JPS59139351A - N-(1-halogenoalkoxy-2,2,2-trichloroethyl)-salicylamide derivative and agricultural and horticultural fungicide containing said derivative - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is Br, Cl or I; n is 2-4; R is H, acetyl, propionyl, butyryl, etc.). EXAMPLE:N-(1-beta-Chloroethoxy-2,2,2-trichloroethyl)-0-acetylsalicylam ide. USE:An agricultural and horticultural fungicide. It exhibitis broad antifungal spectrum against phytopathogenic fungi, and is effective for the control of blights such as late blight of tomato, brown rust of wheat, grey mold of kidney beans, etc. Especially, the agent exhibits high fungicidal activity at a low concentration to the fungi of grey mold which is a main blight of vegetables and fruit trees. PROCESS:The compound of formula I wherein R is acetyl can be prepared by reacting the compound of formula II (R is acetyl) with equimolar amount of an alkylene halohydrin in an organic solvent such as acetone in the presence of equimolar amount of triethylamine. The obtained product is heated and refluxed in a solvent such as methanol in the presence of a small amount of concentrated hydrochloric acid to obtain another compound of formula I wherein R is H.

Description

Detailed Description of the Invention The present invention provides an N-(1-halogenoalkoxy-2,2,2-)lichloroethyl)-tyritylamide derivative represented by the following general formula [■] and an agricultural and horticultural fungicide containing the derivative. Regarding.

(wherein, X represents a bromine atom, a chlorine atom, or an iodo atom, n represents an integer of 2.3 or 4, and R represents a hydrogen atom, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a hexanoyl group, methoxyacetyl group, or 2
- indicates a furoyl group) Conventionally, agricultural and horticultural fungicides have been extensively researched and a large number of fungicides have been put into practical use, but some disease-causing bacteria have become resistant, making it difficult to control them. For example, methyl-1-(butylcarbamoyl)-2-penzimitaso-
7L/(generic name: benomyl), 1,2-bis(3-methoxycarbonyl-2-thioureido)-benzene (generic name: thiophanate methyl) and other benzimidazole-based fungicides and thiophanate-based fungicides (under μ, benzimidazole/thiophanate) However, the emergence of drug-resistant bacteria to these fungicides has caused problems such as reduced efficacy, making it difficult to control gray mold. The development of effective drugs is strongly desired.

Recently, cyclic N-(3,5-dichlorophenyl)imide compounds, including iprodione (trade name Lobraal), have been developed in this field and are expected to be effective control agents against benzimidazole thiophanate fungicide-resistant bacteria. There is.

However, like the benzimidazole/thiophanate fungicides mentioned above, there is concern that resistant bacteria may emerge against cyclic N-(3,5-dichlorophenyl)imide fungicides, and the present inventors have also A gray mold disease resistant to cyclic N-(3,5-dichlorophenyl)imide fungicides has been obtained.

In order to develop new agricultural and horticultural fungicides, the present inventors synthesized and screened a wide range of compounds, and found that the general formula (
The compound shown in 1) exhibits a wide spectrum of virulence against various plant pathogens, and is highly effective in controlling diseases of crops such as tomato late blight, wheat rust, and common bean gray mold, and is particularly effective against vegetables, fruit trees, etc. It was discovered that it has excellent bactericidal efficacy at low concentrations against gray mold fungus, which is a major disease of the world.

The compound of the present invention is an N-(1-substituted-2,2,2-)dichloroethyl)-saltylamide derivative represented by the general formula (1). As an example of application in the field, it is known that some compounds having an alkoxy group, cycloalkoxy group, or phenoxy group as a substituent are effective as soil fungicides (Japanese Unexamined Patent Publication No. 54-39040, (No. 163354, 1977). However, the aboveground diseases of vegetables and fruit trees were unknown.

The compound of the present invention has ω as the substituent of the N-(1-substituted-2,2,2-trichloroethyl)-saltylamide derivative
- It is characterized by having a halogenoalkoxy group, and has activity at significantly lower concentrations than compounds in which the substituent is a normal alkoxy group. Furthermore, the compound of the present invention is effective against the aforementioned benzimidazole-thiophanate fungicide-resistant bacteria, cyclic N-(3,5-dichlorophenyl)imide-based fungicide-resistant bacteria, and wild bacteria susceptible to these drugs (drug-susceptible bacteria). The novel N-(1-halogenoalkoxy-2,2
, 2-trichloroethyl) - an agricultural and horticultural fungicide containing a salicylamide derivative provides an agent that accurately controls gray mold, including drug-resistant bacteria, which is a major disease of vegetables and fruit trees. (1-halogenoalkoxy-2,2,
Examples of 2-trichloroethyl)-salicylamide derivatives are shown in Table 1.

In Table 1 NMB data, S: single line, d: double line, t: triple line, q: quartet, p
: represents triplet, m: represents multiplet.

The compound according to the present invention can be synthesized as follows by Ohji.

(In the formula, X, n, and R have the same meanings as above.) That is, N-
(1,2,2,2-tetrachloroethyl)-〇-acetylsalicylamide (II.

The desired compound CI can be easily obtained by stirring R=COCHs) at room temperature for 30 minutes to several hours in the presence of equimolar alkylene halohydrin and equimolar triethylamine in an organic solvent such as acetone.

R=COCH8) can be obtained. If the compound CD is oily, it can be separated and purified by silica chromatography or the like, and if it is crystalline, it can be purified by recrystallization or the like.

When a compound in which R of compound (1) is a hydrogen atom is desired, by heating and refluxing the acetylated product obtained by the above method with a small amount of concentrated hydrochloric acid in a solvent such as methanol for several hours, (1)
The target compound in which B is a hydrogen atom can be obtained.

Furthermore, the acylated compound [I] can also be obtained by using a compound in which R in [1] is a hydrogen atom and adding an acid chloride such as acetyl chloride in an organic B medium such as acetonitrile in the presence of triethylamine under cooling with ice water. You can get it.

The present invention will be explained in more detail with reference to Examples below.

Tyramide (Synthesis of Compound No. 5) Dissolve 3.49 (0.01 mol) of N-(1,2,2,2-tetrachloroethyl)-〇-acetylsalicylamide in acetone 40- and add ethylene chlorhydride at room temperature. 0.8 g (0.01 mol) of phosphorus was added, and 1.0 g (0.01 mol) of triethylamine was added and stirred for 3 hours.The reaction solution was poured into water, and the oily substance that separated was extracted with chloroform. The chloroform layer was separated, dried over sodium sulfate, and concentrated to give a brown oil.This was washed with benzene:acetone (10
1.59 (yield: 38.5 cm) was obtained.

The results of IR and NMR analysis of this compound are described below.

I R (KBr, cyn') * 3350 (
NH) -1760 (OCO).

1675 (CONH) NMR (d, -DM80) δ (ppm); 222 3)
t(s, Cα”BJ3.69~4,16 4H(m, C
H, Cl+OCH*).

5.94 1H (d J = 10Hz NHCH),
7.2°7-7.83 4H (m benzene ring proton).

9-50 1H (dJ = 10 Hz, NH) N-(1-β-chloroethoxy-2,2,2-trichloroethyl)-〇-acetylsalicylamide 0.9 g (
0,0023-Fnyl) f Dissolved in 3° of methanol, added 02 rnl of concentrated hydrochloric acid, and heated under reflux for 2 hours. After cooling, the reaction solution is poured into water, and the precipitated white crystals are dried apart from P. A small amount of n-hex was obtained.

The analysis results of one liter of the compound and NMR are described below.

I R(KB r + crn ) −343o(N
H) -1650 (CONH) NMR (d, -DMSO) δ (ppm); 3.
70~4.214 H(m, Cl(J+OCR,),
6.05 1H (d.

J=10Hz, NHCH), 6.82~8.20 4H
(m, benzene ring proto:/), 9.49 1H (d.

J = 10 Hz 7 NQ), 11-73 1
H(s, benzene ring-o-H) N-(1-β-iodoethoxy-2,2,2-trichloroethyl)-salithylamide 1.5 g (0,0034
mol) in 30-mol of acetonitrile and 0.32-mol of propionyl chloride. ! After adding 1 l (o,oo 34 moles), 0.35 g (0,0
,0034 mol) was added dropwise. After stirring for 2 hours under cooling with ice water, the reaction solution was poured into water and the separated oil was extracted with chloroform. After drying the chloroform layer with sodium sulfate,
Concentration gave a colorless oil. After that, it solidified and the yield was 83.
Section 3) Obtained.

The analysis results of one liter of the compound and NMR are described below.

IR(, KBrym-'); 3180
(NH), 1760 (OCO), 1655 (CON
H) NMR (d6-1) M2O) δ (ppm); 1.1
8 3H (t y J = 7) Tz s CHt C
Ha ), 2-61 2 H (qtJ=7Hz, CO
C tan x ) e 3.41 2 H (t9 J = 6
H2JCH,I), 4.03 2H(t, J=6Hz,
QC Dan, ).

5.95 1 H (d, J = 10 Hz y NH
Cfl), 721-7.90 4H (m, benzene ring proton), 9.561 H (dt J = 10
H2y NH) Example 4: N-(-1-r-bromopropoxy N-(1,2,2,2-tetrachloroethyl)
-〇-acetylsalithylamide 3.4,! i' (0
, 01 mole) was dissolved in 40 g of acetone, processed with 1.41 g (o, o i mole) of propylene bromohydrin, further added 1.0 g (o, o i mole) of triethylamine, and stirred at room temperature for 2 hours. did. The reaction solution was poured into water, and the separated oil was extracted with chloroform. The chloroform layer was dried over sodium sulfate and concentrated to obtain a brown oil.

Using Wakogel C-200, benzene:acetone (10:1.4 fi (yield: 31.8 yen)) was obtained.

The analysis results of one liter of the compound and NMR are described below.

IR(I(Br cnl-'): 3300(NH)
, 1770 (OCO), 1655 (CONH) NMR (d, -DMSO) a (J)I)m);
1.98~2.382 H (m, C mountain CH * B')
, 2.22 3 H (S JCOCH,) , 3.
52~4.03 4H(m, Cf(, Br+OCHt
), 5-86 1 H (d7 J = 9 Hz,
NHCH).

7.20-7.884H (m-cubenzene ring pro):/)
.

9.43 1H (d, J = 9 Hz, NH) synthesis N-(1-r-bromopropoxy-2,2,2-trichloroethyl)-salicylamide 1.5 g (0,0034
mol) in 40 l of acetonitrile, added 0.3711 (0,0034 mol) of methoxyacetyl chloride, and then dissolved 0.35 g (0.0 mol) of triethylamine under cooling with ice water.
,0034 mol) was added dropwise. After stirring for 1 hour under cooling with ice water, the reaction solution was poured into water, the precipitated semi-solid material was extracted with chloroform, and the chloroform layer was dried over sodium sulfate and concentrated to obtain a colorless oil. Then the hardware number 2v
1.4 as a white crystal,! i' (yield: 79.5cm) was obtained.

The results of IR and NMR analysis of this compound are described below.

I R(KB'7 tyn"""): 32
00 (NH) p 1780 (OCO), 1650 (
CONH) NMl'l, (d, -DM80) δ (ppm); 2.
162H (p.

J=6Hz, CHlCHtBr), 3.43 3H(s
, 0CHJ3-67 2 H(' , J = 6 Hz-
C11t Br ), 3.892 H (t J =6
Hz OCHt ), 4-30 2 H (S/-
! ri"0CHt) p 5.B 3 1 H (dJ = 9
Hz, NHCH).

! 7.23-7.88 4H (benzene ring proton)9.
50 1H(d,J=9H2,NH)N-(1-γ-chloropropoxy2.2.2-trichloroethyl)salicylamide 1.5g (0,004 mol) was dissolved in acetonitrile 4o-, butylene Lyl chloride 0.44 g (0
,004 mol), and then 0.4 fJ (0,004 mol) of triethylamine was added dropwise while cooling with ice water. After stirring for 1.5 hours under cooling with ice water, the reaction solution was poured into water, the oily substance separated was extracted with chloroform, the chloroform layer was dried over sodium sulfate, and concentrated to obtain No. 26) as white crystals. 3 g (yield: 73.9 g) was obtained.

The IB and NMR analysis results of this compound are described below.

IR (KBrt♂'): 3210 (NH)
* 1760 (OCO) 1655 (CONH) NMR (d6-DMSO) δ (pI) Ill): 0.
97 3H (t.

J = 7Hz, CH, CH, ), 1.65 2H (sextet, J = = 7H1, CHt CHs ), 2.06
2 H (pt J = 6 Hz.

C4 (, CH, CJ), 2.51 2H (t, J=7H
z.

COCL ), 3.75 2 H (tJ = 6 F-
1z t C pigeon C1l)! 3.89 2 H (t J = 6 Hz, OCL)
-5-81 evening IH (d, J=10H2, NHC ratio), 7.10-7.
804 H (m s benzene ring proton), 9.39
1F ((d, J=10)-IZ, N11) The present invention uses these compounds as they are or in the form of a carrier (diluent).
It is advantageously used as a sprouticide for agriculture and horticulture in the form of a powder, wettable powder, granule, emulsion, or liquid by mixing with. It is of course possible to ensure the effectiveness of the agricultural and horticultural disease control agent of the present invention by adding auxiliary agents such as spreading agents, emulsifiers, wetting agents, and fixing agents as necessary. In addition, even when mixed with other chemicals, there is no risk of decomposition or deterioration of the chemical itself, and there is no risk of degrading or deteriorating the other chemicals, so it can be used in combination or in combination with other fungicides, insecticides, fertilizers, etc. .

Next, some examples will be shown to demonstrate the effectiveness of the compounds of the present invention, but the carrier (diluent) and auxiliary agents, their mixing ratio, and the active ingredients can be varied within a wide range.

Compound of the present invention (compound number 2) 3 Clay 40 Targ
57 was ground and mixed and used as powder.

Formulation 2: Parts by Weight of Irrigation Compound of the Invention (Compound No. 16) 50 lignin sulfonate 5 alkyl sulfonate 3 diatom ± 42 are ground and mixed to make a wettable powder, which is used after being diluted with water.

Below are biological test examples showing the excellent bactericidal efficacy of the compounds of the present invention.

Example 7: Green bean gray mold control effect test diameter 10I:
For green bean leaves (variety: Taisho Kintoki) at the first true leaf stage grown using a 1N clay body, a water diluted solution of the test compound in the form of a hydrating powder as in Formulation 2 was added per pot at 10 mgtt+.
Sprayed on foliage. After spraying leaf wind, a circular agar section (5 diameter) containing bacteria of drug-resistant or susceptible Botrytis bacterium, cultured in advance at 20°C for 4 days on a sucrose-added potato decoction agar medium, was placed in the center of the leaf. Directly attached, 20-22℃ for 4 days
After keeping the plants in a greenhouse, the disease severity was determined according to the following survey criteria and expressed as the average disease severity. (Use 4 leaves per treatment area) (Survey criteria) 0.5 for non-infected plants 1. for infected plants only directly under or around the inoculated agar piece 1. for infected plants whose area ratio of inoculated leaves is less than 20-2
〃 20～40chi 〃3
〃 40～60chi 〃4
p 60-80% /15
The results are shown in Table 2. Example 8 Nidomado blight control effect test Four-leaf stage tomato seedlings (variety: Fukuju No. 2, 1 plant/pot) grown using a clay pot with a diameter of 10 wounds. An irrigation agent such as Formulation 2 was diluted and suspended in water to a predetermined concentration, and then sprayed on the plants (3 pots/treated area used). After drying the sprayed leaves, a Phytophthora spore suspension cultured in advance on potato tubers was spray inoculated onto the tomato leaves sprayed with chemicals.
After being kept in a greenhouse at 20-22°C for 2 days, it was left in the greenhouse. Four days after inoculation, the degree of disease was investigated according to the following survey criteria and expressed as the average degree of disease per plant.

(Survey criteria) Disease severity Level of disease: 0 No disease: 0.5 Disease: 10 or less disease based on the area ratio of inoculated leaves 1: Disease with an area ratio of 10 to 20% of the inoculated leaves 2: Area ratio of inoculated leaves 3. Infection in about 20-40% of inoculated leaves. 4. Infection in about 60-80% of inoculated leaves. 5. Infection in about 60-80% of inoculated leaves. 5. Table 3 shows the results of disease onset.

Table 3 Example 9: Wheat rot disease control effect test Irrigation as in formulation 2 was applied to young wheat seedlings at the third true leaf stage (variety: Norin No. 64, 16 plants/pot) grown using clay pots with a diameter of 10 crR. The agent was diluted and suspended in water to a predetermined concentration, and then sprayed. After spraying and drying the leaves, the spore liquid of wheat rot rotifolia collected from the diseased leaves was spray inoculated and kept under high humidity conditions at 20 to 25°C for 24 hours. Thereafter, the plants were left in a glass greenhouse, and after 7 days, the disease severity was investigated for the 10 plants according to the following investigation criteria and expressed as the average diseased dust per leaf.

(Survey criteria) Morbidity Degree of disease: 0 No disease: 0.5 Lesion area ratio: 5 cm or less 1
〃 5-10 yen 2 〃 10-30% 3 〃 30 y or more The results are shown in Table 4.

Table 4

Claims (2)

[Claims] (1) General formula (wherein,
Acetyl group, propionyl group, butyryl group, imbutyryl group, hexanoyl group, methoxyacetyl group or ゛2-
An N-(1-halogenoalkoxy-2*2,2-trichloroethyl)-salicylamide derivative represented by (representing a furoyl group). (2) General formula (wherein,
N-(1-halogenoalkoxy-2,2,2-)lichloroethyl)-salicylamide derivatives represented by acetyl group, propionyl group, butyryl group, isobutyryl group, hexanoyl group, methoxyacetyl group or 2-furoyl group) An agricultural and horticultural fungicide containing.