JPH04149159A - N-dichlorobenzyl-n-phenoxyalkylamine and agricultural and horticultural germicide - Google Patents

Abstract

NEW MATERIAL:An N-dichlorobenzyl-N-phenoxyalkylamine expressed by formula I ((n) is 3 or 4). EXAMPLE:N-3,4-Dichlorobenzyl-N-3-(2,4-dichlorophenoxy)propylamine. USE:An agricultural and horticultural germicide. The aforementioned compound is readily produced with great stability and capable of exhibiting excellent antimicrobial action on various plant pathogenic germs. PREPARATION:For example, a phenol expressed by formula II is reacted with a dibromoalkane expressed by formula III in the presence of a base such as sodium hydroxide in a solvent such as water, an alcohol, dimethyl sulfoxide or dimethylformamide to provide a compound expressed by formula IV, which is then made to react with an amine expressed by formula V in the presence of a hydrogen bromide capturing agent in a solvent such as an alcohol or dimethyl sulfoxide to afford the objective compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a new N-dichlorobenzyl-N-phenoxyalkylamine and a new agricultural and horticultural fungicide.

[Prior Art, Invention or Problems to be Solved] Conventionally, inorganic or organic copper agents and antibiotic agents such as streptomycin have been used as fungicides against pathogenic bacteria that cause diseases in agricultural crops.

However, these conventional drugs have problems such as insufficient efficacy for practical use and the occurrence of drug damage, so they have an additional effect of bacteriostatic or bactericidal activity (both collectively referred to as antibacterial activity). It was hoped that the drug would be strong and cause fewer drug-induced injuries.

[Means and effects for solving the problem] As a result of intensive research to solve the problems of the prior art described above, the present inventors have developed a new N-dichlorohensyl-N
The present invention was achieved by discovering phenoxyalkylamines and further discovering that these compounds have bacteriostatic or bactericidal effects against pathogenic bacteria of agricultural and horticultural diseases.

That is, the second invention is an N-dichlorobenzyl-N-phenoxyalkylamine represented by formula I.

[However, in the -ritual II, n represents 3 or 4. The N-dichlorobenzyl-N-phenoxyalkylamine shown in the first ritual I in the second invention is, for example,
It can be manufactured as follows.

That is, ■ Phenol ■ and dibromoalkane ■ are reacted in the presence of a base such as sodium hydroxide in a solvent such as water, alcohol, dimethyl sulfoxide, or dimethyl formamide to convert it to compound ■, and then hydrogen bromide is supplemented. N-dichlorobenzyl-N-phenoxyalkylamine (2) of the present invention is obtained by reacting this compound (1) with amine (2) in a solvent such as alcohol, dimethylsulfoxide or dimethylformamide in the presence of an agent.

Table 1 shows the physical properties of N-dichlorobenzyl-N-phenoxyalkylamine shown in formula I in the present invention.

Further, the second invention is an agricultural and horticultural fungicide characterized by containing at least one type of N-dichlorobenzyl-N-phenoxyalkylamine represented by formula I as an active ingredient.

[In the ritual ■, n indicates 3 or 4] The N-dichlorobenzyl-N phenoxyalkylamine shown in the ritual ■ is
Co of homonas bacteria and tomato canker pathogen
It not only shows strong bacteriostatic or bactericidal action against bacteria of the genus Rynebacterium, but also shows strong antibacterial action against pathogens of other agricultural crop diseases.

All of these N-dichlorohensyl-N-phenoquine alkylamines are chemically stable and can withstand long-term storage.

Therefore, the agricultural and horticultural fungicide of the second invention containing these N-dichlorohensyl-Nphenoquine alkylamines as an active ingredient is highly practical.

In the agricultural and horticultural fungicide of the second invention, the active ingredient N-dichlorohensyl-N-phenoxyalkylamine has a broad antibacterial spectrum.

Therefore, the agricultural and horticultural fungicide of the second invention can be applied to, for example, citrus canker disease, rice leaf blight, peach borer bacterial disease, cabbage black rot, lettuce leaf spot bacterial disease, melon brown spot bacterial disease, and soybean leaf scorch disease. It is effective in controlling a wide range of diseases caused by various pathogens, including tomato canker and tomato canker.

The agricultural and horticultural fungicide of the second invention can be produced by using the novel compound of the first invention, and by a method known per se.
Conventionally used agricultural and horticultural chemicals such as liquids, emulsions, flowables (sols), powders, driftless (DL) powders, and granules, especially as fungicides, can be prepared into any dosage form. can.

As the carrier used in these preparations, those commonly used for agricultural and horticultural chemicals can be used, and there are no particular limitations.

For example, typical examples of solid carriers include mineral powders such as kaolin, bentonite, clay, talc and vermiculite, vegetable powders such as wood flour, starch and crystalline cellulose, petroleum resins, polyvinyl chloride, ketones, etc. There are polymeric compounds such as resin and tanmalgam. Representative examples of liquid carriers include water, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, 1so-propyl alcohol, butanol, ethylene glycol and benzyl alcohol, toluene,
Aromatic hydrocarbons such as benzene, xylene, ethylhensen and methylnaphthalene; halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene, trichlorofluoromethane and dichlorofluoromethane; ethyl ether; Ethers such as ethylene oxide and dioxane, ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate and ethylene glycol acetate, acid amides such as dimethylformamide and dimethylacetamide. sulfoxides such as dimethyl sulfoxide, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, petroleum ethers and solvents. These include industrial gasoline such as naphtha, and petroleum distillates such as paraffins, kerosene, and diesel oil.

Also, various surfactants can be used. Typical examples include nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl esters, anionic surfactants such as alkylbenzenesulfonates and alkyl sulfates, and laurylamine and stearyltrimethylammonium chloride. Examples include cationic surfactants and amphoteric surfactants such as betaine carboxylic acids and sulfuric acid esters.

There is no particular restriction on the content of the compound of the present invention in the above-mentioned preparation, and in practice, it is usually 0.00] to 95 wt%.
The content is preferably about 0.01 to 90 wt%. For example, in practice, the concentration is usually about 0.01 to 5 wt% for powders, DL powders, and granules, and about 1 to 75 wt% for irrigation agents, solutions, and emulsions. Ru.

The formulations prepared in this way, such as powders, driftless formulations and granules, can be applied as is,
Wettable powders, solutions, emulsions and flowables are applied after being diluted with water or a suitable solvent.

Furthermore, the agricultural and horticultural fungicide of the second invention can be used in combination with other agricultural and horticultural fungicides, herbicides, insecticides, plant growth regulators, fertilizers, and the like.

The agricultural and horticultural fungicide of the second invention can be applied as is or after being diluted to the foliage of crops, or applied to the surface of water, water, the surface of soil, or the inside of soil.

The application amount of the agricultural and horticultural fungicide of the second invention includes the type of target disease, the degree of disease, the type of target crop, the application site, the application method,
It varies depending on the time of application and the type of dosage form, but it is generally unspecified, or it is 2 to 6 kg per 10 ares for powders, driftless agents, and granules (all with an active ingredient concentration of 3 wt%). In addition, the active ingredient concentration of all wettable powders, liquids, emulsions, and flowables is 20 wt%)
Natote is used by diluting 0.05-3 kg with 100-5001 water.

The compound of the present invention has a strong antibacterial effect and is highly stable, so it can be applied over a wide range of periods and can be used not only for the treatment of crop diseases but also for their prevention.

[Example] The present invention will be explained in more detail with reference to Examples.

The present invention is not limited to these examples.

Example l Synthesis of N-3,4-dichlorobenzyl-N-3-(24-dichlorophenoxy)propylamine (compound 1) 2.40 g (8,45 mm) of 3-(2,4-dichlorophenoxy)propyl bromide ○1) was dissolved in 30 ml of ethanol, and 0.896 ml of anhydrous sodium carbonate was added to this.
g (8.45 mmol) and 2.64 g (1500 mmol) of 24-dichlorobenzylamine were added and
The mixture was heated to reflux for an hour. After cooling, the reaction mixture was poured into 100 ml of water and extracted with chloroform (30 ml x 3).

After drying the organic layer over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing agent: ethyl acetate/chloroform-4/6).
g (yield 53'%) of the title compound was obtained as a colorless oil.

The physical properties of this compound were as follows.

That is, HNMR (CDC13); δ = 1.55 (s, IH), 1.97 (quin
, J=6Hz, 2)1).

2.82(t, J=6Hz, 2H), 3.82(
s, 2)]).

4.10(t, J=6Hz, 2H), 6.78(
d, J-8t(z, IH).

7, 0-7.5(m, 5)()pi)m.

Elemental analysis: Calculated value C as C, 6H, 5C14NO
・50.69 H: 3.99 N: 3.6
9 (%) Actual value C・50.88 8・4.02 N: 3.61
(%) Example 2 Synthesis of N-3,4-dichlorobenzyl-N-4-(24-dichlorophenoxy)butylamine (compound 2) 4-(2,4-dichlorophenoxy)butyl bromide]
,, ]9g (4,00mmo 1) was dissolved in 20ml of ethanol, and 0.424g of anhydrous sodium carbonate was added to this.
(4,00 mmol) and 3,4-dichlorobenzylamine2. 1 g (12.0 mmol) was added thereto, and the mixture was heated under reflux on an oil bath for 6 hours. After cooling, the reaction mixture was poured into 80ml of water and extracted with chloroform (30ml x 3).

After drying the organic layer over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing agent: ethyl acetate/chloroform = 476).
5 g (72% yield) of the title compound was obtained as a colorless oil.

The physical properties of this compound were as follows.

That is, H-NMR, (CDC13) δ-1,32(s, 1)1), 1.79(m,
4H), 2.66(t, J=6Hz,
2H), 3.69(s, 2H), 3.94
(t, J=6Hz, 2H).

6.69(d, 8Hz, ], t(), 7.
0-7.5 (m, 5H) ppm.

Calculated value C as elemental analysis 1C1□H1□C14N0:
51.94 H: 4.36 N: 3.5
6 (%) Actual value C: 52.22 H: 4.51 N. 3.4
9 (%) Example 3 Synthesis of N-34-dichlorobenzyl-N-3-(34-dichlorophenoxy)propylamine (compound 3) 3-(3,4-dichlorophenoxy)propyl bromide 1.42 g (5 , OOmmol) in 25 ml of ethanol, and to this, 1.06 g of anhydrous sodium carbonate
(10.0 mmol) and 2.11 g (1.2.0 mmol) of 3.4-dichlorobenzylamine were added and heated under reflux on an oil bath for 8 hours. After cooling, the reaction mixture was added to 100 ml
of water and extracted with chloroform (20 ml x 3).

After drying the organic layer over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing agent: ethyl acetate/chloroform = 35/65).
42 g <75% yield) of the title compound was obtained as a colorless oil.

The physical properties of this compound were as follows.

That is, H-NMR (CDC13); δ=1.36 (s, IH), 1.91 (quin,
J=6Hz, 2H), 2.75ct, J=6H
z, 2H), 3.71(s, 2H), 3.97
(t, J=6Hz.

2H), 6.63(dd, J=9.3Hz, I
H), 6.89(d, J=3Hz, ]IH, 7,
04 (dd, J=9.2Hz, 1.8), 7.2
1(d, J=9Hz, 1l-1), 7.28(d
, J=9Hz, IH), 7.33(d, J=2
Hz, 1) 1) ppm.

Elemental analysis; Calculated value C as C, 6H, 5C14NO
: 50.69 H: 3.99 N: 3.6
9 (%) Actual value C: 50.99 H: 4.12 N: 3.
31 (%) Example 4 Synthesis of N-3,4-dichlorobenzyl-N-1-(34-dichlorophenoxy)butylamine (compound 4) 4-(3,4-dichlorophenoxy)butylbromide 1
．． Dissolve 50g (5.03mm, ol) in 30ml of ethanol, and add 0.530g of anhydrous sodium carbonate to this.
(5,00 mmol) and 2.13 g (12.1 mmol) of 3,4-dichlorobenzylamine were added thereto, and the mixture was heated under reflux on an oil bath for 6 hours. After cooling, the reaction mixture was added to 100 ml
of water and extracted with chloroform (30 ml x 3).

After drying the organic layer over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing agent: ethyl acetate/chloroform = 3/7).
g (80% yield) of the title compound was obtained as a colorless oil.

The physical properties of this compound were as follows.

That is, H-NMR (CDC13); δ = 1.28 (s, IH), 1.80 (m, 4
H), 2.67 (t, J・6Hz, 2H), 3
．． 73 (s, 2H), 3.91 (t, J=6Hz
, 2H).

6.64 (dd, J=9.2Hz, IH),
6.94 (d, J=2Hz, IH).

7.04 (dd, J=9.2l-1z, IH)
, 7.26 (d, 9Hz, IH), 7
．． 37.32 (d, J=9Hz, IH),
7.37 (d, J=2Hz, IH) ppm.

Elemental analysis, C10) Calculated as 117C14NO C: 51.94 H: 4.36 N: 3.
56 (%) Actual value C: 52.23 H: 4.53 N: 3
．． 66(γ) Formulation Example 1 (Wettable powder) Ingredients Parts by weight Compound 4 (hydrochloride) 20 Lignosulfonic acid 3 Polyoxyethylene alkyl allyl ether 2 Diatomaceous earth
75 The above ingredients were mixed uniformly to obtain a wettable powder containing 20% by weight of the active ingredient.

Formulation example 2 (powder) Ingredients Parts by weight Compound 4 (hydrochloride) 3 Calcium stearate
l Silicic acid anhydride powder l Clay 48 talc
47 The above ingredients were mixed uniformly to obtain a powder containing 3% by weight of the active ingredient.

Test Example 1 Antibacterial test against plant pathogenic bacteria The antibacterial activity of N-dichlorobenzyl-N-phenoxyalkylamine and N-dichlorobenzyl-N-phenoxyalkylamine salts against various plant pathogenic bacteria was investigated.

That is, Xanthomonas
cam-peStriS pV, campestri
s1 Citrus canker pathogen X.

CampeStriS pV, citri, rice blight fungus X, camp-estris pV, ory
zae, peach borer bacterial pathogen X, camp-eStri
S pV, pruni and tomato canker bacterium Co
ryn-ebacterium michiganen
Se pv, michiganense was used as a test bacterium, and the growth inhibition effect of the bacterium on an agar plate was investigated.

A test compound was mixed into a potato decoction medium with addition of peptone to make a 2-fold dilution series with a maximum concentration of 1100 pp.
An agar plate was created by pouring it into a Petri dish.

The test bacteria were inoculated onto an agar plate, and after culturing at 28°C for 2 days, the presence or absence of bacterial growth was investigated.

The results are shown in Table 2.

The compound of the present invention showed strong antibacterial activity against all pathogenic bacteria.

(Margin below) Table 2 Antibacterial test against plant pathogenic bacteria Minimum inhibitory concentration (ppm) Test example 2 Citrus canker disease control test A leaf piece approximately 1 cm square was cut from a Japanese oak leaf, and the leaf piece was soaked in a chemical solution prepared at a specified concentration for 20 minutes. After soaking, the leaf pieces were taken out from the chemical solution, and after the chemical solution was air-dried, a suspension of citrus canker bacteria (approximately 10''/ml) was inoculated with a needle.

The inoculated leaf pieces were placed in a Petri dish lined with moist filter paper and incubated at 28°C for 10 days.The onset of the disease was investigated, and the degree of disease was calculated according to the following formula.

In addition, the occurrence of drug damage was determined by visual observation.

The results are shown in Table 3.

Table 3: Citrus canker disease control test* Hydrochloride test example 3: Rice leaf blight control test: Spraying an aqueous solution of the test compound prepared at a predetermined concentration onto 5-leaf stage rice (variety Koshihikari) grown in a 6cm diameter pot. did.

One day later, a suspension of rice bacterial leaf blight prepared to 10''/ml was inoculated into leaves.

Three weeks after inoculation, the lesion length was measured, and the control value was calculated according to the following formula.

The results are shown in Table 4.

(Leaving space below) Table 4 Rice blight control test Test example 4 Soft rot control test Radish disks with a diameter of 2 cm and a thickness of 1 cm were prepared and immersed in a chemical solution prepared at a predetermined concentration for 1 hour.

This radish disk was taken out from the aqueous solution of the test compound, air-dried, and a bacterial solution was applied to the center of the disk.
After keeping at 8°C for 24 hours, the degree of disease onset was investigated, and the control value was calculated using the following formula.

Survey tisf number The results are shown in Table 5.

Table 5 Soft rot control test [Effects of the invention] The N-dichlorobenzyl-N-phenoquine alkylamines of the present invention are all new compounds, easy to manufacture, highly stable, and capable of controlling various plant pathogens. Shows excellent antibacterial activity against. Therefore, the agricultural and horticultural fungicide of the present invention is suitably used for controlling various plant diseases.

Claims (1)

[Claims] 1. N-dichlorobenzyl-N- represented by general formula I
Phenoxyalkylamines. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [However, in general formula I, n represents 3 or 4] 2. N-dichlorobenzyl-N- shown in general formula I
An agricultural and horticultural fungicide characterized by containing at least one phenoxyalkylamine as an active ingredient. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [However, in general formula I, n indicates 3 or 4]