CN102617551A - Anthranilic diamide compound containing difluoro (methylene) methyl - Google Patents
Anthranilic diamide compound containing difluoro (methylene) methyl Download PDFInfo
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- CN102617551A CN102617551A CN2012100605819A CN201210060581A CN102617551A CN 102617551 A CN102617551 A CN 102617551A CN 2012100605819 A CN2012100605819 A CN 2012100605819A CN 201210060581 A CN201210060581 A CN 201210060581A CN 102617551 A CN102617551 A CN 102617551A
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- bromo
- chloro
- fluoro
- pyrazoles
- carbonyl
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- QBDQZPLNZFQILP-UHFFFAOYSA-N Cc(cc(cc1C(NCC(F)(F)Sc2ccccc2)=O)Cl)c1NC(c1cc(Br)n[n]1-c1ncccc1Cl)=O Chemical compound Cc(cc(cc1C(NCC(F)(F)Sc2ccccc2)=O)Cl)c1NC(c1cc(Br)n[n]1-c1ncccc1Cl)=O QBDQZPLNZFQILP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an anthranilic diamide compound containing difluoro (methylene) methyl. The anthranilic diamide compound is a compound shown as a formula (I), wherein substituent groups are defined in the claim 1. The anthranilic diamide compound containing the difluoro (methylene) methyl has high insecticidal activity and potential commercial value.
Description
Technical field
The present invention relates to a kind of fluorine-containing adjacent formamido-benzamide compound, specifically, relate to a kind of adjacent formamido-benzamide compound that contains difluoro (Asia) methyl.
Background technology
The use of agricultural chemicals plays crucial effects to growth and guarantor's product, the raising the output that guarantees farm crop.The tradition agricultural chemicals has high poison, low selectivity, high residue, people and animals is endangered drawbacks such as big; Can not adapt to the requirement of modern agriculture production to agricultural chemicals; Therefore, the new varieties of pesticides of exploitation with low toxicity, efficient, low residue, environmental protection caused people's extensive interest.
Since this century; Du pont company is on the basis of the adjacent formamido-benzamides ryania acceptor sterilant fipronil bisamide of Japanese agricultural chemicals company exploitation; Through change, develop the ryania acceptor sterilant-Rynaxypyr of another kind of novel structure to one of them acid amides position in the molecule.This sterilant insecticidal spectrum is wide, and lepidopteran, beetle and aleyrodid are had significant insecticidal activity, and persistence is good.The molecular structure of Rynaxypyr has also become the lead compound of the adjacent formamido-BM of follow-up study insecticides.
Earlier just reach (Syngenta) company and replaced the bromine atoms on the pyrazoles ring in the Rynaxypyr (patent WO2006040113 and WO 2006061200) with trifluoromethyl; Japan Ishihara Sangyo Kaisha, Ltd. has reported and in the structure of Rynaxypyr, has introduced trifluoromethyl (WO 2006080311).The compound of above-mentioned introducing fluoro-containing group still shows insecticidal activity preferably.
Summary of the invention
Contriver of the present invention adopts difluoro (Asia) methyl (to have stronger lipotropy and electrophilic property; And also have obviously different in nature with trifluoromethyl) modify existing Rynaxypyr compounds, obtained the adjacent formamido-benzamide compound that contains difluoro (Asia) methyl of a series of novel structures.Insecticidal activity experiment shows, the adjacent formamido-benzamide compound that contains difluoro (Asia) methyl provided by the invention has higher desinsection (like mythimna separata etc.) activity, has the potential commercial value.
In addition, the present invention has also enriched the kind of Rynaxypyr compounds.
The adjacent formamido-benzamide compound that contains difluoro (Asia) methyl of the present invention is compound shown in the formula I:
Among the formula I, R
1, R
2, R
3And R
4Independently be selected from respectively: H, C
1～C
6The straight or branched alkyl, C
1～C
6The straight or branched perfluoroalkyl, C
1～C
6The straight or branched alkoxyl group, or a kind of in the halogen (F, Cl, Br or I); A is H, group shown in group shown in the formula II or the formula III;
The adjacent formamido-benzamide compound that contains difluoro (Asia) methyl provided by the present invention; Make compound shown in the formula Ia (one of target compound) by the reaction of compound shown in compound shown in the formula IV and the formula V; Compound is through oxidizing reaction shown in the formula Ia; Obtain compound shown in the formula Ib (target compound two), compound shown in the formula Ib is through reduction reaction, obtains compound shown in the formula Ic (target compound three).
Embodiment
In optimized technical scheme of the present invention, A is a group shown in the formula II, R
1, R
2, R
3And R
4Independently be selected from respectively: H, C
1～C
3The straight or branched alkyl, C
1～C
3The straight or branched perfluoroalkyl, C
1～C
3The straight or branched alkoxyl group, or a kind of in the halogen (F, Cl, Br or I);
Preferred technical scheme is: A is a group shown in the formula II, R
1, R
2, R
3And R
4Independently be selected from respectively: H, methyl, methoxyl group, F, Cl, a kind of in Br or the trifluoromethyl.
In another optimized technical scheme of the present invention, A is a group shown in the formula III, R
1, R
2, R
3And R
4Independently be selected from respectively: H, C
1～C
3The straight or branched alkyl, C
1～C
3The straight or branched perfluoroalkyl, C
1～C
3The straight or branched alkoxyl group, or a kind of in the halogen (F, Cl, Br or I);
Preferred technical scheme is: A is a group shown in the formula III, R
1, R
2, R
3And R
4Independently be selected from respectively: H, methyl, methoxyl group, F, Cl, a kind of in Br or the trifluoromethyl.
In another optimized technical scheme of the present invention, A is H, R
1, R
2, R
3And R
4Independently be selected from respectively: H, C
1～C
3The straight or branched alkyl, or a kind of in the halogen (F, Cl, Br or I);
Preferred technical scheme is: A is H, R
1, R
2, R
3And R
4Independently be selected from respectively: H, a kind of among methyl or the Cl.
Prepare the method that contains the adjacent formamido-benzamide compound (compound shown in the formula I) of difluoro (Asia) methyl of the present invention, comprise the steps:
(1) preparation of compound shown in the formula IV:
Compound shown in the formula IV is made through three-step reaction by thiophenol and Bromodifluoroacetic acid ethyl ester, and concrete steps are seen embodiment;
(2) compound shown in the formula IV and 4H-benzoxazinone midbody (compound shown in the formula V) react in reflux state in pyridine solvent; Make compound shown in the formula Ia; Compound shown in the formula Ia and oxygenant (like metachloroperbenzoic acid etc.) carry out oxidizing reaction under room temperature in methylene dichloride; Make compound shown in the formula Ib, compound shown in the formula Ib and reductive agent (like MAGNESIUM METAL 99 etc.) carry out reduction reaction in aprotic polar solvent (like DMF etc.), compound shown in the formula Ic.
The preparation of compound shown in the wherein said formula V, referring to agricultural chemicals, 2010,49 volumes, the 3rd phase, 170-173 page or leaf.
Through embodiment the present invention is done further elaboration below, its purpose only is better to understand content of the present invention.Therefore, the restriction of protection scope of the present invention example of not receiving to be lifted.
Embodiment 1
2, the preparation of 2-two fluoro-2-thiophenyl ethamine (compound shown in the formula IV):
At ambient temperature; Add 5.5 gram thiophenol and 100 milliliters of DMSO 99.8MIN.s in 250 milliliters of single port flasks; Slowly add sodium hydride 2.2 grams of 60% content again, react after one hour, dropwise add 12.2 gram Bromodifluoroacetic acid ethyl esters; Stopped reaction after about 9 hours adds 50 milliliters of saturated ammonium chloride solution cancellation reactions.Use dichloromethane extraction, distinguish water and saturated common salt water washing organic layer, anhydrous Na again
2SO
4Dry organic layer, suction filtration revolves dried bullion, with the sherwood oil post separate colourless liquid 2,2-two fluoro-2-thiophenyl ETHYLE ACETATE 9.6 restrain yield: 83%, GC-MS:m/z=232,159,109,77.
With 2,2-two fluoro-2-thiophenyl ETHYLE ACETATE, 4.64 grams and 30 ml methanol join in 100 milliliters of single port flasks, in reaction solution, feed ammonia again, stir 15 minutes under the room temperature.After underpressure distillation goes out methyl alcohol, get pure article white solid 2,2-two fluoro-2-thiophenyl ethanamides 4.06 grams.Yield: 98%, fusing point: 114.4-115.0 ℃.GC-MS：m/z＝203，159，110，77。
Under the argon shield, in 100 milliliters of there-necked flasks, add 2,20 milliliters of 2-two fluoro-2-thiophenyl-ethanamides, 1.15 grams and anhydrous diethyl ethers, ice bath stirs down.Slowly add lithium aluminium hydride 0.56 gram more in batches, ice bath reaction down, the 1.5h afterreaction finishes.Add a little SODIUM SULPHATE ANHYDROUS 99PCT and handle remaining lithium aluminium hydride with counting to drip.Suction filtration is used the rinsed filter cake, with filtrate decompression distill bullion, with sherwood oil and ETHYLE ACETATE carry out post separate colourless liquid 2,2-two fluoro-2-thiophenyl ethamine 0.54 grams (compound shown in the formula IV), yield: 50%.
1H?NMR(400MHz，CDCl
3)：δ＝1.49(s，2H)，3.13(t，J＝12.6Hz，2H)，7.47-7.38(m，3H)，7.63(d，J＝7.3Hz，2H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝48.6(t，
2J
CF＝27.5Hz)，126.7，129.2，129.4(t，
1J
CF＝279.4Hz)，129.9，136.2ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-82.2(t，J＝12.5Hz，2F)ppm；GC-MS：m/z＝189，160，109，77。
Embodiment 2
3-bromo-N-{4-chloro-2-methyl-6-[(2,2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compound I a-1) synthetic:
In 100 milliliters of single port flasks; Add 2.26 gram 5-methyl-7-chloro-2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazoles]-4H-1 successively; 3-benzoxazine-4-ketone (compound shown in the formula V-1) and 30 milliliters of pyridines; Stir and add 1.89 grams 2,2-two fluoro-2-thiophenyl ethamine (compound shown in the formula IV) down.After dropwising, reflux and finish reaction after 5 hours.Reaction solution is left standstill, treat that it is cooled to room temperature after, pour in the water.Promptly there is solid to generate, filters, washing, oven dry obtains 2.61 gram white solids (compound shown in the formula Ia-1).Yield 85%, fusing point: 194.6-198.3 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝2.17(s，3H)，3.92-4.00(m，2H)，6.49(t，J＝6.2Hz，1H)，7.06(s，1H)，7.22-8.42(m，10H)，9.78(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝18.6，48.6(t，
2J
CF＝28.1Hz)，111.2，124.4，124.8，125.5，125.7，128.2，129.0，129.3，130.3，131.2，132.4，132.5，133.1，136.4，138.5，138.7，138.9，146.8，149.0，156.7，168.1ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-78.8(t，J＝12.2Hz)ppm.
Embodiment 3
3-bromo-N-{2-methyl-6-[(2,2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compound I a-2) synthetic:
Outside compound V-1 in the compound V-2 alternative embodiment 1, other condition is all identical with embodiment 1, can make white solid (compound I a-2), yield 88%, fusing point: 192.5-194.3 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝2.23(s，3H)，3.95-4.02(m，2H)，6.51(t，J＝6.1Hz，1H)，7.04(s，1H)，7.20-8.45(m，11H)，10.02(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝19.1，45.0(t，
2J
CF＝28.7Hz)，110.7，124.6，125.7，126.6，127.5，128.2，129.0，129.1，129.3，130.3，133.7，134.3，136.3，136.7，138.9，139.1，143.7，146.8，149.0，155.7，168.9ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-78.9(t，J＝12.0Hz)ppm.
Embodiment 4
3-bromo-N-{6-[(2,2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compound I a-3) synthetic:
Outside compound V-1 in the compound V-3 alternative embodiment 1, other condition is all identical with embodiment 1, can make white solid (compound I a-3), yield 87%, fusing point: 168.4-170.4 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝4.04-4.12(m，2H)，6.83(t，J＝5.9Hz，1H)，7.02(s，1H)，7.09-8.51(m，12H)，12.06(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝45.0(t，
2J
CF＝28.9Hz)，110.2，119.2，121.4，123.7，125.6，125.9，126.9，127.5，128.2，129.3，129.4，130.3，133.3，136.4，139.0，139.1，139.6，146.9，149.2，155.4，169.0ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-78.7(t，J＝12.4Hz)ppm.
Embodiment 5
3-bromo-N-{2-methoxyl group-6-[(2,2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compound I a-4) synthetic:
Outside compound V-1 in the compound V-4 alternative embodiment 1, other condition is all identical with embodiment 1, can make white solid (compound I a-4), yield 86%, fusing point: 133.1-135.5 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝3.79(s，3H)，3.89-4.96(m，2H)，6.55(t，J＝6.0Hz，1H)，7.04(s，1H)，6.94-7.83(m，10H)，8.43(s，1H)，9.15(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝45.0(t，
2J
CF＝24.2Hz)，56.0，111.1，114.1，114.2，117.5，119.1，123.1，124.6，125.6，127.5，129.2，129.3，130.2，136.4，137.2，139.0，139.1，144.0，146.8，147.1，158.4，168.2ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-78.9(t，J＝11.3Hz)ppm.
Embodiment 6
3-bromo-N-{3-trifluoromethyl-6-[(2,2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compound I a-5) synthetic:
Outside compound V-1 in the compound V-5 alternative embodiment 1, other condition is all identical with embodiment 1, can make white solid (compound I a-5), yield 83%, fusing point: 218.5-220.9 ℃.
1H?NMR(400MHz，DMSO-d
6)：δ＝3.93-4.21(m，2H)，7.26(s，1H)，7.38-8.88(m，11H)，9.59(s，1H)，11.89(s，1H)ppm；
13C?NMR(100MHz，DMSO-d
6)：δ＝45.1(t，
2J
CF＝29.0Hz)，111.0，118.3，121.3，123.8(q，
1’J
CF＝271.3Hz)，124.4，125.9，126.2，127.4，127.7，128.3，130.0，130.3，130.8，136.5，138.3，139.7，140.1，147.8，148.5，150.1，155.7，168.1ppm；
19F?NMR(376MHz，DMSO-d
6)：δ＝-76.4(t，J＝13.0Hz)，-61.9(s)ppm.
Embodiment 7
3-bromo-N-{5-bromo-6-[(2,2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compound I a-6) synthetic:
Outside compound V-1 in the compound V-6 alternative embodiment 1, other condition is all identical with embodiment 1, can make white solid (compound I a-6), yield 85%, fusing point: 184.6-187.2 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝4.10-4.17(m，2H)，6.73(t，J＝6.0Hz，1H)，6.94(s，1H)，7.21-8.50(m，11H)，9.87(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝45.1(t，
2J
CF＝28.5Hz)，110.4，119.0，121.6，125.4，125.8，126.5，127.9，128.1，129.1，129.4，129.6，130.4，132.0，136.4，137.2，138.9，139.1，146.9，148.9，155.5，167.1ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-78.6(t，J＝12.4Hz)ppm.
Embodiment 8
3-bromo-N-{2-bromo-6-[(2,2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compound I a-7) synthetic:
Outside compound V-1 in the compound V-7 alternative embodiment 1, other condition is all identical with embodiment 1, can make white solid (compound I a-7), yield 83%, fusing point: 200.3-203.0 ℃.
1H?NMR(400MHz，DMSO-d
6)：δ＝3.81-3.88(m，2H)，7.37(t，J＝7.8Hz，1H)，7.44-8.47(m，11H)，8.92(t，J＝6.0Hz，1H)，10.47(s，1H)ppm；
13C?NMR(100MHz，DMSO-d
6)：δ＝45.9(t，
2J
CF＝28.4Hz)，111.3，124.2，126.0，127.0，127.2，128.1，128.6，129.5，129.9，130.7，131.3，133.1，134.9，136.5，137.2，139.5，139.6，147.5，149.0，156.1，166.9ppm；
19F?NMR(376MHz，DMSO-d
6)：δ＝-76.6(t，J＝12.9Hz)ppm.
Embodiment 9
3-bromo-N-{3-fluoro-6-[(2,2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compound I a-8) synthetic:
Outside compound V-1 in the compound V-8 alternative embodiment 1, other condition is all identical with embodiment 1, can make white solid (compound I a-8), yield 86%, fusing point: 207.5-209.7 ℃.
1H?NMR(400MHz，DMSO-d
6)：δ＝4.02-4.10(m，2H)，7.16(t，J＝8.4Hz，1H)，7.21(s，1H)，7.47-8.59(m，10H)，9.48(t，J＝6.0Hz，1H)，12.44(s，1H)ppm；
13C?NMR(100MHz，DMSO-d
6)：δ＝45.0(t，
2J
CF＝27.6Hz)，108.1(d，
2’J
CF＝27.2Hz)，110.6，111.3(d，
2”J
CF＝21.9Hz)，117.2，124.4，125.9，127.4，127.7，128.3，129.9，130.8，131.6(d，
4’J
CF＝10.5Hz)，136.5，140.0(d，
3’J
CF＝17.0Hz)，140.6(d，
3”J
CF＝12.1Hz)，147.8，148.5，150.1，155.5，164.3(d，
1J
CF＝249.4Hz)，168.7ppm；
19F?NMR(376MHz，DMSO-d
6)：δ＝-105.0--104.9(m)，-76.4(t，J＝13.1Hz)ppm.
Embodiment 10
3-bromo-N-{4-chloro-2-methyl-6-[(2,2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compounds ib-1) synthetic:
In 100 milliliters of single port flasks, add 1.92 successively and digest compound Ia-1 and 20 milliliters of methylene dichloride, stir the 1.55 gram metachloroperbenzoic acids of adding down, room temperature reaction finished after 10 hours.In reaction solution, add hypo solution reaction 0.5 hour, with dichloromethane extraction three times, organic phase is used saturated sodium carbonate solution and saturated common salt water washing respectively.Behind the anhydrous sodium sulfate drying, suction filtration, methylene dichloride is removed in distillation, obtains 1.78 gram white solids (compounds ib-1), yield 88%, fusing point: 198.1-201.0 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝2.22(s，3H)，4.33-4.41(m，2H)，6.71(t，J＝6.1Hz，1H)，7.05(s，1H)，7.33-8.47(m，10H)，9.73(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝19.0，38.9(t，
2J
CF＝26.7Hz)，110.9，124.8，125.7，127.2，128.2，129.0，129.5，129.6，130.5，130.8，131.6，132.1，132.4，133.9，136.0，138.8，138.9，139.0，146.8，156.0，167.8ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-107.1(t，J＝12.9Hz)ppm.
HRMS (ESI): C
25H
18BrCl
2F
2N
5O
4The calculated value of SNa is 695.9485, and measured value is 695.9489.
Embodiment 11
3-bromo-N-{2-methyl-6-[(2,2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compounds ib-2) synthetic:
Outside compound I a-1 in the compound I a-2 alternative embodiment 10, other condition is all identical with embodiment 10, can make white solid (compounds ib-2), yield 87%, fusing point: 200.2-202.5 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝2.18(s，3H)，4.04-4.13(m，2H)，7.25-8.85(m，13H)，10.22(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝18.3，38.0(t，
2J
CF＝21.6Hz)，111.0，126.3，126.6，127.0，127.2，127.4，128.4，129.9，130.6，130.9，131.9，132.9，133.9，136.8，136.9，139.6，139.8，147.5，148.9，155.9，168.3ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-107.7(t，J＝16.4Hz)ppm.
HRMS (ESI): C
25H
19BrClF
2N
5O
4The calculated value of SNa is 661.9875, and measured value is 661.9885.
Embodiment 12
3-bromo-N-{6-[(2,2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compounds ib-3) synthetic:
Outside compound I a-1 in the compound I a-3 alternative embodiment 10, other condition is all identical with embodiment 10, can make white solid (compounds ib-3), yield 85%, fusing point: 208.5-211.2 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝4.46-4.54(m，2H)，6.99(t，J＝6.1Hz，1H)，7.06(s，1H)，7.17-8.54(m，12H)，12.08(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝39.0(t，
2J
CF＝27.3Hz)，110.2，118.8，121.5，123.8，125.8，126.8，128.2，129.3，129.6，130.8，131.6，133.6，136.0，138.9，139.4，139.7，143.1，146.9，149.2，155.4，169.0ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-107.2(t，J＝12.4Hz)ppm.
HRMS (ESI): C
24H
17BrClF
2N
5O
4The calculated value of SNa is 647.9718, and measured value is 647.9724.
Embodiment 13
3-bromo-N-{2-methoxyl group-6-[(2,2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compounds ib-4) synthetic:
Outside compound I a-1 in the compound I a-4 alternative embodiment 10, other condition is all identical with embodiment 10, can make white solid (compounds ib-4), yield 87%, fusing point: 117.1-119.2 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝3.83(s，3H)，3.89-4.96(m，2H)，6.55(t，J＝6.0Hz，1H)，7.04(s，1H)，6.94-7.83(m，10H)，8.43(s，1H)，9.15(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝38.8(t，
2J
CF＝26.2Hz)，56.1，110.9，114.4，119.3，120.5，123.3，125.6，127.5，128.3，129.2，130.8，131.9，135.8，139.0，139.2，146.8，149.0，153.9，156.1，168.1ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-107.2(t，J＝13.3Hz)ppm.
HRMS (ESI): C
25H
19BrClF
2N
5O
5The calculated value of SNa is 677.9824, and measured value is 677.9839.
Embodiment 14
3-bromo-N-{3-trifluoromethyl-6-[(2,2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compounds ib-5) synthetic:
Outside compound I a-1 in the compound I a-5 alternative embodiment 10, other condition is all identical with embodiment 10, can make white solid (compounds ib-5), yield 86%, fusing point: 189.7-192.3 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝4.23-4.32(m，2H)，7.67-7.69(m，1H)，7.70(s，1H)，7.80-8.54(m，10H)，9.57(t，J＝6.1Hz，1H)，11.70(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝38.5(t，
2J
CF＝22.1Hz)，111.1，118.6，121.4，123.8(q，
1’J
CF＝271.3Hz)，126.7，127.4，127.7，128.3，129.3，130.3，130.7，131.0，132.3，137.0，137.9，139.6，140.1，147.8，148.5，155.7，166.5，168.2ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-107.0(t，J＝15.9Hz)，-61.9(s)ppm.
HRMS (ESI): C
25H
16BrClF
5N
5O
4The calculated value of SNa is 715.9583, and measured value is 715.9587.
Embodiment 15
3-bromo-N-{5-bromo-6-[(2,2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compounds ib-6) synthetic:
Outside compound I a-1 in the compound I a-6 alternative embodiment 10, other condition is all identical with embodiment 10, can make white solid (compounds ib-6), yield 83%, fusing point: 224.4-227.1 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝4.11-4.18(m，2H)，7.33-8.17(m，11H)，8.49(s，1H)，9.28(s，1H)，10.41(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝38.8(t，
2J
CF＝25.7Hz)，110.5，119.0，121.7，124.7，125.8，126.2，128.1，129.1，129.6，129.7，130.8，131.5，132.1，136.0，137.2，138.9，139.1，146.9，148.9，155.5，167.2ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-106.4(t，J＝13.5Hz)ppm.
HRMS (ESI): C
24H
16Br
2ClF
2N
5O
4The calculated value of SNa is 725.8824, and measured value is 725.8832.
Embodiment 16
3-bromo-N-{2-bromo-6-[(2,2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compounds ib-7) synthetic:
Outside compound I a-1 in the compound I a-7 alternative embodiment 10, other condition is all identical with embodiment 10, can make white solid (compounds ib-7), yield 86%, fusing point: 157.3-158.9 ℃.
1H?NMR(400MHz，DMSO-d
6)：δ＝4.02-4.11(m，2H)，7.32-8.45(m，12H)，8.92(t，J＝5.9Hz，1H)，10.45(s，1H)ppm；
13C?NMR(100MHz，DMSO-d
6)：δ＝38.1(t，
2J
CF＝21.0Hz)，111.3，121.5，124.0，127.0，127.1，128.1，128.6，129.4，130.6，130.9，132.0，133.2，135.1，136.7，136.9，139.4，139.5，147.4，149.0，156.0，167.1ppm；
19F?NMR(376MHz，DMSO-d
6)：δ＝-107.6(t，J＝16.3Hz)ppm.
HRMS (ESI): C
24H
16Br
2ClF
2N
5O
4The calculated value of SNa is 725.8824, and measured value is 725.8823.
Embodiment 17
3-bromo-N-{3-fluoro-6-[(2,2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compounds ib-8) synthetic:
Outside compound I a-1 in the compound I a-8 alternative embodiment 10, other condition is all identical with embodiment 10, can make white solid (compounds ib-8), yield 86%, fusing point: 103.1-105.2 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝4.41-4.49(m，2H)，6.82(t，J＝7.0Hz，1H)，7.03(s，1H)，7.14(t，J＝5.5Hz，1H)，7.45-8.54(m，10H)，12.34(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝38.8(t，
2J
CF＝25.7Hz)，108.6(d，
2’J
CF＝27.8Hz)，110.3，110.9(d，
2”J
CF＝22.6Hz)，114.7(d，
4’J
CF＝3.1Hz)，120.4，126.0，128.3，129.1(d，
3”J
CF＝10.6Hz)，129.3，129.7，130.8，131.5，136.1，139.1，139.3，141.6(d，
3’J
CF＝12.6Hz)，147.0，149.1，155.5，165.3(d，
1J
CF＝253.3Hz)，168.4ppm；
19F?NMR(376MHz，CDCl
3)：δ＝-107.1(t，J＝12.1Hz)，-102.1--102.0(m)ppm.
HRMS (ESI): C
24H
16BrClF
3N
5O
4The calculated value of SNa is 665.9615, and measured value is 665.9594.
Embodiment 18
3-bromo-N-{4-chloro-2-methyl-6-[(2,2-difluoroethylamine base) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides (compound I c-1) synthetic:
In 100 milliliters of single port flasks, add 1.34 successively and digest compound Ib-1 and 20 milliliters of DMF, add 1: 1 (v/v) buffered soln (8mol/L) of HOAc/NaOAc of 1.2 milliliters again.Add 0.72 gram magnesium chips at last more in batches, stir after 8 hours under the room temperature, reaction solution is poured in the water, the adularescent solid is separated out.Suction filtration obtains 0.86 gram white solid (compound I c-1), yield 80%, fusing point: 145.3-148.0 ℃.
1H?NMR(400MHz，CDCl
3)：δ＝2.18(s，3H)，3.71-3.80(m，2H)，5.89(tt，J
1＝55.6Hz，J
2＝3.9Hz，1H)，6.54(t，J＝6.1Hz，1H)，7.07(s，1H)，7.26-8.47(m，5H)，9.74(s，1H)ppm；
13C?NMR(100MHz，CDCl
3)：δ＝18.8，42.1(t，
2J
CF＝26.6Hz)，110.9，113.2(t，
1J
CF＝241.9Hz)，124.7，125.8，128.2，129.0，131.3，131.7，132.3，133.5，138.6，138.7，139.0，146.8，148.9，156.3，168.3ppm；
19F?NMR(376MHz，CDCl
3)：-122.7(dt，J
1＝55.8Hz，J
2＝14.9Hz)ppm.
HRMS (ESI): C
19H
14BrCl
2F
2N
5O
2The calculated value of SNa is 555.9553, and measured value is 555.9557.
Embodiment 19
The mensuration of insecticidal activity:
(1) examination the choosing of worm: choose 2 age armyworm larvae be tested object.
(2) insecticidal activity testing method: get an amount of former medicine and be dissolved in the organic solvent, add the aqueous solution that a little emulsifying agent is arranged, be made into the soup of 1-500mg/L concentration, fresh leaf of Semen Maydis is immersed in the soup, wait to soak into the taking-up of complete back and dry subsequent use.At diameter is in the petridish of 7cm, puts into 10 of oriental armyworm 2 instar larvaes, and above-mentioned off-the-shelf leaf of Semen Maydis is put into petridish, seals with hospital gauze.The soup of each concentration is provided with three and repeats to observe.Whenever changed fresh blade at a distance from 24 hours after one day, begin to observe mortality ratio after 72 hours, be 4-5 days observing time, and mortality ratio is for observing the per-cent of dead fully examination worm with examination worm sum, and concrete outcome is seen table 1.
Table 1
Continuous table 1
Claims (10)
1. an adjacent formamido-benzamide compound that contains difluoro (Asia) methyl is characterized in that, described adjacent formamido-benzamide compound is a compound shown in the formula I:
Among the formula I, R
1, R
2, R
3And R
4Independently be selected from respectively: H, C
1～C
6The straight or branched alkyl, C
1～C
6The straight or branched perfluoroalkyl, C
1～C
6The straight or branched alkoxyl group, or a kind of in the halogen; A is H, group shown in group shown in the formula II or the formula III;
2. adjacent formamido-benzamide compound as claimed in claim 1 is characterized in that wherein A is a group shown in the formula II, R
1, R
2, R
3And R
4Independently be selected from respectively: H, C
1～C
3The straight or branched alkyl, C
1～C
3The straight or branched perfluoroalkyl, C
1～C
3The straight or branched alkoxyl group, or a kind of in the halogen.
3. adjacent formamido-benzamide compound as claimed in claim 2 is characterized in that, wherein R
1, R
2, R
3And R
4Independently be selected from respectively: H, methyl, methoxyl group, F, Cl, a kind of in Br or the trifluoromethyl.
4. adjacent formamido-benzamide compound as claimed in claim 3; It is characterized in that; Described adjacent formamido-benzamide compound is: 3-bromo-N-{4-chloro-2-methyl-6-[(2; 2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{2-methyl-6-[(2; 2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{6-[(2; 2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{2-methoxyl group-6-[(2; 2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{3-trifluoromethyl-6-[(2; 2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{5-bromo-6-[(2; 2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{2-bromo-6-[(2,2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides or 3-bromo-N-{3-fluoro-6-[(2,2-two fluoro-2-thiophenyl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides.
5. adjacent formamido-benzamide compound as claimed in claim 1 is characterized in that wherein A is a group shown in the formula III, R
1, R
2, R
3And R
4Independently be selected from respectively: H, C
1～C
3The straight or branched alkyl, C
1～C
3The straight or branched perfluoroalkyl, C
1～C
3The straight or branched alkoxyl group, or a kind of in the halogen.
6. adjacent formamido-benzamide compound as claimed in claim 5 is characterized in that, wherein R
1, R
2, R
3And R
4Independently be selected from respectively: H, methyl, methoxyl group, F, Cl, a kind of in Br or the trifluoromethyl.
7. adjacent formamido-benzamide compound as claimed in claim 6; It is characterized in that; Described adjacent formamido-benzamide compound is: 3-bromo-N-{4-chloro-2-methyl-6-[(2; 2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{2-methyl-6-[(2; 2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{6-[(2; 2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-is than pyridine base)-1H-pyrazoles-5-acid amides, 3-bromo-N-{2-methoxyl group-6-[(2; 2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{3-trifluoromethyl-6-[(2; 2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{5-bromo-6-[(2; 2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides, 3-bromo-N-{2-bromo-6-[(2,2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides or 3-bromo-N-{3-fluoro-6-[(2,2-two fluoro-2-benzene sulfuryl ethylamino-s) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides.
8. adjacent formamido-benzamide compound as claimed in claim 1 is characterized in that wherein A is H, R
1, R
2, R
3And R
4Independently be selected from respectively: H, C
1～C
3The straight or branched alkyl, or a kind of in the halogen.
9. adjacent formamido-benzamide compound as claimed in claim 8 is characterized in that, wherein R
1, R
2, R
3And R
4Independently be selected from respectively: H, a kind of among methyl or the Cl.
10. adjacent formamido-benzamide compound as claimed in claim 9; It is characterized in that; Described adjacent formamido-benzamide compound is: 3-bromo-N-{4-chloro-2-methyl-6-[(2,2-difluoroethylamine base) carbonyl] phenyl }-1-(3-chloro-2-pyridyl)-1H-pyrazoles-5-acid amides.
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Cited By (3)
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| CN105712973A (en) * | 2014-12-02 | 2016-06-29 | 沈阳中化农药化工研发有限公司 | Pyrazole amide compound and application thereof |
| CN106977494A (en) * | 2016-01-16 | 2017-07-25 | 海利尔药业集团股份有限公司 | Substituted pyrazolecarboxylic amides compound and its application |
| CN107001325A (en) * | 2014-11-05 | 2017-08-01 | 江苏中旗作物保护股份有限公司 | O-formammidotiazol-benzamide compounds and its application |
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| CN1829707A (en) * | 2003-01-28 | 2006-09-06 | 杜邦公司 | Cyano anthranilamide insecticides |
| CN101061110A (en) * | 2004-10-11 | 2007-10-24 | 辛根塔参与股份公司 | Novel insecticides |
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| CN101061110A (en) * | 2004-10-11 | 2007-10-24 | 辛根塔参与股份公司 | Novel insecticides |
| WO2006080311A1 (en) * | 2005-01-25 | 2006-08-03 | Ishihara Sangyo Kaisha, Ltd. | Anthranilamide compound, method for producing same and pest control agent containing same |
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| CN107001325A (en) * | 2014-11-05 | 2017-08-01 | 江苏中旗作物保护股份有限公司 | O-formammidotiazol-benzamide compounds and its application |
| CN107001325B (en) * | 2014-11-05 | 2020-06-16 | 江苏中旗科技股份有限公司 | O-formamido benzamide compound and application thereof |
| CN105712973A (en) * | 2014-12-02 | 2016-06-29 | 沈阳中化农药化工研发有限公司 | Pyrazole amide compound and application thereof |
| CN106977494A (en) * | 2016-01-16 | 2017-07-25 | 海利尔药业集团股份有限公司 | Substituted pyrazolecarboxylic amides compound and its application |
| CN106977494B (en) * | 2016-01-16 | 2021-04-30 | 海利尔药业集团股份有限公司 | Substituted pyrazole amide compounds and application thereof |
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