JPH04321652A - Secondary amine organic acid salt and agricultural and horticultural fungicide - Google Patents

Abstract

PURPOSE:To obtain a new readily producible salt comprising an N-benzyl-N- dichlorophenoxyethylamine and an organic acid, suitable for controlling various plant disease damages, showing excellent antifungal actions on various plant pathogenic fungi, having high stability free from phytotoxicity. CONSTITUTION:A salt comprising an N-benzyl-N-dichlorophenoxyethylamine shown by formula I (n is 2 or 3; m is 1 or 2 with the proviso that a compound wherein m=1, the 4-position is substituted and the 2,4-positions of phenoxy group are substituted is omitted; HX is organic group) and an organic acid, such as N-3,4-dichlorobenzyl-N-2-(3, 4-dichlorophenoxy)ethylamine benzoate. The compound shown by formula I, for example, is obtained by reacting dichlorophenol with dibromoethane in the presence of a base, then reacting the resulting substance with an amine shown by formula II to give an N-benzyl- N-dichlorophenoxythylamine shown by formula III and further reacting this compound with an organic acid.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention provides novel N-benzyl-
The present invention relates to a salt consisting of N-dichlorophenoxyethylamine and an organic acid, and a novel fungicide for agricultural and horticultural use. BACKGROUND OF THE INVENTION Conventionally, inorganic or organic copper agents, and antibiotic agents such as streptomycin have been used as bactericidal agents against pathogenic bacteria that cause diseases in agricultural crops. However, these conventional drugs include
Since the efficacy is not sufficient for practical use and there are problems such as the occurrence of drug damage, it is necessary to have an additional bacteriostatic or bactericidal effect (
There was a desire for a drug that had a strong antibacterial effect (both of which are sometimes referred to collectively as ``antibacterial activity'') and that caused less drug damage. [Means for Solving the Problems and Effects] As a result of extensive research to solve the problems of the prior art described above, the present inventors have developed a novel N-benzyl-N-dichlorophenoxyethylamine and an organic acid. The present invention was achieved by discovering the following salts and also by discovering that these compounds have bacteriostatic or bactericidal effects against pathogenic bacteria of agricultural and horticultural diseases. That is, the first invention is a salt consisting of N-benzyl-N-dichlorophenoxyethylamine represented by Chemical Formula 1 and an organic acid. [In Chemical Formula 1, n represents 2 or 3, and m represents 1 or 2. However, m is 1 and the 4th position is substituted, excluding compounds in which the 2nd and 4th positions of the phenoxy group are substituted. Moreover, HX represents an organic acid. [0002] The salt of N-benzyl-N-dichlorophenoxyethylamine and an organic acid represented by Formula 1 in the first invention can be produced, for example, as follows. That is, [Chemical formula 2] Phenol (a) and dibromoethane (b) are reacted in the presence of a base such as sodium hydroxide in a solvent such as water, alcohol, dimethyl sulfoxide or dimethylformamide to form compound (c). After conversion, this compound (c) is dissolved in a solvent such as alcohol, dimethyl sulfoxide or dimethyl formamide in the presence of a hydrogen bromide scavenger.
and amine (d) are reacted to obtain N-benzyl-N-dichlorophenoxyethylamine. Next, (Chemical formula 1) is obtained by reacting this N-benzyl-N-dichlorophenoxyethylamine with an organic acid. [0003] The organic acid used in this case is not particularly limited, but typical examples include carboxylic acid, thiocarboxylic acid,
Mention may be made of sulfonic acids, sulfinic acids, or organic phosphoric acids. More specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, citric acid, pivalic acid, decanoic acid, lauric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, Aliphatic dicarboxylic acids such as adipic acid, maleic acid, fumaric acid, carbocyclic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, substituted benzoic acid, naphthoic acid, cinnamic acid, furocarboxylic acid, thiophene Carboxylic acid, pyrrolecarboxylic acid,
Heterocyclic carboxylic acids such as pyridinecarboxylic acid, sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-methylbenzenesulfonic acid (p-toluenesulfonic acid), monobutyl phosphate, dibutyl phosphate,
Monobenzyl phosphate, dibenzyl phosphate,
Organic phosphoric compounds such as 2-ethylexyl phosphate, di-(2-ethylhexyl) phosphate, etc. may be used. [0004] Further, in the production of these salts, a reaction solvent is not necessarily required, but alcohols, ethers, esters, and other commonly used reaction solvents as well as water can also be used as reaction solvents. Moreover, there is no particular restriction on the reaction temperature. The salt consisting of N-benzyl-N-dichlorophenoxyethylamine and an organic acid of the first invention is solid or liquid at room temperature, and if it is solid, it can be separated from the reaction product by ordinary solid-liquid separation means such as filtration and centrifugation. The recovered crystals can be purified, if desired, by washing and recrystallization from alcohol or water. Table 1 shows the physical properties of N-benzyl-N-dichlorophenoxyethylamine, which is a precursor in the present invention, and Table 2 shows the melting points of solid organic acid salts thereof. [Table 1] Table 1 Physical properties of N-benzyl-N-dichlorophenoxyethylamine 1st stage Compound number, Cl2, Clm 2nd stage and subsequent stages ■State, melting point
■NMR measurement value 1H-NMR
(CDCl3) δppm
1 2,4-Cl2
2-Cl ■ Colorless columnar crystals
Melting point 54 ~ 55℃ ■
2.05 (s, 1H), 3.01 (t, J=5Hz,
2H), 3.93(s, 2H),
4.07(t, J=5Hz, 2H), 6.73(
d, J=9Hz, 1H), 7
．． 11 (dd, J=9, 2Hz, 1H), 7.2-7.
5(m,5H) 2 2,4-C
l2 3-Cl ■ Colorless oil Melting point (hydrochloride) 135 ~ 137
°C ■ 1.76 (s, 1H), 3
．． 01(t, J=5Hz, 2H), 3.85(s, 2H
), 4.09(t, J=5
Hz, 2H), 6.79 (d, J=9Hz, 1H),
7.14 (dd, J=9,2H
z, 1H), 7.20 (s, 4H), 7.32 (d, J
=2Hz, 1H) 3 2,4-
Cl2 3,4-Cl2
■ Colorless needle crystals Melting point 42-43℃
■ 1.87 (s, 1H), 2.9
9 (t, J=5Hz, 2H), 3.81 (s, 2H),
4.08 (t, J=5Hz
, 2H), 6.75 (d, J=8Hz, 1H), 7.0
-7.4 (m, 5H) 4 3,
4-Cl2 2-Cl ■
Colorless columnar crystals Melting point 64-66℃
■ 1.91 (s, 1H), 3.00 (
t, J=5Hz, 2H), 3.93(s, 2H),
4.02(t, J=5Hz, 2
H), 6.67 (dd, J=9, 2.5Hz, 1H),
6.93 (d, J=2.5
Hz, 1H), 7.1-7.5 (m, 5H)
5 3,4-Cl2 3-Cl
■ Colorless oil Melting point (hydrochloride) 180 ~ 182℃ ■ 1
．． 75 (s, 1H), 2.97 (t, J=5Hz, 2H
), 3.81(s, 2H),
4.01 (t, J=5Hz, 2H), 6.68 (dd
, J=9, 2.5Hz, 1H),
6.95 (d, J=2.5Hz, 1H), 7.1
-7.3 (m, 5H) 6 3,4
-Cl2 4-Cl ■
Colorless needle crystals Melting point 63-65℃
■ 1.76 (s, 1H), 2.96 (t
, J=5Hz, 2H), 3.80(s, 2H),
4.00 (t, J=5Hz, 2H
), 6.69 (dd, J=9, 2.5Hz, 1H),
6.94 (d, J=2.5H
z, 1H), 7.23 (s, 4H), 7.29 (d, J
=9Hz, 1H) 7 3,4-C
l2 2,4-Cl2
■ Colorless columnar crystals Melting point 37-39℃
■ 1.83 (s, 1H), 3.00
(t, J=5Hz, 2H), 3.82(s, 2H),
4.06(t, J=5Hz,
2H), 6.73 (dd, J=9, 2.5Hz, 1H)
, 6.98 (d, J=2.
5Hz, 1H), 7.1-7.4 (m, 4H)
8 3,4-Cl2 3,4
-Cl2 ■ Colorless oil
Melting point (hydrochloride) 154-156℃
■ 1.76 (s, 1H), 2.97 (t, J=
5Hz, 2H), 3.80(s, 2H),
4.05 (t, J=5Hz, 2H), 6
．． 67 (dd, J=8, 2Hz, 1H),
6.9-7.4 (m, 5H)
9 2,5-Cl2 3,4
-Cl2 ■ Colorless columnar crystals
Melting point 34-36℃ ■ 2.
61 (s, 1H), 3.00 (t, J=5Hz, 2H)
,3.81(s,2H),
4.08 (t, J=5Hz, 2H), 6.7-7.5 (
m,6H) 10 2,6-Cl2
3,4-Cl2 ■
Colorless oil Melting point (hydrochloride) 162 ~ 16
4 ℃ ■ 2.10 (s, 1H),
2.98 (t, J=5Hz, 2H), 3.80 (s, 2
H), 4.13(t, J=
5Hz, 2H), 6.7-7.5 (m, 6H)
11 2,3-Cl2 3,4
-Cl2 ■ Colorless columnar crystals
Melting point 52-53℃ ■ 1.84
(s, 1H), 2.97 (t, J=5Hz, 2H), 3
．． 81 (s, 1H), 4.
10 (t, J=5Hz, 2H), 6.73 (dd, J=
8, 3.5Hz, 1H),
7.0-7.5 (m, 5H) 12
3,5-Cl2 3,4-Cl2
■ Colorless columnar crystals Melting point 29
~30℃ ■ 1.40 (s, 1H
), 2.97 (t, J=5Hz, 2H), 3.80 (s
, 2H), 4.05(t,
J=5Hz, 2H), 6.73(d, J=1.5Hz,
2H), 6.89(t, J=
1.5Hz, 1H), 7.13(dd, J=8, 1.5
Hz, 1H), 7.29(
d, J=1.5Hz, 1H), 7.34(d, J=8H
z, 1H) 13 2,3-Cl2
2,4-Cl2 ■
Colorless columnar crystals Melting point 84-86℃
■ 1.97 (s, 1H), 3.03 (t
, J=5Hz, 2H), 3.92(s, 2H),
4.13 (t, J=5Hz, 2H
), 6.25 (dd, J=7.3Hz, 1H),
7.0-7.5 (m, 5H)
14 3,5-Cl2
2,4-Cl2 ■ Colorless oil
Melting point (hydrochloride) 168-170℃
■ 2.02 (s, 1H), 2.93 (t, J
=5Hz, 2H), 3.75(s, 2H),
3.97 (t, J=5Hz, 2H),
6.68 (d, J=1.5Hz, 2H),
6.81 (t, J=1.5Hz, 1H),
7.06 (dd, J=9, 1.5Hz, 1H),
7.24 (d, J=9Hz, 1H
), 7.36 (d, J=1.5Hz, 1H)
15 3,4-Cl2 2,6
-Cl2 ■ Colorless oil
Melting point (hydrochloride) 196-198℃
■ 2.06 (s, 1H), 2.97 (t,
J=5Hz, 2H), 3.97(t, J=5Hz
, 2H), 4.09(s,
2H), 6.66(dd, J=9, 3Hz,
1H), 6.91(d, J
=9Hz, 1H), 7.0-7.3(m, 4H)
16 2,3-Cl2
2,6-Cl2 ■ Colorless needle crystals Melting point 77-78℃
■ 1.33 (s, 1H), 3.05 (t,
J=5Hz, 2H), 4.10(t, J=5Hz
, 2H), 4.15(s,
2H), 6.71(dd, J=6.4Hz, 1
H), 6.9-7.4 (m, 5H)
17 3,5-Cl2 2,6-Cl
2 ■ Colorless columnar crystals
Melting point 46-47℃ ■ 2.0
4(s, 1H), 3.00(t, J=5Hz,
2H), 4.00(t, J=5Hz, 2H),
4.13(s, 2H), 6
．． 08 (d, J=1.5Hz, 1H), 6.90
(t, J=1.5Hz, 1H),
7.23 (m, 3H) 18 2
,6-Cl2 2,6-Cl2
■ Colorless columnar crystals Melting point
50~52℃ ■ 2.39(s, 1
H), 3.07 (t, J=5Hz, 2H), 4
．． 18 (t, J=5Hz, 2H),
4.19(s, 2H), 6.8-7.4
(m, 6H) 19 2,5-Cl2
2,6-Cl2 ■
Colorless needle crystals Melting point 71-73℃
■ 2.30 (s, 1H), 3.
06(t, J=5Hz, 2H), 4.09(t,
J=5Hz, 2H), 4
．． 15(s, 2H), 6.7-7.0(m, 2H
), 7.1-7.4 (m, 2H)
20 2,4-Cl2 2,6-Cl
2 ■ Colorless oil
Melting point (hydrochloride) 190-192℃
■ 2.33 (s, 1H), 3.03 (t, J=
5Hz, 2H), 4.05(t, J=5Hz,
2H), 4.12(s, 2
H), 6.71 (d, J=9Hz, 1H), 7
．． 0-7.3 (m, 5H) 21 3
,4-Cl2 2,3-Cl2
■ Colorless oil Melting point (hydrochloride) 175-177℃ ■ 1.98 (
s, 1H), 3.00(t, J=5Hz, 2H
), 3.96(s, 2H),
4.05 (t, J=5Hz, 2H), 6.71
(dd, J=9, 2Hz, 1H),
6.98 (d, J=2Hz, 1H),
7.1-7.5 (m, 4H) 22
2,3-Cl2 2,3-Cl2
■ Colorless columnar crystals Melting point
105-106 ℃ ■ 1.98 (
brs, 1H), 3.04(t, J=5Hz,
2H), 4.01(s, 2H),
4.16 (t, J=5Hz, 2H), 6.
7-7.5 (m, 6H) 23 2
,6-Cl2 2,3-Cl2
■ Colorless oil Melting point (hydrochloride) 148-150 °C ■ 2.21
(s, 1H), 3.07(t, J=5Hz, 2
H), 4.01(s, 2H),
4.20 (t, J=5Hz, 2H),
6.8-7.4 (m, 6H) 24
2,4-Cl2 2,3-Cl2
■ Colorless oil melting point (
Hydrochloride) 189-191℃ ■ 2
．． 96 (s, 1H), 3.05 (t, J=5Hz
, 2H), 4.00(s, 2H),
4.12 (t, J=5Hz, 2H),
6.82 (d, J=9Hz, 1H), 7.0-7
．． 5(m, 5H) 25 3,5-C
l2 2,3-Cl2
■ Colorless oil Melting point (hydrochloride) 172
~174℃ ■ 1.90(s,
1H), 3.00(t, J=5Hz, 2H),
3.96(s, 2H), 4
．． 05(t, J=5Hz, 2H), 6.76(d
, J=2Hz, 2H), 6
．． 92 (t, J=2Hz, 1H), 7.30 (m
, 3H) 26 2,5-Cl2
2,3-Cl2 ■
Colorless columnar crystals Melting point 67-69℃
■ 2.08 (s, 1H), 3.05 (t
, J=5Hz, 2H), 3.99(s, 2H)
, 4.12(t, J
=5Hz, 2H), 6.7-7.5(m, 6H)
27 3,4-Cl2
3,5-Cl2 ■ Colorless oil Melting point (hydrochloride) 199-201 °C
■ 1.80 (s, 1H), 2.9
7(t, J=5Hz, 2H), 3.80(s,
2H), 4.03(t, J=
5Hz, 2H), 6.67(dd, J=9, 2
．． 5Hz, 1H), 6.98
(d, J=2.5Hz, 1H), 7.23(s,
3H), 7.34(d,
J=9Hz, 1H) 28 2,3
-Cl2 3,5-Cl2
■ Colorless oil Melting point (hydrochloride)
163-165℃ ■ 1.77 (s,
1H), 2.99(t, J=5Hz, 2H),
3.83(s, 2H), 4
．． 06(t, J=5Hz, 2H), 6.79(t
, J=1.8Hz, 2H),
6.97 (d, J=1.8Hz, 1H), 7.
25(s, 3H) 29 2,4-C
l2 3,5-Cl2
■ Colorless oil Melting point (hydrochloride) 17
1~172℃ ■ 1.90(s
, 1H), 3.00 (t, J=5Hz, 2H)
, 3.84(s, 2H),
4.11(t, J=5Hz, 2H), 6.81(
d, J=9Hz, 1H),
7.18 (dd, J=9, 2.5Hz, 1H),
7.24(s, 3H), 7
．． 35 (d, J=2.5Hz, 1H)
30 3,5-Cl2 3,5-Cl
2 ■ Colorless oil
Melting point (hydrochloride) 171-172℃
■ 1.83 (s, 1H), 3.03 (t,
J=5Hz, 2H), 3.87(s, 2H),
4. 14(t, J=5Hz
, 2H), 6.7-7.2(m, 3H), 7.
25(s, 3H) 31 2,6-C
l2 3,5-Cl2
■ Colorless oil Melting point (hydrochloride) 15
4～156℃■ 2.07(s,
1H), 3.03(t, J=5Hz, 2H),
3.86 (s, 2H), 4.
20 (t, J=5Hz, 2H), 6.8-7.4
(m, 6H) 32 2,5-Cl
2 3,5-Cl2
■ Colorless oil Melting point (hydrochloride) 186
-187 ■ 1.99(s, 1
H), 3.04 (t, J=5Hz, 2H), 3
．． 86(s, 2H), 4.1
3(t, J=5Hz, 2H), 6.8-7.0(
m, 2H), 7.28(s, 3H),
7.29 (d, J=9Hz, 1H)
33 3,4-Cl2
2,5-Cl2 ■ Colorless oil Melting point (hydrochloride) 153-155 °C
■ 1.94 (s, 1H), 3.0
1 (t, J=5Hz, 2H), 3.90 (s,
2H), 4.05(t, J=
5Hz, 2H), 6.72(dd, J=9, 3
Hz, 1H), 6.98(
d, J=3Hz, 1H), 7.2-7.5(m,
4H) 34 2,4-Cl2
2,5-Cl2 ■ Colorless oil Melting point (hydrochloride) 204-206
°C ■ 2.04 (s, 1H)
, 3.00 (t, J=5Hz, 2H), 3.9
0(s, 2H), 4.11(
t, J=5Hz, 2H), 6.73(d, J=
9Hz, 1H), 7.0-7.4(m, 5H)
35 2,5-Cl2
2,5-Cl2 ■ Colorless oil Melting point (hydrochloride) 191-192 °C
■ 2.22 (s, 1H), 3.06
(t, J=5Hz, 2H), 3.93(s, 2
H), 4.02(t,
J=5Hz, 2H), 6.8-6.9(m, 2
H), 7.2-7.3(m, 3H),
7.46 (d, J=2Hz, 1H)
36 2,3-Cl2 2
,5-Cl2 ■ Colorless columnar crystals
Melting point 58 ~ 60℃
■ 2.05 (s, 1H), 3.05 (t, J=
5Hz, 2H), 3.92(s, 2H),
4.17(t, J=5Hz, 2H
), 6.76 (dd, J=7, 4Hz, 1H)
, 7.0-7.3(m, 4H
), 7.45 (d, J=2Hz, 1)
37 2,6-Cl2 2,5-C
l2 ■ Colorless oil
Melting point (hydrochloride) 192-193℃
■ 2.22(s, 1H), 3.02(
t, J=5Hz, 2H), 3.90(s, 2H
), 4.16(t, J=5H
z, 2H), 6.7-7.3(m, 5H), 7
．． 15 (d, J=2Hz, 1H) 3
8 3,5-Cl2 2,5-Cl2
■ Colorless columnar crystals
Melting point 48 ~ 49℃ ■
1.92 (s, 1H), 3.00 (t, J=5H
z, 2H), 3.89(s, 2H),
4.04 (t, J=5Hz, 2H),
6.73 (d, J=2Hz, 2H),
6.89 (t, J=2Hz, 1H),
7.18 (m, 2H), 7.41 (d, J=2
Hz, 1H) [Table 2] Table 2 Physical properties of salt consisting of N-benzyl-N-dichlorophenoxyethylamine and organic acid


Compound number Secondary amine
HX mp (℃)
39
11 p-TsO
H 188-189 40
11
54 97-98
41 4
p-TsOH 164-166
42 6
p-TsOH 17
0~171 43
8 p-TsOH
173-175 44
8 55
112-113 45
8
56 94-95
46 8B
enzoic acid 108-110
47 8
54 13
4～135 48
8 Propionic acid
64-65 49
8 Acetic acid
72～74 50
9 p.
-TsOH 168-170
51 12
p-TsOH 140-146
52 12
54 11
1-113 53
12 Benzoic acid
89-91
In the table, the secondary amine is the compound number in Table 1, p
-TsOH represents p-toluenesulfonic acid, 54 represents 2-thiophenecarboxylic acid, 55 represents 3-phenyl-5-methylisoxazole-4-carboxylic acid, and 56 represents m-trifluoromethylbenzoic acid. [0007] Furthermore, the second invention provides an N-
This is an agricultural and horticultural fungicide characterized by containing as an active ingredient at least one salt of benzyl-N-dichlorophenoxyethylamine and an organic acid. [However, in Chemical Formula 1, n represents 2 or 3, and m represents 1 or 2. However, m is 1 and the 4th position is substituted, excluding compounds in which the 2nd and 4th positions of the phenoxy group are substituted. Moreover, HX represents an organic acid. [0008] The salt consisting of N-benzyl-N-dichlorophenoxyethylamine and an organic acid represented by formula 1 can be used to treat bacteria of the genus Xanthomonas such as citrus canker and Clavibacto such as tomato canker.
It not only exhibits strong bacteriostatic or bactericidal activity against bacteria of the genus r, but also exhibits strong antibacterial activity against pathogens of other crop diseases. These salts of N-benzyl-N-dichlorophenoxyethylamine and organic acids are chemically stable and can withstand long-term storage. Therefore,
The agricultural and horticultural fungicide of the second invention, in combination with the strong bacteriostatic or bactericidal action of the salt consisting of N-benzyl-N-dichlorophenoxyethylamine and an organic acid, is suitable for agricultural and horticultural fungicides containing this compound as an active ingredient. Germicidal disinfectants are highly practical. The agricultural and horticultural fungicide of the second invention has a salt consisting of N-benzyl-N-dichlorophenoxyethylamine and an organic acid as its active ingredient, and has a broad antibacterial spectrum. It is effective in controlling a wide range of diseases caused by various pathogens, such as rice leaf blight, peach borer disease, cabbage black rot, lettuce bacterial spot, melon brown spot bacterial disease, soybean leaf blight, and tomato canker disease. . The agricultural and horticultural fungicide of the second invention can be produced by using the novel compound of the first invention into wettable powders, liquids, emulsions, flowables (sols), powders, and driftless powders by methods known per se. (DL) It can be prepared into any dosage form that can be employed as a conventionally used agricultural and horticultural agent, especially a fungicide, such as a powder or a granule. 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, representative 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;
Examples include petroleum resins, polyvinyl chloride, ketone resins, and polymeric compounds such as dammar gum. Typical examples of liquid carriers include water, methyl alcohol, ethyl alcohol,
Alcohols such as n-propyl alcohol, iso-propyl alcohol, butanol, ethylene glycol and benzyl alcohol, aromatic hydrocarbons such as toluene, benzene, xylene, ethylbenzene and methylnaphthalene, chloroform, carbon tetrachloride, dichloromethane, chloroethylene , monochlorobenzene, halogenated hydrocarbons such as trichlorofluoromethane and dichlorofluoromethane, ethers such as ethyl ether, ethylene oxide and dioxane, acetone,
Ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate and ethylene glycol acetate; acid amides such as dimethyl formamide and dimethyl acetamide; sulfoxides such as dimethyl sulfoxide; ethylene glycol monomethyl ether and ethylene. Alcohol ethers such as glycol monoethyl ether, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, industrial gasoline such as petroleum ether and solvent naphtha, and petroleum distillates such as paraffins, kerosene and gas oil, etc. There is. Moreover, various surfactants can also be used. Representative examples include nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl esters, anionic surfactants such as alkylbenzene sulfonates and alkyl sulfates, and cationic surfactants such as laurylamine and stearyltrimethylammonium chloride. Examples include ionic surfactants and amphoteric surfactants such as betaine-type carboxylic acids and sulfuric acid esters. Although there is no particular restriction on the content of the compound of the first invention in the above-mentioned formulation, practically,
Usually, it is about 0.001 to 95 wt% (represented as a compound represented by Chemical Formula 1, the same applies hereinafter), preferably about 0.01 to 90 wt%. For example, in practice, powders, DL powders, granules, etc. are usually 0.
In wettable powders, liquids, emulsions, etc., it is about 1 to 75 wt%. The preparations prepared in this way, for example, powders, driftless preparations, and granules, are applied as they are, while wettable powders, solutions, emulsions, and flowable preparations are diluted with water or an appropriate solvent before application. be done. 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 used as is,
Or, dilute it and spray it on the foliage of crops, or on the water surface,
Applied in water, on the soil surface or inside the soil. The application amount of the agricultural and horticultural fungicide of the second invention varies depending on the type of target disease, degree of disease, type of target crop, application site, application method, application time, type of dosage form, etc., and cannot be specified in general. However, as a compound represented by chemical formula 1 of the first invention,
Per 10 ares, powders, driftless agents, and granules (
In both cases, the active ingredient concentration is 3wt%), 2 to 6k.
g, and in wettable powders, liquids, emulsions, flowables (all with active ingredient concentration 20wt%), etc.
．． It is used by diluting 0.5 to 3 kg in 100 to 500 L of water. The compound of the first invention has a strong antibacterial effect and is highly stable, so it can be applied over a wide period of time, and
It can be used not only to treat crop diseases, but also to prevent them. [Example] The present invention will be explained in more detail with reference to Examples. The present invention is not limited to these examples. Example 1 N-3,4-dichlorobenzyl-N-2-(3,4-dichlorophenoxy)ethylamine benzoate (compound 4
Synthesis of 6) Synthesis was carried out in two steps as follows. 1) N-3,4-dichlorobenzyl-N-2-(3,4
-Synthesis of dichlorophenoxy)ethylamine 2-(3,
5.40 g of 4-dichlorophenoxy)ethyl bromide (
Dissolve 20.0 mmol) in 50 ml of isopropyl alcohol, and add 4.26 g of anhydrous sodium carbonate (
40.0 mmol) and 6.30 g (35.8 mmol) of 3,4-dichlorobenzylamine were added, and the mixture was heated under reflux on an oil bath for 8 hours. After cooling, the reaction mixture was poured into 200 ml of water and extracted with chloroform (40 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) to give 5.89 g (
The title compound (yield: 81%) was obtained as a colorless oil. The physical properties of this compound were as follows. That is, 13C-NMR spectrum (CDCl3); 47
．． 90(t), 52.47(t), 68.21(t
), 114.46(d), 116.44(d), 1
24.09(s), 127.24(d), 129.8
0(d), 130.22(d), 130.59(d
), 130.74 (s), 132.36 (s), 1
32.78 (s), 140.53 (s), 157.
76(s) ppm infrared absorption spectrum (oil film method); νm
ax = 2820m, 1580s, 1560
s, 1445s, 1255s, 1220s
, 1115s , 1020s , 800s ,
655 s cm-1 mass spectrum; m/e = 3
69 (M + +6,1%), 368 (M + +5,
1%), 367 (M + +4.4%), 366 (M
+ +3.2%), 365 (M + +2.8%)
, 364 (M + +1,1%), 363 (M +
, 6%), 204 (3%), 202 (5%), 1
92 (11%), 191 (7%), 190 (64%)
, 189 (11%), 188 (98%), 163 (
13%), 162 (7%), 161 (70%), 1
60 (9%), 159 (100%), 126 (3%
), 125 (5%), 124 (6%), 123 (8
%). Ultraviolet absorption spectrum (EtOH); λmax = 219 sh(17,100), 22
8 sh (15,000), 276 sh (1,23
0), 282 (1,830), 291 (1,460)
nm elemental analysis; calculated value as C15H13Cl4NO C: 49.35 H: 3.59 N: 3
．． 84 (%) Actual value C: 49.59 H: 3.53 N: 4.
09(%) 2) Synthesis of N-3,4-dichlorobenzyl-N-2-(3,4-dichlorophenoxy)ethylamine benzoate 365 mg (1.00 mmol) of the amine obtained in 1) was
ml of ether and add 122 mg (1.00
mmol) of benzoic acid was added. The solution was cooled, and the precipitated crystals were filtered, washed with cold ether, and dried for 3
61 mg (yield 74%) of the title compound was obtained as a white powder. Melting point: 108-110°C. Example 2 N-4-chlorobenzyl-N-2-(3,4-dichlorophenoxy)ethylamine p-toluenesulfonate (
Synthesis of Compound 42) It was synthesized in two steps as follows. 1) Synthesis of N-4-chlorobenzyl-N-2-(3,4-dichlorophenoxy)ethylamine 2-(3,4-dichlorophenoxy)ethyl bromide 2
．． Dissolve 70g (10.0mmol) in 30ml of ethanol, and add 1.06g (10.0mmol) of anhydrous sodium carbonate to this.
．． 0 mmol) and 4.25 g of 4-chlorobenzylamine
(30.0 mmol) was added and heated under reflux on an oil bath for 7 hours. After cooling, the reaction mixture was poured into 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 = 4/6) to give 2.99 g (yield: 90
%) of the title compound as a colorless oil. The physical properties of this compound were as follows. That is, mass spectrum; m/e = 330 (M+ +1.1%), 298 (3
%), 297 (6%), 296 (30%), 29
5 (19%), 294 (38%), 293 (22%)
, 170 (4%), 168 (5%), 157 (3
%), 156 (34%), 155 (8%), 154 (
92%), 127 (44%), 126 (8%),
125 (100%), 90 (7%), 89 (20%)
．． Ultraviolet absorption spectrum (EtOH); λmax = 218 sh(13,200), 23
0 sh(8,340), 281sh(1,200)
, 286 (1,700), 292 (1,500) nm
Elemental analysis; Calculated value C as C15H14Cl3NO
:54.49 H:4.27 N:4.2
4 (%) Actual value C: 54.61 H: 4.38 N: 4.
01 (%) 2) N-4-chlorobenzyl-
Synthesis of N-2-(3,4-dichlorophenoxy)ethylamine p-toluenesulfonate 331 mg (1.00 mmol) of the amine obtained in 1) was
Dissolve in 1.00 ml of ether and add 190 mg (1.00
mmol) of p-toluenesulfonic acid monohydrate was added. The acid was dissolved by ultrasonication, and the newly precipitated crystals were filtered, washed with ether, and dried to give 322 mg (
The title compound (yield: 80%) was obtained as colorless flaky crystals. Melting point: 170-171°C Formulation example 1 (wettable powder) Ingredients
Part by weight Compound 46
20 lignin sulfonic acid
3 Polyoxyethylene alkyl allyl ether
2 diatomaceous earth
75 Mix the above ingredients uniformly to obtain active ingredient 2.
A wettable powder containing 0% by weight was obtained. Formulation example 2 (powder) Ingredients
Part by weight Compound 46
3 Calcium stearate
1 Silicic acid anhydride powder
1 clay
48 talc

47 Mix the above ingredients uniformly to obtain 3% by weight of the active ingredient.
A powder containing the following was obtained. Test Example 1 Antibacterial test against plant pathogenic bacteria The antibacterial activity of a salt consisting of N-benzyl-N-dichlorophenoxyethylamine and an organic acid against various plant pathogenic bacteria was investigated. In other words, cabbage black rot fungus Xant
homonas campestris pv. ca
mpestris, Citrus canker X. camp
estris pv. citri, rice leaf blight fungus
X. campestris pv. oryzae,
Peach borer bacterial pathogen X. campestris pv
．． pruni and tomato canker fungus Clavib
actor michiganensis subs
p. michiganensis was used as a test bacterium, and its growth inhibitory effect on an agar plate was investigated. The test compound was mixed into peptone-added potato decoction medium and 1
A 2-fold dilution series with a maximum concentration of 0.00 ppm was prepared and poured into a Petri dish to prepare an agar plate. 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 examined. The results are shown in Table 3. The compound of the present invention showed strong antibacterial activity against all pathogenic bacteria. [Table 3] Table 3 Antibacterial test against plant pathogenic bacteria
minimum inhibitory concentration
(ppm) Compound number
Xc Xi Xo
Xp Cm 43
12.5 12.5 6.3
6.3 12.5 46
6.3 6.3
3.2 3.2 6.3
47 6.3
6.3 3.2 3.2
6.3 48 6.3
6.3 3.2 3.
2 12.5 49
6.3 6.3 6.3
3.2 6.3 50
12.5 12.5
12.5 12.5 3.2
51 12.5 12
．． 5 6.3 6.3
3.2 52 25
12.5 12.5 12.5
6.3 53
12.5 12.5 6.3
12.5 6.3 Strephtomycin* 25 25
6.3 25 6.3
*Commercially available control drug A leaf piece was cut, and the leaf piece was immersed in a chemical solution prepared to a predetermined concentration for 20 minutes, then the leaf piece was taken out from the chemical solution, and after the chemical solution was air-dried, a suspension of citrus canker bacteria (approximately 10 8 /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 4. [0020] In the above equation, n0: Number of leaf pieces with disease index 0 (no disease) n1: Number of leaf pieces with disease index 1 (slightly diseased) n2: Number of leaf pieces with disease index 2 (currently diseased) n3: Disease index 3 (no disease) number of leaves N
: Number of investigated leaf pieces [Table 4] Table 4 Citrus canker disease control test compound number Concentration (ppm) Severity (%) Plant damage** 39
300 16.7
-40
300 7.4
-41 3
00 9.5
-42 300
14.3-
44 300
16.7 -
45 300
13.3-46
300
16.7-47
300 0.
0-48
300 0.0
-49
300 20.8
-50
300 7.4
-52 300
20.8
-53 300
4.8 - Cosite hydrating agent* 2000 times
26.7 ±
No dilution treatment
66.7
*Commercial control drug** -: No drug damage ±: Slight but drug damage +: Drug damage (same below) [0022]
Test Example 3 Rice leaf blight control test An aqueous solution of the test compound prepared at a predetermined concentration was sprayed on five-leaf stage rice (variety Koshihikari) grown in pots with a diameter of 6 cm. 1 day later
A suspension of rice bacterial leaf blight prepared to 108 cells/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 5. [Table 5] Table 5 Rice leaf blight control test Compound number Concentration (ppm) Control value (%) Plant damage 40
500 8
3.7-44
500 95.1
-45
500 80.5
-46
500 75.6
-47 5
00 90.0
-49 500
88.2 -
53 500
96.3 - Phenacin hydrating agent * 500 times 6
0.1-
dilution
*Commercially available control drug 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, a bacterial solution was poured onto the center of the disk, and the disk was kept at 28°C for 24 hours.
The degree of disease onset was investigated, and the control value was calculated using the following formula. The results are shown in Table 6. [Table 6] Table 6 Soft rot control test compound number Concentration (ppm) Control value (%) Plant damage 40
400 90
-46
400 100
-49
400 90
-53 400
100-
Cosite Hydrating Agent* 2000 times
80 ±
dilution
*Commercial control drug [0024] [Effects of the invention] The salt of the present invention consisting of N-benzyl-N-dichlorophenoxyethylamine and an organic acid is a new compound, easy to manufacture, highly stable, and free from drug damage. Moreover, it shows excellent antibacterial activity against various plant pathogenic bacteria. Therefore, the agricultural and horticultural fungicide of the present invention is suitably used for controlling various plant diseases.

Claims (2)

[Claims] Claims 1. A salt consisting of N-benzyl-N-dichlorophenoxyethylamine represented by formula 1 and an organic acid. [In Chemical Formula 1, n represents 2 or 3, and m represents 1 or 2. However, m is 1 and the 4th position is substituted, excluding compounds in which the 2nd and 4th positions of the phenoxy group are substituted. Moreover, HX represents an organic acid. ] 2. A fungicide for agriculture and horticulture, which contains as an active ingredient at least one salt consisting of N-benzyl-N-dichlorophenoxyethylamine and an organic acid represented by Chemical Formula 1 [Chem. 1] However, in Chemical Formula 1, n represents 2 or 3, and m represents 1 or 2. However, m is 1 and the 4th position is substituted, excluding compounds in which the 2nd and 4th positions of the phenoxy group are substituted. Moreover, HX represents an organic acid. ]