Indian Patents. 272067:A BENZOXAZOL-2-YLOXY SUBSTITUTED DICHLOROPROPENE COMPOUND

Title of Invention	A BENZOXAZOL-2-YLOXY SUBSTITUTED DICHLOROPROPENE COMPOUND
Abstract	A dichloropropene compound with novel structure represented by formula I and the uses thereof: I Wherein R1 or R2 is H, halo, C1-C3 alkyl or C1-C3 haloalkyl, with the proviso that R1 or R2 is H; and wherein n=0, 1, 2 or 3. The compound represented by formula I has excellent insecticidal activity and is useful for the prevention and control of various insect pests.

Full Text	FORM 2 THE PATENTS ACT 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See section 10 and rule 13) 1. ' DICHLOROPROPENE COMPOUNDS AND USES THEREOF ' 2. 1. (A) SINOCHEM CORPORATION. (B) China. (C) 28 Fuxingmennei Dajie, Xicheng District Beijing 100031 China. 2. (A) SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY CO., LTD. (B) China. (C) 8 Shenliaodong Road, Tiexi District Shenyang, Liaoning 110021 China. The following specification particularly describes the invention and the manner in which it is to be performed. FIELD OF THE INVENTION The present invention relates to insecticide. Specifically to a dichloropropene compound and the uses thereof. BACKGROUND OF THE INVENTION Since insect pests will become resistant to insecticides used for a period of time, it is necessary to invent continuously new compounds and compositions with improved insecticidal activity. At the same time, with the increase of need for agricultural and livestock products and attention to environmental protection, new insecticides with lower cost and environmental compatibility have been in demand. The patent CN1169147A disclosed some dichloropropene compounds with benzoheterocycle group and insecticidal activity thereof, for example, the dichloropropene compounds containing benzothiazole group and benzimidazole group, represented by KC1 and KC2 respectively, and their biological data controlling Spodoptera litura were published. KC1 KC2 The above patent focused on the disclosure of the compounds with better insecticidal activity containing pyridin-2-yloxy moiety, for example, KC3 (the structure is shown as follows), which can be used to control diamondback moth at 50ppm. This compound had been developed to be a commercialized insecticide with common name of pyridalyl: KC3 (pyridalyl) In the existing technology, the preparation and insecticidal activity of dichloropropene compounds containing benzoxazol-2-yloxy moiety has not been reported. SUMMARY OF THE INVENTION The object of the present invention is to provide a dichloropropene compound with novel structure and better insecticidal activity, which can be applied in agriculture, forestry or public health to control insects. Detailed description of the invention is as follows: The present invention provides a dichloropropene compound having general formula I: I Wherein: R1 or R2 is selected from H, halo, C1-C3alkyl or C1-C3haloalkyl, with the proviso that R1 or R2 is H; n=0, 1, 2 or 3. The preferred compounds of general formula I of this invention are: R1 or R2 is selected from H, Cl, CH3, CF3 or i-C3F7, with the proviso that R1 or R2 is H; n=0, 1 or 2. Futher more, the preferred compounds of general formula I of this invention are: R1 is CF3; R2 is H; n=1 or 2. It must be noted that, as used in this specification, the appended claims and the general formular I, The “alkyl” stands for straight-chain or branched alkyl, such as methyl, ethyl, n-propyl or isopropyl. The “haloalkyl” stands for straight or branched chain alkyl, for example, methyl, ethyl, n-propyl or isopropyl is (are) substituted with one or more halogen atom(s), such as trifluoromethyl or heptafluoro isopropyl. The “halo” denotes fluorine, chlorine, bromine or iodine. The compounds represented by the general formula I were prepared according to the following method, each group of formulas is as defined above, unless otherwise specified. II III I The target compounds represented by the general formula I were prepared by reaction of the compounds represented by the general formula II with the compounds represented by the general formula III in proper solvent and in the presence of proper base at the range of -10? to boiling point for 0.5-48h. The proper solvent mentioned may be selected from dichloromethane, chloroform, tetrachloromethane, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, DMF or DMSO and so on. The proper base mentioned may be selected from hydride of alkali metal like lithium, sodium or potassium such as sodium hydride, or hydroxide of alkali metal like lithium, sodium or potassium such as sodium hydroxide, also selected from carbonate of alkali metal such as sodium carbonate and selected from organic base such as triethylamine, sodium tert-butoxide and so on. The compounds of the general formula II can be prepared according to the methods introduced in the following literatures: J. Org. Chem. 1996, 61, 3289-3297;Bioorganic & Medicinal Chemistry Letters 17 (2007) 4689-4693;WO2009023844;Journal of Medicinal Chemistry,2008, 51(5), 1482-1486? The compounds of the general formula III can be prepared according to the methods discribed in CN1860874A (Examples 1, 2 and 3): The structures and physical properties of some compounds represented by general formula I were shown in Table 1. Table 1 I Compound R1 R2 n Appearance(mp(?) 1 H Cl 0 yellow solid (104-106) 2 H CF3 0 yellow oil 3 CF3 H 0 yellow solid (66-69) 4 H Cl 1 white solid (58-60) 5 Cl H 1 yellow oil 6 CH3 H 1 yellow oil 7 H CF3 1 yellow oil 8 CF3 H 1 yellow oil 9 H Cl 2 white solid (63-65) 10 H CF3 2 yellow oil 11 CF3 H 2 yellow 12 H i-C3F7 1 yellow 1HNMR spectrum (300MHz, CDCl3) of some compounds of the present invention are as follows: Compound 1:4.39-4.42 (m, 2H), 4.59 (d, 2H), 7.833 (d, 1H), 4.89-4.92 (m, 2H), 6.11 (t, 1H), 6.85 (s, 2H), 7.22-7.27 (m, 1H), 7.8-7.41 (m, 2H)? Compound 2:4.40-4.43 (m, 2H), 4.59 (d, 2H), 7.833 (d, 1H), 4.93-4.96 (m, 2H), 6.11 (t, 1H), 6.85 (s, 2H), 7.56 (s, 2H), 7.65 (s, 1H)? Compound 3:4.40-4.43 (m, 2H), 4.58 (d, 2H), 7.833 (d, 1H), 4.92-4.95 (m, 2H), 6.11 (t, 1H), 6.85 (s, 2H), 7.47-7.48 (m, 2H), 7.75 (s, 1H)? Compound 4:2.34-2.42 (m, 2H), 4.14 (t, 2H), 4.58 (d, 2H), 4.87 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.21-7.26 (m, 2H), 7.38-7.41 (m, 1H)? Compound 5:2.36-2.40 (m, 2H), 4.14 (t, 2H), 4.58 (d, 2H), 4.88 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.15 (dd, 1H), 7.25-7.28 (m, 1H), 7.47 (d, 1H)? Compound 6:2.35-2.39 (m, 2H), 2.42 (s, 3H),4.14 (t, 2H), 4.56 (d, 2H), 4.85 (t, 2H), 6.10 (t, 1H), 6.82 (s, 2H), 7.25 (d, 2H), 7.15 (dd, 1H), 7.28-7.29 (m, 2H)? Compound 7:2.37-2.42 (m, 2H), 4.15 (t, 2H), 4.58 (d, 2H), 4.92 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.55-7.56 (m, 2H), 7.62 (d, 1H)? Compound 8:2.35-2.41 (m, 2H), 4.15 (t, 2H), 4.58 (d, 2H), 4.91 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.42-7.46 (m, 2H), 7.76 (s, 1H)? Compound 9:1.99-2.06 (m, 2H), 2.17-2.21 (m, 2H), 4.03 (t, 2H), 4.58 (d, 2H), 4.67 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 6.85-7.26 (m, 1H), 7.37-7.40 (m, 1H)? Compound 10:2.00-2.05 (m, 2H), 2.19-2.23 (m, 2H), 4.03 (t, 2H), 4.58 (d, 2H), 4.71 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.54 (d, 2H), 7.62 (s, 1H)? Compound 11:2.02-2.05 (m, 2H), 2.18-2.21 (m, 2H), 4.04 (t, 2H), 4.58 (d, 2H), 4.71 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.44-7.46 (m, 2H), 7.74-7.75 (m, 1H)? Compound 12:2.38-2.42 (m, 2H), 4.15 (t, 2H), 4.58 (d, 2H), 4.59 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.50-7.61 (m, 2H), 7.63 (d, 1H)? The dichloropropene compounds containing benzoxazol-2-yloxy moiety were prepared successfully in this invention and their excellent insecticidal activity have been proved by extensive research and experiments. During the course of further research, the inventors found surprisingly that in benzoxazole ring of the compounds represented by general formula I, introducing substituents to 5-position was more beneficial than to 6-position. Compared to the compounds with higher bioactivity in the existing technology, the compounds of present invention were used at lower dosage, normally more than once lower at the same control, showing unexpected high insecticidal activity. Therefore, the present invention also includes the use of the compounds having general formula I as insecticides to control insect pests. A further object of the present invention also includes insecticidal compositions containing the compounds having general formula I as active ingredient, and the weight percentage of the active ingredient in the composition is 1-99%. The insecticidal compositions also include the carrier being acceptable in agriculture, forestry, public health. The compositions of the present invention can be used in the form of various formulations. Usually, the compounds having general formula I as active ingredient can be dissolved in or dispersed in carriers or made to a formulation so that they can be easily dispersed as an insecticide. For example: these chemical formulations can be made into wettable powder or emulsifiable concentrate. Therefore, in these compositions, at least a liquid or solid carrier is added, and suitable surfactant(s) can be added when needed. Still also provided by the present invention are the application methods for controlling insects, which is to apply the compositions of the present invention to the insects as mentioned above or their growing loci. The suitable effective dosage of the compounds of the present invention is usually within a range of 10 g/ha to 1000 g/ha, preferably from 20 g/ha to 500 g/ha. For some applications, one or more other fungicides, insecticides, herbicides, plant growth regulators or fertilizer can be added into the insecticidal compositions of the present invention to make additional merits and effects. It should be noted that variations and changes are permitted within the claimed scopes in the present invention. DESCRIPTION OF THE INVENTION IN DETAIL The following preparation examples and biological results are illustrative of the present invention, but without being restricted thereby. Example 1 The preparation of compound 7 (1) The preparation of 2-chloro-6-(trifluoromethyl)benzoxazole (a) The preparation of 2-nitro-5-(trifluoromethyl)phenol To a flask, 3-(trifluoromethyl)phenol(20.00 g, 123 mmol, available in market) was added, 60% of Salpeter solution pre-prepared (a mixture of 11.60 g of fuming nitric acid and 7.40 g of water) was added dropwise, after completion of addition, the reaction mixture was stirred for 24 hours at room temperature. Then the reaction mixture was neutralized with saturated sodium bicarbonate and extracted with ethyl acetate (3×800 mL), the organic phase was washed with brine (3×400 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent:ethyl acetate/petroleum ether=1:100) to give the product (5.00 g) as a yellow oil in 20% yield. 1H NMR (300MHz, CDCl3):7.24 (dd, 3H), 7.46 (s, 1H), 8.24 (d, 1H), 10.60(d, 1H)? (b) The preparation of 2-amino-5-(trifluoromethyl)phenol To a flask,2-nitro-5-(trifluoromethyl)phenol (5.00 g, 24.2 mmol) and glacial acetic acid (60 mL) were added, the reaction mixture was heated slowly to 50?, and then iron powder (5.41 g, 96.6 mmol) was added to the above solution in portions. After completion of addition, the reaction mixture was heated to 70? for 2 hours. Then the reaction mixture was poured into water (200 mL) and extracted with ethyl acetate (3×400 mL), the organic phase was washed with brine (3×200 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography(Fluent: ethyl acetate/petroleum ether=1:2) to give the product (2.69 g) as a yellow solid in 63% yield. 1H NMR (300MHz, CDCl3):6.74 (d, 1H), 6.94 (s, 1H), 7.05 (d, 1H)? (c) The preparation of 6-(trifluoromethyl)benzoxazole-2-thiol To a flask, potassium hydroxide (25.70 g, 459 mmol), ethanol (250 mL) and water (100 mL) were added sequentially, CS2 (19.16 g, 252 mmol) was added dropwise under stirring, after completion of addition, the reaction mixture was stirred for another 15 minutes, followed by the addition of 2-amino-5-(trifluoromethyl) phenol (40.50 g, 229 mmol), the reaction mixture was heated to reflux for 4 hours. The reaction mixture was acidified to pH~4 with dilute hydrochloric acid and then poured into water (200 mL), extracted with ethyl acetate (3×800 mL), the organic phase was washed with brine (3×200 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:5) to give the product (24.09 g) as a yellow solid in 48% yield. mp: 194-196?. 1H NMR (300MHz, CDCl3): 7.30 (d, 1H), 7.58-7.62 (m, 2H), 10.84 (s, 1H)? (d) The preparation of 2-chloro-6-(trifluoromethyl)benzoxazole To a flask, 6-(trifluoromethyl)benzoxazole-2-thiol (1.20 g, 5.5 mmol), SOCl2(15 mL) and DMF (2 drops) were added sequentially, the reaction mixture was heated slowly to 70? for 2 hours, excessive SOCl2 was removed under reduced pressure, the reaction mixture was added water (50 mL) and extracted with ethyl acetate (3×150 mL), the organic phase was washed with saturated sodium bicarbonate (3×50 mL), brine (3×50 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent:ethyl acetate/petroleum ether=1:100) to give the product (1.01 g) as a yellow solid in 83% yield. mp: 245-247?. 1H NMR (300MHz, CDCl3):7.65-7.68 (m, 2H), 7.80 (d, 1H)? (2) The preparation of Compound 7 To a flask, 3-(2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy)propan-1-ol (0.35 g, 1.0 mmol, synthesized according to the examples 1, 2 and 3 in CN1860874A) and THF (5 mL) were added, the reaction mixture was stirred to be dissolved at room temperature, 60% of NaH (0.08 g, 1.0 mmol) was added to the above solution, after being stirred for 2 hours, 2-chloro-6-(trifluoromethyl)benzoxazole (0.22 g, 1.0 mmol) was added, the reaction mixture was stirred for another 5 hours at room temperature. The reaction mixture was poured into water (50 mL) and extracted with ethyl acetate (3×150 mL), the organic phase was washed with saturated sodium bicarbonate (3×50 mL), brine (3×50 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:20) to give the product (0.27 g) as a colorless oil in 52% yield. Example 2 The preparation of compound 8 (1) The preparation of 2-chloro-5-(trifluoromethyl)benzoxazole (a) The preparation of 2-nitro-4-(trifluoromethyl)phenol To a flask, tert.-butyl alcohol(29.60 g, 400 mmol) and DMSO(250 mL) were added, and then KOH (30.24 g, 540 mmol) was added, the reaction mixture was heated to 100?, 1-chloro-2-nitro-4-(trifluoromethyl)benzene (22.50 g,100 mmol, commercially available) was added dropwise to the above solution, after completion of addition, the reaction mixture was kept further at this temperature for 2 hours. Then the reaction mixture was cooled down to room temperature, poured into water (500 mL), acidified to pH~4 with dilute hydrochloric acid, extracted with ethyl acetate (3×1000 mL), the organic phase was washed with saturated brine (3×500 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:5) to give the product (11.20g) as a yellow oil in 54% yield. 1H NMR (300MHz, CDCl3):7.31 (d, 1H), 7.82 (dd, 1H), 8.42(d, 1H), 10.80 (s, 1H)? (b) The preparation of 2-amino-4-(trifluoromethyl)phenol To a flask, 2-nitro-4-(trifluoromethyl)phenol(4.60 g, 22.2 mmol) and AcOH (100 mL) were added, the reaction mixture was heated slowly to 50?, and then iron powder(4.98 g, 88.9 mmol) was added in portions to the above solution, after completion of addition, the reaction mixture was heated to 70? for 2 hours. Then the reaction mixture was poured into water (200 mL), extracted with ethyl acetate (3×400 mL), the organic phase was washed with saturated brine (3×200 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:5) to give the product (3.19g) as a yellow solid in 82% yield. mp: 139-141?. (c) The preparation of 5-(trifluoromethyl) benzoxazole-2-thiol To a flask, KOH (25.62 g, 457 mmol), ethanol (250 mL) and water (100 mL) were added sequentially, CS2 (19.13 g, 251 mmol) was added dropwise under stirring, after completion of addition, the reaction mixture was stirred for another 15 minutes, followed by the addition of 2-amino-4-(trifluoromethyl) phenol (40.50 g, 229 mmol), the reaction mixture was heated slowly to reflux for 4 hours. The reaction mixture was acidified to pH~4 with dilute hydrochloric acid and then poured into water (500 mL), extracted with ethyl acetate (3×1000 mL), the organic phase was washed with saturated brine (3×500 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:5) to give the product (18.75g) as a yellow solid in 30% yield. mp: 181-183?. 1H NMR (300MHz, CDCl3):7.45-7.50 (m, 2H), 7.57 (d, 1H), 11.21 (s, 1H)? (d) The preparation of 2-chloro-5-(trifluoromethyl)benzoxazole To a flask, 5-(trifluoromethyl)benzoxazole-2-thiol (2.70 g, 12.3 mmol), SOCl2 (20 mL) and DMF (2 drops) were added sequentially, the reaction mixture was heated slowly to 70? for 2 hours, excessive SOCl2 was removed under reduced pressure, the reaction mixture was added water (100 mL), extracted with ethyl acetate (3×300 mL), the organic phase was washed with saturated sodium bicarbonate (3×100 mL), saturated brine (3×100 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent:ethyl acetate/petroleum ether=1:100) to give the product (1.40g) as a yellow solid in 51% yield. mp: 176-178?. 1H NMR (300MHz, CDCl3):7.61-7.66 (m, 2H), 7.97 (s, 1H)? (2) The preparation of Compound 8 To a flask, 3-(2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy)propan-1-ol (0.35 g, 1.0 mmol) and THF (5 mL) were added, the reaction mixture was stirred to be dissolved at room temperature, 60% of NaH (0.08 g, 2 mmol) was added to the above solution, after being stirred for 2 hours, 2-chloro-5-(trifluoromethyl)benzoxazole (0.22 g, 1.0 mmol) was added, the reaction mixture was stirred for another 5 hours at room temperature. Then the reaction mixture was poured into water (50 mL), extracted with ethyl acetate (3×150 mL), the organic phase was washed with saturated sodium bicarbonate (3×50 mL), saturated brine (3×50 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:20) to give the product (0.18g) as a colourless oil in 35% yield. Example 3 The preparation of compound 11 To a flask, 4-(2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy)butan-1-ol (0.36 g, 1.0 mmol, synthesized according to the examples 1, 2 and 3 in CN1860874A) and THF (5 mL) were added, the reaction mixture was stirred to be dissolved at room temperature, 60% of NaH (0.08 g, 2 mmol) was added to the above solution, after being stirred for 2 hours, 2-chloro-5-(trifluoromethyl)benzoxazole (0.22 g, 1.0 mmol) was added, the reaction mixture was stirred for another 5 hours at room temperature. Then the reaction mixture was poured into water (50 mL), extracted with ethyl acetate (3×150 mL), the organic phase was washed with saturated sodium bicarbonate (3×50 mL), saturated brine (3×50 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:20) to give the product (0.11g) as a yellow oil in 20% yield. Example 4 The preparation of compound 12 (1)The preparation of 2-chloro-6-(perfluoropropan-2-yl)benzoxazole (a)The preparation of 2-amino-5-(perfluoropropan-2-yl)phenol To a flask, 2-aminophenol (10.00 g, 91 mmol, commercially available), water and ethyl ether (200 mL respectively), 1,1,1,2,3,3,3-heptafluoro-2-iodopropane(35.32 g, 120 mmol, commercially available), Na2S2O4(20.88 g,120 mmol),NaHCO3(10.08 g,120 mmol),(n-Bu)4NHSO4(2.70 g,10.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature overnight. Then the reaction mixture was poured into water (300 mL), extracted with ethyl acetate (3×600 mL), the organic phase was washed with 1 mol/L HCl (3×300 mL), 5% sodium bicarbonate (3×300 mL), saturated brine (3×300 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent:ethyl acetate/petroleum ether=1:10) to give the product (10.0g) as a yellow solid in 40% yield. mp: 142-144?. 1H NMR (300MHz, CDCl3):3.84 (d, 3H), 7.39 (d, 1H), 7.57 (d, 1H), 7.97 (d, 1H)? (b)The preparation of 6-(perfluoropropan-2-yl)benzoxazol-2(3H)-one To a flask, 2-amino-5-(perfluoropropan-2-yl)phenol (5.00 g, 18.0 mmol), and CH2Cl2 (50 mL) were added sequentially, bis(trichloromethyl) carbonate(2.67 g, 9.0 mmol, commercially available) was added under stirring, then triethylamine(3.65 g, 36.1 mmol) was added to the above solution. The reaction mixture was stirred at room temperature overnight. Then the reaction mixture was poured into water (200 mL), extracted with CH2Cl2 (3×400 mL), the organic phase was washed with saturated sodium bicarbonate (3×200 mL), saturated brine (3×200 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:10) to give the product (4.00g) as a yellow solid in 74% yield. mp: 162-164?. 1H NMR (300MHz, CDCl3):7.22(d, 1H), 7.47 (d, 2H), 9.06 (s, 1H)? (c)The preparation of 6-(perfluoropropan-2-yl)benzoxazole-2-thiol To a flask, 6-(perfluoropropan-2-yl)benzoxazol-2(3H)-one (4.00 g, 13.2 mmol) and toluene (100 mL) were added, the reaction mixture was stirred to be dissolved at room temperature, Lawesson's reagent (8.00 g, 19.8 mmol, commercially available) was added to the above solution. The reaction mixture was heated to reflux for 15 hours. The reaction mixture was cooled down to room temperature, poured into water (200 mL), extracted with toluene (3×400 mL), the organic phase was washed with saturated sodium bicarbonate (3×200 mL), saturated brine (3×200 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent:ethyl acetate/petroleum ether=1:15) to give the product (1.60g) as a white solid in 38% yield. mp: 168-170?. 1H NMR (300MHz, CDCl3):7.35 (d, 1H), 7.57 (d, 1H), 7.63 (s, 1H), 11.10(s, 1H)? (d)The preparation of 2-chloro-6-(perfluoropropan-2-yl)benzoxazole To a flask, 6-(perfluoropropan-2-yl)benzoxazole-2-thiol (1.00 g, 3.1 mmol), SOCl2 (15 mL) and DMF (2 drops) were added sequentially, the reaction mixture was heated slowly to 70? for 2 hours, excessive SOCl2 was removed under reduced pressure, the reaction mixture was added water (100 mL), extracted with ethyl acetate (3×100 mL), the organic phase was washed with saturated sodium bicarbonate (3×100 mL), saturated brine (3×100 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:100) to give the product (0.40g) as a yellow oil in 42% yield. 1H NMR (300MHz, CDCl3):7.66 (d, 1H), 7.83 (t, 2H)? (2)The preparation of Compound 12 To a flask, 3-(2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy)propan-1-ol (0.43 g, 1.1 mmol) and THF (10 mL) were added, the reaction mixture was stirred to be dissolved at room temperature, 60% of NaH (0.09 g, 2 mmol) was added to the above solution, after being stirred for 2 hours, 2-chloro-6-(perfluoropropan-2-yl)benzoxazole(0.36 g, 1.1 mmol) was added, the reaction mixture was stirred for another 5 hours at room temperature. The reaction mixture was poured into water (50 mL), extracted with ethyl acetate (3×150 mL), the organic phase was washed with saturated sodium bicarbonate (3×50 mL), saturated brine (3×50 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:100) to give the product (0.38g) as a colourless oil in 48% yield. Other compounds of the general formula I of the present invention were prepared according to the above examples. Test of Biological Activity Example 5: Tests of Insecticidal Activity According to the solubility of test compounds, the compounds are dissolved in acetone or dimethyl sulfoxide, and then diluted with 0.1% aqueous solution of Tween 80 to form 50 ml test liquid, the content of acetone or dimethyl sulfoxide in the total solution is not more than 10%. Example 5.1 Test against Dianmondback Moth (Plutella xylostella) The cabbage leaves were made into plates of 1cm diameter by punch. A test solution (0.5 ml) was sprayed by airbrush to both sides of every plate. 8 Third instar larvae were put into the petri-dishes after the leaf disc air-dried and 3 replicates were set for each treatment. Then the insects were maintained in observation room (24?, 60~70% R.H.). The number of surviving insects was investigated and mortality was calculated after 72hrs. Some test compounds and KC1?KC2 and KC3 (pyridalyl) (compound 40, 39 nd 36 in CN 1169147A respectively)were chosen to parallel activity test against diamondback moth. The test results were listed in Table 2. Table 2:Activity against diamondback moth (mortality, %) 50 25 12.5 4 100 90 22 5 100 75 58 7 100 90 40 8 100 100 92 11 100 90 60 KC1 75 20 /* KC2 0 / / KC3 90 33 / note: “/” stands for no data. Example 5.2 Test against Beet Armyworm (Laphygma exigua Hubner) The cabbage leaves were made into plates of 1cm diameter by punch. A test solution (0.5 ml) was sprayed by airbrush to both sides of every plate. 8 Third instar larvae were put into the petri-dishes after the leaf disc air-dried and 3 replicates were set for each treatment. Then the insects were maintained in observation room (24?, 60~70% R.H.). The number of surviving insects was investigated and mortality was calculated after 96hrs. Some test compounds and KC3 (pyridalyl) with high insecticidal activity were chosen to parallel activity test against beet armyworm. The test results were listed in Table 3. Table 3:Activity against beet armyworm (mortality, %) 10 1 7 100 87.5 8 100 100 11 100 87.5 KC3 100 50 Example 5.3 Test against Tea Geometrid (Ectropis grisescens Warreh) Using leaf-dipping method, fresh treetops of tea tree dry up naturally by airing after dipping into testing solution for 10 seconds, and then were set in testing bottles, 5 treetops of tea tree in each bottle. 20 Sencond instar larvae were put into the testing bottles and 4 replicates were set for each treatment. Then the insects were maintained in observation room (24±0.5?, light period L:D=12:12). The number of surviving insects was investigated and mortality was calculated after 120hrs. Compounds 8 and 11 of the present invention and the known compound KC3 (pyridalyl) were chosen to parallel activity test against geometrid. The test results were listed in the following Table 4. Table 4:Activity against tea geometrid (mortality, %) 50 25 12.5 8 90 75 63 11 92 84 77 KC3 80 57 34 We Claim: 1. A dichloropropene compound represented by general formula I: I wherein: R1 or R2 is selected from H, halo, C1-C3alkyl or C1-C3 haloalkyl, with the proviso that R1 or R2 is H; n=0, 1, 2 or 3. 2. The compounds according to the claim 1, characterized in that wherein general formula I: R1 or R2 is selected from H, Cl, CH3, CF3 or i-C3F7, with the proviso that R1 or R2 is H; n=0, 1 or 2. 3. The compounds according to the claim 2, characterized in that wherein general formula I: R1 is CF3; R2 is H; n=1 or 2. 4. The compounds having the general formular I according to the claim 1 are used for controlling insects. 5. An insecticidal composition, comprising the compound having general formula I of the claim 1 as an active ingredient and acceptable carrier in agriculture, forestry or public health, in which the weight percentage of the active ingredient(s) is in the range of 1-99%. 6. A method of controlling insects, characterized in that: applying the composition of claim 5 to pests or its growth medium with effective dosage within a range of 10 g/ha to 1000 g/ha. Dated this 29th Day of September, 2011.

Full Text

FORM 2
THE PATENTS ACT 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10 and rule 13)

1. ' DICHLOROPROPENE COMPOUNDS AND USES THEREOF '

2.

1. (A) SINOCHEM CORPORATION.
(B) China.
(C) 28 Fuxingmennei Dajie, Xicheng District Beijing 100031 China.

2. (A) SHENYANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY CO., LTD.
(B) China.
(C) 8 Shenliaodong Road, Tiexi District Shenyang, Liaoning 110021 China.

The following specification particularly describes the invention and the manner in which it is to be performed.

FIELD OF THE INVENTION

The present invention relates to insecticide. Specifically to a dichloropropene compound and the uses thereof.

BACKGROUND OF THE INVENTION

Since insect pests will become resistant to insecticides used for a period of time, it is necessary to invent continuously new compounds and compositions with improved insecticidal activity. At the same time, with the increase of need for agricultural and livestock products and attention to environmental protection, new insecticides with lower cost and environmental compatibility have been in demand.

The patent CN1169147A disclosed some dichloropropene compounds with benzoheterocycle group and insecticidal activity thereof, for example, the dichloropropene compounds containing benzothiazole group and benzimidazole group, represented by KC1 and KC2 respectively, and their biological data controlling Spodoptera litura were published.

KC1 KC2

The above patent focused on the disclosure of the compounds with better insecticidal activity containing pyridin-2-yloxy moiety, for example, KC3 (the structure is shown as follows), which can be used to control diamondback moth at 50ppm. This compound had been developed to be a commercialized insecticide with common name of pyridalyl:

KC3 (pyridalyl)

In the existing technology, the preparation and insecticidal activity of dichloropropene compounds containing benzoxazol-2-yloxy moiety has not been reported.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a dichloropropene compound with novel structure and better insecticidal activity, which can be applied in agriculture, forestry or public health to control insects.

Detailed description of the invention is as follows:
The present invention provides a dichloropropene compound having general formula I:

I
Wherein:
R1 or R2 is selected from H, halo, C1-C3alkyl or C1-C3haloalkyl, with the proviso that R1 or R2 is H;
n=0, 1, 2 or 3.
The preferred compounds of general formula I of this invention are:
R1 or R2 is selected from H, Cl, CH3, CF3 or i-C3F7, with the proviso that R1 or R2 is H;
n=0, 1 or 2.
Futher more, the preferred compounds of general formula I of this invention are:
R1 is CF3;
R2 is H;
n=1 or 2.
It must be noted that, as used in this specification, the appended claims and the general formular I,
The “alkyl” stands for straight-chain or branched alkyl, such as methyl, ethyl, n-propyl or isopropyl. The “haloalkyl” stands for straight or branched chain alkyl, for example, methyl, ethyl, n-propyl or isopropyl is (are) substituted with one or more halogen atom(s), such as trifluoromethyl or heptafluoro isopropyl. The “halo” denotes fluorine, chlorine, bromine or iodine.
The compounds represented by the general formula I were prepared according to the following method, each group of formulas is as defined above, unless otherwise specified.

II III I
The target compounds represented by the general formula I were prepared by reaction of the compounds represented by the general formula II with the compounds represented by the general formula III in proper solvent and in the presence of proper base at the range of -10? to boiling point for 0.5-48h.
The proper solvent mentioned may be selected from dichloromethane, chloroform, tetrachloromethane, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, DMF or DMSO and so on.
The proper base mentioned may be selected from hydride of alkali metal like lithium, sodium or potassium such as sodium hydride, or hydroxide of alkali metal like lithium, sodium or potassium such as sodium hydroxide, also selected from carbonate of alkali metal such as sodium carbonate and selected from organic base such as triethylamine, sodium tert-butoxide and so on.
The compounds of the general formula II can be prepared according to the methods introduced in the following literatures: J. Org. Chem. 1996, 61, 3289-3297;Bioorganic & Medicinal Chemistry Letters 17 (2007) 4689-4693;WO2009023844;Journal of Medicinal Chemistry,2008, 51(5), 1482-1486?
The compounds of the general formula III can be prepared according to the methods discribed in CN1860874A (Examples 1, 2 and 3):
The structures and physical properties of some compounds represented by general formula I were shown in Table 1.
Table 1 I
Compound R1 R2 n Appearance(mp(?)
1 H Cl 0 yellow solid (104-106)
2 H CF3 0 yellow oil
3 CF3 H 0 yellow solid (66-69)
4 H Cl 1 white solid (58-60)
5 Cl H 1 yellow oil
6 CH3 H 1 yellow oil
7 H CF3 1 yellow oil
8 CF3 H 1 yellow oil
9 H Cl 2 white solid (63-65)
10 H CF3 2 yellow oil
11 CF3 H 2 yellow
12 H i-C3F7 1 yellow
1HNMR spectrum (300MHz, CDCl3) of some compounds of the present invention are as follows:
Compound 1:4.39-4.42 (m, 2H), 4.59 (d, 2H), 7.833 (d, 1H), 4.89-4.92 (m, 2H), 6.11 (t, 1H), 6.85 (s, 2H), 7.22-7.27 (m, 1H), 7.8-7.41 (m, 2H)?
Compound 2:4.40-4.43 (m, 2H), 4.59 (d, 2H), 7.833 (d, 1H), 4.93-4.96 (m, 2H), 6.11 (t, 1H), 6.85 (s, 2H), 7.56 (s, 2H), 7.65 (s, 1H)?
Compound 3:4.40-4.43 (m, 2H), 4.58 (d, 2H), 7.833 (d, 1H), 4.92-4.95 (m, 2H), 6.11 (t, 1H), 6.85 (s, 2H), 7.47-7.48 (m, 2H), 7.75 (s, 1H)?
Compound 4:2.34-2.42 (m, 2H), 4.14 (t, 2H), 4.58 (d, 2H), 4.87 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.21-7.26 (m, 2H), 7.38-7.41 (m, 1H)?
Compound 5:2.36-2.40 (m, 2H), 4.14 (t, 2H), 4.58 (d, 2H), 4.88 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.15 (dd, 1H), 7.25-7.28 (m, 1H), 7.47 (d, 1H)?
Compound 6:2.35-2.39 (m, 2H), 2.42 (s, 3H),4.14 (t, 2H), 4.56 (d, 2H), 4.85 (t, 2H), 6.10 (t, 1H), 6.82 (s, 2H), 7.25 (d, 2H), 7.15 (dd, 1H), 7.28-7.29 (m, 2H)?
Compound 7:2.37-2.42 (m, 2H), 4.15 (t, 2H), 4.58 (d, 2H), 4.92 (t, 2H), 6.11 (t, 1H), 6.83 (s, 2H), 7.55-7.56 (m, 2H), 7.62 (d, 1H)?
Compound 8:2.35-2.41 (m, 2H), 4.15 (t, 2H), 4.58 (d, 2H), 4.91 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.42-7.46 (m, 2H), 7.76 (s, 1H)?
Compound 9:1.99-2.06 (m, 2H), 2.17-2.21 (m, 2H), 4.03 (t, 2H), 4.58 (d, 2H), 4.67 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 6.85-7.26 (m, 1H), 7.37-7.40 (m, 1H)?
Compound 10:2.00-2.05 (m, 2H), 2.19-2.23 (m, 2H), 4.03 (t, 2H), 4.58 (d, 2H), 4.71 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.54 (d, 2H), 7.62 (s, 1H)?
Compound 11:2.02-2.05 (m, 2H), 2.18-2.21 (m, 2H), 4.04 (t, 2H), 4.58 (d, 2H), 4.71 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.44-7.46 (m, 2H), 7.74-7.75 (m, 1H)?
Compound 12:2.38-2.42 (m, 2H), 4.15 (t, 2H), 4.58 (d, 2H), 4.59 (t, 2H), 6.11 (t, 1H), 6.84 (s, 2H), 7.50-7.61 (m, 2H), 7.63 (d, 1H)?
The dichloropropene compounds containing benzoxazol-2-yloxy moiety were prepared successfully in this invention and their excellent insecticidal activity have been proved by extensive research and experiments. During the course of further research, the inventors found surprisingly that in benzoxazole ring of the compounds represented by general formula I, introducing substituents to 5-position was more beneficial than to 6-position. Compared to the compounds with higher bioactivity in the existing technology, the compounds of present invention were used at lower dosage, normally more than once lower at the same control, showing unexpected high insecticidal activity. Therefore, the present invention also includes the use of the compounds having general formula I as insecticides to control insect pests.
A further object of the present invention also includes insecticidal compositions containing the compounds having general formula I as active ingredient, and the weight percentage of the active ingredient in the composition is 1-99%. The insecticidal compositions also include the carrier being acceptable in agriculture, forestry, public health.
The compositions of the present invention can be used in the form of various formulations. Usually, the compounds having general formula I as active ingredient can be dissolved in or dispersed in carriers or made to a formulation so that they can be easily dispersed as an insecticide. For example: these chemical formulations can be made into wettable powder or emulsifiable concentrate. Therefore, in these compositions, at least a liquid or solid carrier is added, and suitable surfactant(s) can be added when needed.
Still also provided by the present invention are the application methods for controlling insects, which is to apply the compositions of the present invention to the insects as mentioned above or their growing loci. The suitable effective dosage of the compounds of the present invention is usually within a range of 10 g/ha to 1000 g/ha, preferably from 20 g/ha to 500 g/ha.
For some applications, one or more other fungicides, insecticides, herbicides, plant growth regulators or fertilizer can be added into the insecticidal compositions of the present invention to make additional merits and effects.
It should be noted that variations and changes are permitted within the claimed scopes in the present invention.

DESCRIPTION OF THE INVENTION IN DETAIL

The following preparation examples and biological results are illustrative of the present invention, but without being restricted thereby.
Example 1 The preparation of compound 7
(1) The preparation of 2-chloro-6-(trifluoromethyl)benzoxazole
(a) The preparation of 2-nitro-5-(trifluoromethyl)phenol

To a flask, 3-(trifluoromethyl)phenol(20.00 g, 123 mmol, available in market) was added, 60% of Salpeter solution pre-prepared (a mixture of 11.60 g of fuming nitric acid and 7.40 g of water) was added dropwise, after completion of addition, the reaction mixture was stirred for 24 hours at room temperature. Then the reaction mixture was neutralized with saturated sodium bicarbonate and extracted with ethyl acetate (3×800 mL), the organic phase was washed with brine (3×400 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent:ethyl acetate/petroleum ether=1:100) to give the product (5.00 g) as a yellow oil in 20% yield.
1H NMR (300MHz, CDCl3):7.24 (dd, 3H), 7.46 (s, 1H), 8.24 (d, 1H), 10.60(d, 1H)?

(b) The preparation of 2-amino-5-(trifluoromethyl)phenol

To a flask,2-nitro-5-(trifluoromethyl)phenol (5.00 g, 24.2 mmol) and glacial acetic acid (60 mL) were added, the reaction mixture was heated slowly to 50?, and then iron powder (5.41 g, 96.6 mmol) was added to the above solution in portions. After completion of addition, the reaction mixture was heated to 70? for 2 hours. Then the reaction mixture was poured into water (200 mL) and extracted with ethyl acetate (3×400 mL), the organic phase was washed with brine (3×200 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography(Fluent: ethyl acetate/petroleum ether=1:2) to give the product (2.69 g) as a yellow solid in 63% yield.
1H NMR (300MHz, CDCl3):6.74 (d, 1H), 6.94 (s, 1H), 7.05 (d, 1H)?

(c) The preparation of 6-(trifluoromethyl)benzoxazole-2-thiol

To a flask, potassium hydroxide (25.70 g, 459 mmol), ethanol (250 mL) and water (100 mL) were added sequentially, CS2 (19.16 g, 252 mmol) was added dropwise under stirring, after completion of addition, the reaction mixture was stirred for another 15 minutes, followed by the addition of 2-amino-5-(trifluoromethyl) phenol (40.50 g, 229 mmol), the reaction mixture was heated to reflux for 4 hours. The reaction mixture was acidified to pH~4 with dilute hydrochloric acid and then poured into water (200 mL), extracted with ethyl acetate (3×800 mL), the organic phase was washed with brine (3×200 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:5) to give the product (24.09 g) as a yellow solid in 48% yield. mp: 194-196?.
1H NMR (300MHz, CDCl3): 7.30 (d, 1H), 7.58-7.62 (m, 2H), 10.84 (s, 1H)?

(d) The preparation of 2-chloro-6-(trifluoromethyl)benzoxazole

To a flask, 6-(trifluoromethyl)benzoxazole-2-thiol (1.20 g, 5.5 mmol), SOCl2(15 mL) and DMF (2 drops) were added sequentially, the reaction mixture was heated slowly to 70? for 2 hours, excessive SOCl2 was removed under reduced pressure, the reaction mixture was added water (50 mL) and extracted with ethyl acetate (3×150 mL), the organic phase was washed with saturated sodium bicarbonate (3×50 mL), brine (3×50 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent:ethyl acetate/petroleum ether=1:100) to give the product (1.01 g) as a yellow solid in 83% yield. mp: 245-247?.
1H NMR (300MHz, CDCl3):7.65-7.68 (m, 2H), 7.80 (d, 1H)?

(2) The preparation of Compound 7

To a flask, 3-(2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy)propan-1-ol (0.35 g, 1.0 mmol, synthesized according to the examples 1, 2 and 3 in CN1860874A) and THF (5 mL) were added, the reaction mixture was stirred to be dissolved at room temperature, 60% of NaH (0.08 g, 1.0 mmol) was added to the above solution, after being stirred for 2 hours, 2-chloro-6-(trifluoromethyl)benzoxazole (0.22 g, 1.0 mmol) was added, the reaction mixture was stirred for another 5 hours at room temperature. The reaction mixture was poured into water (50 mL) and extracted with ethyl acetate (3×150 mL), the organic phase was washed with saturated sodium bicarbonate (3×50 mL), brine (3×50 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:20) to give the product (0.27 g) as a colorless oil in 52% yield.

Example 2 The preparation of compound 8
(1) The preparation of 2-chloro-5-(trifluoromethyl)benzoxazole
(a) The preparation of 2-nitro-4-(trifluoromethyl)phenol

To a flask, tert.-butyl alcohol(29.60 g, 400 mmol) and DMSO(250 mL) were added, and then KOH (30.24 g, 540 mmol) was added, the reaction mixture was heated to 100?, 1-chloro-2-nitro-4-(trifluoromethyl)benzene (22.50 g,100 mmol, commercially available) was added dropwise to the above solution, after completion of addition, the reaction mixture was kept further at this temperature for 2 hours. Then the reaction mixture was cooled down to room temperature, poured into water (500 mL), acidified to pH~4 with dilute hydrochloric acid, extracted with ethyl acetate (3×1000 mL), the organic phase was washed with saturated brine (3×500 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:5) to give the product (11.20g) as a yellow oil in 54% yield.
1H NMR (300MHz, CDCl3):7.31 (d, 1H), 7.82 (dd, 1H), 8.42(d, 1H), 10.80 (s, 1H)?

(b) The preparation of 2-amino-4-(trifluoromethyl)phenol

To a flask, 2-nitro-4-(trifluoromethyl)phenol(4.60 g, 22.2 mmol) and AcOH (100 mL) were added, the reaction mixture was heated slowly to 50?, and then iron powder(4.98 g, 88.9 mmol) was added in portions to the above solution, after completion of addition, the reaction mixture was heated to 70? for 2 hours. Then the reaction mixture was poured into water (200 mL), extracted with ethyl acetate (3×400 mL), the organic phase was washed with saturated brine (3×200 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:5) to give the product (3.19g) as a yellow solid in 82% yield. mp: 139-141?.

(c) The preparation of 5-(trifluoromethyl) benzoxazole-2-thiol

To a flask, KOH (25.62 g, 457 mmol), ethanol (250 mL) and water (100 mL) were added sequentially, CS2 (19.13 g, 251 mmol) was added dropwise under stirring, after completion of addition, the reaction mixture was stirred for another 15 minutes, followed by the addition of 2-amino-4-(trifluoromethyl) phenol (40.50 g, 229 mmol), the reaction mixture was heated slowly to reflux for 4 hours. The reaction mixture was acidified to pH~4 with dilute hydrochloric acid and then poured into water (500 mL), extracted with ethyl acetate (3×1000 mL), the organic phase was washed with saturated brine (3×500 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:5) to give the product (18.75g) as a yellow solid in 30% yield. mp: 181-183?.
1H NMR (300MHz, CDCl3):7.45-7.50 (m, 2H), 7.57 (d, 1H), 11.21 (s, 1H)?

(d) The preparation of 2-chloro-5-(trifluoromethyl)benzoxazole

To a flask, 5-(trifluoromethyl)benzoxazole-2-thiol (2.70 g, 12.3 mmol), SOCl2 (20 mL) and DMF (2 drops) were added sequentially, the reaction mixture was heated slowly to 70? for 2 hours, excessive SOCl2 was removed under reduced pressure, the reaction mixture was added water (100 mL), extracted with ethyl acetate (3×300 mL), the organic phase was washed with saturated sodium bicarbonate (3×100 mL), saturated brine (3×100 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent:ethyl acetate/petroleum ether=1:100) to give the product (1.40g) as a yellow solid in 51% yield. mp: 176-178?.
1H NMR (300MHz, CDCl3):7.61-7.66 (m, 2H), 7.97 (s, 1H)?

(2) The preparation of Compound 8

To a flask, 3-(2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy)propan-1-ol (0.35 g, 1.0 mmol) and THF (5 mL) were added, the reaction mixture was stirred to be dissolved at room temperature, 60% of NaH (0.08 g, 2 mmol) was added to the above solution, after being stirred for 2 hours, 2-chloro-5-(trifluoromethyl)benzoxazole (0.22 g, 1.0 mmol) was added, the reaction mixture was stirred for another 5 hours at room temperature. Then the reaction mixture was poured into water (50 mL), extracted with ethyl acetate (3×150 mL), the organic phase was washed with saturated sodium bicarbonate (3×50 mL), saturated brine (3×50 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:20) to give the product (0.18g) as a colourless oil in 35% yield.

Example 3 The preparation of compound 11

To a flask, 4-(2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy)butan-1-ol (0.36 g, 1.0 mmol, synthesized according to the examples 1, 2 and 3 in CN1860874A) and THF (5 mL) were added, the reaction mixture was stirred to be dissolved at room temperature, 60% of NaH (0.08 g, 2 mmol) was added to the above solution, after being stirred for 2 hours, 2-chloro-5-(trifluoromethyl)benzoxazole (0.22 g, 1.0 mmol) was added, the reaction mixture was stirred for another 5 hours at room temperature. Then the reaction mixture was poured into water (50 mL), extracted with ethyl acetate (3×150 mL), the organic phase was washed with saturated sodium bicarbonate (3×50 mL), saturated brine (3×50 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:20) to give the product (0.11g) as a yellow oil in 20% yield.

Example 4 The preparation of compound 12
(1)The preparation of 2-chloro-6-(perfluoropropan-2-yl)benzoxazole
(a)The preparation of 2-amino-5-(perfluoropropan-2-yl)phenol

To a flask, 2-aminophenol (10.00 g, 91 mmol, commercially available), water and ethyl ether (200 mL respectively), 1,1,1,2,3,3,3-heptafluoro-2-iodopropane(35.32 g, 120 mmol, commercially available), Na2S2O4(20.88 g,120 mmol),NaHCO3(10.08 g,120 mmol),(n-Bu)4NHSO4(2.70 g,10.0 mmol) were added sequentially. The reaction mixture was stirred at room temperature overnight. Then the reaction mixture was poured into water (300 mL), extracted with ethyl acetate (3×600 mL), the organic phase was washed with 1 mol/L HCl (3×300 mL), 5% sodium bicarbonate (3×300 mL), saturated brine (3×300 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent:ethyl acetate/petroleum ether=1:10) to give the product (10.0g) as a yellow solid in 40% yield. mp: 142-144?.
1H NMR (300MHz, CDCl3):3.84 (d, 3H), 7.39 (d, 1H), 7.57 (d, 1H), 7.97 (d, 1H)?

(b)The preparation of 6-(perfluoropropan-2-yl)benzoxazol-2(3H)-one

To a flask, 2-amino-5-(perfluoropropan-2-yl)phenol (5.00 g, 18.0 mmol), and CH2Cl2 (50 mL) were added sequentially, bis(trichloromethyl) carbonate(2.67 g, 9.0 mmol, commercially available) was added under stirring, then triethylamine(3.65 g, 36.1 mmol) was added to the above solution. The reaction mixture was stirred at room temperature overnight. Then the reaction mixture was poured into water (200 mL), extracted with CH2Cl2 (3×400 mL), the organic phase was washed with saturated sodium bicarbonate (3×200 mL), saturated brine (3×200 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:10) to give the product (4.00g) as a yellow solid in 74% yield. mp: 162-164?.
1H NMR (300MHz, CDCl3):7.22(d, 1H), 7.47 (d, 2H), 9.06 (s, 1H)?

(c)The preparation of 6-(perfluoropropan-2-yl)benzoxazole-2-thiol

To a flask, 6-(perfluoropropan-2-yl)benzoxazol-2(3H)-one (4.00 g, 13.2 mmol) and toluene (100 mL) were added, the reaction mixture was stirred to be dissolved at room temperature, Lawesson's reagent (8.00 g, 19.8 mmol, commercially available) was added to the above solution. The reaction mixture was heated to reflux for 15 hours. The reaction mixture was cooled down to room temperature, poured into water (200 mL), extracted with toluene (3×400 mL), the organic phase was washed with saturated sodium bicarbonate (3×200 mL), saturated brine (3×200 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent:ethyl acetate/petroleum ether=1:15) to give the product (1.60g) as a white solid in 38% yield. mp: 168-170?.
1H NMR (300MHz, CDCl3):7.35 (d, 1H), 7.57 (d, 1H), 7.63 (s, 1H), 11.10(s, 1H)?

(d)The preparation of 2-chloro-6-(perfluoropropan-2-yl)benzoxazole

To a flask, 6-(perfluoropropan-2-yl)benzoxazole-2-thiol (1.00 g, 3.1 mmol), SOCl2 (15 mL) and DMF (2 drops) were added sequentially, the reaction mixture was heated slowly to 70? for 2 hours, excessive SOCl2 was removed under reduced pressure, the reaction mixture was added water (100 mL), extracted with ethyl acetate (3×100 mL), the organic phase was washed with saturated sodium bicarbonate (3×100 mL), saturated brine (3×100 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:100) to give the product (0.40g) as a yellow oil in 42% yield.
1H NMR (300MHz, CDCl3):7.66 (d, 1H), 7.83 (t, 2H)?

(2)The preparation of Compound 12

To a flask, 3-(2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy)propan-1-ol (0.43 g, 1.1 mmol) and THF (10 mL) were added, the reaction mixture was stirred to be dissolved at room temperature, 60% of NaH (0.09 g, 2 mmol) was added to the above solution, after being stirred for 2 hours, 2-chloro-6-(perfluoropropan-2-yl)benzoxazole(0.36 g, 1.1 mmol) was added, the reaction mixture was stirred for another 5 hours at room temperature. The reaction mixture was poured into water (50 mL), extracted with ethyl acetate (3×150 mL), the organic phase was washed with saturated sodium bicarbonate (3×50 mL), saturated brine (3×50 mL), dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography (Fluent: ethyl acetate/petroleum ether=1:100) to give the product (0.38g) as a colourless oil in 48% yield.

Other compounds of the general formula I of the present invention were prepared according to the above examples.

Test of Biological Activity

Example 5: Tests of Insecticidal Activity
According to the solubility of test compounds, the compounds are dissolved in acetone or dimethyl sulfoxide, and then diluted with 0.1% aqueous solution of Tween 80 to form 50 ml test liquid, the content of acetone or dimethyl sulfoxide in the total solution is not more than 10%.

Example 5.1 Test against Dianmondback Moth (Plutella xylostella)
The cabbage leaves were made into plates of 1cm diameter by punch. A test solution (0.5 ml) was sprayed by airbrush to both sides of every plate. 8 Third instar larvae were put into the petri-dishes after the leaf disc air-dried and 3 replicates were set for each treatment. Then the insects were maintained in observation room (24?, 60~70% R.H.). The number of surviving insects was investigated and mortality was calculated after 72hrs.

Some test compounds and KC1?KC2 and KC3 (pyridalyl) (compound 40, 39 nd 36 in CN 1169147A respectively)were chosen to parallel activity test against diamondback moth. The test results were listed in Table 2.
Table 2:Activity against diamondback moth (mortality, %)

50 25 12.5
4 100 90 22
5 100 75 58
7 100 90 40
8 100 100 92
11 100 90 60
KC1 75 20 /*
KC2 0 / /
KC3 90 33 /

note: “/” stands for no data.

Example 5.2 Test against Beet Armyworm (Laphygma exigua Hubner)
The cabbage leaves were made into plates of 1cm diameter by punch. A test solution (0.5 ml) was sprayed by airbrush to both sides of every plate. 8 Third instar larvae were put into the petri-dishes after the leaf disc air-dried and 3 replicates were set for each treatment. Then the insects were maintained in observation room (24?, 60~70% R.H.). The number of surviving insects was investigated and mortality was calculated after 96hrs.
Some test compounds and KC3 (pyridalyl) with high insecticidal activity were chosen to parallel activity test against beet armyworm. The test results were listed in Table 3.

Table 3:Activity against beet armyworm (mortality, %)

10 1
7 100 87.5
8 100 100
11 100 87.5
KC3 100 50

Example 5.3 Test against Tea Geometrid (Ectropis grisescens Warreh)
Using leaf-dipping method, fresh treetops of tea tree dry up naturally by airing after dipping into testing solution for 10 seconds, and then were set in testing bottles, 5 treetops of tea tree in each bottle. 20 Sencond instar larvae were put into the testing bottles and 4 replicates were set for each treatment. Then the insects were maintained in observation room (24±0.5?, light period L:D=12:12). The number of surviving insects was investigated and mortality was calculated after 120hrs.
Compounds 8 and 11 of the present invention and the known compound KC3 (pyridalyl) were chosen to parallel activity test against geometrid. The test results were listed in the following Table 4.

Table 4:Activity against tea geometrid (mortality, %)

50 25 12.5
8 90 75 63
11 92 84 77
KC3 80 57 34

We Claim:

1. A dichloropropene compound represented by general formula I:

I
wherein:
R1 or R2 is selected from H, halo, C1-C3alkyl or C1-C3 haloalkyl, with the proviso that R1 or R2 is H;
n=0, 1, 2 or 3.

2. The compounds according to the claim 1, characterized in that wherein general formula I:
R1 or R2 is selected from H, Cl, CH3, CF3 or i-C3F7, with the proviso that R1 or R2 is H;
n=0, 1 or 2.

3. The compounds according to the claim 2, characterized in that wherein general formula I:
R1 is CF3;
R2 is H;
n=1 or 2.

4. The compounds having the general formular I according to the claim 1 are used for controlling insects.

5. An insecticidal composition, comprising the compound having general formula I of the claim 1 as an active ingredient and acceptable carrier in agriculture, forestry or public health, in which the weight percentage of the active ingredient(s) is in the range of 1-99%.

6. A method of controlling insects, characterized in that: applying the composition of claim 5 to pests or its growth medium with effective dosage within a range of 10 g/ha to 1000 g/ha.

Dated this 29th Day of September, 2011.

Documents:

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Patent Number

272067

Indian Patent Application Number

2044/MUMNP/2011

PG Journal Number

12/2016

Publication Date

18-Mar-2016

Grant Date

16-Mar-2016

Date of Filing

29-Sep-2011

Name of Patentee

SINOCHEM CORPORATION

Applicant Address

28 Fuxingmennei Dajie Xicheng District Beijing 100031 China

Inventors:

#	Inventor's Name	Inventor's Address
1	LI Bin	8 Shenliaodong Road Tiexi District Shenyang Liaoning 110021 China
2	GUAN Aiying	8 Shenliaodong Road Tiexi District Shenyang Liaoning 110021 China
3	WANG Junfeng	8 Shenliaodong Road Tiexi District Shenyang Liaoning 110021 China
4	QIN Yukun	8 Shenliaodong Road Tiexi District Shenyang Liaoning 110021 China
5	ZHANG Hong	8 Shenliaodong Road Tiexi District Shenyang Liaoning 110021 China
6	YU Haibo	8 Shenliaodong Road Tiexi District Shenyang Liaoning 110021 China
7	LIANG Songjun	8 Shenliaodong Road Tiexi District Shenyang Liaoning 110021 China

PCT International Classification Number

A01N 43/52,A01P 7/00

PCT International Application Number

PCT/CN2010/071688

PCT International Filing date

2010-04-12

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	200910081857.X	2009-04-14	China