated water and distill off about 1009 methyl isobutyl ketone. After cooling on ice, the precipitated crystals were collected and washed sequentially with methanol and n-hexane to give crude crystals of 430.09
was gotten. The washed solution and washing solution were combined and concentrated, and methanol was added to the residue to obtain 59.79 crude crystals (total yield 489.79, yield 96.2%).

When this product is recrystallized from methanol, the melting point is 97-98.
Pale yellow crystals with a temperature of .degree. C. were obtained. Elemental analysis value (5) C
,,Calculated value as Hl, NO2 C, 77.79:H,
6.53;N, 4.77 experimental value C, 77.6O:H,
6.5 l; N, 4.8 l (b) 162 f of 3-methylphthalic anhydride in a round bottom flask equipped with a water separator! ,2,
6-diethylaniline 1649 and n-butanol 2
After adding 00d and heating under reflux for 3 hours, about 10d of water was separated. After cooling, the generated crystals were collected and mixed with methanol, n
- After successive washing with hexane and drying, crystals 2109 of the target compound having a melting point of 97-98°C were obtained. (yield 7
1.6%) 3-methylphthalic anhydride 14 was added to the obtained solution.
89 and 2,6-diethylaniline 1499 under reflux.
After adding dropwise, the mixture was further heated under reflux for 3 hours, and about 15 ml of water was separated.

After cooling, the reaction mixture was treated in the same manner as above to obtain the target compound 266.19. (Yield 90.7%) Furthermore, 3-methylphthalic anhydride 1489 and 2,6-diethylaniline 1499 were added to the obtained liquid and heated under reflux for 3 hours to separate about 16 ml of water. After cooling, the reaction mixture was treated in the same manner as above to obtain the target compound 282.59. (Yield 96.3%). N-butanol was distilled off from the bottom liquid, and n-hexane was added to the residue. Methanol was added to the resulting mass, washed with a small amount of methanol, and then dried to obtain 70.1 g of the target compound. Total yield 828.79 (94.2% yield). The following compounds were produced according to the above method. Exemplary compound washing Melting point 141
65-166 The novel phthalimide derivative (1) of the present invention is useful as an agricultural and horticultural fungicide.

Traditionally, organic arsenic agents and antibiotics have been widely used to treat rice sheath blight, and pentachloronitrobenzene (hereinafter abbreviated as PCNB) to treat damping off, but these are not necessarily safe for livestock, fish, shellfish, and crops. No, no.

For example, organic arsenic agents have a strong bactericidal effect, but they are chronically toxic to humans and animals, and cause phytotoxicity that affects rice yields. Antibiotics are low in toxicity but have little residual effect, and PCNB also causes growth problems in young seedlings that require control. There are problems such as inducing cancer, and there is a strong desire for the development of new and improved drugs.

The present inventors have demonstrated that the compound having the general formula (1) has excellent control effects against various plant diseases, and has particularly shown excellent efficacy and residual efficacy in controlling sheath blight, which is a major disease of rice. They found that the toxicity to humans, animals, fish, and shellfish was extremely low, and no chemical damage was observed to the target crops or other crops.

When the compound of the present invention is used as an agricultural and horticultural fungicide, it can be applied directly or mixed with a carrier and, if necessary, other adjuvants, to form a pesticide formulation. "X": Used as a double layer.

Suitable solid carriers include inorganic materials such as clay talc, clay, kaolin, bentonite, clay, calcium carbonate, diatomaceous earth, anhydrous silicic acid, and synthetic calcium silicates.

Suitable liquid carriers include ligroin, kerosene,
Aliphatic hydrocarbons such as mineral oil; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; chlorinated hydrocarbons such as chloroform and dichloroethane; alcohols such as methanol, isopropanol, and n-butanol; acetone, methyl ethyl ketone, Ketones such as cyclohexanone; amine derivatives such as ethanolamine and dimethylformamide; and the like. In addition, various nonionic and ionic surfactants, high molecular compounds such as sodium alginate, carboxymethyl cellulose, methyl cellulose, and polyvinyl alcohol, and sulfite waste liquid are used to improve the properties of the preparation or enhance its biological effects. You may add auxiliary agents such as.

It is preferable that other fungicides are added to the above-mentioned preparation of the present invention in order to broaden the fungicidal spectrum, and in some cases, a synergistic effect can be expected.

Examples of such other fungicides include, for example, methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate; methyl benzimidazole-2-carbamate; 1,2-bis(5-methoxycarbonyl-2-carbamate);
-Thioureidobenzene; 3-hydroxy-5-methylisoxazole; N-2,3-dichlorophenyltetrachlorophthalamic acid; 5-methyl-S-triazole (3,4-b)benzthiazole; 0, 0-diisopropyl-S-benzyl phosphorothioate; PCNB; cascamycin; blasticidin S; 4,5,6,7-
Examples include, but are not limited to, disinfectants such as tetrachlorophthalide. In addition, other insecticides, acaricides, herbicides, plant growth regulators, nematicides,
It can also be used in combination with bactericides or fertilizers. The above formulations contain 1 to 1 active ingredient per 10 ares.
10009, preferably 5 to 2009, is used by spraying on the foliage of crops, or by irrigating the soil or applying in water.

Next, examples of formulations of the agricultural and horticultural fungicides of the present invention will be given.

In the text, all parts simply refer to parts by weight. Formulation Example 1 Powder 3 parts of compound number 1, 47 parts of talc, 47 parts of clay
1 part and 3 parts of white carbon are uniformly mixed in a mixer and ground in a hammer mill to obtain a powder.

Formulation Example 2 Wettable powder Compound No. 2 50 parts, white carbon 5 parts,
5 parts of Solpol AC-2495G (trade name of Toho Kagaku Co., Ltd.) and 40 parts of clay are mixed uniformly in a mixer and ground in a hammer mill to obtain a wettable powder.

Formulation Example 3 Emulsion 10 parts of compound No. 3, 10 parts of xylene, 12 parts of Paracol PS-2 (trade name of Nippon Nyukazai Co., Ltd.) and 68 parts of cyclohexanone are mixed and uniformly dissolved to obtain an emulsion.

Formulation Example 4 Granules Mix 5 parts of compound No. 4, 20 parts of bentonite, 1 part of calcium lignosulfonate, and 74 parts of clay, add an appropriate amount of water, knead, and granulate using a single-screw extruder granulator. Granules are obtained by drying and sizing.

Next, a test example showing the effect of the compound of the present invention as an agricultural and horticultural fungicide will be given.

The test drug was manufactured according to Formulation Example 2, and a wettable powder containing 50% of the compound of the present invention was used. Test Example 1 Rice sheath blight control test When rice (variety: Jinnanfeng) grown in a plastic container (30 x 50c! N1 depth 25°) in a greenhouse reached the seed stage, each control test was conducted. Served.

1) Preventive spraying: A solution of a predetermined concentration of the compound of the present invention is sprayed at a ratio of 1002/10a with a spray gun, and after 7 days, it is sprayed on rice sheath blight fungus (Pellieula) cultured in advance on barley medium.
riasasakii) was inoculated at the base of rice plants.

Thereafter, the plants were kept indoors at a temperature of 26 to 28° C. and a humidity of 90% or more, and the lesion length was measured on the 10th and 20th day after inoculation, and the control value was calculated according to the following formula. The results are shown in Table 1. 2) Treatment spraying: Rice sheath blight fungi were inoculated in the same manner as in the preventive spraying, and 3 days later, a solution of the compound of the present invention at a predetermined concentration was sprayed at a ratio of 10011/10a using a spray gun.

After checking the lesions formed during spraying with ink, keep the lesions indoors at a temperature of 26-28℃ and a humidity of 90% or higher, measure the lesion length on the 10th and 20th day after inoculation, and inoculate the area with a new one. The control value was calculated from the progressed lesion length. The results are shown in Table 2. Test Example 2 Rhizoctonia disease control test Oat grains were cultured at 28°C for 2 weeks with seedling damping-off fungus (Rhi).
zOctOniasOlani) was uniformly mixed with soil and stored at 20 to 25°C for one month to prepare diseased soil.

After each test compound was made into a 10% powder, it was mixed uniformly with diseased soil at a ratio of 40.20 ppm (W/W) as an active ingredient concentration to the soil, and then placed in a plastic container (20 x 30 CWL 1 depth 10 c!n). I put it in.

Sow 30 seeds of cucumber (variety: Sagami Hanshiro),
After keeping the plants in a greenhouse at ℃ for 2 weeks, the number of seedlings affected by seedling damping-off was investigated. Each ward will be divided into three series, and the total values are shown in Table 3.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 and R_2 represent an ethyl group or an isopropyl group, or when X_1 is a methyl group, X_2 is a hydrogen atom).