JPS61191659A - Novel n-(1-halogenoalkoxy-2,2,2-trichloroethyl)-o-acylated salicylamide derivative - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (X is Br, Cl; n is 2, 4; R is ethyl, n-propyl, isopropyl, methoxymethyl). EXAMPLE:N-[1-(2-Bromethoxy)-2,2,2-trichloroethyl]-O-butyrylsalicylamide. USE:A fungicide for agricultural and horticultural purpose. PREPARATION:N-(1-Halogenoalkoxy-2,2,2-trichlorethyl)salicylamide of formula II is allowed to react with an equimolar amount of an acid chloride in the presence of triethylamine in an organic solvent such as acetanilide under stirring for 30min to several hours to give a compound of formula I. When the product is liquid, it is isolated and purified by means of silica-gel chromatography and the crystalline product is purified by recrystallization.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the following general formula fi1 00R (wherein, or methoxymethyl group), a novel N-(1-)logenoalkoxy 2,2.2-
) -o-y sylated salicylamide derivatives.

BACKGROUND ART N-(1-substituted-2,2゜2-
Some salicylamide derivatives similar to trichloroethyl)-0-acylated salicylamide derivatives are known. For example, in an N-(1-substituted-su2.2-)lichloroethyl)-〇-acylated salicylamide derivative, the substituent is an alkoxy group.

Compounds having a cycloalkoxy group or a phenoxy group have already been disclosed (JP-A-54-39040, JP-A-57-163354).

The compound according to the present invention has an ω-haloalkoxy group as the above-mentioned substituent (N-(1-substituted-2,2°2-)! J
This is a loethyl)-〇-acylated naritylamide derivative, which is a novel compound synthesized for the first time by the present inventors and which has not been described in any literature. The compounds according to the present invention will be explained in detail below.

Structure of the Invention Next, specific examples of the compounds according to the present invention and their physical and chemical properties are shown in Table 1.

The compound of the present invention can be easily obtained by adding triethylamine in an equimolar amount to chloride and stirring for 30 minutes to several hours. If the target compound is oily, it can be separated and purified by silica gel column chromatography or the like, and if it is crystalline, it can be purified by recrystallization or the like.

Specific examples of synthesis of the compounds of the present invention are shown below.

Synthesis of 1.9 g (0,0048
T-ru) with acetonitrile 30dK? i! n-butyryl chloride a529 (0,004
After adding triethylamine o (9 mol) under ice water cooling,
, sg (o, o 04 ra soru) was added dropwise.

After stirring for 2 hours, the reaction solution was poured into ice water, and the precipitated oil was extracted with chloroform. The chloroform layer was separated, dried over anhydrous sodium sulfate, and concentrated to obtain 12 g of a pale yellow oil.

This was purified by silica gel chromatography (developed with benzene) to obtain L59 (yield 6&2%) as compound number 1 of t L 5369 as a colorless oil.

IR (NaOt, ff1-”): 3400 (NH
), 2950, 2s5G (aQ.

1750 (000), 1660 (OONH) order NMR (00t4) δ (ppm): LO3 (3H,
t, Jffi7H! :Co(On,),cB,),
L73 (2H, sextuple line, J = 7H!: 000H Gonobu OH
@) e L60 (2H-te J”= 7H
z:000&), 141i1(2H,t, J
”6Hx: 0HJr).

408 (2H*t-J=6 Hz: OOH)
-&89(I H-d, J=10Hz: NH
OH), 7.08~&10 (5H, m: benzene ring once + r Tsui) Synthesis of rusalicylamide (compound number 4) N-(1-(
1.7 g (0,0049 moles) of salicylamide (2-chloroethoxy)-2,2,2-trichloroethyl) was dissolved in acetonitrile 25-, and propionyl chloride α469 (0,Q O49 moles) was added to this at room temperature. After adding triethylamine o, s g (α
0049 mol) was dissolved in acetonitrile 3- and added dropwise.

After stirring for 2 hours, the reaction solution was poured into ice water, and the precipitated oil was extracted with chloroform. The chloroform layer was separated, dried over anhydrous sodium sulfate, and concentrated to obtain a pale yellow oil L99. This was purified by silica gel chromatography (developed with benzene) to obtain 1.3 g of colorless oil (
A yield of 66% was obtained.

It became crystallized while standing, so it was recrystallized from n-hexane to give m and p.
, Compound No. 4 at 65-7°C as white crystals 1,1
g (yield 58%) was obtained.

IR (KBr, ca): 3200 (NH),
295G(OH,), 1745(000),
164G (OONH) NMa, oaz, ) δ (ppm)
: L21 (3H, t + J = 7Hx :OH 禦Oj
i#), 162 (2H, q, J=7Hz:
00 fluent).

&63 (2H, t, J = 5H work: OH, oz), 40
0 (2H.

t, J=5H! : O(%), &86(IH
, d, J=10H Fuji NHqΩ, 7.02~&02
(SH, m: benzene monkey) N-(1-(2-chloroethoxy)-2,λ2-trichloroethyl)-salicylamide α7g (0,0G 2mol) was dissolved in acetonitrile 2o-, To this was added 22 g (α002 mol) of methoxyacetylamide α at room temperature, and then 0.2 g of triethylamine ((
1002 mol) was dissolved in 2sdK acetonitrile and added dropwise. After stirring for 1 hour, the reaction solution was poured into ice water. The precipitated white crystals were washed with P separately and dried, and then recrystallized with a 5:1 mixed solvent of n-hexane and benzene 25-m, p,
83 Compound No. 7 at 5°C as white crystals α6g (
Yield: 72%).

CKBr, am-”): 3200 (NH), 2
940 (OH,), 1770 (000), 1650
(OONH)NMR')a@-DM80)δ(pI
) m) : 142 (3H-a : 00!!j) 16
3~418 (4H-m: O!!jOt+OO!b)
, 430 (2H1s:0OOH*)e&90(IHl
d-J-9Hx: MW Dan), 7.20-7.88 (4H
, m: benzene ring).

9.52 (IH, d, J=9Hz:) However) N-(1
-(4-chlorobutoxy)-2-2-trichloro is ethyl] 1.6 g (0,0042 mol) of salicylamide is dissolved in acetonitrile/L/25 mg, and 45 g of isobutyryl chloride α (0,0, After adding 0.439 (0.042 mol) of triethylamine under cooling with ice water,
,0042 mol) was dissolved in acetonitrile 3- and added dropwise. After stirring for 3 hours, the reaction solution was poured into ice water. After separating the precipitated white crystals in a furnace, washing with water, and drying them, the n-
Recrystallization from 18-hexane gave 1.39 (yield 70%) of Compound No. 10 with m, p, 80 2°C as white crystals.

IR (KBr, cm): 3210 (NH), 29
50(OH,), 175G(000), 1660(
OONH)NMR*(007m)δ(ppm): u9
(6H, ds, r=7H!: 0H(0!!j)*) #
16ON102 (4H, m: (OH*) snow) -2
, 80 (IH, septet line: 0OOH<) , 149 (
2H,t.

Jx6kh: 0HIOt), 3.72(2H,
t, J=6Hx:0%), &69(IH,
d, J=10Hz: NHO! Ω.

6.90-7.98 (5H, m: benzene ring once + trace)
The NMR data for each of the above synthesis examples are shown below.

*s: single line, d: double line, t: triple line.

q: quartet, 1m: multiplet, J: coupling constant.

Utility of the Invention The N-(1-halogenoalkoxy-&2.2-)lichloroethyl)-〇-acylated salicylamide derivative of the present invention has a broad spectrum of antibacterial activity against various plant pathogenic bacteria. In particular, it exhibits excellent bactericidal efficacy in controlling diseases of agricultural crops such as tomato late blight, cucumber downy mildew, and common bean gray mold.

The bactericidal effect of the compound according to the present invention against the above-mentioned pathogenic bacteria will be specifically explained below.

The compound of the present invention is advantageously used as an agricultural and horticultural fungicide as it is or in the form of a powder, wettable powder, etc. by mixing with a carrier (diluent).

In the present invention, if necessary, auxiliary agents such as spreading agents, emulsifiers, wetting agents, and fixing agents can be added to the agricultural and horticultural pest control agent to ensure the effect. .

Next, some formulation examples and test examples are shown to demonstrate the bactericidal effectiveness of the compounds of the present invention, but the types of carriers (diluents) and auxiliaries, their mixing ratios, and active ingredients can be varied within a wide range. It is something.

[Formulation Example 1] Form 2 Powder Parts by weight of the compound of the present invention (compound number 4) 3 parts clay 40 parts talc are pulverized and mixed and used as a powder.

[Formulation Example 2] Form 2 hydrating powder Parts by weight Compound of the present invention (Compound No. 5) 50 Lignin sulfonate
5 Alkyl sulfonate 3 Diatoms ± 42 are crushed and mixed and used as an irrigation agent by diluting with water.

Examples of biological tests showing the excellent bactericidal efficacy of the compounds of the present invention are shown below.

[Test Example 11 j7) Epidemic control effect Vermilion wildebeest scoop diameter 10cm
Four-leaf stage tomato seedlings (varieties;
Formulation example 2 for Fukuju No. 2, 1 plant/pot, 3 pots/treated area)
An irrigation agent such as the following was diluted and suspended in water to a predetermined concentration and then sprayed. After air-drying the sprayed leaves, the spore liquid of tomato Phytophthora blight collected from the diseased leaves was spray inoculated and kept in a greenhouse at 20-22°C for 24 hours.
It was then placed in a glass greenhouse. Five days after inoculation, the degree of disease was investigated according to the following survey criteria and expressed as the average degree of disease per tree.

(Survey criteria) Disease severity: 0 No disease: 0.5 Disease: 10% or less of inoculated leaf area 1
Infection occurs in 10-20% of the area of inoculated leaves 2
20 to 40% of inoculated leaves are infected 3
4. Infection with 40-60% of the area of inoculated leaves
Table 2 shows the results of 5 cases where the area ratio of the inoculated leaves was 60 to 80% and the area ratio of the inoculated leaves was 80% or more.

Table 2 Compound number Active ingredient Morbidity concentration (ppIn) 1 500 0.52
l 1 3 l O 4l α5 5 l 0 6 I 1 8 l α5 10 # 111
I 1 No treatment 5 [Test Example 2] Cucumber and disease control effect test diameter 10c+
Cucumber leaves at the second true leaf stage grown using ++ unglazed remains (variety: Sumo Hanshiro, 1 sown/pot.

An irrigation agent such as Formulation Example 2 was diluted and suspended in water to a predetermined concentration and then sprayed on 3 pots/treated area). After drying, the sprayed leaves were spray-inoculated with cucumber and the spore solution of the diseased bacteria collected from the diseased leaves.
It was kept under high humidity conditions of 2 to 23°C for 24 hours, and then left in a greenhouse. 7 days after inoculation, one leaf/pot according to the following investigation criteria.
The disease severity was investigated for 3 pots/treatment and expressed as the average disease severity per leaf.

(Survey criteria) Disease severity Disease severity O No symptoms 0.5 Diseases with an area ratio of 10% or less of inoculated leaves 1
Infection occurs in 10-20% of the area of inoculated leaves 2
20 to 40% of inoculated leaves are infected 3
4. Infection with 40-60% of the area of inoculated leaves
Table 3 shows the results of 5 cases where the area ratio of the inoculated leaves was 60 to 80% of the disease onset and 80% or more of the area ratio of the inoculated leaves.

Table 3 Compound number Active ingredient Morbidity concentration (ppnl) 1 500 α5 2 1 (L53
1 G4 l
O 5I α5 6 l α57
l O 8# 0.5 9 l 0 10 l 111
No IO treatment 5 [Test Example 3] Green bean gray mold control effect test diameter 10
An irrigation agent such as Formulation Example 2 was diluted and suspended in water to a predetermined concentration and sprayed on green beans (cultivar: Taisho Kintoki) grown in 0II+ clay pots at the first true leaf stage. After air-drying the sprayed leaves, incubate them at 20°C using a potato decoction agar medium containing sucrose in advance.
A calligraphic agar circular section (diameter 5 haze) of Botrytis cinerea that had been cultured for 1 day was directly attached to the center of the leaf and kept at 20-22°C for 4 days.
After keeping the plants in a greenhouse, the degree of disease was determined according to the following survey criteria and expressed as an average degree of disease. (Using 4 leaves per treatment area) (Survey criteria) Disease severity Disease severity 0 No symptoms α5 Diseases developed only directly under or around the inoculated calligraphic agar piece 1 Diseases occurring in 20% or less of the area of inoculated leaves thing 2
20 to 40% of inoculated leaves are infected 3
Infections with an area ratio of 40 to 60% on inoculated leaves 4 Infections with an area ratio of 60 to 80x on inoculated leaves 5 Infections with an area ratio of 80% or more on inoculated leaves The results are shown in Table 4. .

Table 4 Compound number Active ingredient Morbidity concentration (p) 2 l O 3I α5 4 1 G5
I 0 11 #0 No processing
5

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents a prom atom or a chlorine atom, n represents an integer of 2 or 4, and R represents A novel N-(1-halogenoalkoxy-2,2,2-trichloroethyl)-0-acylated salicylamide derivative represented by ethyl group, n-propyl group, isopropyl group or methoxymethyl group.