JPS60136503A - Dialkylaminomethylaniline agricultural and horticultural fungicide - Google Patents

Abstract

PURPOSE:To provide an agricultural and horticultural fungicide having excellent activity to the pathogen of e.g. late blight of tomato, powdery mildew and anthracnose of cucumber, blast or rice, etc., by using a specific dialkylaminomethylaniline derivative as an active component. CONSTITUTION:The objective fungicide for agricultural and horticultural use contains the dialkylaminomethylanilin ederivtive of formula I (R<1> and R<2> are lower alkyl or together with adjacent N form a ring; X<1> and X<2> are halogen; lis 0 or 1; m is 0 or 1) {e.g. N-[2-(diethylaminomethyl)phenyl]-N'-phenylurea, etc.} as an active component. The compound can be produced e.g. by treating the methyl-substituted nitrobenzene of formula II with a halognation agent, reacting with a secondary amine, reducing the product, and finally reacting with benzoyl chloride or dialkylaminomethylaniline. EFFECT:There is no phytotoxicity to useful crops.

Description

DETAILED DESCRIPTION OF THE INVENTION A fungicide for cliff gardening containing dialkylaminomethylaniline represented by the general formula (1), J4 form as an active ingredient.

In the above m1 formula, R1j=- and kt2t- can be used to represent a lower ``gammagyl group'' such as a methyl group, ethyl acid, globyl group, butyl group, or the nitrogen atom to which these are bonded. 1.h&C is biarydin 11, pyrroline ring, thiazolidine ring, piperidine ring, morpholine ring, piperidine ring, perhydroacevin ring 7. c. ! Knee 05~
A 7μ ring is formed, and m is an integer of It or 2.

X11/J contains halogen atoms such as chlorine atom, bromine atom, fluorine atom, and iodine atom, nl is Oifc is l
I cum from the canter. X2 represents a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc.1,, R2
represents the adjustment El of O support or l. l is 0 or 1 V
D: To disguise the number.

11) - A number of cross-linking agents, such as organic phosphorus agents and organic chlorine All, have been developed and applied as disinfectants for gardening.

These cross-cutting agents have led to an increase in the yield of agricultural products, but recently problems such as soil contamination, phytotoxicity to plants, toxicity to humans, and persistence of these cross-linking agents have been raised. Due to the emergence of resistant bacteria to quinoxaline, benomyl, etc., which have been applied to kill grasshoppers, the application of these drugs is currently being restricted. Therefore, there is a strong desire in the industrial field of VC to develop a fungicide for general use in agriculture, which exhibits the full μ-control effect against plant diseases of 4.5% and does not cause the above-mentioned disadvantages.

The present inventors investigated the anti-inflammatory activity of a wide range of compounds in order to develop new agricultural and horticultural fungicides. As a result, the dialkylaminomethylaniline spindle represented by the general formula (+) was found to be effective against tomato extract disease. Powdery mildew of cucumbers,
The present invention was completed based on the discovery that it has excellent antibacterial activity against plant pathogens such as Tanso disease and Imona disease.

In addition to the above-mentioned plant pathogenic bacteria, the dialkylaminomethylaniline conductor represented by the general formula (1) is also known for its use in plant pathogens such as Mahanor's disease, Moncare's disease, cucumber rot, Nump's disease in Japanese cabbage, and Japanese japonicus. It also exhibits antibacterial activity 1 against undocumented red rust, has a broad antibacterial spectrum (1 [1], and has no effect on agricultural crops.

Representative examples of the dialkyl amitumenal aniline fatty acids represented by the general formula (1) are listed below.

2 eNHc(JNfl-C>CH2N(CzH5)z
mp, ] 53.34 Q-COIliQ-0M2
N'(C2H,5)2 mp, 113.65 ChyC(JNMo-C1-12N(C2f(5)2 mp
, 171.5, 11, -4χ The sialylaminotylaniline compound represented by the formula (1) can be easily prepared, for example, by the following method.

”)nl(Ill (X')nl utD(X”)
・"(V) c j",': A, R1, R2, Xl, X2, m,
nl and n2iJ tjil notation χ and ``...ri'', and Yit=rogen atom kt4was3. ) i.e.
By treating the methyl-substituted di-11-cobenzene represented by the general formula (II) with a halokenating agent,
) The total amount of nitrobenzene shown by the formula (1) is reacted with a secondary amino acid represented by the general formula (1v) (by which the dialkylamitumenal nitrobenzene represented by the general formula (V) is obtained). 111. Next, by reducing this, dialkylaminomethylaniline with the general formula (■) J<g is obtained.
ting. Kregczy,' Bulletin
De la Society Ehimique de
i(rance (4), 19, 399; and Friedlinder, PJlosczyc, B.
erichte derl)eutscllen Ch
emischen Gesellsclaft, 2
8. 1141],) By reacting the dialkylamitumenalaniline represented by the general formula (Vl) with the acid chloride of benzoic acid represented by the general formula (■) by a conventional method, a compound represented by the general formula (1-■) is prepared. By reacting sialgylaminomethylaniline represented by the general formula (■) with phenylincyana-1. represented by the general formula (■) by a conventional method. A dialkylaminononalaniline derivative represented by the general formula (1-2) is obtained.

It may consist only of the dialkylaminononalaniline derivative represented by the formula (1) of the present invention (1 kikawa fr. is 2 widths, on a target), t 7
'(-A'a dialkylaminomethylaniline compound, one or more 4J4-'l or 261x1 or more is added to the conventional technique on agricultural chestnut preparations (!゛e and Sode-suke ζ'If ms or Granules, powders, tablets, aqueous solution [1 agent, emulsion, oil agent%]
In some cases, it is formulated in the form of aerosols, etc. Inactive 1i1 Jt4 body is liquid, I [!・The liquid carrier may be benzene,
Toluene, xylone, methylnaphthalene, solvent naphtha, kerosene, dimeterporporin amide, tuminal sulfoxide, dimethylacetamide, methanol,
4 common moxibustion bath media such as ethanol, ethylene alcohol, pyridine, acetonitrile, cellosolve, freon, rogenated ashing water cord, lower fat ester, acetate, methyl ethyl ketone, and citalohegibunone, solid 11, 1 body To L -C F.J Kruk, clay, noroline, bentonite, acid clay, diatomaceous earth, anthracite calcium, phosphor calcium, nitrocellulose, nato tF=
&f: 6 It's a monkey. Examples of adjuvants include IT emulsifiers, dispersants, and dispersants. +! Sukehari no Kiseki V Sutitori, polyoxyethylene alkylaryl ether, alkyl 7° lyl polyoxyethylene glycol ether, alkylaryl sulfonate, higher alcohol sulfate ester, alkyl dimezurbe/
11% of non-ions, anions, cations, and 1min such as ``muno-ride'', lignin sulfone salt, stearin removal salt, polyvinyl alcohol, CMC, starch, gum arabic, etc. >1 <-
It is not limited to what you can do.

- In the preparation of the dialkylamitumenal-jniline represented by the general formula (1), the proportion of 1. ,
When using granules, M 111 or oil h 11, 01 to 10 φ as a 7i'i component, and emulsion or water conservancy. be.

(The length of the 5th chamber varies depending on the useful Vv product, growth condition, weather conditions, degree of disease occurrence or its tendency, and other factors, but in the case of liquid preparations, the active ingredient and 17% are usually 1%.
00-20001) Treated with pIn chemical solution.

1 kiln, of the present invention! Horticultural fungicides must contain at least one or more of the following fertilizers, soil conditioners, insecticides, fungicides, and herbicides, within the range that does not significantly adversely affect the effectiveness of the active ingredients. Can be used in conjunction with

The fat horticulture killing method of the present invention has a 7-level effect on various plant diseases.
Demonstrates pest control effect. The present invention is applied to agriculture (separately used information) to protect against the attack of water, field crops, fruit stalks, horticultural crops, forestry W and timber stands and stalks.
1. Tomatoes can be grown from the Eki fungus, and powdery mildew and Tanso fungi can be grown from the tomato fungus to Gyuriwo and soil potato rot.
Kara Inasume: Can be continuously protected. Others
4 (Gypsophila disease in ij, Moncare disease, downy mildew in cucurbits, Temp disease in kj<sai, Ginkaff disease in kidney beans,
Wheat red 1] Tanigami a. ii) It is necessary to identify and control the pathogen in the country. ) When applying the agricultural pesticide 4-2 of the present invention, a major advantage is that it does not cause damage to crops within the practical gravel level range.

Below are 7 examples of the synthesis, working examples, and tasting examples of the active ingredient compound of ``Killing Grain'' for gardening. In the examples, "part" means part by weight. Compound No. t is representative of the dialkylamitumenalaniline derivatives represented by the above-mentioned general formula (1) (1) to (8).

Synthesis Example 1 2-(diethylaminemethyl)aniline 2,0 was added to chicken;
Water benzene 2Qml! Then, 1,3f phenyl isocyanate (phenylisocyanate) was added to this solution, and the mixture was stirred at room temperature for 48 hours. D, N'-[,2-
2.31 (diethylamitumenal)phenyl]-N'-phenylurea [compound (1)] was obtained.

Compounds (2) and (8) were prepared in the same manner as in Synthesis Example 1.
Synthesis Example 2 Dissolve benzoyl chloride 2.0&'4 in 30 ml of anhydrous benzene, and then add 4-(diethylamine methyl) to this solution.
Aniline 2. Og and zml of triethylamine were added, and the mixture was stirred at room temperature for 48 hours. Add all dienal ether to the reaction mixture, wash with water, and purify the organic layer with e. r, 2.
8 y get fc.

Compounds (5) to (8) were obtained by the same method as Synthesis Example 2! c.

Example 1 A 1-component combination of 50 parts of γ-alkyl sodium sulfate and 5 parts of quartzite earth was homogeneously mixed and pulverized with I/C to make a wettable powder containing 50% of the active ingredient. Each of the compounds (2J (8) t50%
Mizukai 11 agents were obtained. When using it, dilute it with enough water and spray.

Example 2 Emulsion compound (1) 20 parts xylene 40 parts hexane 35 parts holoxyethylene phenyl ether 5 parts were mixed to prepare an emulsion of immobile component 2 (). In the same way, an emulsion containing 20 parts of each of the petrified minerals (2) to (2) was prepared.
do.

Example 3 powder Horror (1) 2 capitals Merck 98 copies The mixture was uniformly mixed and pulverized to form a powder containing 2% of the active ingredient.

In the same manner, powders containing 2% of each of compounds (2) to (8) were obtained.After use, they were sprayed as they were.

Test Example 1 Tomato Extract Disease Control Test Tomato seedlings (variety: Red Naery) at the 5th to 6th leaf stage were treated with Yuzueto one plant per bot, and 50 ml of rJi constant linearity chemical solution was applied per 3 pots. Sprayed with a spray gun using a table, and applied &O chemical solution treatment 2 special to the pond. 1m
In this case, fcI-mado.
1 peak suspension of Extract fungus spores (3 x 10 spores/
ml) +1 s°C for 3 hours (50 botts * 50 ml of sporangia in which four or more germinations of -1 play spores were observed) were used.

The angle after the contact is 1d to the 20℃ contact, and after the 1st contact is 31
54. The control value was calculated by multiplying by 6x using the following formula. The results are shown in Table 1.

Table 1 Nor (W 0 -- Compound (]) 25O!ノ← 1゜t/QJ //81 t/〃 (3)〃J, l) 11 tt〃(4)〃89
〃 “ (5) ” l 0 (l tt // ('I) // 79 〃 (8) ] 00 u n') Jlα compound CG-117 Note 0 2511 B g None Difer Hall) 175 (l J37 tt03 2) Differ = 8 Test Example 2 Control test against powdery mildew on cucumbers Two rows of cucumbers, which had been stacked in advance with one per pot, were placed in pot 3.
A 50 miq chemical solution of a predetermined quality was applied to each individual using a spray gun using a turntable. When that certain ridge becomes dry, powdery mildew disease (fuiiigi)
nea) was inoculated. At the time of inoculation, cucumber
Conidia dropped from a powdery mildew lesion into a petri dish were washed with distilled water.
A spore suspension adjusted to have 5 spores per 1.0 times the number of spores was used.

The young 6 children of 4-ri bales were left in an isolated temperature-controlled greenhouse, and the number of lesions was measured 10 days after contact.

Pest control 14 was determined according to the following formula, and the results of Tomo r-C are shown in Table 2.

2nd table Fish treatment -0- conversion f fig C1)], 000 8 (1'/1
1°// (2) tt 1o.

〃 (3) 〃97〃 〃 (4J 〃 1 (Mon) 〃 〃 (5) 〃94〃 tt (6) // 89 tt 〃 (7) 〃8z〃 〃(8) 〃8b〃 Control compound test example 3 To prevent the phantom of cucumbers, apply 50 tl of a chemical solution of the specified linearity to the cucumber seedlings, which had been planted and grown in advance per pot, on a turntable in 3 pots. It was sprayed with a spray gun.When the chemical solution dried and reached 7 days, cucumber tanso disease 7 (CCo11et) was detected.
otrichu lagenarium). At the time of inoculation, the spores infected with tanshu were cultured in advance in a sweet corn medium, and the obtained spores were adjusted to about 350 in one field of view (microscopic magnification: 100x) with distilled water. A spore suspension was used. Seedlings in bales were placed in a constant temperature and humidity chamber at a temperature of 27°C and a humidity of 70% or higher in the dark at night, and then exposed to light for 3 days. L L After leaving the cucumber seedlings in the greenhouse for another 7 days, the degree of disease onset of the cucumber seedlings was measured, and the pest control 111II was calculated in the same manner as in Test Example 2.
, the results are shown in Table 3.

Table 3 Test compound Spreading gravel level (pprn) Prevention and control (related) Nashiiwa no treatment O- Kamomono (1) 10 () 092 None II (2) tt 8: (7/ // (81tt 85 〃 (, piece // 9 rl// 〃(5〃8() /l ((+) // 87 // u (7) 〃!JO// // (8) 84 Control compound test example 4 Sprayed glaze After (7 grains per bottle) grows for about 14 days.
+Allow the formation of the specified concentration on the seedlings of iFh (Product 4Mi: Kananfu) + ]' 1~, When the formation of the seedlings has dried up, add Imona disease bacteria to 11 + 1 young 11 in a long and narrow box. "Spraying" is compromising. When polarized 1~ci・:r, Imona disease 14 yen 11
The spores were cultured in advance in a medium for about 13 days, and the spores (il: 1 field of view with distilled water (extra magnification: 150x)) were cultured in advance for 30 spores. The video of the video using ceramics is temperature 1 27 degrees Celsius, humidity 1 temperature 90 or more.
MLk was released for 3H into a glass Y crystal after 2 days in the dark in a -1 temperature and humidity chamber. After that, the disease severity If of the video of rice was investigated, and the pest control 111IJ'fr was calculated according to the following formula. The results are shown in Table 4. 1. Clothing test compound Spreading performance (ppm) Control value (・p) Apricot no treatment 0 - Compound (1) l (10 (l 1.011 None//
(2) // 82 tt a (a) p 93 tt 〃 (6) l/ 87 1/ Comparative compound fusaride Note 5) 501) 'J Riri] 7 Tokken Applicant Rira Co., Ltd. Representative Patent Attorney Ken Honda

Claims (1)

[Claims] Formula -1a (lower, middle, Ijl and R2 each represent a lower alkyl group, or the nitrogen 111 to which they are bonded) X'a and X2V1 each halokene atom (i-cloth wa t,, 71 has 10 or 1 approval, nl ij: 1. t / koha 2 j
lt'i H k 'iQ wa j7, 11' and R2 represent the stress Ml of sα 0 or 1. ) 1 ton 1 artistic sterilization paste containing dialkylaminomethylaniline fatty conductor as an active ingredient.