CN106489962B - One kind [1,2,4] triazole [4,3-a] pyridines sulfur-containing compound is preparing the application in insecticide - Google Patents

One kind [1,2,4] triazole [4,3-a] pyridines sulfur-containing compound is preparing the application in insecticide Download PDF

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CN106489962B
CN106489962B CN201610914576.8A CN201610914576A CN106489962B CN 106489962 B CN106489962 B CN 106489962B CN 201610914576 A CN201610914576 A CN 201610914576A CN 106489962 B CN106489962 B CN 106489962B
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chloroform
nmr
mhz
pyridine
triazolo
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CN106489962A (en
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吴剑
徐方舟
薛伟
王艳艳
余刚
冯社垒
熊恩琪
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Guizhou University
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Abstract

The invention discloses one kind [1,2,4] triazole [4,3-a] pyridines sulfur-containing compounds to prepare the application in insecticide.

Description

One kind [1,2,4] triazole [4,3-a] pyridines sulfur-containing compound is in preparing insecticide Application
Technical field
The invention belongs to agriculture field of pesticides, relate in particular to one kind [1,2,4] triazole [4,3-a] pyridines and contain Sulphur compound is preparing the application in insecticide.
Background technique
[1,2,4] triazole [4,3-a] pyridine derivatives have a variety of biologies, as weeding (Pest Manag. Sci. 2015,71,292-301), bactericidal activity (Chin. J. Struct. Chem. 2016,35,457-464； Chin. J. Struct. Chem., 2016,35,651-655； Chem. Biol. Drug Des. 84 (2014) 342-347), it is anti-frightened Faint (Arzneimittelforsch. 2012,62,372-377) etc., it is the hot fields of the research and development of novel drugs.
In addition, sulfur-containing compound is also a kind of active material being concerned in recent years, wherein thioether, sulfone compound exist More (the J. Heterocyclic Chem. 2016,53,865-875 of the report of disinfectant use in agriculture；Bioorg. & Med. Chem. 2007,15,3981-3989；Chin. J. Struct. Chem. 2016,35,457-464；Chin. J. Struct. Chem., 2016,35,651-655), wherein the compound of some Sulfide-containing Hindereds is reported living with preferable desinsection Property (Aust. J. Chem. 2014,67,1491-1503；Pestic. Sc. 48 (1996) 31-35；Chem. Pap. 68 (2014) 969-975；Chinese Chemical Letters, 2013,24,673-676).In the recent period, some Sulfide-containing Hindereds [1,2,4] triazole [4,3-a] pyridine compounds and their is reported with good anti-Sclerotinia sclerotiorum, Rhizoctonia solani Kuhn, sharp spore Sickle-like bacteria, Fusarium nivale, aspergillus fumigatus and Candida albicans isoreactivity (Chem. Biol. Drug Des., 2014,84, 342-347).
[1,2,4] triazole [4,3-a] pyridine compounds and their of thioether the application aspect of fungicide have it is involved (Chem. Biol. Drug Des., 2014,84,342-347), but so far, there are no any reports by [1,2,4] triazole [4,3- A] application of the pyridines sulfur-containing compound as insecticide.
Summary of the invention
The purpose of the present invention is to provide one kind [1,2,4] triazole [4,3-a] pyridines sulfur-containing compound it is anti-in preparation Application in plant virus agent.
One kind [1,2,4] triazole [4,3-a] pyridines sulfur-containing compound includes tobacco, rice, vegetables, jade in preparation prevention and treatment Application in the pests such as aphid, brown paddy plant hopper, bollworm, diamondback moth, beet armyworm, cigarette aphid noctuid on the crops such as rice, semen viciae fabae.
Application especially in prevention and treatment diamondback moth, bollworm, beet armyworm.
[1,2,4] triazole [4,3-a] pyridines sulfur-containing compound of the invention is preparing the application in insecticide, compound Structure is as shown in general formula I:
In formula: n selects 0,2；R is selected from-CH3, ethyl, the fluoro- 3- alkene -1- butyl of 3,4,4- tri-, halogeno-benzyl, methyl replace benzyl Base, methoxy substitution benzyl, halogenated methoxy substituted benzyl, halogenated methoxy replace 1,3,4- oxadiazoles -2- ylmethyl, halogenated Pyridine -2- ylmethyl, trifluoro ethoxy substituted pyridines -2- ylmethyl.
Further, as n=0, compound representated by general formula I is as follows:
As n=2, compound representated by general formula I is as follows:
Logical compound of formula I of the invention can be prepared according to method shown in following synthetic route, wherein Ge Gezhong It is prepared by the method that mesosome 1,2,3 and target compound 4 can refer to the report of patent CN 105017247;Target compound 5 is joined According to documentPestic. Biophy. Biochem. 2011, 101, 6-15；Molecules. 2010, 15(2), 766- 779；Bioorg. & Med. Chem. 15, 3981–3989It is prepared by the method for equal reports:
In reaction equation, the substituent group of compound is same as described above.
Synthesized obtained target compound nuclear magnetic data is as follows:
Compound 4a: Yield: 94.8%;Yellow solid; m.p. 114.6-116.6 °C;1H NMR (500 MHz, Chloroform-D) δ 7.73 (dt, 3 J = 8.6 Hz, 4 J = 4.3 Hz, 1H), 7.33 (d, 3 J = 1.8 Hz, 1H), 7.29 (dd, 3 J = 7.2, 3 J = 0.7 Hz, 1H), 7.00 – 6.93 (m, 2H, Ph-H), 6.72 (t, 3 J = 7.0 Hz, 1H, P-H), 4.38 (s, 2H, -CH2-). 13C NMR (125 MHz, Chloroform-D) δ 149.19, 141.95, 134.76, 134.71, 133.18, 131.72, 129.73, 127.38, 126.53, 122.75, 121.39, 113.92, 37.07. Anal. Calc. for C13H8Cl3N3S: C 45.30%, H 2.34%, N 12.19%. Found: C 45.32%, H 2.36%, N 12.17%.
Compound 4b: Yield: 84.7%;Faint yellow solid; m.p. 88,6-90.1 °C;1H NMR (500 MHz, Chloroform-D) δ 7.67 (d, 3 J= 6.9 Hz, 1H, Ar-H), 7.26 (d, 3 J= 9.4 Hz, 1H, Ar-H), 7.09 (dd, 3 J= 8.5 Hz, 3 J= 5.3 Hz, 2H, Ar-H), 6.87 – 6.79 (m, 2H, Ph-H), 6.68 (t,3 J= 7.0 Hz, 1H, Ar-H), 4.27 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 162.42 (d, 1 J C-F = 247.6 Hz), 149.06, 142.24, 132.62, 130.56 (d, 2 J C-F =21.6 Hz), 126.47, 122.62, 121.46, 115.75 (d, 2 J C-F 21.6 Hz), 113.77, 39.39; Anal. Calc. for C13H9ClFN3S: C 53.15%, H 3.09%, N 14.30%. Found: C 53.17%, H 3.19%, N 14.33%.
Compound 4c:Yield: 98.5%;Yellow solid; m.p. 76.4-78.3 °C; 1H NMR (500 MHz, Chloroform-D) δ 7.67 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.25 (d, 3 J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.02 (d, 3 J = 8.6 Hz, 1H, Ph-H), 6.67 (d, 3 J = 8.6 Hz, 1H, Ph-H), 6.64 (t, 3 J = 7.0 Hz, 1H, [1, 2,4]triazolo [4,3-a]pyridine-H), 4.26 (s, 2H, -CH2-), 3.71 (s, 3H, -CH3). 13C NMR (126 MHz, Chloroform-D) δ 159.38, 154.10, 149.01, 143.47, 130.06, 128.66, 126.37, 123.14, 122.48, 121.69, 115.12, 114.18, 113.56, 55.39, 39.98; Anal. Calc. for C14H12ClN3OS: C 54.99%, H 3.96%, N 13.74%. Found: C 54.86%, H 3.97%, N 13.84%.
Compound 4d:Yield: 27.3%;Yellow solid; m.p. 108.4-109.1°C; 1H NMR (500 MHz, Chloroform-D) δ 8.26 (d, 3 J = 2.5 Hz, 1H), 7.77 (d,3 J = 6.9 Hz, 1H), 7.53 (dd,3 J = 8.2, 4 J = 2.5 Hz, 1H), 7.30 (d,3 J = 7.2 Hz, 1H), 7.13 (d, 3 J = 8.2 Hz, 1H), 6.77 (t, 3 J = 7.0 Hz, 1H), 4.35 (s, 2H,- CH2-). 13C NMR (126 MHz, Chloroform-D) δ 151.03, 149.81, 149.20, 141.61, 139.29, 131.80, 126.58, 124.26, 122.90, 121.21, 114.21, 35.63; Anal. Calc. for C12H8Cl2N4S: C 46.32%, H 2.59%, N 18.00%. Found: C 46.37%, H 2.63%, N 18.05%.
Compound 4e:Yield: 76.8%; Brown solid; m.p. 67.9-68.8 °C;1H NMR (500 MHz, Chloroform-D) δ 8.27 (d, 3 J = 7.1 Hz, 1H, [1,2,4]triazolo [4,3-a] pyridine-H), 7.38 (d, 3 J = 7.2 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 6.78 (t, 3 J = 7.1 Hz, 1H [1,2,4]triazolo [4,3-a]pyridine-H), 4.06 (s, 3H, - CH3); 13C NMR (126 MHz, Chloroform-D) δ149.06, 144.30, 126.19, 122.81, 121.54, 113.82, 16.61; Anal. Calc. for C7H6ClN3S: C 42.11%, H 3.03%, N 21.05%. Found: C 42.16%, H 3.13%, N 21.15%.
Compound 4f:Yield: 76.8%;Yellow solid; m.p. 96.7-97.8 °C;1H NMR (500 MHz, Chloroform-D) δ 8.04 (d, 3 J = 6.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.32 (d, 3 J = 7.8 Hz, 1H, Ar-H), 6.85 (t, 3 J = 7.0 Hz, 1H, Ar-H), 3.16 (q, 3 J = 7.3 Hz, 2H, -CH2-), 1.34 (t, 3 J = 7.2 Hz, 3H, -CH3); 13C NMR (126 MHz, Chloroform-D) δ 145.78, 136.39, 126.32, 122.80, 121.73, 113.90, 29.33, 15.38; Anal. Calc. for C8H8ClN3S: C 44.97%, H 3.77%, N 19.66%. Found: C 44.02%, H 3.79%, N 19.68%.
Compound 4g:Yield: 99.3%; Brown solid; m.p. 79.8-81.1 °C;1H NMR (500 MHz, Chloroform-D) δ 7.51 (d, J = 6.9 Hz, 1H, Ar-H), 7.25 (d, 3 J = 6.3 Hz, 1H, Ar-H), 7.11 – 7.04 (m, 2H, Ar-H), 6.85 (t, 3 J = 7.2 Hz, 1H, Ar-H), 6.76 (d, 3 J = 7.5 Hz, 1H, Ar-H), 6.58 (t, 3 J = 7.0 Hz, 1H, Ar-H), 4.28 (s, 2H, - CH2-), 2.39 (s, 3H, -CH3). 13C NMR (125 MHz, Chloroform-D) δ 149.05, 142.47, 136.53, 134.58, 130.80, 129.60, 128.37, 126.44, 126.33, 122.43, 121.49, 113.59, 38.58, 19.18; Anal. Calc. for C14H12ClN3S: C 58.03%, H 4.17%, N 14.50%. Found: C 58.13%, H 4.13%, N 14.52%.
Compound 4h: Yield: 79.5%;Gray solid; m.p. 90.2-91.3 °C;1H NMR (500 MHz, Chloroform-D) δ 7.62 (dd, 3 J = 6.9 Hz, 4 J =0.7 Hz, 1H, [1,2,4]triazolo[4,3-a] pyridine-H), 7.27 (d, 4 J = 0.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.15 (d, 2H, Ph-H), 6.99 (d, J = 8.1 Hz, 2H, Ph-H), 6.64 (t, 3 J = 7.1 Hz, 1H, [1, 2,4]triazolo[4,3-a]pyridine-H), 4.28 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 149.12, 148.82, 141.94, 135.76, 130.30, 126.48, 122.65, 121.42, 121.31, 119.35, 113.80, 77.38, 77.13, 76.87, 39.40; Anal. Calc. for C14H12ClN3S: 46.74%, H 2.52%, N 11.68%. Found: C 46.72%, H 2.53%, N 11.78%.
Compound 4i:Yield: 58.9%;White solid; m.p. 101.1-102.2 °C; 1H NMR (500 MHz, Chloroform-D) δ7.63 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.41 (d, 3 J = 7.9 Hz, 2H, Ph-H), 7.27 (d, 3 J = 7.7 Hz, 2H, Ph-H), 7.25 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.66 (t, 3 J = 7.1 Hz, 1H), 4.35 (s, 2H, -CH2-). 13C NMR (126 MHz, Chloroform-D) δ 149.12, 148.82, 141.94, 135.76, 130.30, 126.48 (q, 1 J C-F = 129.1 Hz), 123.45, 122.65, 121.42, 121.31, 119.35, 117.31, 113.80, 77.38, 77.13, 76.87, 39.40, 0.09; Anal. Calc. for C14H9ClF3N3S: 48.92%, H 2.64%, N 12.22%. Found: C 48.82%, H 2.56%, N 12.08%.
Compound 4j:Yield: 89.2%;Brown; m.p. 109.7-110.8 °C;1H NMR (500 MHz, Chloroform-D) δ 7.73 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.60 (d, 3 J = 7.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.33 – 7.20 (m, 3H, Ph-H), 7.10 (d, 3 J = 7.5 Hz, 1H), 6.70 (dd, 3 J = 9.0, 3 J = 5.0 Hz, 1H, Ph- H), 4.46 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 149.20, 142.14, 135.08, 132.20, 131.72, 128.67 (q, 1 J C-F = 129.4 Hz), 127.95, 127.56, 126.61, 125.38, 123.20, 122.67, 121.47, 113.97, 77.40, 77.15, 76.89, 36.59; Anal. Calc. for C14H9ClF3N3S: 48.92%, H 2.64%, N 12.22%. Found: C 48.85%, H 2.57%, N 12.18%.
Compound 4k:Yield: 90.5%;White solid; m.p. 100.0-101.7 °C;1H NMR (500 MHz, Chloroform-D) δ 7.80 (dd, 3 J =6.9 Hz, 4 J = 0.6 Hz, 1H), 7.30 (dd, 3 J = 7.2 Hz, 4 J = 0.7 Hz, 1H), 7.02 (td, 3 J =8.6, 3 J = 6.3 Hz, 1H), 6.77 – 6.70 (m, 2H, Ph-H), 6.62 (dd, J = 7.1, 1.6 Hz, 1H), 4.30 (s, 2H); 13C NMR (126 MHz, Chloroform-D) δ 162.86 (d, 1 J C-F = 257.1 Hz), 160.59 (d, 1 J C-F = 213.4 Hz), 152.33, 149.19, 142.04, 131.75 (d, 2 J C-F = 9.7 Hz), 126.54, 122.78, 121.40, 120.00, 111.54 (d, 2 J C-F = 21.2 Hz), 104.25 (t, 2 J C-F = 25.3 Hz), 32.64; Anal. Calc. for C13H8ClF2N3S: 50.09 %, H 2.59%, N 13.48%. Found: 50.19 %, H 2.61%, N 13.50%.
Compound 4l:Yield: 84.6%;Yellow solid; m.p. 89.7-90.5 °C;1H NMR (500 MHz, Chloroform-D) δ 7.82 (dd, 3 J = 6.9, 0.8 Hz, 1H, [1,2,4]triazolo[4,3-a] pyridine-H), 7.33 – 7.29 (m, 1H, Ar-H), 6.93 (td, 3 J = 8.9 Hz, 4 J = 4.5 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.86 (m, 2H, Ar-H), 6.75 (t, 3 J = 7.0 Hz, 1H, ArH), 4.30 (s, 2H, -CH2-). 13C NMR (126 MHz, Chloroform-D) δ 158.39 (d, 1 J C-F = 241.9 Hz), 156.70 (d, 1 J C-F = 244.9 Hz), 149.25, 141.89, 126.55, 122.85, 121.40, 117.39, 116.83 (d, 2 J C-F = 8.6 Hz), 116.64 (d, 2 J C-F = 8.5 Hz), 116.48 (d, 2 J C-F = 8.5 Hz), 116.29 (d, 2 J C-F = 8.4 Hz), 114.00, 32.75; Anal. Calc. for C13H8ClF2N3S: 50.09 %, H 2.59%, N 13.48%. Found: 50.19 %, H 2.61%, N 13.50%.
Compound 4m:Yield: 88.1%; Brown solid; m.p. 145.2-146.2 °C; 1H NMR (500 MHz, Chloroform-D) δ 7.95 (dd, 3 J = 6.9, 4 J = 0.6 Hz, 1H, [1,2,4]triazolo[4,3- a]pyridine-H), 7.33 (dd, 3 J = 7.2, 4 J =0.8 Hz, 1H, [1,2,4]triazolo[4,3-a] pyridine-H), 7.21 (dd, 3 J = 7.2, 4 J =4.5,1H, [1,2,4]triazolo[4,3-a]pyridine- H), 6.77 (m, 3H, PH-H), 4.25 (s, 2H); 13C NMR (126 MHz, Chloroform-D) δ 161.03 (d, 1 J C-F = 250.5 Hz), 160.97 (d, 1 J C-F = 250.4 Hz), 149.34, 141.58, 130.09, 130.01, 129.93, 126.67, 122.92, 121.58, 114.04, 113.31, 113.16 (t, J = 19.0 Hz), 111.54 (d, 2 J C-F = 20.4 Hz), 111.51 (d, 2 J C-F = 20.3 Hz), 26.85; Anal. Calc. for C13H8ClF2N3S: 50.09 %, H 2.59%, N 13.48%. Found: 50.12 %, H 2.63%, N 13.51%.
Compound 4n:Yield: 95.7%; White solid; m.p. 112.7-113.5 °C;1H NMR (500 MHz, Chloroform-D) δ 7.78 (dd, 3 J = 6.85 Hz, 4 J = 1.8 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 7.31 (dd, 3 J = 6.8 Hz, 4 J = 0.85 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 7.15 (dd, 3 J = 9.3 Hz, 4 J = 1.8 Hz, 1H, Ar-H), 7.02 (dd,3 J = 8.3 Hz, 4 J = 1.8 Hz, 1H, Ar-H), 6.92 (t, J = 8.1 Hz, 1H, Ar-H), 6.75 (t,J = 7.1 Hz, 1H, Ar-H), 4.27 (s, 2H, -CH2); 13C NMR (126 MHz, Chloroform-D) δ 160.44 (d, 1 J C-F = 253.0 Hz), 149.20, 141.90, 131.96, 131.93, 127.70, 126.59, 123.34 (d, 2 J C-F = 14.7 Hz), 122.47 (d, 2 J C-F = 9.6 Hz), 122.43, 121.40, 119.47, 119.28, 114.03, 32.64; Anal. Calc. for C13H8BrClFN3S: 41.90 %, H 2.16%, N 11.28%, Found: 41.95%, H 2.23%, N 11.25%.
Compound 4o: Yield: 99.1%;Yellow solid; m.p. 121.1-122.3 °C;1H NMR (500 MHz, Chloroform-D) δ 7.74 (dd, 3 J = 6.9, 4 J = 0.9 Hz, 1H, [1,2,4]triazolo[4,3- a]pyridine-H), 7.29 (dd, 3 J = 7.2, 4 J = 0.9 Hz, 1H, [1,2,4]triazolo[4,3-a] pyridine-H), 7.07 (dd, 3 J = 8.4, 4 J = 2.6 Hz, 1H, Ph-H), 7.00 (dd, J = 8.6, 6.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.73 – 6.67 (m, 2H, Ph-H), 4.38 (s, 2H, -CH2); 13C NMR (126 MHz, Chloroform-D) δ 162.22 (d, 1 J C-F = 251.4 Hz), 149.17, 142.03, 134.81, 132.05, 131.98, 130.56, 126.53, 122.71, 121.40, 117.34 (d, 2 J C-F = 25.0 Hz), 114.34 (d, 2 J C-F = 20.9 Hz), 113.89, 37.05; Anal. Calc. for C13H8Cl2FN3S: 47.58 %, H 2.46%, N 12.80%, Found: 47.54 %, H 2.33%, N 12.88%.
Compound 4p: Yield: 82.8%;Yellow solid; m.p. 105.4-107.3 °C;1H NMR (500 MHz, CHLOROFORM-D) δ 7.79 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo [4,3-a] pyridine-H), 7.29 (d, 3 J =7.1 Hz, 1H, Ar-H), 7.23 – 7.18 (m, 1H, Ar-H), 6.90 (dd, 3 J = 10.3 Hz, 4 J = 3.8 Hz, 1H), 6.80 (t, 3 J = 7.8 Hz, 1H, Ar-H), 6.74 (t,3 J = 7.0 Hz, 1H, Ar-H), 4.33 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 156.19 (d, 1 J C-F = 250.6 Hz), 149.19, 141.82, 130.55, 129.21, 126.58, 125.80 (d, 2 J C-F = 14.5 Hz), 124.74, 124.71,122.72, 121.40, 113.95, 33.21; Anal. Calc. for C13H8Cl2FN3S: 47.58 %, H 2.46%, N 12.80%, Found: 47.49%, H 2.53%, N 12.85%.
Compound 4q: Yield: 88.23%; Drab solid; m.p. 168.7-169.3 °C;1H NMR (500 MHz, CHLOROFORM-D) δ 7.75 (d, 3 J = 6.9 Hz, 1H, ArH), 7.45 (dd, 3 J = 8.8, 3 J = 5.2 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.29 (d, 3 J = 7.2 Hz, 1H, Ar- H), 6.86 (dd, 3 J =8.7 Hz, 4 J = 2.9 Hz, 1H, ArH), 6.80 (td,3 J = 8.4 Hz, 4 J = 3.0 Hz, 1H, ArH), 6.72 (t,3 J =7.0 Hz, 1H, ArH), 4.39 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 161.71 (d, 1 J C-F = 248.8 Hz), 149.26, 141.85, 138.22, 126.53, 122.80, 121.42, 118.48, 118.03 (d, J = 23.5 Hz), 116.89 (d, J = 22.5 Hz), 113.92, 39.99; Anal. Calc. for C13H8BrClFN3S: 41.90 %, H 2.16%, N 11.28%, Found: 41.93 %, H 2.17%, N 11.31%.
Compound 4r: Yield: 99.6%; White solid; m.p. 168.1-168.6 °C;1H NMR (500 MHz, Chloroform-D) δ 7.74 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a] pyridine-H), 7.74 (d, 3 J = 6.9 Hz, 1H, Ar-H), 7.30 – 7.23 (m, 3H, Ar-H), 7.01 (dd, 3 J = 8.5, 3 J =5.9 Hz, 1H, Ar-H), 6.73 (dd,3 J = 11.2, 3 J = 4.8 Hz, 2H, Ar- H), 4.40 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 161.99 (d, 1 J C-F = 252.4 Hz), 149.18, 141.98, 132.25, 131.98, 131.91, 126.5, 124.53, 122.70, 121.44, 120.52 (d, 2 J C-F = 24.9 Hz), 114.88 (d, 2 J C-F = 20.8 Hz), 113.88, 39.65; Anal. Calc. for C13H8Cl2FN3S: 41.90 %, H 2.16%, N 11.28%, Found: 41.93 %, H 2.17%, N 11.31%; Anal. Calc. for C13H8BrClFN3S: 41.90 %, H 2.16%, N 11.28%, Found: 41.95 %, H 2.14%, N 11.33%.
Compound 4s:Yield: 53.1%;Yellow solid; m.p. 90.0-91.1 °C;1H NMR (500 MHz, Chloroform-D) δ 8.08 (d,3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.41 (d, 3 J = 7.2 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.93 (t, 3 J = 7.1 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.55 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 165.30, 155.95 (q, 1 J C-F = 44.8 Hz), 149.62, 139.74, 127.13, 123.18, 121.57, 117.00, 114.82, 28.82. Anal. Calc. for C10H5ClF3N5OS: 35.78%, H 1.50%, N 20.86%, Found: 35.85%, H 1.52%, N 20.87%.
Compound 4t: Yield: 57.1%; Gray solid; m.p. 110.0-112.0 °C;1H NMR (500 MHz, Chloroform-D) δ 8.18 (d, 3 J = 5.6 Hz, 1H, pyridine-H), 7.95 (d, 3 J = 6.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.31 (d, 3 J = 7.1 Hz, 1H, pyridine-H), 6.78 (t, 3 J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.60 (d, 3 J = 5.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.51 (s, 2H, - CH2-), 4.37 (q,3 J = 7.8 Hz, 2H, -CH2-CF3), 2.21 (s, 3H); 13C NMR (126 MHz, Chloroform-D) δ 161.70, 155.54, 149.14, 148.12, 142.54, 126.40, 122.74, 121.89, 121.48, 113.75, 105.70, 65.43 (q, 1 J C-F = 36.7 Hz), 39.13, 10.68; Anal. Calc. for C15H12ClF3N4OS: C 46.34%, H 3.11%, N 14.41%, Found: 46.41%, H 3.16%, N 14.48%.
Compound 4u:Yield: 76.8%; White solid; m.p. 92.1-93.2 °C; 1H NMR (500 MHz, Chloroform-D) δ 7.76 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a] pyridine-H), 7.48 – 7.42 (m, 1H, Ar-H), 7.31 – 7.26 (m, 2H, Ph-H), 7.09 (t,3 J = 8.9 Hz, 1H, Ph-H), 6.73 (t, 3 J = 7.0 Hz, 1H), 4.34 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 162.41 (d, 1 J C-F = 254.4 Hz), 128.21, 127.32, 125.31 (d, 2 J C-F = 15.9 Hz), 124.35, 122.91, 122.19, 121.19, 116.42 (d, 2 J C-F = 22.8 Hz), 114.13, 32.83; Anal. Calc. for C14H8BrClF4N3S: C 46.48%, H 2.23%, N 11.62%, Found: C 46.53%, H 2.27%, N 11.64%.
Compound 4v: Yield: 76.8%;Yellow solid; m.p. 46.8-47.5 °C;1H NMR (500 MHz, Chloroform-D) δ 8.28 (d, 3 J = 7.2 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.40 (d, 3 J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.80 (t, 3 J = 7.1 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.67 (t, 3 J = 7.2 Hz, 2H, -CH2-), 3.03 – 2.95 (m, 2H, -CH2CF=CF2); 13C NMR (126 MHz, Chloroform-D) δ 153.76 (ddd, 1 J C-F = 287.8, 1 J C-F =274.6, 2 J C-F = 45.7 Hz), 149.17, 142.21, 127.60 (ddd, 1 J C-F = 234.9 Hz, J = 53.3 Hz, 2 J C-F = 16.9 Hz) , 126.43, 122.92, 121.47, 114.12, 30.22, 26.62 (d, 2 J C-F = 21.6 Hz); Anal. Calc. for C10H7ClF3N3S: C 40.90%, H 2.40%, N 14.31%, Found: C 40.87%, H 2.43%, N 14.34%.
Compound 5a: Yield: 61.8%;Yellow solid;1H NMR (500 MHz, Chloroform-D) δ 7.74 (dt, 3 J = 8.6 Hz, 4 J = 4.3 Hz, 1H), 7.36 (d, 3 J = 1.8 Hz, 1H), 7.27 (dd, 3 J = 7.2, 3 J = 0.7 Hz, 1H), 7.00 – 6.94 (m, 2H, Ph-H), 6.71 (t, 3 J = 7.0 Hz, 1H, P- H), 4.59 (s, 2H, -CH2-). 13C NMR (125 MHz, Chloroform-D) δ 149.2, 141.8, 134.76, 134.73, 133.2, 131.8, 129.8, 127.5, 126.6, 122.7, 121.4, 114.2, 37.17.
Compound 5b: Yield: 47.2%;Faint yellow solid;1H NMR (500 MHz, Chloroform-D) δ 7.69 (d, 3 J= 6.9 Hz, 1H, Ar-H), 7.29 (d, 3 J= 9.4 Hz, 1H, Ar-H), 7.19 (dd, 3 J= 8.5 Hz, 3 J= 5.3 Hz, 2H, Ar-H), 6.76 – 6.89 (m, 2H, Ph-H), 6.87 (t,3 J= 7.0 Hz, 1H, Ar-H), 4.89 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 162.46 (d,1 J C-F = 247.6 Hz), 149.66, 142.66, 132.7, 130.7 (d, 2 J C-F =21.6 Hz), 126.8, 122.7, 121.7, 115.7 (d, 2 J C-F 21.6 Hz), 113.8, 39.5.
Compound 5c:Yield: 63.5%;Yellow solid; 1H NMR (500 MHz, Chloroform-D) δ 7.69 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.28(d, 3 J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.04 (d, 3 J = 8.6 Hz, 1H, Ph-H), 6.66 (d, 3 J = 8.6 Hz, 1H, Ph-H), 6.67 (t, 3 J = 7.0 Hz, 1H, [1,2,4]triazolo [4,3-a] pyridine-H), 4.57 (s, 2H, -CH2-), 3.73 (s, 3H, -CH3). 13C NMR (126 MHz, Chloroform-D) δ 159.4, 154.3, 1493, 143.5, 130.4, 128.7, 126.6, 123.3 1226, 121.7, 115.4, 114.3, 113.6, 55.4, 39.4.
Compound 5d:Yield: 47.3%;Yellow solid; 1H NMR (500 MHz, Chloroform-D) δ 8.31 (d, 3 J = 2.5 Hz, 1H), 7.79 (d,3 J = 6.9 Hz, 1H), 7.54 (dd, 3 J = 8.2, 4 J = 2.5 Hz, 1H), 7.33 (d,3 J = 7.2 Hz, 1H), 7.16 (d, 3 J = 8.2 Hz, 1H), 6.79 (t, 3 J = 7.0 Hz, 1H), 4.57 (s, 2H,- CH2-). 13C NMR (126 MHz, Chloroform-D) δ 151.1, 149.8, 149.5, 141.7, 139.3, 131.8, 126.58, 124.5, 122.92, 121.3, 114.3, 35.5; Anal. Calc. for C12H8Cl2N4S: C 46.32%, H 2.59%, N 18.00%. Found: C 46.37%, H 2.63%, N 18.05%.
Compound 5e:Yield: 67.8%;Brown solid;1H NMR (500 MHz, Chloroform-D) δ 8.29 (d, 3 J = 7.1 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 7.37 (d, 3 J = 7.2 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 6.79 (t, 3 J = 7.1 Hz, 1H [1, 2,4]triazolo [4,3-a]pyridine-H), 4.46 (s, 3H, -CH3); 13C NMR (126 MHz, Chloroform-D) δ 149.06, 144.33, 126.18, 122.84, 121.59, 113.88, 17.66.
Compound 5f:Yield: 72.8%;Yellow solid;1H NMR (500 MHz, Chloroform-D) δ 8.24 (d, 3 J = 6.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.32 (d, 3 J = 7.8 Hz, 1H, Ar-H), 6.95 (t, 3 J = 7.0 Hz, 1H, Ar-H), 3.36 (q, 3 J = 7.3 Hz, 2H, -CH2-), 1.54 (t, 3 J = 7.2 Hz, 3H, -CH3); 13C NMR (126 MHz, Chloroform-D) δ 145.79, 136.38, 126.32, 122.81, 121.73, 113.91, 29.32, 15.39.
Compound 5g:Yield: 34.3%;Brown solid;1H NMR (500 MHz, Chloroform-D) δ 7.54 (d, J = 6.9 Hz, 1H, Ar-H), 7.27 (d, 3 J = 6.3 Hz, 1H, Ar-H), 7.10 – 7.08 (m, 2H, Ar-H), 6.88 (t, 3 J = 7.2 Hz, 1H, Ar-H), 6.77 (d, 3 J = 7.5 Hz, 1H, Ar-H), 6.59 (t, 3 J = 7.0 Hz, 1H, Ar-H), 4.48 (s, 2H, -CH2-), 2.38 (s, 3H, -CH3). 13C NMR (125 MHz, Chloroform-D) δ 149.07, 142.49, 136.57, 134.59, 130.84, 129.63, 128.34, 126.43, 126.32, 122.42, 121.48, 113.57, 38.52, 19.19.
Compound 5h: Yield: 79.5%;Gray solid;1H NMR (500 MHz, Chloroform-D) δ 7.68 (dd, 3 J = 6.85 Hz, 4 J =0.75 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.28 (d, 4 J = 0.85 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.14 (d, 2H, Ph- H), 6.87 (d, J = 8.0 Hz, 2H, Ph-H), 6.66 (t, 3 J = 7.0 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 4.48 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 149.17, 148.82, 141.99, 135.78, 130.32, 126.49, 122.63, 121.41, 121.32, 119.34, 113.82, 77.35, 77.12, 76.83, 39.43.
Compound 5i:Yield: 34.6%;White solid;; 1H NMR (500 MHz, Chloroform-D) δ7.63 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.41 (d, 3 J = 7.9 Hz, 2H, Ph-H), 7.27 (d, 3 J = 7.7 Hz, 2H, Ph-H), 7.25 (d, 3 J = 6.9 Hz, 1H, [1,2,4] triazolo[4,3-a]pyridine-H), 6.66 (t, 3 J = 7.1 Hz, 1H), 4.35 (s, 2H, -CH2-).13C NMR (126 MHz, Chloroform-D) δ 149.12, 148.82, 141.94, 135.76, 130.30, 126.48 (q, 1 J C-F = 129.1 Hz), 123.45, 122.65, 121.42, 121.31, 119.35, 117.31, 113.80, 77.38, 77.13, 76.87, 39.40, 0.09; Anal. Calc. for C14H9ClF3N3S: 48.92%, H 2.64%, N 12.22%. Found: C 48.82%, H 2.56%, N 12.08%.
Compound 5j:Yield: 67.8 %;Brown;1H NMR (500 MHz, Chloroform-D) δ 7.74 (d, 3 J = 6.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.62 (d, 3 J = 7.5 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.32 – 7.21 (m, 3H, Ph-H), 7.10 (d, 3 J = 7.0 Hz, 1H), 6.72 (dd, 3 J = 9.5, 3 J = 5.5 Hz, 1H, Ph-H), 4.66 (s, 2H, - CH2-); 13C NMR (126 MHz, Chloroform-D) δ 149.20, 142.14, 135.08, 132.22, 131.71, 128.64 (q, 1 J C-F = 129.4 Hz), 127.92, 127.52, 126.63, 125.33, 123.25, 122.69, 121.45, 113.94, 77.42, 79.95, 79.89, 36.62.
Compound 5k:Yield: 56.5%;White solid;1H NMR (500 MHz, Chloroform-D) δ 7.82 (dd, 3 J =6.8 Hz, 4 J = 0.7 Hz, 1H), 7.32 (dd, 3 J = 7.1 Hz, 4 J = 0.8 Hz, 1H), 7.12 (td, 3 J =8.5, 3 J = 6.0 Hz, 1H), 6.77 – 6.71 (m, 2H, Ph-H), 6.60 (dd, J = 7.2, 1.6 Hz, 1H), 4.33 (s, 2H); 13C NMR (126 MHz, Chloroform-D) δ 162.84 (d,1 J C-F = 257.1 Hz), 160.53 (d, 1 J C-F = 213.4 Hz), 152.31, 149.12, 142.14, 131.72 (d, 2 J C-F = 9.7 Hz), 126.52, 122.72, 121.42, 120.02, 111.52 (d, 2 J C-F = 21.2 Hz), 104.23 (t, 2 J C-F = 25.3 Hz), 32.64.
Compound 5l:Yield: 78.6%;Yellow solid;1H NMR (500 MHz, Chloroform-D) δ 7.85 (dd, 3 J = 6.8, 0.8 Hz, 1H, [1,2,4]triazolo[4,3-a] pyridine-H), 7.33 – 7.28 (m, 1H, Ar-H), 6.95 (td, 3 J = 8.5 Hz, 4 J = 4.5 Hz, 1H, [1,2,4]triazolo[4,3-a] pyridine-H), 6.84 (m, 2H, Ar-H), 6.70 (t, 3 J = 7.0 Hz, 1H, ArH), 4.33 (s, 2H, -CH2-). 13C NMR (126 MHz, Chloroform-D) δ 158.42 (d, 1 J C-F = 241.9 Hz), 156.72 (d, 1 J C-F = 244.9 Hz), 149.23, 141.87, 126.53, 122.89, 121.42, 117.34, 116.85 (d, 2 J C-F = 8.6 Hz), 116.66 (d, 2 J C-F = 8.5 Hz), 116.47 (d, 2 J C-F = 8.5 Hz), 116.25 (d, 2 J C-F = 8.4 Hz), 114.03, 32.71.
Compound 5m:Yield: 56.1%;Brown solid; 1H NMR (500 MHz, Chloroform-D) δ 7.98 (dd, 3 J = 6.85, 4 J = 0.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.33 (dd,3 J = 7.15, 4 J =0.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.24 (dd, 3 J = 7.0, 4 J =4.3,1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.72 (m, 3H, PH-H), 4.55 (s, 2H); 13C NMR (126 MHz, Chloroform-D) δ 161.03 (d, 1 J C-F = 250.5 Hz), 160.97 (d, 1 J C-F = 250.4 Hz), 149.34, 141.58, 130.09, 130.01, 129.93, 126.67, 122.92, 121.58, 114.04, 113.31, 113.16 (t, J = 19.0 Hz), 111.54 (d, 2 J C-F = 20.4 Hz), 111.51 (d, 2 J C-F = 20.3 Hz), 26.85; Anal. Calc. for C13H8ClF2N3S: 50.09 %, H 2.59%, N 13.48%. Found: 50.12 %, H 2.63%, N 13.51%.
Compound 5n:Yield: 62.7%;White solid;1H NMR (500 MHz, Chloroform-D) δ 7.83 (dd, 3 J = 6.9 Hz, 4 J = 1.8 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.35 (dd, 3 J = 6.8 Hz, 4 J = 0.85 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.19 (dd, 3 J = 9.3 Hz, 4 J = 1.8 Hz, 1H, Ar-H), 7.22 (dd, 3 J = 8.3 Hz, 4 J = 1.8 Hz, 1H, Ar-H), 6.97 (t, J = 8.1 Hz, 1H, Ar-H), 6.85 (t, J = 7.1 Hz, 1H, Ar-H), 4.37 (s, 2H, -CH2); 13C NMR (126 MHz, Chloroform-D) δ 160.46 (d, 1 J C-F = 253.0 Hz), 149.25, 141.91, 131.97, 131.92, 127.76, 126.58, 123.34 (d, 2 J C-F = 14.7 Hz), 122.46 (d, 2 J C-F = 9.6 Hz), 122.42, 121.43, 119.46, 119.21, 114.01, 32.62.
Compound 5o: Yield: 43.1%;Yellow solid;1H NMR (500 MHz, Chloroform-D) δ 7.76 (dd, 3 J = 6.85, 4 J = 0.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.26 (dd,3 J = 7.2, 4 J = 0.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.17 (dd, 3 J = 8.4, 4 J = 2.6 Hz, 1H, Ph-H), 7.04 (dd, J = 8.6, 6.0 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 6.73 – 6.62 (m, 2H, Ph-H), 4.69 (s, 2H, -CH2); 13C NMR (126 MHz, Chloroform-D) δ 162.21 (d, 1 J C-F = 251.4 Hz), 149.13, 142.13, 134.11, 132.15, 131.93, 130.54, 126.54, 122.73, 121.42, 117.33 (d, 2 J C-F = 25.0 Hz), 114.14 (d, 2 J C-F = 20.9 Hz), 113.85, 37.15.
Compound 5p: Yield: 61.4%;Yellow solid;1H NMR (500 MHz, CHLOROFORM-D) δ 7.82 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo [4,3-a]pyridine-H), 7.34 (d, 3 J =7.1 Hz, 1H, Ar-H), 7.24 – 7.19 (m, 1H, Ar-H), 6.93 (dd, 3 J = 9.3 Hz, 4 J = 3.8 Hz, 1H), 6.82 (t, 3 J = 7.5 Hz, 1H, Ar-H), 6.78 (t, 3 J = 7.0 Hz, 1H, Ar-H), 4.54 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 156.16 (d, 1 J C-F = 250.6 Hz), 149.34, 141.80, 130.15, 129.24, 126.52, 125.81 (d, 2 J C-F = 14.5 Hz), 124.77, 124.72,122.76, 121.43, 113.85, 33.24.
Compound 5q: yield: 65.3%;Gray solid;1H NMR (500 MHz, CHLOROFORM-D) δ 7.78 (d, 3 J = 6.85 Hz, 1H, ArH), 7.43 (dd, 3 J = 8.5, 3 J = 5.0 Hz, 1H, [1,2,4] triazolo[4,3-a]pyridine-H), 7.25 (d, 3 J = 7.2 Hz, 1H, Ar-H), 6.87 (dd, 3 J =8.5 Hz, 4 J = 2.9 Hz, 1H, ArH), 6.85 (td,3 J = 8.0 Hz, 4 J = 3.0 Hz, 1H, ArH), 6.70 (t,3 J =7.0 Hz, 1H, ArH), 4.55 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 161.73 (d, 1 J C-F = 248.8 Hz), 149.24, 141.85, 138.24, 126.56, 122.82, 121.41, 118.47, 118.13 (d, J = 23.5 Hz), 116.86 (d, J = 22.5 Hz), 113.91, 40.91;
Compound 5r: Yield: 63.4%;Yellow solid;1H NMR (500 MHz, Chloroform-D) δ 7.78 (d, 3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.75 (d, 3 J = 6.9 Hz, 1H, Ar-H), 7.30 – 7.21 (m, 3H, Ar-H), 7.21 (dd, 3 J = 8.5, 3 J =5.9 Hz, 1H, Ar- H), 6.72 (dd,3 J = 11.2, 3 J = 4.8 Hz, 2H, Ar-H), 4.51 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 161.90 (d, 1 J C-F = 252.4 Hz), 149.15, 143.32, 132.25, 131.78, 131.92, 126.54, 124.45, 122.71, 121.43, 120.54 (d, 2 J C-F = 24.9 Hz), 114.82 (d, 2 J C-F = 20.8 Hz), 113.81, 40.65.
Compound 5s:Yield: 53.1%;Yellow solid;1H NMR (500 MHz, Chloroform-D) δ 8.18 (d,3 J = 6.9 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.44 (d, 3 J = 7.2 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.92 (t, 3 J = 7.1 Hz, 1H, [1,2,4] triazolo[4,3-a]pyridine-H), 4.72 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform- D) δ 165.31, 155.94 (q, 1 J C-F = 44.8 Hz), 149.65, 139.74, 127.12, 123.19, 121.54, 117.01, 114.82, 29.89.
Compound 5t: Yield: 53.7%;White solid;1H NMR (500 MHz, Chloroform-D) δ 8.21 (d, 3 J = 5.5 Hz, 1H, pyridine-H), 7.89 (d, 3 J = 6.5 Hz, 1H, [1,2,4] triazolo[4,3-a]pyridine-H), 7.34 (d, 3 J = 7.1 Hz, 1H, pyridine-H), 6.77 (t, 3 J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.65 (d, 3 J = 5.6 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 4.73 (s, 2H, -CH2-), 4.35 (q,3 J = 7.8 Hz, 2H, -CH2-CF3), 2.22 (s, 3H); 13C NMR (126 MHz, Chloroform-D) δ 161.71, 155.52, 149.15, 148.11, 142.53, 126.43, 122.73, 121.83, 121.43, 113.73, 105.73, 65.46 (q, 1 J C-F = 36.7 Hz), 40.13, 10.45.
Compound 5u:Yield: 62.6%;White solid; 1H NMR (500 MHz, Chloroform-D) δ 7.75 (d, 3 J = 6.85 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.43 – 7.38 (m, 1H, Ar-H), 7.32 – 7.24 (m, 2H, Ph-H), 7.05 (t, 3 J = 8.5 Hz, 1H, Ph-H), 6.71 (t, 3 J = 7.05Hz, 1H), 4.64 (s, 2H, -CH2-); 13C NMR (126 MHz, Chloroform-D) δ 162.42 (d, 1 J C-F = 254.4 Hz), 128.23, 127.32, 125.33 (d, 2 J C-F = 15.9 Hz), 124.32, 122.93, 122.15, 121.15, 116.41 (d, 2 J C-F = 22.8 Hz), 114.11, 35.82.
Compound 5v: Yield: 54.3%;Yellow solid;1H NMR (500 MHz, Chloroform-D) δ 8.18 (d, 3 J = 7.15 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 7.37 (d, 3 J = 7.0 Hz, 1H, [1,2,4]triazolo[4,3-a]pyridine-H), 6.82 (t, 3 J = 7.1 Hz, 1H, [1, 2,4]triazolo[4,3-a]pyridine-H), 4.68 (t, 3 J = 7.2 Hz, 2H, -CH2-), 3.13 – 2.94 (m, 2H, -CH2CF=CF2); 13C NMR (126 MHz, Chloroform-D) δ 153.72 (ddd, 1 J C-F = 287.8, 1 J C-F =274.6, 2 J C-F = 45.7 Hz), 149.27, 142.23, 127.61 (ddd, 1 J C-F = 234.9 Hz, J = 53.3 Hz, 2 J C-F = 16.9 Hz), 126.44, 122.92, 121.45, 114.22, 35.22, 26.79 (d, 2 J C-F = 21.6 Hz).
The insecticide of the compound of the present invention preparation, be mainly used for it is anti-eliminate aphis, brown paddy plant hopper, diamondback moth, bollworm, beet The crop pests such as noctuid.
Specific embodiment
For killing diamondback moth, bollworm and the activity of beet armyworm, but it is other not limit the compounds of this invention prevention and treatment The application of pest.
Embodiment 1: to the insecticidal activity of diamondback moth
Itd is proposed using international resistance Action Committee (IRAC) leaf dipping method (J. Agric. Food Chem., 2007, 55(23): 9614–9619.).With prepared medical fluid to be measured.With straight peen ophthalmology tweezers impregnate cabbage leaves, time 3-5 second, Get rid of extraction raffinate.1 tablet once, and totally 3, each sample.It is successively placed on processing paper by sample flag sequence.After medical fluid is dry, it is put into Have in the straight type pipe of markd 10 cm long, accesses 2 age diamondback moth larvae 30, cover nozzle with gauze.Test process is set In in standard process chamber, 96 h inspection results touch polypide with pulling needle, and motionless person is death.Calculating the death rate, (3 weights are done in experiment It is multiple, be averaged).Using commercially available medicine chlopyrifos as comparison medicament.
Calculate the death rate and corrected mortality:
(1)
In formula: P1- the death rate;K-death borer population;The total borer population of N-processing.
(2)
In formula: P2- corrected mortality；Pt- processing the death rate; P0- blank control the death rate.If compareing death rate < 5%, without correction；The death rate is compareed between 5-20%, should be corrected by formula (2)；Death rate > 20% is compareed, test needs It reforms.
The Activity Results of part of compounds such as table 1.
Insecticidal activity of 1 part of compounds of table to diamondback moth
Embodiment 2: the insecticidal activity of bollworm is tested
Medicine method is mixed using feed, from being pipetted in configured solution in the rigid configured feed that 3 mL are added to 27 g, Obtain the required concentration of ten times of dilution.Medicament equably pours into 24 clean orifice plates after mixing, and 24 cotton bolls are accessed after cooling down Worm, inspection result after observation 3-4 days.
Calculate the death rate and corrected mortality:
(1)
In formula: P1- the death rate;K-death borer population;The total borer population of N-processing.
(2)
In formula: P2- corrected mortality；Pt- processing the death rate; P0- blank control the death rate.If compareing death rate < 5%, without correction；The death rate is compareed between 5-20%, should be corrected by formula (2)；Death rate > 20% is compareed, test needs It reforms.
The Activity Results of part of compounds such as table 2.
Insecticidal activity of 2 part of compounds of table to bollworm
Embodiment 3: to the insecticidal activity of beet armyworm
Leaf dipping method (J. Agric. Food Chem., 2007,55 (23): 9614-9619.) of use.With preparing Medical fluid to be measured, by cabbage leaves impregnate 3-5 seconds, get rid of extraction raffinate.It is successively placed on processing paper by sample flag sequence.To medical fluid It after dry, is put into the culture dish for having markd 60 cm long, accesses 3 age beet exigua larvae 30, cover lid.It will test Processing is placed in standard process chamber, and 96 h inspection results touch polypide with pulling needle, and motionless person is death.Calculate the death rate (experiment 3 repetitions are done, are averaged).
Calculate the death rate and corrected mortality:
(1)
In formula: P1- the death rate;K-death borer population;The total borer population of N-processing.
(2)
In formula: P2- corrected mortality；Pt- processing the death rate; P0- blank control the death rate.If compareing death rate < 5%, without correction；The death rate is compareed between 5-20%, should be corrected by formula (2)；Death rate > 20% is compareed, test needs It reforms.
The Activity Results of part of compounds such as table 3.
Insecticidal activity of 3 part of compounds of table to beet armyworm
Embodiment 4: to the IC of diamondback moth50Measurement
Using test method same as Example 1, doubling dilution is used in setting in concentration, to part of compounds IC50Value is tested (using chlopyrifos as comparison medicament), its virulence equation and IC are calculated50Value.Shown in acquired results table 4.
IC of 4 part of compounds of table to diamondback moth50Value
Embodiment 5: to the IC of bollworm50Measurement
Using test method same as Example 2, doubling dilution is used in setting in concentration, to part of compounds IC50Value is tested (using chlopyrifos as comparison medicament), its virulence equation and IC are calculated50Value.Shown in acquired results table 5.
IC of 5 part of compounds of table to bollworm50Value
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form, appoint What is to the above embodiments according to the technical essence of the invention any simply to repair without departing from technical solution of the present invention content Change, equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.

Claims (2)

1. a kind of [1,2,4] triazole [4,3-a] pyridines sulfur-containing compound preparation it is anti-eliminate aphis, brown paddy plant hopper, bollworm, pickles Moth, beet armyworm, the application in tobacco leaf noctuid vegetable insecticide；
The compound structure general formula is as shown in general formula I:
In formula: n selects 0,2；R is selected from-CH3, ethyl, the fluoro- 3- alkene -1- butyl of 3,4,4- tri-, halogeno-benzyl, methyl substituted benzyl, first Oxygroup substituted benzyl, halogenated methoxy substituted benzyl, halogenated methoxy replace 1,3,4- oxadiazoles -2- ylmethyl, haloperidid - 2- ylmethyl, trifluoro ethoxy substituted pyridines -2- ylmethyl.
2. [1,2,4] triazole [4,3-a] pyridines sulfur-containing compound as described in claim 1 is in preparation prevention and treatment bollworm, small Application in diamond-back moth, beet armyworm vegetable insecticide.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2861076A (en) * 1956-06-14 1958-11-18 Eastman Kodak Co Process for the preparation of 1:2:4-triazole-3-thiols
DE2438789A1 (en) * 1974-08-13 1976-02-26 Bayer Ag 2-(Thiono)phosphor(on)yl)-3-oxo-triazolopyridine derivs. - prepd. by reacting (thiono)phosphor(on)yl halides with 3-hydroxy-1,2,4-triazolo-(4,3-a)pyridine
JP2011140463A (en) * 2010-01-07 2011-07-21 Tottori Univ Technique for controlling plant disease using waste mushroom bed of edible mushroom
CN102159543A (en) * 2008-07-18 2011-08-17 赛诺菲-安万特 Novel triazolo(4,3-a)pyridine derivatives, process for preparation thereof, use thereof as medicaments, pharmaceutical compositions and novel use, in particular as met inhibitors
JP2016108336A (en) * 2014-12-02 2016-06-20 日産化学工業株式会社 Salt of heterocycle amide compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2861076A (en) * 1956-06-14 1958-11-18 Eastman Kodak Co Process for the preparation of 1:2:4-triazole-3-thiols
DE2438789A1 (en) * 1974-08-13 1976-02-26 Bayer Ag 2-(Thiono)phosphor(on)yl)-3-oxo-triazolopyridine derivs. - prepd. by reacting (thiono)phosphor(on)yl halides with 3-hydroxy-1,2,4-triazolo-(4,3-a)pyridine
CN102159543A (en) * 2008-07-18 2011-08-17 赛诺菲-安万特 Novel triazolo(4,3-a)pyridine derivatives, process for preparation thereof, use thereof as medicaments, pharmaceutical compositions and novel use, in particular as met inhibitors
JP2011140463A (en) * 2010-01-07 2011-07-21 Tottori Univ Technique for controlling plant disease using waste mushroom bed of edible mushroom
JP2016108336A (en) * 2014-12-02 2016-06-20 日産化学工業株式会社 Salt of heterocycle amide compound

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