Nootkatone thioether derivative containing 1,3,4-oxadiazole ring as well as preparation method and application of notkatone thioether derivative

A technology of nokadone sulfide and oxadiazole ring, applied in the preparation of natural product pesticides, nokadone derivatives, nokadone sulfide derivatives and their preparation fields, can solve the problem of insecticide The problems of narrow insecticidal effect, less research on the synthesis of nokadone, and general activity have achieved the effects of low cost, good insecticidal activity, and simple preparation process

A technology of nokadone sulfide and oxadiazole ring, applied in the preparation of natural product pesticides, nokadone derivatives, nokadone sulfide derivatives and their preparation fields, can solve the problem of insecticide The problems of narrow insecticidal effect, less research on the synthesis of nokadone, and general activity have achieved the effects of low cost, good insecticidal activity, and simple preparation process

CN113461630AActive Publication Date: 2021-10-01ZHENGZHOU UNIV
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  • Nootkatone thioether derivative containing 1,3,4-oxadiazole ring as well as preparation method and application of notkatone thioether derivative
  • Nootkatone thioether derivative containing 1,3,4-oxadiazole ring as well as preparation method and application of notkatone thioether derivative
  • Nootkatone thioether derivative containing 1,3,4-oxadiazole ring as well as preparation method and application of notkatone thioether derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Embodiment 1 contains the synthesis of noka ketone thioether derivatives of 1,3,4-oxadiazole ring

[0036] (1) Synthesis of 13-chloronokadone

[0037] Weigh nokadone (1mmol) in a 50mL round-bottomed flask, add 5mL of anhydrous dichloromethane to dissolve it, then add NCS (1.5mmol), heat and stir at 40°C, and detect with thin layer chromatography (TLC). After completion, the mixed solution was evaporated under reduced pressure, 20 mL of distilled water was added, extracted three times with ethyl acetate (30 mL), the organic layers were combined, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and separated by column chromatography to obtain 13-chloronokatone .

[0038] The physical and chemical properties of 13-chloronokadone:

[0039] 1), yellow liquid.

[0040] 2), the infrared spectrogram (IR) feature of 13-chloronokatone:

[0041] Using potassium bromide tablet method: 2937cm -1 Stretching vibration absorption for saturated hydrocarbons...

Embodiment 2

[0055] Example 2 Synthesis of Nokadone Sulfide Derivatives Containing 1,3,4-Oxadiazole Ring (Compound 2)

[0056] Using the method described in Example 1, compound 2 was synthesized. The structure and physicochemical properties of compound 2 are as follows:

[0057]

[0058] 1), yellow liquid.

[0059] 2), the infrared spectrogram (IR) feature of this compound:

[0060] Using potassium bromide tablet method: 2933cm -1 Stretching vibration absorption for saturated hydrocarbons, 1665cm -1 It is the stretching vibration of ketone carbonyl, 1473cm -1 It is saturated hydrocarbon deformation vibration, 1178, 1068cm -1 are the stretching vibrations of C-O and C-S.

[0061] 3), the nuclear magnetic resonance spectrum of this compound ( 1 HNMR, 400MHz) Features:

[0062] With deuterated chloroform as solvent, TMS as internal standard, wherein each peak belongs to: 1 H NMR (400MHz CDCl 3 )δ: 7.88(d, J=8.4Hz, 2H, -Ar), 7.29(d, J=8.0Hz, 2H, -Ar), 5.77(s, 1H, H-1), 5.21(s, 1H, ...

Embodiment 3

[0065] Example 3 Synthesis of Nokadone Sulfide Derivatives Containing 1,3,4-Oxadiazole Ring (Compound 3)

[0066] Using the method described in Example 1, compound 3 was synthesized. The structure and physicochemical properties of compound 3 are as follows:

[0067]

[0068] 1), white solid, melting point 92-93°C.

[0069] 2), the infrared spectrogram (IR) feature of this compound:

[0070] Using potassium bromide tablet method: 2934cm -1 Stretching vibration absorption for saturated hydrocarbons, 1675cm -1 It is the stretching vibration of ketone carbonyl, 1465cm -1 It is saturated hydrocarbon deformation vibration, 1193, 1071cm -1 are the stretching vibrations of C-O and C-S.

[0071] 3), the nuclear magnetic resonance spectrum of this compound ( 1 HNMR, 400MHz) Features:

[0072] With deuterated chloroform as solvent, TMS as internal standard, wherein each peak belongs to: 1 H NMR (400MHz CDCl 3 )δ:7.86-7.88(m,2H,-Ar),7.63-7.65(m,2H,-Ar),5.77(s,1H,H-1),5.22(s,1H,H...

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Abstract

The invention discloses a series of novel nookatone thioether derivatives each containing a 1,3,4-oxadiazole ring, and a preparation method and application of the novel nookatone thioether derivatives. According to the series of compounds, nootkatone serves as a raw material, chlorine atoms are introduced to the allyl position of nootkatone to synthesize 13-chloro nootkatone, the 13-chloro nootkatone and 5-aryl-2-sulfydryl-1,3,4-oxadiazole are subjected to a substitution reaction to generate a series of novel nootkatone derivatives, and the structural general formula of the nootkatone derivatives is shown in the formula (I). According to the nootkatone thioether derivatives, the 1,3,4-oxadiazole group has various biological activities, especially in the aspect of insecticidal activity, after the nootkatone thioether derivative is combined with nootkatone, the derivative has good insecticidal activity, and the nootkatone thioether derivative is expected to be used for preparing a novel natural product insecticide; and the compound is simple in preparation process, low in cost and relatively non-toxic to non-standard target biological fish and shrimp seeds. In the formula, R is selected from non-substituted or substituted phenyl or pyridyl, and the substituted phenyl is phenyl substituted by halogen, C1-C4 alkyl, C1-C4 alkoxy, nitro or cyano.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and relates to nokatone derivatives, in particular to a series of nokatone sulfide derivatives containing 1,3,4-oxadiazole rings with insecticidal activity, a preparation method thereof and the Application of a series of derivatives in the preparation of natural product insecticides. Background technique [0002] [0003] Nootkatone, also known as pomelo ketone, cedarone, the English name is (+)-Nootkatone, the system name is (4R,4aS,6R)-4,4a,5,6,7,8-hexahydro-4 ,4a-Dimethyl-6-(1-methylvinyl)-naphthen-2(3H)-one, a bicyclic sesquiterpene ketone belonging to the Yarcanane series. The pure product of nokadone is a white crystal with a pungent fragrance. Erdtman, H. and Hirose, Y. In 1962, nokatone was first isolated from the heartwood of the Alaskan cork Callitropsis nootkatensis. [0004] Studies in recent years have shown that nokadone has a wide range of biological activities, including ins...

Claims

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Application Information

Patent Timeline
01 Oct 2021
Publication
CN113461630A
IPC
C07D271/113; C07D413/04; A01N43/824; A01P7/00; A01P7/04
CPC
C07D271/113; C07D413/04; A01N43/82; C07B2200/07; Y02A50/30
Inventors
杨瑞阁; 程晚晴