KR20090024394A - Synthesis of new fluoroaromatic formamidines and their biological activity - Google Patents

Abstract

A derivative from fluorine-containing phenyl formamidine is provided to secure excellent insecticidal activity for prevention the breeding and extermination of harmful insects while maintaining useful plants. A derivative from fluorine-containing phenyl formamidine is represented by the formula I. In the formula 1, F is fluorine; X indicates a hydrogen atom, cyano, amino, carbo C1-C2 alkoxy, C1-C2 alkylcarbamoyl, C1-C4 alkyl or an alkoxy group; R1 shows a hydrogen atom or a C1-C4 alkyl group; Y is a C1-C8 alkyl or a dialkyl aminosulphenyl group; and n is 1,2,3 or 4. If the Y is the dialkyl aminosulphenyl group, the derivative from fluorine-containing phenyl formamidine is represented by the formula II.

Description

Synthesis of New Fluoroaromatic Formamidines and Their Biological Activity

The present invention is effective as a pesticide for controlling pests of vegetables and fruit trees, and is particularly effective for insecticides that do not harm crops and insects. It relates to a pesticide for agricultural and horticultural use containing as a component and a method of applying the same.

[Formula I]

Wherein F is fluorine;

X is a hydrogen atom, a cyanide furnace, amino ^{[NR 2 R 3: R 2} , R 3 is a hydrogen atom, a C _{1 -2} alkyl, acetyl, carbonyl C _{1 -2} alkoxy, C _{1 -2} alkyl-carbamoyl], carboxylic beam C _{1 -2} alkoxy, C _{1 -2} alkyl, carbamoyl, C _{1 -4} alkyl or alkoxy [oR ^4: R ⁴ is a hydrogen atom, C _{1 -2} alkyl, acetyl, carbonyl C _{1 -2} alkoxy, C _{1 -2} alkylcarbamoyl;

R ¹ is a hydrogen atom, C _{1 -4} alkyl;

Y is a C _{1 -8} alkyl or dialkyl [R ^5, R ⁶ ] aminosulphenyl group (R ⁵ , R ⁶ is a C _{1 -8} alkyl, C _{1 -6} haloalkyl or C ₅ cyclic _-6 alkyl);

n represents 1, 2, 3 or 4.

Synthesis method of compound (A) having a structure similar to the amidine-based compound represented by the formula (I) characterized in the present invention is described in US Patent No. 3,284,289 (1966), US 3,496,270 (1970), US Patent US 3,781,355 (1973), United States Patent US 3929883 (1975), US patent US 4,128,652 (1978), Swiss patent CH 63186 (1978) and the like.

In addition, phenylformamidine derivatives effective as pest control agents, plant growth regulators, and insecticides and their preparation are disclosed in DE 2621077 (1976), US 3,998,969 (1976), US 4,356,194 (1982) as compounds represented by the following general formula ( B ). .

Looking at the claims of the comparative document, the claims relating to the phenyl group (Ph) refers to “mono-, di- or tri-substituted phenyl groups, depending on the bond, one, two or three halogen atoms and / or C _1-4 alkyl or a phenyl group substituted with an alkoxy, trifluoromethyl group, cyano group, and / or nitro group. ”A compound in which a halogen atom is substituted for a phenyl group, but a compound substituted with fluoro Is not specifically described.

In addition, any of the documents known to date are known fluorine-containing phenyl amidine derivatives represented by the above formula (I), which are characterized by the present invention, or do not describe the pesticidal activity against these compounds.

On the other hand, pest control is very important for improving productivity of agriculture, and various kinds of insecticides have been used. However, there are still many pests that cause loss in agriculture, and the conventional acaricides used in growing vegetables and fruits are respiratory penpyroximate, pyridaben, tebufenpyrad, phenazaquine, pyrimidipene and acequine. Various agents have been used, such as nosyl, neurombermectin and growth regulator ethoxazole. With the continued use of these drugs, the emergence of resistant pests has been reported, and there is an urgent need for the development of pesticides with new mechanisms of action to control them. In particular, there is a demand for the development of environmentally friendly, high-activity insecticides capable of selectively controlling only the pests without harming cultivated crops and insects.

Therefore, the inventors of the present invention, while developing new agricultural and horticultural insecticides, prepare fluorine-containing phenyl amidine derivatives represented by the general formula (I) of the present invention among the phenylamidine derivative compounds reported to have excellent insecticidal effects in the prior art, and The present invention has been completed by confirming that the compound exhibits excellent pesticidal effects compared to the compounds disclosed in DE 2621077 and US 3,998,969.

 Accordingly, an object of the present invention is to provide a fluorine-containing phenyl amidine derivative compound represented by the formula (I) and an insecticide containing the same as an active ingredient.

In order to achieve the above object, the present invention is a novel fluorine-containing phenylamidine derivative represented by the following general formula (I) having the effect of selectively controlling mites and mites without harming crops useful as agricultural horticultural insecticides To provide a compound.

[Formula I]

Wherein F is fluorine,

X is a hydrogen atom, a cyanide furnace, amino ^{[NR 2 R 3: R 2} , R 3 is a hydrogen atom, a C _{1 -2} alkyl, acetyl, carbonyl C _{1 -2} alkoxy, C _{1 -2} alkyl-carbamoyl], carboxylic beam C _{1 -2} alkoxy, C _{1 -2} alkyl, carbamoyl, C _{1 -4} alkyl or alkoxy [oR ^4: R ⁴ is a hydrogen atom, C _{1 -2} alkyl, acetyl, carbonyl C _{1 -2} alkoxy, C _{1 -2} alkylcarbamoyl;

R ¹ is a hydrogen atom, C _{1 -4} alkyl;

Y is a C _{1 -8} alkyl or dialkyl [R ^5, R ⁶ ] aminosulphenyl group (R ⁵ , R ⁶ is a C _{1 -8} alkyl, C _{1 -6} haloalkyl or C ₅ cyclic _-6 alkyl);

n represents 1, 2, 3 or 4.

In more detail, the compounds represented by Formula 1 according to the present invention are as follows.

number F n X R ₁ R ₂ ¹ H NMR (CDCl ₃ ) One 2- One H H CH ₃ 70% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.99 (s, 3H), 6.89-7.06 (m, 4H), 7.69 (s, 1H); MS (70 eV) m / z 152 (M ⁺ , 100), 133, 122, 111 2 3- One H H CH ₃ 72% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.99 (s, 3H), 4.97 (br, 1H), 6.64-6.75 (m, 3H), 7.16-7.23 (m, 1H); 7.63 (s, 1 H); MS (70 eV) m / z 152 (M ⁺ , 100), 133, 122 3 4- One H H CH ₃ 72% yield brown solid; mp = 57-60; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.99 (s, 3H), 5.41 (br, 1H), 6.79-6.94 (m, 4H), 7.51 (s, 1H); MS (70 eV) m / z 152 (M ⁺ , 100), 133, 122, 111 4 2,4- 2 H H CH ₃ 73% yield white solid, mp = 86-87; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.96 (s, 3H), 5.29 (br, 1H), 6.72 ~ 6.91 (m, 3H), 7.63 (s, 1H); MS (70eV) m / z 170 (M ⁺ , 100), 151, 140, 129 5 2,5- 2 H H CH ₃ 64% yield white solid, mp = 77; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.01 (s, 3H), 4.95 (br, 1H), 6.58 to 6.71 (m, 2H), 6.93 to 7.01 (m, 1H), 7.71 (s, 1H); MS (70eV) m / z 170 (M ⁺ , 100), 169, 140, 129 6 2,6- 2 H H CH ₃ 60% yield white solid, mp = 108-109; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.03 (s, 3H), 4.91 (br, 1H), 6.82-6.88 (m, 3H), 7.78 (s, 1H); MS (70eV) m / z 170 (M ⁺ , 100), 151, 140, 129, 120 7 3,4- 2 H H CH ₃ 60% yield purple solid, mp = 71-73; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.96 (s, 3H), 5.03 (br, 1H), 6.62˜6.79 (m, 2H), 7.01 to 7.07 (m, 1H), 7.58 (s, 1H); MS (70eV) m / z 170 (M ⁺ , 100), 169, 142, 129, 113 8 2,3,4- 3 H H CH ₃ 58% yield white solid, mp = 69-70; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.00 (s, 3H), 5.08 (br, 1H), 6.60-66.6 (m, 1H), 6.78-6.88 (m, 1H), 7.67 (s, 1H); MS (70 eV) m / z 188 (M ⁺ , 100), 169, 158, 147, 131, 119 9 2,4,5- 3 H H CH ₃ 54% yield white solid, mp = 68-69; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.00 (s, 3H), 4.88 (br, 1H), 6.74-6.95 (m, 2H), 7.68 (s, 1H); MS (70 eV) m / z 188 (M ⁺ , 100), 187, 158, 147, 131, 119 10 2,4,6- 3 H H CH ₃ 83% yield white solid, mp = 110; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.02 (s, 3H), 4.92 (br, 1H), 6.60˜6.70 (m, 2H), 7.73 (s, 1H); MS (70 eV) m / z 188 (M ⁺ , 100), 169, 158, 147, 138, 131, 119 11 2,3,6- 3 H H CH ₃ 89% yield white solid, mp = 99; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.04 (s, 3H), 4.98 (br, 1H), 6.65˜6.82 (m, 2H), 7.79 (s, 1H); MS (70 eV) m / z 188 (M ⁺ , 100), 169, 158, 147, 138, 131, 119

number F n X R ₁ R ₂ ¹ H NMR (CDCl ₃ ) 12 2,3,5,6- 4 H H CH ₃ 85% yield white solid, mp = 117-119; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.04 (s, 3H), 5.28 (br, 1H), 6.59 ~ 6.70 (m, 1H), 7.81 (s, 1H), MS (70eV) m / z 206 (M ⁺ , 100), 187, 176, 165, 149, 137, 113 13 3- One 2-CH ₃ H CH ₃ 78% yield brown solid, mp 50-51; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.18 (s, 3H), 2.92 (s, 3H), 5.25 (br, 1H), 6.52 (d, J = 7.8Hz, 1H), 6.67 ~ 6.73 (m, 1H ), 6.97-7.04 (q, J = 7.8 Hz, 1H), 7.45 (s, 1H); MS (70 eV) m / z 166 (M ⁺ , 100), 151, 136, 125, 124, 109 14 4- One 2-CH ₃ H CH ₃ 75% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.22 (s, 3H), 2.94 (s, 3H), 4.65 (br, 1H), 6.63 ~ 6.68 (m, 1H), 6.73 ~ 6.86 (m, 2H), 7.45 (s, 1 H); MS (70 eV) m / z 166 (M ⁺ , 100), 151, 136, 125, 124, 109 15 5- One 2-CH ₃ H CH ₃ 56% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.21 (s, 3H), 2.98 (s, 3H), 4.63 (br, 1H), 6.79 (dd, J = 2.4Hz, 1H), 6.60 ~ 6.66 (m, 1H ), 7.05 (t, J = 7.8 Hz, 1H), 7.51 (s, 1H); MS (70 eV) m / z 166 (M ⁺ , 100), 161, 145, 142, 125, 111 16 2- One 5-CH ₃ H CH ₃ 57% yield white solid, mp 68-69; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.21 (s, 3H), 2.98 (s, 3H), 6.70-6.96 (m, 3H), 7.71 (s, 1H); MS (70 eV) m / z 166 (M ⁺ , 100), 147, 136, 125, 124, 109 17 3- One 4-CH ₃ H CH ₃ 52% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.19 (s, 3H), 2.99 (s, 3H), 4.77 (br, 1H), 6.55 (d, J = 7.8Hz, 1H), 6.68 ~ 6.98 (m, 1H ), 7.14 (q, J = 8.1 Hz, 1H), 7.52 (s, 1H); MS (70 eV) m / z 166 (M ⁺ , 100), 151, 136, 124, 109 18 2- One 4-Cl H CH ₃ 62% yield white solid, mp = 107-110; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.01 (s, 3H), 4.78 (br, 1H), 6.88 (t, J = 9.0 Hz, 1H), 6.99-7.09 (m, 2H); 7.69 (s, 1 H); MS (70 eV) m / z 186 (M ⁺ , 100), 167, 158, 145, 129, 109 19 2- One 4-CH ₃ H CH ₃ 84% yield; Liquid; 1 H NMR (CDCl 3, 200 MHz) δ 2.28 (s, 3H), 3.02 (s, 6H), 6.82 (m, 3H), 7.56 (s, 1H); MS (70eV) m / z 180 (M +, 100), 165, 161, 138, 136, 109 20 4- One 2- OMe H CH ₃ 81% yield white solid, mp = 78-82 (observed); ¹ H NMR (CDCl ₃ , 200 MHz) δ 2.97 (s, 3H), 3.79 (m, 3H), 6.57 (m, 2H), 6.74 (m, 1H), 7.57 (s, 1H); MS (70eV) m / z 182 (M ⁺ , 90), 169, 151, 141, 126 21 4- One 2- NO ₂ H CH ₃ 78% yield; yellow solid, mp = 83; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.00 (s, 3H), 4.84 (br, 1H), 6.92 (m, 1H), 7.18 (m, 1H), 7.50 (m, 1H); 7.58 (s, 1 H); MS (70 eV) m / z 197 (M ⁺ , 100), 196, 167, 151, 136, 123

number F n X R ₁ R ₂ ¹ H NMR (CDCl ₃ ) 22 2- One H CH ₃ CH ₃ 49% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.04 (s, 6H), 6.88-7.07 (mm, 4H), 7.58 (s, 1H); MS (70 eV) m / z 166 (M ⁺ , 100), 151, 138, 124, 122 23 3- One H CH ₃ CH ₃ 74% yield liquid R _f = 0.12 ( n -Hex / EtOAc = 1/1); ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.02 (s, 6H), 6.63˜6.75 (m, 2H), 7.17˜7.21 (m, 1H), 7.51 (s, 1H); MS (70 eV) m / z 166 (M ⁺ , 100), 165, 151, 124, 122 24 4- One H CH ₃ CH ₃ 42% yield liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 3.01 (s, 6H), 6.84-6.99 (m, 4H), 7.47 (s, 1H); MS (70 eV) m / z 166 (M ⁺ , 100), 151, 138, 124, 122 25 2,4- 2 H CH ₃ CH ₃ 75% yield liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 3.03 (s, 6H), 6.70 to 6.63 (m, 3H), 7.53 (s, 1H); MS (70 eV) m / z 184 (M ⁺ , 100), 169, 165, 142, 140, 113 26 2,5- 2 H CH ₃ CH ₃ 76% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.05 (s, 6H), 6.55 to 6.69 (m, 2H), 6.91 to 7.00 (m, 1H), 7.58 (s, 1H); MS (70 eV) m / z 184 (M ⁺ , 97), 169, 165, 142, 140, 113 27 2,6- 2 H CH ₃ CH ₃ 76% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.02 (s, 3H), 3.07 (s, 3H), 6.78-6.89 (m, 3H), 7.86 (s, 1H); MS (70 eV) m / z 184 (M ⁺ , 85), 165, 149, 142, 129, 120 28 3,4- 2 H CH ₃ CH ₃ 60% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.01 (s, 6H), 6.60 ~ 66 (m, 1H), 6.71 ~ 6.79 (m, 1H), 6.96 ~ 7.06 (m, 1H), 7.46 (s, 1H) ; MS (70 eV) m / z 184 (M ⁺ , 100), 169, 156, 142, 140, 113 29 2,3,4- 3 H CH ₃ CH ₃ 65% yield liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 3.02 (s, 6H), 6.54-6.67 (m, 1H), 6.81-66.8 (m, 1H), 7.52 (s, 1H); MS (70eV) m / z 202 (M ⁺ , 30), 183, 181, 160, 158, 149, 131 30 2,4,5- 3 H CH ₃ CH ₃ 79% yield white solid, mp = 53-55; ¹ H NMR (CDCl ₃ , 200 MHz) δ 3.03 (s, 6H), 6.67-6.96 (mm, 2H), 7.54 (s, 1H); MS (70eV) m / z 202 (M ⁺ , 100), 187, 183, 160, 158, 131, 119 31 2,4,6- 3 H CH ₃ CH ₃ 56% yield white solid, mp = 40-43; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.03 (s, 3H), 3.05 (s, 3H), 6.59-66.6 (m, 2H), 7.61 (s, 1H); MS (70eV) m / z 202 (M ⁺ , 100), 183, 181, 160, 158, 138, 131

number F n X R ₁ R ₂ ¹ H NMR (CDCl ₃ ) 32 2,3,6- 3 H CH ₃ CH ₃ 76% yield liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 3.05 (s, 3H), 3.08 (s, 3H), 6.58-6.83 (m, 2H), 7.68 (s, 1H); MS (70eV) m / z 202 (M ⁺ , 100), 183, 181, 160, 158, 138, 131 33 2,3,5,6- 4 H CH ₃ CH ₃ 51% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.06 (s, 3H), 3.08 (s, 3H), 6.54-6.65 (m, 1H), 7.69 (s, 1H); MS (70eV) m / z 220 (M ⁺ , 100), 201, 199, 178, 176, 149, 130 34 3- One 2-CH ₃ CH ₃ CH ₃ 45% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.18 (s, 3H), 3.01 (s, 6H), 6.65 ~ 6.71 (m, 1H), 6.96 ~ 7.04 (q, J = 7.8Hz, 1H), 7.40 (s , 1H); MS (70eV) m / z 180 (M ⁺ , 100), 165, 149, 136, 122, 109 35 4- One 2-CH ₃ CH ₃ CH ₃ 72% yield; liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.24 (s, 3H), 2.99 (s, 6H), 6.63-66.6 (m, 1H), 6.73-66.8 (m, 2H), 7.35 (s, 1H); MS (70eV) m / z 180 (M ⁺ , 100), 165, 149, 136, 124, 109 36 5- One 2-CH ₃ CH ₃ CH ₃ 76% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.21 (s, 3H), 3.02 (s, 6H), 6.45 ~ 6.50 (m, 1H), 6.51 ~ 6.61 (m, 1H), 7.02 ~ 7.04 (m, 1H) , 7.40 (s, 1 H); MS (70eV) m / z 180 (M ⁺ , 100), 165, 153, 149, 136, 124, 109 37 2- One 5-CH ₃ CH ₃ CH ₃ 52% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.18 (s, 3H), 3.02 (s, 6H), 6.67-6.75 (m, 2H), 6.86-6.93 (m, 1H); 7.56 (s, 1 H); MS (70eV) m / z 180 (M ⁺ , 100), 165, 161, 138, 136, 109 38 3- One 4-CH ₃ CH ₃ CH ₃ 40% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 2.20 (s, 3H), 2.99 (s, 6H), 6.60 ~ 6.66 (m, 2H), 7.02 (q, J = 8.4Hz, 1H), 7.49 (s, 1H ); MS (70eV) m / z 180 (M ⁺ , 100), 165, 152, 138, 124, 109 39 2- One 4-Cl CH ₃ CH ₃ 71% yield liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 3.02 (s, 6H), 6.81-7.7 (mm, 3H), 7.54 (s, 1H); MS (70eV) m / z 200 (M ⁺ , 100), 158, 181, 172, 158, 143, 136, 129, 109 40 2,4,6- 3 H CH ₃ n-butyl 51% yield Liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.94 (t, J = 6.8 Hz, 3H), 1.30 (m, 2H), 1.54 (m, 2H), 3.02 (s, 3H), 3.22 (t, J = 7.0 Hz, 2H), 3.37 (s, 3H), 6.62 (m, 2H), 7.63 (s, 1H) MS (70eV) m / z 244 (M ⁺ , 50), 229, 215, 202, 187, 183, 158, 147, 138, 131 41 4- One 2-CH ₃ CH ₃ n-butyl 36% yield Liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.96 (t, J = 7.1 Hz, 3H), 1.36 (m, 2H), 1.60 (m, 2H), 2.25 (s, 3H), 2.98 (s, 3H), 3.28 (m, 2H), 6.67 (m, 1H), 6.82 (m, 2H), 7.38 (s, 1H) MS (70eV) m / z 222 (M ⁺ , 100), 207, 193, 180, 165, 151, 136, 125

number F n X R ₁ R ₂ ¹ H NMR (CDCl ₃ ) 42 2- One H n-butyl n-butyl 77% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.81 to 0.95 (m, 6H), 1.15 to 1.38 (m, 4H), 1.41 to 1.80 (m, 4H), 3.03 (m, 4H), 3.41 (s, 3H ), 6.94-7.08 (m, 4H), 8.03 (s, 1H); MS (70eV) m / z 311 (M ⁺ , 10), 288, 270, 250, 245, 235, 205, 184, 176, 161, 139, 126 43 3- One H n-but n-but 61% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.92 (m, 6H), 1.31 (m, 4H), 1.57 (m, 4H), 3.03 (m, 4H), 3.38 (s, 3H), 6.73 (m, 3H ), 7.25 (m, 1 H), 7.94 (s, 1 H); MS (70eV) m / z 311 (M ⁺ , 5), 288, 245, 229, 184, 183, 160, 152, 128 44 4- One H n-butyl n-butyl 81% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.85 to 0.96 (m, 6H), 1.25 to 1.38 (m, 4H), 1.48 to 1.64 (m, 4H), 3.03 (m, 4H), 3.37 (s, 3H ), 6.89-7. 1 (m, 4H), 7.91 (s, 1H); MS (70eV) m / z 311 (M ⁺ , 10), 288, 270, 250, 245, 235, 205, 184, 176, 161, 139, 126, 119 45 2,4- 2 H n-butyl n-butyl 71% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.83 to 0.95 (m, 6H), 1.23 to 1.38 (m, 4H), 1.50 to 1.64 (m, 4H), 3.05 (m, 4H), 3.39 (s, 3H) , 6.75-6.95 (m, 3 H), 7.99 (s, 1 H); MS (70eV) m / z 330 (M ⁺ , 75), 320, 309, 287, 268, 253, 239, 225, 201, 193, 168, 168, 147, 126 46 2,5- 2 H n-butyl n-butyl 76% yield; liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ0.88 to 0.96 (m, 6H), 1.25 to 1.38 (m, 4H), 1.50 to 1.69 (m, 4H), 3.06 (m, 4H), 3.39 (s, 3H ), 6.64-6.72 (m, 2H), 6.95-7.03 (m, 1H), 8.02 (s, 1H); MS (70eV) m / z 329 (M ⁺ , 5), 309, 288, 245, 231, 202, 192, 170, 161, 140, 128, 118 47 2,6- 2 H n-butyl n-butyl 73% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.88 to 0.96 (m, 6H), 1.28 to 1.39 (m, 4H), 1.50 to 1.67 (m, 4H), 3.06 (m, 4H), 3.42 (s, 3H) 6.85-6.92 (m, 3 H), 8.10 (s, 1 H); MS (70eV) m / z 329 (M ⁺ , 20), 320, 288, 268, 245, 239, 202, 201, 191, 161, 160, 150, 116 48 3,4- 2 H n-butyl n-butyl 71% yield; liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.86 to 0.95 (m, 6H), 1.25 to 1.37 (m, 4H), 1.50 to 1.64 (m, 4H), 3.07 (m, 4H), 3.35 (s, 3H) ), 6.65-6.69 (m, 1H), 6.75-6.82 (m, 1H), 7.05 (q, J = 8.7 Hz, 1H), 7.90 (s, 1H); MS (70eV) m / z 329 (M ⁺ , 45), 309, 287, 277, 245, 231, 204, 201, 190, 161, 154, 142, 119 49 2,3,4- 3 H n-butyl n-butyl 72% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.86 to 0.95 (m, 6H), 1.26 to 1.37 (m, 4H), 1.54 to 1.64 (m, 4H), 3.06 (m, 4H), 3.38 (s, 3H) , 6.65-6.70 (m, 1H), 6.81-6.91 (m, 1H), 7.99 (s, 1H); MS (70eV) m / z 347 (M ⁺ , 10), 320, 329, 304, 277, 263, 221, 220, 192, 188, 158, 147, 128, 118 50 2,4,5- 3 H n-butyl n-butyl 75% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.86 to 0.96 (m, 6H), 1.26 to 1.37 (m, 4H) 1.50 to 1.63 (m, 4H), 3.07 (m, 4H), 3.37 (s, 3H), 6.75-6.97 (m, 2 H), 7.99 (s, 1 H); MS (70eV) m / z 347 (M ⁺ , 50), 321, 320, 304, 288, 263, 245, 222, 221, 189, 179, 159, 146, 131, 119, 1161

number F n X R ₁ R ₂ ¹ H NMR (CDCl ₃ ) 51 2,4,6- 3 H ethyl ethyl 71% yield Liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 1.17 (m, 6H), 2.97 (m, 4H), 3.30 (s, 3H), 6.66 (m, 2H), 7.93 (s, 1H) MS (70eV) m / z 291 (M ⁺ , 65), 220, 219, 188, 179, 158, 147, 138, 131, 104, 90, 72, 62, 56 52 2,4,6- 3 H n-propyl n-propyl 49% yield Liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.92 (m, 6H), 1.59 (m, 4H), 3.03 (m, 4H), 3.40 (s, 3H), 6.67 (t, J = 7.8 Hz, 2H), 8.07 (s, 1H) MS (70eV) m / z 319 (M ⁺ , 65), 264, 232, 220, 219, 188, 179, 158, 132, 131, 104, 100, 86, 72, 71, 62 , 56 53 2,4,6- 3 H n-butyl n-butyl 53% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.89 to 0.95 (m, 6H), 1.26 to 1.37 (m, 4H), 1.43 to 1.64 (m, 4H), 3.06 (m, 4H), 3.40 (s, 3H) , 6.64-6.69 (m, 2 H), 8.07 (s, 1 H); MS (70eV) m / z 347 (M ⁺ , 10), 288, 220, 219, 188, 169, 158, 147, 128, 118 54 2,4,6- 3 H n-pentyl n-pentyl 71% yield Liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.90 (t, J = 6.8 Hz, 6H), 1.30 (m, 8H), 1.60 (m, 4H), 3.05 (m, 4H), 3.40 (s, 3H), 6.66 (m, 2H), 8.07 (s, 1H) MS (70 eV) m / z 376 (M ⁺ , 15), 220, 188, 179, 156, 147, 132, 55 2,4,6- 3 H methyl n- buty 73% yield Liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.85 (t, J = 6.8 Hz, 3H), 1.28 (m, 2H), 1.50 (m, 2H), 2.86 (s, 3H), 2.96 (t, J = 7.2 Hz, 2H), 3.37 (s, 3H), 6.58 (m, 2H), 8.02 (s, 1H) MS (70eV) m / z 305 (M ⁺ , 5), 268, 244, 220, 215, 202, 488, 169, 158, 147, 138, 131 56 2,4,6- 3 H Morpholino 54% yield Liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 3.19 (t, J = 4.8 Hz, 4H), 3.46 (s, 3H), 3.68 to 3.72 (m, 4H), 6.67 (t, J = 8.4 Hz, 2H), 8.08 (s, 1 H); MS (70eV) m / z 305 (M ⁺ , 60), 281, 264, 220, 219, 188, 179, 177, 158, 138, 118 57 2,3,6- 3 H n-butyl n-butyl 81% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.89 to 0.95 (m, 6H), 1.25 to 1.38 (m, 4H), 1.54 to 1.64 (m, 4H), 3.07 (m, 4H), 3.42 (s, 3H) , 6.72-6.81 (m, 2H), 8.11 (s, 1H); MS (70eV) m / z 347 (M ⁺ , 5), 320, 263, 220, 219, 188, 179, 158, 147, 128 58 2,3,5,6- 4 H n-butyl n-butyl 78% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.89 to 0.99 (m, 6H), 1.16 to 1.41 (m, 4H), 1.54 to 1.68 (m, 4H), 2.93 (m, 4H), 3.42 (s, 3H) , 6.70-6.77 (m, 1 H), 8.11 (s, 1 H); MS (70 eV) m / z 369 (M ⁺ , 95), 355, 341, 295, 281, 221, 207, 147, 135, 111 59 3- One 2-CH ₃ n-butyl n-butyl 79% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.81 to 1.00 (m, 6H), 1.25 to 1.64 (m, 8H), 3.07 (m, 4H), 3.39 (s, 3H), 6.55 (d, J = 7.8 Hz, 1H), 6.75 (t, J = 8.4 Hz, 1H), 7.05 (q, J = 7.8 Hz, 1H), 7.84 (s, 1H); MS (70eV) m / z 325 (M ⁺ , 10), 320, 288, 284, 264, 245, 221, 194, 192, 165, 160, 135, 122 60 5- One 2-CH ₃ n-butyl n-butyl 83% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.82-0.96 (m, 6H), 1.20-1.69 (m, 8H), 3.03 (m, 4H), 3.39 (s, 3H), 6.49 (dd, J = 2.7 Hz , 1H), 6.68 (m, 1H), 7.07 (t, J = 8.1 Hz, 1H), 7.83 (s, 1H); MS (70eV) m / z 325 (M ⁺ , 10), 320, 288, 284, 264, 245, 221, 194, 192, 165, 160, 135, 122

number F n X R ₁ R ₂ ¹ H NMR (CDCl ₃ ) 61 2- One 5-CH ₃ n-butyl n-butyl 72% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.84-0.96 (m, 6H), 1.20-1.70 (m, 8H), 3.05 (m, 4H), 3.39 (s, 3H), 6.78 (m, 2H), 6.94 (m, 1 H), 8.02 (s, 1 H); MS (70 eV) m / z 325 (M ⁺ , 10), 320, 288, 284, 264, 245, 221, 194, 192, 165, 160, 135, 122, 62 3- One 4-CH ₃ n-butyl n-butyl 84% yield liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.82 to 0.96 (m, 6H), 1.20 to 1.64 (m, 8H), 3.03 (m, 4H), 3.39 (s, 3H), 6.55 (d, J = 7.8 Hz , 1H), 6.75 (t, J = 8.7 Hz, 1H), 7.04 (m, 1H), 7.85 (s, 1H); MS (70eV) m / z 325 (M ⁺ , 10), 320, 288, 284, 264, 245, 221, 194, 192, 165, 160, 135, 122 63 2- One 4-Cl n-butyl n-butyl 85% yield liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.92 (t, J = 7.0 Hz, 6H), 1.25-1.52 (m, 4H), 1.55-1.63 (m, 4H), 3.05 (m, 4H), 3.39 (s , 3H), 6.89 (m, 1 H), 7.06 (m, 2 H), 8.01 (s, 1 H); MS (70eV) m / z 345 (M ⁺ , 150), 218, 192, 177, 156, 145, 128, 118 64 4- One 2-CH ₃ ethyl ethyl 81% yield Liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 1.22 (m, 6H), 2.28 (s, 3H), 3.47 (m, 7H), 6.85 (m, 3H), 8.24 (s, 1H) MS (70eV) m / z 269 (M ⁺ , 20), 261, 239, 224, 211, 190, 188, 167, 149, 136, 124 65 4- One 2-CH ₃ n-propyl n-propyl 77% yield Liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.89 (m, 6H), 1.62 (m, 4H), 3.02 (m, 4H), 3.37 (s, 3H), 6.63-6.89 (mm, 3H), 7.81 (s , 1H) MS (70eV) m / z 297 (M ⁺ , 30), 198, 164, 157, 136, 124 66 4- One 2-CH ₃ n-butyl n-butyl 71% yield liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.81 to 1.00 (m, 6H), 1.25 to 1.64 (m, 8H), 3.03 (m, 4H), 3.37 (s, 3H), 6.63 to 6.89 (mm, 3H) , 7.81 (s, 1 H); MS (70 eV) m / z 325 (M ⁺ , 30), 198, 165, 157, 147, 136, 128, 118 67 4- One 2-CH ₃ n- penty n- penty 79% yield Liquid; ¹ H NMR (CDCl ₃ , 300 MHz) δ 0.92 (t, J = 6.6 Hz, 6H), 1.30 (m, 8H), 1.60 (m, 4H), 2.24 (s, 3H), 3.06 (m, 4H), 3.41 (s, 3H), 6.67 (m, 1H), 6.83 (m, 2H), 7.81 (s, 1H) MS (70eV) m / z 353 (M ⁺ , 10), 220, 198, 188, 166, 156, 132 68 4- One 2-CH ₃ methyl n-butyl 54% yield Liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.93 (t, J = 7.2 Hz, 3H), 1.31 (m, 2H), 1.60 (m, 2H), 2.25 (s, 3H), 2.92 (s, 3H), 3.02 (m, 2H), 3.41 (s, 3H), 6.70 (m, 1H), 6.84 (m, 2H), 7.84 (s, 1H) MS (70 eV) m / z 283 (M ⁺ , 15), 267 , 236, 221, 198, 197, 169, 165, 149, 136, 124 69 4- One 2-CH ₃ n-octyl n-octyl 80% yield Liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.88 (t, J = 6.3 Hz, 6H), 1.27 (m, 20H), 1.56 (m, 4H), 2.24 (s, 3H), 3.03 (m, 4H), 3.37 (s, 3H), 6.67 (m, 1H), 6.85 (m, 2H), 7.81 (s, 1H) MS (70eV) m / z 438 (M ⁺ , 50), 437, 413, 376, 361, 307, 304, 272, 242, 238, 197, 168, 141 70 4- One 2- OCH ₃ n-butyl n-butyl 81% yield liquid; R _f = 0.29 ( n- Hex / EtOAc = 8/1); ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.92 (m, 6H), 1.30 (m, 4H), 1.59 (m, 4H), 3.05 (m, 4H), 3.40 (m, 3H), 3.80 (s, 3H ), 6.58 (m, 2 H), 6.74 (m, 1 H), 7.94 (s, 1 H); MS (70eV) m / z 341 (M ⁺ , 10), 300, 288, 214, 213, 182, 171, 152, 128, 118

number F n X R ₁ R ₂ ¹ H NMR (CDCl ₃ ) 71 4- One 2-NO ₃ n-butyl n-butyl 67% yield liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.92 (m, 6H), 1.31 (m, 4H), 1.57 (m, 4H), 3.07 (m, 4H), 3.35 (s, 3H), 6.92 (m, 1H ), 7.20 (m, 2 H), 7.55 (m, 1 H), 7.85 (s, 1 H); MS (70 eV) m / z 356 (M ⁺ , 25), 315, 313, 304, 272, 261, 229, 228, 198, 184, 160, 159, 129 72 2- One 4-CH ₃ n-butyl n-butyl 67% yield liquid; ¹ H NMR (CDCl ₃ , 200 MHz) δ 0.92 (m, 6H), 1.31 (m, 4H), 1.57 (m, 4H), 3.07 (m, 4H), 3.35 (s, 3H), 6.92 (m, 1H ), 7.20 (m, 2 H), 7.55 (m, 1 H), 7.85 (s, 1 H); MS (70 eV) m / z 356 (M ⁺ , 25), 315, 313, 304, 272, 261, 229, 228, 198, 184, 160, 159, 129, 119

In addition, the compound represented by the formula (I) according to the present invention may be classified into three types of monoalkyl amidine (A1), dialkyl amidine (A2) and sulfenyl amidine (B), and conventional organic synthesis It can be synthesized by applying the method.

The compound represented by Formula A1 may form various compounds by reacting aniline derivatives with triethylol phosphatemate to form formimate, and then reacting various monoamines, as shown in Scheme 1 below. As shown in Scheme 2, it can be synthesized by reacting an aniline derivative with N -monoalkylformamide.

Scheme 1

Scheme 2

In the preparation method according to Scheme 1, the imidate is synthesized by heating under reflux using a toluene solvent, concentrated under reduced pressure to remove excess solvent, and then 3 to 5 hours at room temperature with a monoamine compound in a tetrahydrofuran (THF) solvent. Stirred for a while to obtain a compound represented by the formula (A1). In addition, in the preparation method according to Scheme 2, 1 equivalent of toluenesulfonyl chloride and excess N-monoalkylformamide were stirred at room temperature for 3 hours to obtain a compound represented by Chemical Formula A1. After the reaction is completed, the reaction mixture can be purified by general separation and purification, for example, diluted with an organic solvent and washed with water, followed by concentration under reduced pressure or, if necessary, separation and purification.

Compound of the formula A2 is reacted with a formaldehyde imidate and various dialkyl amine prepared in scheme 1 can be synthesized, and N in reaction scheme 2 with a dialkyl formamide -alkyl formamide instead of N It can be synthesized under the same reaction conditions.

The compound represented by the formula (B) was synthesized by reacting dialkylaminosulphenyl chloride with N -alkylformamidine, as shown in Scheme 3 below.

Dialkylaminosulphenyl chloride was synthesized using known methods using dialkylamine and sulfadichloride as starting materials (Scheme 4).

Scheme 3

Scheme 4

In Reaction Scheme 3, R ₂ , R ₃ are as defined in the text. In the preparation method according to Scheme 3, the compound of formula B was obtained in good yield at low temperature.

Dialkylaminosulphenyl chloride was synthesized as in Scheme 4 at low temperature using dialkylamine, sulfamonochloride, and sulfuryl chloride.

The range of the action of the compound represented by the formula (I) can be used in various pest control agents generated in agriculture and horticultural crops. This compound is not only effective for adults, but also for all metamorphic stages such as eggs, larvae, nymphs or pupa.

The compounds according to the invention are effective for the control of animal parasites and, in particular, plant hospital mites, namely mites such as Tetranychidae, mite, Argasidae and Deermanysidae.

In addition, the compound represented by the formula (I) shows excellent insecticidal action against insects that harm plants and animals. Therefore, it can be used to control insects such as Acrididae, Wheel, Cricket, Dropod, Chiliaceae, Bedbug, Asteraceae, Chimney, Aphid, Delphacidae, Pike, Pseudococcidae, Pleudococcidae Ladybug, Bean weevil, Chaferaceae, Sugerenaceae, Mesothelidae, Weevil, Grain Moth, Chestnut Moth , Housefly, black fly, clown fly, and Pulicidae. Among these, it is especially effective against mites and aphids. The compounds of formula (I) prepared according to the invention are therefore particularly suitable for pest control of fruits, vegetables, rice and ornamental plants.

The pesticides of the present invention can be used alone or in combination with other herbicides or pesticides. By mixing with other herbicides or pesticides, these actions can be substantially enhanced, and suitable additives include organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, urea, steroids, carbamates and chlorinated hydrocarbons. Can be.

The compounds of formula (I) according to the invention may also be used alone or in combination with suitable carriers and / or additives. Suitable carriers and additives may be solid or liquid, and include natural or recycled materials, solvents, dispersants, wetting agents, adhesives, binders and / or fertilizers used in conventional formulations. When used as a pesticide, the compound of formula (I) may be prepared according to conventional methods in the form of conventional preparations, for example powders, emulsions, granules, dispersions, sprays, solutions or suspensions. It may also be prepared from bottle dips and spray races used in the preparation of fluids.

The composition can also be obtained according to conventional methods for the complete mixing and / or grinding of the active substance of formula (I) by addition of a suitable carrier and an inert dispersant or solvent to the active substance.

In addition, the pesticide of the present invention can be used up to 10 g to 500 g per hectare (ha) as an active ingredient, preferably 10 g to 200 g. The choice of dosage is determined by factors such as the incidence of the pest, the extent of growth, and the preparation, but is not limited thereto.

Compounds of formula (I) of the present invention can be used as an alternative medicine because it is 5-6 times better activity than Amitraz and excellent in safety.

Hereinafter, the present invention will be described in more detail with reference to Examples. Since these examples are only for illustrating the present invention, the scope of the present invention is not to be construed as being limited by these examples.

Example  One: N ' -(2- Fluorophenyl )- N - Of methylformamidine (1)  synthesis

2-fluoroaniline (1.11 g, 10 mmol) was added to a solvent of N-methylformamide (11 ml), and p -toluenesulfonyl chloride (2.38 g, 12.5 mmol) was slowly added at room temperature, followed by stirring for 3 hours. After confirming that the reaction was completed by TLC, the reaction was poured into iced water and the pH was adjusted to basic with 10N aqueous sodium hydroxide solution while maintaining the temperature below 10 ° C. The reaction solution was extracted three times with ethyl acetate, and the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by evaporation under reduced pressure. Purified by n-hexane / ethyl acetate = 1/1) to give a yellow liquid compound 1 (1.06g, 70.0%).

Compound No. 1 to compound No. 21 shown in Table 1 of the present invention were synthesized and used in the same manner as in Example 1.

Example  2: N ' -(2- Fluorophenyl )- N ,  N - Of dimethylformamidine (22)  synthesis

2-fluoroaniline (1.11 g, 10 mmol) was dissolved in N , N -dimethylformamide (11 ml), and then p -toluenesulfonylchloride (2.38 g, 12.5 mmol) was slowly added at room temperature and stirred for 3 hours. After confirming completion of the reaction by TLC, the reaction was poured into iced water and the pH was adjusted to basic with 10N aqueous sodium hydroxide solution while maintaining the temperature below 10 ° C. The reaction solution was extracted three times with ethyl acetate, and the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by evaporation under reduced pressure. n-hexane / ethyl acetate = 1/1) was purified and purified to give a yellow liquid compound 36 (0.81 g, 49%).

Compounds 22 to 41 shown in Table 1 of the present invention were synthesized and used in the same manner as in Example 2.

Example  3:

N-((di-n- Butylamino ) Sulfenyl )- N ' -(2- Fluorophenyl ) -N- Methylformamidine  Synthesis of 42

Compound (1) (1.52 g, 10 mmol) was added to tetrahydrofuran (15 ml) under nitrogen stream, and the temperature was cooled to 0 ° C. in an ice water bath, n-dibutylaminosulphenyl chloride (2.35 g, 12 mmol) and tri Ethylamine (1.52 g, 15 mmol) was added slowly and stirred at room temperature for 2 hours. After confirming that the reaction was completed by TLC, the reaction was concentrated by evaporation under reduced pressure, water and dichloromethane were added, and extracted three times with dichloromethane. The extracted organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated by evaporation under reduced pressure, and the concentrated mixture was separated and purified by column chromatography (developing solvent: n-hexane / ethyl acetate = 8/1) to obtain compound 54 (2.40 g, 77%).

Compounds 42 to 72 shown in Table 2 of the present invention were synthesized and used in the same manner as in Example 3. However, each starting material was used in compounds 1 to 21.

Those skilled in the art can easily synthesize the compounds exemplified in Tables 1 and 2 using or applying the synthesis methods exemplified in the above examples.

The following is an example of testing the pest control effect exhibited by the compounds of the present invention.

Example  4: Light Bulb Brown planthopper , Nilaparvata lugens ) Action

Three-year-old nymphs were used as experimental fertilization, and four host nurses of Chucheong rice, one week after sowing, were used as host plants. The drug (500ppm) was treated by the spray method, and rice wool was rolled and pushed into cotton wool in a test tube having a diameter of 3 cm and a height of 15 cm, inoculated with 10 rice craters, and treated with a chemical stopper. The assay determined the insecticidal effect as a percentage from the number of live larvae after 24 and 48 hours. Carbofuran was used as a reference drug (LC50, ppm).

As a result of the test, Compound No. 10, 14, 15, 25, 34, 35, 36, 39, 53 and 66 showed effective activity.

Example  5: peach aphid Green peach aphid , Myzus persicae ) Action

The adult insects were used as experimental fetuses and tobacco leaf slices were used as host plants. The drug (500ppm) treatment method is to immerse a tobacco leaf section of 4.5 cm in diameter in the chemical solution for 30 seconds, then shade it in a hood, filter paper in a disposable petri dish of 6 cm in diameter, put the leaves and inoculate 10 adults. It was. The assay determined the insecticidal effect as a percentage from the number of live larvae after 24 and 48 hours. Acetate was used as a reference drug (LC50, ppm).

As a result of the test, Compound No. 34, 45, 47, 53, 59 and 66 showed effective activity.

Example  6: spotted mite Two - spotted spider mite , Tetranychus urticae ) Action

The adult insects were used as experimental fertilization and kidney bean leaf slices were used as host plants. The cotton wool was put on 6 cm diameter Petri-Dish and moistened with distilled water, and 3.5 cm diameter kidney bean leaf slices were placed, 30 adult seeds were inoculated, and the small spray was used to treat the drug (500 ppm). The assay examined the insecticide rate after 24 and 48 hours. Dicopol (Dicofol (29.9)) and cyhexatin (Cyhexatin (11.8)) were used as reference drugs (LC50, ppm).

As a result of the test, Compound No. 3, 4, 6, 10, 13, 14, 15, 18, 31, 34, 35, 45, 53, 59, 63 and 66 showed effective activity.

Example  7: spotted mites Reference drug Amitraz and  United States Patent US  In 3,998,969 N -[( die - n - Butylamino ) Sulfenyl ]- N ' -(4- Chloro -2- Methylphenyl )- N - Methylformamidine  And this patent compound No . Insecticidal activity of 66

As shown in Table 3 below, Compound No. 66 is Amitraz, which is a reference agent, or an existing patent compound [ N -[(di- n -butylamino) sulphenyl] -N ' -(2,4-dimethylphenyl) -N -methylformamidine] It was confirmed to exhibit 6 times higher activity.

compound Concentration (ppm) Insecticide Rate (%) 24 hours 48 hours No. 66 125 90 98 63 93 93 31 79 93 16 83 93 8 39 49 Amitraz 125 83 89 63 51 70 31 18 26 16 23 26 8 3 6 United States Patent 3,998,969 Compound 125 90 100 63 65 65 31 60 60 16 45 50 8 20 20

As described above, in the present invention, the fluorine-containing phenylamidine derivative compounds represented by the general formula (I) of the present invention among the phenylamidine derivative compounds that have been reported to have an insecticidal effect in the prior art are disclosed in the comparative document. It was confirmed that chlorine and bromine have superior pesticidal activity than substituted phenylamidine derivative compounds. In addition, the fluorine-containing phenylamidine derivative compound of the present invention has a high activity of 5 to 6 times higher than the commercially available control drug Amitraz, and thus can be expected to have an excellent control effect as an agricultural or horticultural pest control agent. .

Claims (7)

A pest control agent comprising the fluorine-containing phenyl amidine derivative represented by the following formula (I) as an active ingredient: [Formula I]

Wherein F is fluorine; X is hydrogen atom, cyano, amino [NR ² R ³ : R ² , R ³ is hydrogen atom, C _1-2 alkyl, acetyl, carbo C _1-2 alkoxy, C _1-2 alkylcarbamoyl], car Bo C _1-2 alkoxy, C _1-2 alkylcarbamoyl, C _1-4 alkyl or alkoxy [OR ⁴ : R ⁴ is a hydrogen atom, C _1-2 alkyl, acetyl, carbo C _1-2 alkoxy, C _{1 -2} alkylcarbamoyl; R ¹ is a hydrogen atom, C _1-4 alkyl; Y is C _1-8 alkyl or dialkyl [R ⁵ , R ⁶ ] aminosulphenyl group (R ⁵ , R ⁶ is C _1-8 alkyl, C _1-6 haloalkyl or C _{5-6 cyclicalkyl} ); n represents 1, 2, 3 or 4. A compound according to claim 1, wherein when Y is dialkylaminosulphenyl, Formula II ]

In formula II, F is fluorine; X is cyanide furnace, amino ^{[NR 2 R 3: R 2} , R 3 is a hydrogen atom, C _{1 -2} alkyl, acetyl, carbonyl C _{1 -2} alkoxy, C _{1 -2} alkyl-carbamoyl], carbonyloxy C _{1 -2} alkoxy, C _{1 -2} alkyl-carbamoyl, 2-C _1-4 alkyl or 2-alkoxy [oR ^4: R ⁴ is a hydrogen atom, C _{1 -2} alkyl, acetyl, carbonyl C _{1 -2} alkoxy, C _{1 -2} alkylcarbamoyl; R ¹ is methyl; n is 1, 2 or 3; R ⁵ , R ⁶ is the pesticide comprises a C _{1 -8} alkyl, C _{1 -6} which is a compound selected from haloalkyl or C _{5 -6} cyclic alkyl. The fluorine-containing phenylamidine derivative according to claim 2, wherein the fluorine-containing phenylamidine derivative is N -[(di-alkylamino: R ⁵ , R ⁶ ) sulphenyl] -N ' -(2,4,6-trifluorophenyl) -N -methylformamidine. The fluorine-containing phenylamidine derivative according to claim 2, wherein the fluorine-containing phenylamidine derivative is N -[(di-alkylamino: R ⁵ , R ⁶ ) sulphenyl] -N ' -(4-fluoro-2-methylphenyl) -N -methylformamidine. The fluorine-containing phenylamidine derivative according to claim 2, wherein the fluorine-containing phenylamidine derivative is N -[(di-alkylamino: R ⁵ , R ⁶ ) sulphenyl] -N ' -(4-fluoro-2-amino: NR ² R ³ ) -N -methylformamidine. The fluorine-containing phenylamidine derivative according to claim 2, wherein the fluorine-containing phenylamidine derivative is N -[(di-alkylamino: R ⁵ , R ⁶ ) sulphenyl] -N ' -(4-fluoro-2-alkoxy: OR ⁴ ) -N -methylformamidine. A pest control agent, characterized in that the pest is mite or mite.