CN114920753B - 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and synthetic method and application thereof - Google Patents
6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and synthetic method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of pesticide, medicine and material synthesis, and particularly relates to a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative, and a synthesis method and application thereof. The derivative is prepared by mixing trifluoromethyl olefin, pyrazolone, alkali or alkali salt with an organic solvent and then reacting. The method is efficient, the reaction has good adaptability to functional groups, the adaptability to substrates is wide, and the product yield is high; the raw materials are cheap and easy to obtain, can be amplified to gram-grade or larger-scale production, and are simple and safe to operate, and the reaction conditions are mild. The obtained 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative has better insecticidal activity on plutella xylostella and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of pesticide and medicine material synthesis, and particularly relates to a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative, and a synthesis method and application thereof.
Background
Dihydropyrano [2,3-C ] pyrazole derivatives have important application values in the fields of pesticides, medicines, materials and the like, such as GTPase Ral inhibitors, AKR1C3 inhibitors, anti-inflammatory agents, analgesics and active pesticides (figure 1). The introduction of fluorine atoms into the molecule can effectively improve the physical, chemical and biological activities of the parent molecule. The structural unit of the monofluoroolefin is a biological isostere of an amide bond, but synthesis and application research of the monofluoroolefin modified dihydropyran [2,3-c ] pyrazole derivative are not reported yet. Therefore, from the simple raw materials, development of a high-efficiency synthesis method of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and research on insecticidal activity of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative on plutella xylostella still remain a problem to be solved.
Disclosure of Invention
To solve the drawbacks and deficiencies of the prior art, a primary object of the present invention is to provide a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative.
The second object of the present invention is to provide a method for synthesizing the above 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative.
A third object of the present invention is to provide the use of the above 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative.
The first object of the invention is achieved by the following technical scheme:
a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative having the structural formula:
wherein R is 1 Is one of phenyl, 2-naphthyl, p-methylphenyl, m-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, p-alkynylphenyl, p-trifluoromethylphenyl, p-acetamidophenyl, p-fluorophenyl, m-fluorophenyl, o-fluorophenyl, p-chlorophenyl, m-chlorophenyl, 3, 5-dichlorophenyl or 3-benzothienyl;
R 2 is one of phenyl, 2-naphthyl, p-methylphenyl, m-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, p-trifluoromethylphenyl, p-cyanophenyl, p-fluorophenyl, m-fluorophenyl, o-fluorophenyl, p-chlorophenyl, o-chlorophenyl or methyl;
R 3 methyl, ethyl, benzyl.
The second object of the invention is achieved by the following technical scheme:
a method for synthesizing 6-fluoro-dihydropyran [2,3-c ] pyrazole derivatives comprises the following specific steps:
mixing trifluoromethyl olefin, pyrazolone, alkali or alkali salt with an organic solvent, then reacting, removing the solvent by decompression rotary evaporation, and separating and purifying by column chromatography to obtain a target product 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative;
the reaction equation involved is as follows:
preferably, the base is at least one of lithium hydroxide, potassium carbonate, cesium carbonate, lithium tert-butoxide, and sodium tert-butoxide.
Preferably, the organic solvent is one of dimethyl sulfoxide or N, N-dimethylformamide.
Preferably, the molar ratio of the pyrazolone to the trifluoromethyl olefin is 1:1.5-2.
Preferably, the molar ratio of the alkali or alkali salt to pyrazolone is 2.5-4: 1.
preferably, the reaction temperature is 25-100 ℃ and the reaction time is 12-24 h.
Preferably, the extract is ethyl acetate and water.
Preferably, the column chromatography purification refers to the column chromatography purification of eluent after petroleum ether and ethyl acetate are mixed according to the volume ratio of 2-10:1.
The third object of the present invention is achieved by the following technical scheme:
the application of 6-fluoro-dihydropyran [2,3-c ] pyrazole derivatives in chemical control of plutella xylostella.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The synthesis method is efficient and has good selectivity; the raw materials are cheap and easy to obtain; no catalyst is required; no metal is required; the reaction has good adaptability to functional groups, wide adaptability to substrates and high product yield;
(2) The synthesis method can be amplified to gram-grade or larger-scale production, is simple and safe to operate, has mild reaction conditions, and has good industrial application prospect;
(3) The 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative of the invention has good insecticidal activity on plutella xylostella and has wide application in the fields of pesticides, medicines and materials.
Drawings
FIG. 1 is a structural formula of a prior art pharmaceutically active compound containing a dihydropyran [2,3-c ] pyrazole structural unit;
FIG. 2 is a hydrogen spectrum of the products obtained in examples 1 to 7;
FIG. 3 is a graph of the carbon spectra of the products obtained in examples 1 to 7;
FIG. 4 shows fluorine spectra of the products obtained in examples 1 to 7.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
The same 6-fluoro-dihydropyran [2,3-c ] pyrazole derivatives were prepared in examples 1 to 7 below. The structural formula of the product is as follows:
the hydrogen spectrum, the carbon spectrum and the fluorine spectrum of the obtained product are respectively shown in fig. 2,3 and 4; the structural characterization data are shown below:
yellow solid,mp:89-90℃；
1 H NMR(500MHz,CDCl 3 )δ7.63(dd,J＝8.5,1Hz,2H),7.30-7.38(m,6H), 7.17-7.23(m,2H),3.55(d,J＝5.5Hz,2H),2.20(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ152.3(d, 1 J F-C ＝259.6Hz),146.1,144.8(d, 3 J F-C ＝7.6Hz),137.8,134.4(d, 4 J F-C ＝3.8Hz),129.2,128.5,127.4,127.3,126.3, 120.5,95.6,87.5(d, 2 J F-C ＝13.9Hz),22.8(d, 4 J F-C ＝3.8Hz),12.8；
19 F NMR(471MHz,CDCl 3 )δ-99.1(s,1F)；
IR(KBr):3052,2921,1694,1600,1513,1226,1132,1066cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 19 H 15 FN 2 O+H,307.1241；found, 307.1236
example 1
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The preparation method comprises the following steps: sequentially adding 0.2 mmol of 5-methyl-2-phenyl-2, 4-dihydropyrazol-3-one, 0.8 mmol of potassium carbonate and 0.3 mmol of alpha-trifluoromethyl styrene into a 25 ml test tube, stirring and reacting for 12 hours at 80 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, removing a solvent by reduced pressure rotary evaporation, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate in the used column chromatography eluent is 3:1; the yield of the product was 56%.
Example 2
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The preparation method comprises the following steps: sequentially adding 0.2 mmol of 5-methyl-2-phenyl-2, 4-dihydropyrazol-3-one, 0.6 mmol of lithium tert-butoxide and 0.3 mmol of alpha-trifluoromethyl styrene into a 25 ml test tube, stirring and reacting for 12 hours at 80 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, removing a solvent by reduced pressure rotary evaporation, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate in the used column chromatography eluent is 3:1; the product yield was 67%.
Example 3
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The preparation method comprises the following steps: sequentially adding 0.2 mmol of 5-methyl-2-phenyl-2, 4-dihydropyrazol-3-one, 0.5 mmol of potassium tert-butoxide, 0.4 mmol of alpha-trifluoromethyl styrene and 2 ml of N, N-dimethylformamide into a 25 ml test tube, stirring and reacting for 12 hours at 20 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, removing a solvent by reduced pressure rotary evaporation, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate of the used column chromatography eluent is 10:1; the yield of the product was 18%.
Example 4
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The preparation method comprises the following steps: adding 0.2 millimole of 5-methyl-2-phenyl-2, 4-dihydro-pyrazol-3-ketone, 0.5 millimole of cesium carbonate and 0.4 millimole of alpha-trifluoromethyl styrene into a 25 ml test tube in sequence, stirring and reacting for 24 hours at 100 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, removing a solvent by reduced pressure rotary evaporation, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate of the used column chromatography eluent is 2:1; the yield of the product was 58%.
Example 5
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The preparation method comprises the following steps: sequentially adding 0.2 mmol of 5-methyl-2-phenyl-2, 4-dihydropyrazol-3-one, 0.8 mmol of lithium tert-butoxide and 0.3 mmol of alpha-trifluoromethyl styrene into a 25 ml test tube, stirring and reacting for 12 hours at 80 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, removing a solvent by reduced pressure rotary evaporation, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate of the used column chromatography eluent is 5:1; the product yield was 67%.
Example 6
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The preparation method comprises the following steps: sequentially adding 0.2 mmol of 5-methyl-2-phenyl-2, 4-dihydropyrazol-3-one, 0.8 mmol of sodium tert-butoxide and 0.3 mmol of alpha-trifluoromethyl styrene into a 25 ml test tube, stirring and reacting for 12 hours at 80 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, removing a solvent by reduced pressure rotary evaporation, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate in the used column chromatography eluent is 3:1; the yield of the product was 41%.
Example 7
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The preparation method comprises the following steps: sequentially adding 6 mmol of 5-methyl-2-phenyl-2, 4-dihydropyrazol-3-one, 18 mmol of lithium tert-butoxide, 9 mmol of alpha-trifluoromethyl styrene and 60 ml of dimethyl sulfoxide into a 250 ml reaction bottle provided with a reflux condenser, stirring and reacting for 12 hours at 80 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, removing a solvent by reduced pressure rotary evaporation, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate of the used column chromatography eluent is 3:1; the yield of the product was 60%.
Example 8
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
yellow solid,mp:102-103℃；
1 H NMR(500MHz,CDCl 3 )δ7.54(s,1H),7.49(d,J＝10.0Hz,1H),7.44(d,J＝10.0Hz, 2H),7.39(t,J＝5.0Hz,2H),7.27-7.33(m,2H),7.08(d,J＝7.5Hz,1H),3.58(d,J＝4.0Hz,2H), 2.41(s,3H),2.27(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ152.3(d, 1 J F-C ＝260.8Hz),145.9,144.7(d, 3 J F-C ＝6.3Hz), 139.3,137.8,134.5(d, 4 J F-C ＝2.5Hz),129.0,128.5,127.4(d, 4 J F-C ＝5.0Hz),127.3,127.1,121.2, 117.6,95.5,87.5(d, 2 J F-C ＝13.9Hz),22.8(d, 4 J F-C ＝3.8Hz),21.5,12.8；
19 F NMR(471MHz,CDCl 3 )δ-99.1(s,1F)；
IR(KBr):2920,1693,1609,1511,1391,1224,1123cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 20 H 17 FN 2 O+H,321.1398；found,321.1393.
Example 9
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: adding 0.4 millimole of 5-methyl-2- (p-fluorophenyl) -2, 4-dihydro-pyrazol-3-ketone, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl styrene and 4 milliliters of dimethyl sulfoxide into a 25 milliliter test tube in sequence, stirring and reacting for 12 hours at 80 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, removing a solvent by decompression rotary evaporation, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate of the used column chromatography eluent is 5:1; the product yield was 68%.
The structural characterization data of the product obtained in this example are shown below:
yellow solid,mp:118-119℃；
1 H NMR(500MHz,CDCl 3 )δ7.66(dd,J＝9.0,5.0Hz,2H),7.37-7.44(m, 4H),7.29(t,J＝6.5Hz,1H),7.12(t,J＝8.5Hz,2H),3.57(s,2H),2.25(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ160.9(d, 1 J F-C ＝245.7Hz),152.2(d, 1 J F-C ＝ 259.6Hz),146.1,144.6(d, 3 J F-C ＝7.6Hz),134.3(d, 4 J F-C ＝3.8Hz),134.0(d, 4 J F-C ＝ 2.5Hz),128.5,127.4(d, 4 J F-C ＝3.8Hz),127.3,122.2,116.0(d, 2 J F-C ＝22.7Hz),95.5, 87.6(d, 2 J F-C ＝13.9Hz),22.8,12.8；
19 F NMR(471MHz,CDCl 3 )δ-99.2(s,1F),-115.8(s,1F)；IR(KBr):2923, 1692,1629,1519,1394,1224,1122cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 19 H 14 F 2 N 2 O+H,325.1147；found, 325.1143.
example 10
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: adding 0.4 millimole of 5-methyl-2- (2-chlorophenyl) -2, 4-dihydro-pyrazol-3-one, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl styrene and 4 milliliters of dimethyl sulfoxide into a 25 milliliter test tube in sequence, stirring and reacting for 12 hours at 80 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, decompressing and steaming to remove a solvent, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate of the used column chromatography eluent is 5:1; the yield of the product was 85%.
The structural characterization data of the product obtained in this example are shown below:
yellow oil；
1 H NMR(500MHz,CDCl 3 )δ7.42-7.44(m,1H),7.34-7.38(m,3H),7.27-7.31 (m,4H),7.18-7.21(m,1H),3.53(d,J＝5.0Hz,2H),2.19(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ152.3(d, 1 J F-C ＝260.8Hz),146.8,146.0(d, 3 J F-C ＝7.6Hz),134.6,134.5(d, 4 J F-C ＝2.5Hz),131.6,130.4,130.3,129.3,128.5,127.6, 127.4(d, 4 J F-C ＝3.8Hz),127.3,94.4,87.5(d, 2 J F-C ＝13.9Hz),23.1(d, 4 J F-C ＝3.8 Hz),12.9；
19 F NMR(471MHz,CDCl 3 )δ-99.5(s,1F)；IR(KBr):3057,2923,1699,1532, 1227,1116cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 19 H 14 ClFN 2 O+H,341.0852；found, 341.0849.
example 11
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: adding 0.4 millimole of 5-methyl-2- (4-cyanophenyl) -2, 4-dihydro-pyrazol-3-ketone, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl styrene and 4 milliliters of dimethyl sulfoxide into a 25 milliliter test tube in sequence, stirring and reacting for 12 hours at 80 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, decompressing and steaming to remove a solvent, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate of the used column chromatography eluent is 5:1; the yield of the product was 40%.
The structural characterization data of the product obtained in this example are shown below:
white solid,mp:188-189℃；
1 H NMR(500MHz,CDCl 3 )δ7.89(d,J＝8.5,2H),7.69(d,J＝8.5Hz,2H), 7.38–7.44(m,4H),7.31(t,J＝7.0Hz,1H),3.56(d,J＝5.5Hz,2H),2.26(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ151.9(d, 1 J F-C ＝262.1Hz),147.8,145.3(d, 3 J F-C ＝7.6Hz),141.2,133.9(d, 4 J F-C ＝2.5Hz),133.4,128.6,127.6,127.3(d, 4 J F-C ＝5.0 Hz),119.5 118.5,109.0,96.9,87.8(d, 2 J F-C ＝13.9Hz),22.7(d, 4 J F-C ＝3.8Hz),12.9；
19 F NMR(471MHz,CDCl 3 )δ-99.2(s,1F)；
IR(KBr):2921,2219,1695,1601,1513,1410,1220cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 20 H 14 FN 3 O+H,332.1194；found, 332.1190.
example 12
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: adding 0.4 mmol of 5-ethyl-2-phenyl-2, 4-dihydropyrazol-3-one, 1.2 mmol of lithium tert-butoxide, 0.6 mmol of alpha-trifluoromethyl styrene and 4 ml of dimethyl sulfoxide into a 25 ml test tube in sequence, stirring and reacting for 12 hours at 80 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, removing a solvent by reduced pressure rotary evaporation, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate in the used column chromatography eluent is 5:1; the yield of the product was 55%.
The structural characterization data of the product obtained in this example are shown below:
yellow solid,mp:89-90℃；
1 H NMR(500MHz,CDCl 3 )δ7.72(d,J＝8.0Hz,2H),7.37-7.45(m,6H), 7.24-7.30(m,2H),3.63(d,J＝5.5Hz,2H),2.66(q,J＝7.5Hz,2H),1.29(t,J＝7.5 Hz,3H)；
13 C NMR(126MHz,CDCl 3 )δ152.3(d, 1 J F-C ＝259.6Hz),151.3,144.8(d, 3 J F-C ＝6.3Hz),137.9,134.5(d, 4 J F-C ＝3.8Hz),129.2,128.5,127.4(d, 4 J F-C ＝5.0Hz), 127.3,126.2,120.6,94.8,87.5(d, 2 J F-C ＝13.9Hz),23.1(d, 4 J F-C ＝2.5Hz),21.4, 12.9；
19 F NMR(471MHz,CDCl 3 )δ-99.1(s,1F)；
IR(KBr):2924,1697,1600,1517,1450,1404,1345,1227,1132cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 20 H 17 FN 2 O+H,321.1398；found, 321.1394.
example 13
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: 0.4 millimole of 5-methyl-2- (2-chlorophenyl) -2, 4-dihydro-pyrazol-3-ketone, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl-2-naphthalene ethylene and 4 milliliters of dimethyl sulfoxide are sequentially added into a 25 milliliter test tube, stirring is stopped after the mixture is stirred and reacted for 12 hours at 80 ℃, ethyl acetate and water extraction reaction liquid are added, the solvent is removed by reduced pressure rotary evaporation, and then the target product is obtained through separation and purification by column chromatography, wherein the volume ratio of the petroleum ether to the ethyl acetate of the used column chromatography eluent is 5:1; the yield of the product was 91%.
The structural characterization data of the product obtained in this example are shown below:
yellow solid,mp:107-108℃；
1 H NMR(500MHz,CDCl 3 )δ7.80–7.83(m,4H),7.57(d,J＝9.0Hz,1H), 7.44–7.51(m,4H),7.33–7.35(m,2H),3.68(d,J＝4.5Hz,2H),2.29(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ152.6(d, 1 J F-C ＝260.8Hz),146.8,146.0(d, 1 J F-C ＝6.3Hz),134.6,133.3,132.5,132.0(d, 4 J F-C ＝2.5Hz),131.6,130.5,130.3,129.3, 128.0,128.0,127.6,126.4,126.2,126.2,125.5(d, 3 J F-C ＝6.3Hz),94.4,87.6(d, 2 J F-C ＝13.9Hz),23.1(d, 4 J F-C ＝3.8Hz),12.9；
19 F NMR(471MHz,CDCl 3 )δ-98.8(s,1F)；
IR(KBr):2922,1690,1529,1386,1236,1117cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 23 H 16 ClFN 2 O+H,391.1008；found, 391.1004.
example 14
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: 0.4 millimole of 5-methyl-2- (2-chlorophenyl) -2, 4-dihydro-pyrazol-3-ketone, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl p-tert-butylstyrene and 4 milliliters of dimethyl sulfoxide are sequentially added into a 25 milliliter test tube, stirring is stopped after the mixture is stirred and reacted for 12 hours at 80 ℃, ethyl acetate and water extraction reaction liquid are added, the solvent is removed by reduced pressure rotary evaporation, and then the target product is obtained through column chromatography separation and purification, wherein the volume ratio of the petroleum ether to the ethyl acetate of the used column chromatography eluent is 5:1; the yield of the product was 80%.
The structural characterization data of the product obtained in this example are shown below:
yellow oil；
1 H NMR(500MHz,CDCl 3 )δ7.51–7.53(m,1H),7.45–7.47(m,1H),7.36–7.42 (m,6H),3.61(d,J＝5.0Hz,2H),2.28(s,3H),1.33(s,9H)；
13 C NMR(126MHz,CDCl 3 )δ152.2(d, 1 J F-C ＝260.8Hz),150.3,146.8,146.1 (d, 3 J F-C ＝7.6Hz),134.6,131.6,131.4(d, 4 J F-C ＝3.8Hz),130.4,130.3,129.3,127.5 127.0(d, 4 J F-C ＝3.8Hz),125.4,94.4,87.3(d, 2 J F-C ＝13.9Hz),34.6,31.3,22.9(d, 4 J F-C ＝2.5Hz),12.9；
19 F NMR(471MHz,CDCl 3 )δ-99.7(s,1F)；
IR(KBr):3055,2960,1696,1575,1528,1395,1229,1104,1044cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 23 H 22 ClFN 2 O+H,397.1478；found, 397.1473.
example 15
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: 0.4 millimole of 5-methyl-2- (2-chlorophenyl) -2, 4-dihydro-pyrazol-3-ketone, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl-p-methylstyrene and 4 milliliters of dimethyl sulfoxide are sequentially added into a 25 milliliter test tube, stirring is stopped after the mixture is stirred and reacted for 12 hours at 80 ℃, ethyl acetate and water extraction reaction liquid are added, the solvent is removed by decompression rotary evaporation, and then the target product is obtained through column chromatography separation and purification, wherein the volume ratio of the petroleum ether to the ethyl acetate of the used column chromatography eluent is 5:1; the yield of the product was 80%.
The structural characterization data of the product obtained in this example are shown below:
yellow solid,mp:110-111℃；
1 H NMR(500MHz,CDCl 3 )δ7.49-7.51(m,1H),7.44-7.46(m,1H),7.34-7.36 (m,2H),7.25(dd,J＝17.8,2.0Hz,4H),3.59(d,J＝1.3Hz,2H),2.34(s,3H),2.27 (s,3H)；
13 C NMR(126MHz,CDCl 3 )δ152.1(d, 1 J F-C ＝260.8Hz),146.7,146.1(d, 1 J F-C ＝6.3Hz),137.1,134.7,131.6,131.5(d, 3 J F-C ＝2.5Hz),130.4,130.2,129.3,129.2, 127.5,127.2(d, 4 J F-C ＝5.0Hz),94.4,87.4(d, 3 J F-C ＝13.9Hz),23.1(d, 3 J F-C ＝3.8 Hz),21.2,12.9；
19 F NMR(471MHz,CDCl 3 )δ-99.8(s,1F)；
IR(KBr):3052,2921,1694,1600,1513,1226,1132,1066cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 20 H 16 ClFN 2 O+H,355.1008；found, 355.1004.
example 16
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: 0.4 millimole of 5-methyl-2- (2-chlorophenyl) -2, 4-dihydro-pyrazol-3-ketone, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl-p-methoxystyrene and 4 milliliters of dimethyl sulfoxide are sequentially added into a 25 milliliter test tube, stirring is stopped after the mixture is stirred and reacted for 12 hours at 80 ℃, ethyl acetate and water extraction reaction liquid are added, the solvent is removed by decompression rotary evaporation, and then the target product is obtained through column chromatography separation and purification, wherein the volume ratio of the petroleum ether to the ethyl acetate of the used column chromatography eluent is 5:1; the yield of the product was 65%.
The structural characterization data of the product obtained in this example are shown below:
yellow solid,mp:87-88℃；
1 H NMR(500MHz,CDCl 3 )δ7.51–7.53(m,1H),7.45–7.47(m,1H),7.36(d,J ＝7.5Hz,4H),6.92(d,J＝8.5Hz,2H),3.81(s,3H),3.58(d,J＝5.0Hz,2H),2.28(s, 3H)；
13 C NMR(126MHz,CDCl 3 )δ158.7,152.0(d, 1 J F-C ＝259.6Hz),146.72,146.1 (d, 3 J F-C ＝6.3Hz),134.7,131.6,130.4,130.2,129.3,128.5(d, 4 J F-C ＝5.0Hz),127.5, 126.7(d, 4 J F-C ＝3.8Hz),113.9,94.3,87.0(d, 2 J F-C ＝13.9Hz),55.3,23.2(d, 4 J F-C ＝ 2.5Hz),12.9；
19 F NMR(471MHz,CDCl 3 )δ-100.5(s,1F)；
IR(KBr):2840,1693,1605,1516,1228,1181,1097,1034cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 20 H 16 ClFN 2 O 2 +H,371.0957；found, 371.0954
example 17
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: 0.4 millimole of 5-methyl-2- (2-chlorophenyl) -2, 4-dihydro-pyrazol-3-ketone, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl-p-fluorostyrene and 4 milliliters of dimethyl sulfoxide are sequentially added into a 25 milliliter test tube, stirring is stopped after the mixture is stirred and reacted for 12 hours at 80 ℃, ethyl acetate and water extraction reaction liquid are added, the solvent is removed by decompression rotary evaporation, and then the target product is obtained through separation and purification by column chromatography, wherein the volume ratio of the petroleum ether to the ethyl acetate of the used column chromatography eluent is 5:1; the yield of the product was 77%.
yellow oil；
1 H NMR(500MHz,CDCl 3 )δ7.50-7.52(m,1H),7.44-7.46(m,1H),7.35–7.40 (m,4H),7.05(t,J＝8.5Hz,2H),3.57(d,J＝5.0Hz,2H),2.27(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ161.8(d, 1 J F-C ＝247.0Hz),152.3(d, 1 J F-C ＝ 259.6Hz),146.7,145.9(d, 3 J F-C ＝6.3Hz),134.6,131.6,130.4,130.3,129.3,129.1 (d, 3 J F-C ＝7.6Hz),129.1(d, 3 J F-C ＝5.0Hz),127.6,115.4(d, 2 J F-C ＝20.2Hz),94.2(d, 4 J F-C ＝1.3Hz),86.8(d, 2 J F-C ＝13.9Hz),23.2(d, 4 J F-C ＝3.8Hz),12.8；
19 F NMR(471MHz,CDCl 3 )δ-99.7(s,1F),-114.4(s,1F)；
IR(KBr):3065,2925,1702,1584,1511,1232,1126cm -1 ；
HRMS(ESI,m/z):[M+Na] + Calcd.for C 19 H 13 ClF 2 N 2 O+H,359.0757；found, 359.0753.
Example 18
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: sequentially adding 0.4 mmol of 5-methyl-2- (2-chlorophenyl) -2, 4-dihydropyrazol-3-one, 1.2 mmol of lithium tert-butoxide, 0.6 mmol of alpha-trifluoromethyl p-chlorostyrene and 4 ml of dimethyl sulfoxide into a 25 ml test tube, stirring and reacting for 12 hours at 80 ℃, stopping stirring, adding ethyl acetate and water extraction reaction liquid, removing solvent by reduced pressure rotary evaporation, and separating and purifying by column chromatography to obtain a target product, wherein the volume ratio of petroleum ether to ethyl acetate of the used column chromatography eluent is 5:1; the yield of the product was 86%.
yellow solid,mp:101-102℃；
1 H NMR(500MHz,CDCl 3 )δ7.50–7.52(m,1H),7.44–7.46(m,1H),7.34–7.37 (m,6H),3.58(d,J＝5.0Hz,2H),2.28(s,1H)；
13 C NMR(126MHz,CDCl 3 )δ152.4(d, 1 J F-C ＝260.8Hz),146.7,145.8(d, 1 J F-C ＝7.6Hz),134.6,133.0,132.9(d, 4 J F-C ＝2.5Hz),131.6,130.4,130.3,129.3,128.7, 128.6,127.6,94.1,86.7(d, 2 J F-C ＝13.9Hz),22.9(d, 4 J F-C ＝2.5Hz),12.9；
19 F NMR(471MHz,CDCl 3 )δ-98.4(s,1F)；
IR(KBr):2924,1692,1517,1232,1097cm -1 ；
HRMS(ESI,m/z):[M+Na] + Calcd.for C 19 H 13 Cl 2 FN 2 O+H,375.0462；found, 375.0459.
Example 19
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: 0.4 millimole of 5-methyl-2- (2-chlorophenyl) -2, 4-dihydro-pyrazol-3-ketone, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl-p-trifluoromethyl-styrene and 4 milliliters of dimethyl sulfoxide are sequentially added into a 25 milliliter test tube, stirring is stopped after the mixture is stirred and reacted for 12 hours at 80 ℃, ethyl acetate and water extraction reaction liquid are added, the solvent is removed by reduced pressure rotary evaporation, and then the target product is obtained through separation and purification by column chromatography, wherein the volume ratio of the petroleum ether to the ethyl acetate of the used column chromatography eluent is 5:1; the yield of the product was 92%.
yellow oil；
1 H NMR(500MHz,CDCl 3 )δ7.60(dd,J＝4.0,5.0Hz,4H),7.52–7.54(m, 1H),7.46–7.48(m,1H),7.38–7.40(m,2H),3.64(d,J＝5.0Hz,2H),2.29(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ153.0(d, 1 J F-C ＝263.3Hz),146.7,145.7(d, 3 J F-C ＝7.6Hz),138.3,134.5,131.6,130.4,130.4,129.3,127.6,127.6(d, 4 J F-C ＝1.3 Hz),125.4(q, 4 J F-C ＝3.8Hz),124.1(d, 1 J F-C ＝273.4Hz),94.1,86.8(d, 2 J F-C ＝12.6 Hz),22.8(d, 4 J F-C ＝3.8Hz),12.9；
19 F NMR(471MHz,CDCl 3 )δ-62.6(s,3F),-97.3(s,1F)；
IR(KBr):2923,1688,1572,1391,1324,1267,1119cm -1 ；
HRMS(ESI,m/z):[M+Na] + Calcd.for C 20 H 13 ClF 4 N 2 O+H,409.0725；found, 409.0722.
Example 20
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: 0.4 millimole of 5-methyl-2- (2-chlorphenyl) -2, 4-dihydro-pyrazol-3-ketone, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl-3-benzothiophene ethylene and 4 milliliters of dimethyl sulfoxide are sequentially added into a 25 milliliter test tube, stirring is stopped after the mixture is stirred and reacted for 12 hours at 80 ℃, ethyl acetate and water extraction reaction liquid are added, the solvent is removed by reduced pressure rotary evaporation, and then the target product is obtained through separation and purification by column chromatography, wherein the volume ratio of the petroleum ether to the ethyl acetate of the used column chromatography eluent is 5:1; the yield of the product was 37%.
yellow solid,mp:141-142℃；
1 H NMR(500MHz,CDCl 3 )δ7.88(d,J＝8.0Hz,1H),7.75(d,J＝7.5Hz,1H), 7.53–7.55(m,1H),7.48–7.50(m,1H),7.38–7.40(m,5H),3.63(d,J＝5.0Hz,2H), 2.26(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ152.2(d, 1 J F-C ＝259.6Hz),146.7,146.3(d, 3 J F-C ＝6.3Hz),140.0,137.5,134.6,131.7,130.5,130.4,130.0,129.3,127.6,124.9,124.6, 124.3,122.9,122.8(d, 4 J F-C ＝2.5Hz),94.4,82.6(d, 2 J F-C ＝18.9Hz),24.4(d, 4 J F-C ＝ 2.5Hz),12.9；
19 F NMR(471MHz,CDCl 3 )δ-95.6(s,1F)；
IR(KBr):3069,2924,1705,1529,1246,1102,1039cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 21 H 14 ClFN 2 OS+H,397.0572；found, 397.0569.
Example 21
This example provides a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative and a process for producing the same.
The structural formula of the 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative is as follows:
the preparation method comprises the following steps: 0.4 millimole of 5-methyl-2- (2-chlorophenyl) -2, 4-dihydro-pyrazol-3-ketone, 1.2 millimole of lithium tert-butoxide, 0.6 millimole of alpha-trifluoromethyl phenylethynyl ethylene and 4 milliliters of dimethyl sulfoxide are sequentially added into a 25 milliliter test tube, stirring is stopped after the mixture is stirred and reacted for 12 hours at 80 ℃, ethyl acetate and water extraction reaction liquid are added, the solvent is removed by decompression rotary evaporation, and then the target product is obtained through column chromatography separation and purification, wherein the volume ratio of petroleum ether to ethyl acetate of the used column chromatography eluent is 5:1; the product yield was 79%.
yellow solid,mp:80-81℃；
1 H NMR(500MHz,CDCl 3 )δ7.50–7.52(m,1H),7.43–7.46(m,3H),7.36–7.38 (m,2H),7.30–7.32(m,3H),3.48(d,J＝5.0Hz,2H),2.25(s,3H)；
13 C NMR(126MHz,CDCl 3 )δ157.8(d, 1 J F-C ＝264.6Hz),146.6,145.4(d, 4 J F-C ＝5.0Hz),134.4,131.6,131.4,130.4,130.4,129.2,128.3,127.6,123.0,93.9,93.7(d, 4 J F-C ＝5.0Hz),81.8(d, 4 J F-C ＝2.5Hz),73.1(d, 2 J F-C ＝16.4Hz),22.9,12.9；
19 F NMR(471MHz,CDCl 3 )δ-89.3(s,1F)；
IR(KBr):2924,1686,1620,1527,1389,1261,1121cm -1 ；
HRMS(APCI,m/z):[M+H] + Calcd.for C 21 H 14 ClFN 2 O+H,365.0852；found, 365.0850.
Example 22
This example provides insecticidal activity data for 6-fluoro-dihydropyran [2,3-c ] pyrazole derivatives against plutella xylostella.
The insecticidal activity test method is as follows:
the indoor virulence of the compound on 2-year larvae of plutella xylostella is determined by adopting a leaf dipping method. The test compound 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative (example 8, example 9, example 10, example 13, example 17, example 18, example 19, example 21) was dissolved in dimethyl sulfoxide, and diluted with dechlorinated water containing 0.1% tween 80 to a concentration of 0.1mg/mL to obtain a test sample. Fresh cabbage tender leaves (1.5 cm in diameter) are cut, soaked in different samples to be tested for 30 seconds, taken out, naturally dried, placed in culture dishes, each culture dish is used for stocking 30 larvae, sealed by a plastic box cover with gauze, and placed in a climatic chamber for breeding. The number of larvae dead per treatment was counted after 48 hours (larvae were unable to voluntarily move as dead). Each test sample was repeated 3 times and corrected mortality was calculated using dechlorinated water containing 0.1% tween 80 and 0.01% dimethyl sulfoxide as a control.
The obtained insecticidal activity data are shown in table 1:
table 16 insecticidal Activity of fluoro-dihydropyran [2,3-c ] pyrazole derivatives against Plutella xylostella
From the experimental results, the 6-fluoro-dihydropyran [2,3-c ] pyrazole is a brand new framework structure with high-efficiency insecticidal activity on plutella xylostella. Wherein the insecticidal activity of the compound obtained in example 19 against plutella xylostella was as high as 100%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. A 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative characterized by the following structural formula:
wherein R is 1 Is one of phenyl, 2-naphthyl, p-methylphenyl, m-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, p-alkynylphenyl, p-trifluoromethylphenyl, p-acetamidophenyl, p-fluorophenyl, m-fluorophenyl, o-fluorophenyl, p-chlorophenyl, m-chlorophenyl and 3, 5-dichlorophenyl;
R 2 is one of phenyl, 2-naphthyl, p-methylphenyl, m-methylphenyl, p-methoxyphenyl, m-methoxyphenyl, p-trifluoromethylphenyl, p-cyanophenyl, p-fluorophenyl, m-fluorophenyl, o-fluorophenyl, p-chlorophenyl and o-chlorophenyl;
R 3 methyl and ethyl.
2. A process for the synthesis of 6-fluoro-dihydropyran [2,3-c ] pyrazole derivatives according to claim 1, characterized by the following specific steps:
to trifluoromethyl olefins
Pyrazolone->
Mixing alkali and organic solvent, reacting, extracting, vacuum rotary evaporating to remove solvent, separating and purifying by column chromatography to obtain target product 6-fluoro-dihydropyrano [2,3-c]Pyrazole derivatives;
the reaction equation involved is as follows:
the organic solvent is one of dimethyl sulfoxide or N, N-dimethylformamide.
3. The method for synthesizing a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative according to claim 2, wherein the base is at least one of lithium hydroxide, potassium carbonate, cesium carbonate, lithium t-butoxide, and sodium t-butoxide.
4. The method for synthesizing a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative according to claim 2, wherein a molar ratio of the pyrazolone to the trifluoromethyl olefin is 1:1.5 to 2.
5. The method for synthesizing a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative according to claim 2, wherein a molar ratio of the base to the pyrazolone is 2.5 to 4:1.
6. the method for synthesizing a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative according to claim 2, wherein the reaction temperature is 25 to 100 ℃ and the reaction time is 12 to 24 hours.
7. The method for synthesizing a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative according to claim 2, wherein the extract is ethyl acetate and water.
8. The method for synthesizing a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative according to claim 2, wherein the separation and purification by column chromatography are performed by mixing petroleum ether and ethyl acetate in a volume ratio of 2-10:1 and then purifying by column chromatography of an eluent.
9. Use of a 6-fluoro-dihydropyran [2,3-c ] pyrazole derivative according to claim 1 for the chemical control of plutella xylostella.
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