CN110437191B - 13-amino xanthatin derivative and preparation method and application thereof - Google Patents

13-amino xanthatin derivative and preparation method and application thereof Download PDF

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CN110437191B
CN110437191B CN201910754845.2A CN201910754845A CN110437191B CN 110437191 B CN110437191 B CN 110437191B CN 201910754845 A CN201910754845 A CN 201910754845A CN 110437191 B CN110437191 B CN 110437191B
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xanthatin
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郅晓燕
李婷
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Abstract

The invention provides a 13-amino xanthatin derivative, which has a chemical general formula as follows:
Figure DDA0002168418710000011
the preparation method comprises the step of carrying out the ring-out Michael addition reaction on xanthatin and secondary amine to prepare the xanthatin. The invention synthesizes a series of novel 13-amino xanthatin derivatives which have stronger poisoning activity on diamondback moth; has certain inhibition effect on spore germination of tomato early blight bacteria, fusarium solani, tomato gray mold bacteria and cucumber colletotrichum. So it can be used for preparing high-effective low-toxic plant source pesticideInsect repellent and bacteriostatic agents.

Description

13-amino xanthatin derivative and preparation method and application thereof
Technical Field
The invention relates to the technical field of xanthatin derivatives, in particular to a 13-amino xanthatin derivative and a preparation method and application thereof.
Background
Xanthatin is a sesquiterpene lactone compound in Xanthium (Xanthium L) plants of Compositae (Compositae), and is a focus of research due to the biological activity of Xanthatin in many aspects such as anti-tumor, anti-inflammatory, insecticidal and antibacterial effects.
In the existing literature, a certain research is made on the aspects of tumor resistance, cancer resistance, inflammation resistance, ulcer resistance, enzyme activity inhibition, insect killing, bacteriostasis and the like of xanthatin and derivatives thereof: literature [ Geng Ya-di, Zhang Lei, Wang Guo-Yu, et al2/M cell cycle arrest,autophagy and apoptosis via ROS/XIAP signaling in human colon cancer cells[J].Natural product research,2018:1-5.]Xanthatin is found to inhibit and mediate human colon cancer cell apoptosis and autophagy, and the mechanism of xanthatin is researched. And the literature [ Shi Tian-Lu, Zhang Lei, Cheng Qi-Yao, et al.Xanthatin indices side by activating endogenous thermoplastic cells [ J].European journal of pharmacology,2019,843:1-11.]Studies find that xanthatin can cause morphological changes of 3 liver cancer cells and reduce cell survival rate. And the literature [ Shen Mei, Zhou Xue-Zhi, Ye Lei, et al, xanthatin inhibitors coronary inhibition by inhibiting the VEGFR2-mediated STAT3/PI3K/Akt signaling pathway [ J].International journal of molecular medicine,2018,42:769-778.]The mechanism of xanthatin in inhibiting corneal neovascularization and inflammatory protective effects in an alkali burn model is reported. Therefore, xanthatin can be used for developing a novel medicine for treating corneal alkali burn. Literature [ Hiromasa Yokoe, Kentaro Noboru, Yuki Manabe, et al, Artificial selective synthesis of 8-epi-xanthatin and biological evaluation of xanthanolides and them derivatives [ J].Chemical&Pharmaceutical Bulletin,2012,60:1340-1342.]The xanthatin is proved to inhibit the growth of drosophila larvae. Literature [ Monsanto, Shenhumin, Xanthium sibiricum extract structure modification and its insecticidal activity determination [ J]University of Gansu agriculture, 2015,50:102-]The study on the structural modification of xanthatin shows that the modification of the structure of xanthatin can improve the insecticidal activity of the xanthatin on tetranychus urticae koch and armyworm. Literature [ E.Ginesta-Peris, F.J.Garcia-Breijo, E.Primo-Yufera.Antichronobiological activity of xanthophyll from Xanthium spinosumsum L.[J]Letters in Applied Microbiology.1994,18,206-208.]After the antibacterial activity of xanthatin is researched, the xanthatin is found to have an inhibiting effect on bacillus and staphylococcus and have a good control effect on anthrax. Literature [ Dipanwita Saha, Ramasishku, S.Ghosh, et al.control of folear diseases of tea with Xanthium strumarium leaf extract [ J].Industrial Crops and Products,2012,37:376-382.]The xanthatin is found to have an inhibiting effect on both brown spot and gray spot of tea trees.
In view of the above, studies on antitumor, anti-inflammatory, antiulcer, insecticidal and antibacterial aspects of xanthatin and derivatives thereof are currently carried out, but no reports are found on the activity studies of xanthatin and derivatives thereof on diamond back moth poisoning and inhibition of spore germination of various plant pathogenic fungi.
Disclosure of Invention
The invention aims to provide a series of novel ring-out Michael addition type 13-amino xanthatin derivatives and a preparation method of the derivatives. According to the test, the 13-amino xanthatin derivative has high-efficiency and low-toxicity insecticidal and bacteriostatic activity, and can be used for preparing botanical insecticides and bacteriostatic agents.
In order to realize the task, the invention is realized by the following technical measures:
the 13-amino xanthatin derivative has a chemical general formula as follows:
Figure BDA0002168418690000021
r in the chemical formula is respectively:
Figure BDA0002168418690000022
the preparation method of the xanthatin derivative comprises the step of carrying out an exocyclic Michael addition reaction on xanthatin serving as a raw material and secondary amine to obtain the series of 13-amino xanthatin derivatives.
The preparation method specifically comprises the following steps:
dissolving a certain amount of xanthatin and corresponding secondary amine with methanol, stirring at room temperature or under oil bath for reaction, tracking and detecting by TLC, concentrating the reaction solution under reduced pressure after the reaction is finished, and performing chromatographic separation on a silica gel thin plate to obtain the required target product.
The invention synthesizes a series of novel 13-amino xanthatin derivatives which have stronger poisoning activity on diamondback moth; has certain inhibition effect on spore germination of tomato early blight bacteria, fusarium solani, tomato gray mold bacteria and cucumber colletotrichum. Therefore, the preparation method can be used for preparing high-efficiency and low-toxicity botanical pesticide and bacteriostatic agent.
Drawings
FIG. 1 is a NMR hydrogen spectrum of Compound 9;
FIG. 2 is a NMR hydrogen spectrum of Compound 14;
FIG. 3 is a NMR hydrogen spectrum of Compound 16.
Detailed Description
The invention is explained in further detail below by means of the figures and examples given by the inventors.
Example 1:
the following synthetic routes for compounds 1-20 are provided:
dissolving a certain amount of xanthatin and secondary amine by using methanol, then stirring and reacting at room temperature or under an oil bath, tracking and detecting by TLC, after the reaction is finished, concentrating the reaction solution under reduced pressure, and preparing silica gel for chromatographic separation to obtain the required target product.
The numbers of the compounds 1 to 20 correspond one-to-one to the numbers (1) to (20) of R in the chemical general formula, respectively.
Figure BDA0002168418690000041
The physicochemical properties of compound 1 are as follows:
1) a light yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.07(d,J＝16.0Hz,1H,2-H),6.26(d,J＝9.0Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.29-4.34(m,1H,8-H),3.02-3.07(m,1H,9-H),2.92-2.97(m,1H,10-H),2.74(d,J＝12.5Hz,1H,13-H),2.56-2.60(m,1H,13-H),2.49-2.54(m,1H,7-H),2.33-2.35(m,1H,6-H),2.29(s,3H,15-H),2.24(s,6H,-N(CH 3)2),2.15-2.20(m,1H,6-H),1.87-1.94(m,1H,11-H),1.71-1.76(m,1H,9-H),1.17(d,J＝7.0Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.55,176.98,148.65,144.45,139.64,124.44,81.30,58.74,48.89,45.88,45.08,36.27,29.02,28.71,27.80,18.58.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C17H26NO3([M+H]+)292.1913,found 292.1917。
The physicochemical properties of compound 2 are as follows:
1) white solid, melting point 50.7-51.4 deg.C;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.26(d,J＝8.5Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.28-4.32(m,1H,8-H),3.02-3.07(m,2H),2.91(d,J＝13.0Hz,1H,13-H),2.62-2.67(m,1H),2.56-2.59(m,2H),2.42-2.49(m,3H),2.32-2.35(m,1H,6-H),2.29(s,3H,15-H),2.12-2.17(m,1H,6-H),1.84-1.91(m,1H,11-H),1.70-1.75(m,1H,9-H),1.17(d,J＝6.5Hz,3H,14-H),1.01(t,J＝6.0Hz,6H,-N(CH2C 3H)2)；13C NMR(125MHz,CDCl3)δ:198.57,177.30,148.72,144.48,139.85,124.42,81.32,52.99,49.25,47.13,45.36,36.31,29.01,28.94,27.74,18.56,11.72。
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C19H30NO3([M+H]+)320.2226,found 320.2225。
The physicochemical properties of compound 3 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.25(d,J＝8.5Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.28-4.32(m,1H,8-H),3.00-3.05(m,2H),2.91-2.94(m,1H,13-H),2.67-2.71(m,1H,13-H),2.49(brs,1H,7-H),2.32-2.34(m,2H),2.29(s,3H,15-H),2.23(brs,3H),2.12-2.18(m,1H,6-H),1.84-1.91(m,1H,11-H),1.75-1.78(m,3H),1.71-1.72(m,2H),1.61-1.63(m,1H),1.18-1.25(m,4H),1.16(d,J＝6.5Hz,3H,14-H),1.05-1.10(m,1H)；13C NMR(125MHz,CDCl3)δ:198.59,177.44,148.77,144.46,139.98,124.38,81.32,63.71,53.22,49.06,45.20,37.97,36.32,29.01,28.91,28.14,27.75,26.29,26.05,25.99,18.58。
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C22H34NO3([M+H]+)360.2539,found 360.2534。
The physicochemical properties of compound 4 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.27(dd,J＝8.5,3.5Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.29-4.34(m,1H,8-H),3.01-3.07(m,1H,9-H),2.91-2.96(m,1H,10-H),2.87(brs,2H),2.53-2.56(m,5H),2.32-2.35(m,1H,6-H),2.29(s,3H,15-H),2.16-2.21(m,1H,6-H),1.91-1.98(m,1H,11-H),1.71-1.78(m,5H),1.17(d,J＝5.5Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.59,176.99,148.73,144.39,139.79,124.42,81.34,54.72,54.47,48.62,45.99,36.28,29.70,29.00,28.69,27.78,23.61,18.59.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C19H28NO3([M+H]+)318.2069,found 318.2072。
The physicochemical properties of compound 5 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.27(d,J＝9.0Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.27-4.32(m,1H,8-H),3.12-3.17(m,1H,10-H),3.01-3.06(m,1H,9-H),2.86-2.91(m,2H),2.66(d,J＝13.0Hz,1H,13-H),2.56-2.60(m,1H),2.32-2.35(m,1H,6-H),2.29(s,3H,15-H),2.22-2.26(m,1H),2.12-2.17(m,1H,6-H),1.98-2.04(m,1H),1.77-1.84(m,1H,11-H),1.70-1.75(m,1H,9-H),1.58-1.67(m,3H),1.41-1.49(m,1H),1.25-1.32(m,2H),1.16(d,J＝6.0Hz,3H,14-H),1.04(d,J＝4.0Hz,3H)；13C NMR(125MHz,CDCl3)δ:198.59,177.47,148.78,144.45,140.02,124.42,81.32,56.18,53.88,52.17,50.24,44.15,36.30,34.74,28.98,27.70,25.95,23.73,19.41,18.56.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C21H32NO3([M+H]+)346.2382,found 346.2388。
The physicochemical properties of compound 6 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.26(d,J＝8.0Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.28-4.32(m,1H,8-H),2.98-3.03(m,2H),2.75-2.79(m,2H),2.67(brs,1H),2.56(brs,2H),2.32-2.34(m,1H,6-H),2.29(s,3H,15-H),2.13-2.18(m,1H,6-H),2.02-2.05(m,1H),1.86-1.92(m,2H),1.60-1.75(m,5H),1.47-1.54(m,1H),1.16(d,J＝6.0Hz,3H,14-H),0.86(d,J＝6.0Hz,3H)；13C NMR(125MHz,CDCl3)δ:198.56,177.26,148.73,144.41,139.90,124.41,81.32,55.47,53.22,49.35,49.23,44.54,44.45,36.30,32.72,29.00,28.80,27.75,19.67,19.56,18.57.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C21H32NO3([M+H]+)346.2382,found 346.2380。
The physicochemical properties of compound 7 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.27(d,J＝9.0Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.28-4.32(m,1H,8-H),2.97-3.02(m,2H,9-H and 10-H),2.73-2.82(m,3H),2.57(d,J＝8.0Hz,2H),2.32-2.35(m,1H,6-H),2.29(s,3H,15-H),2.09-2.18(m,2H),1.85-1.95(m,2H),1.70-1.75(m,1H,9-H),1.58-1.62(m,2H),1.35(brs,1H),1.21-1.25(m,2H),1.16(d,J＝5.5Hz,3H,14-H),0.86(d,J＝4.0Hz,3H)；13C NMR(125MHz,CDCl3)δ:198.56,177.27,148.75,144.40,139.88,124.43,81.32,58.01,55.58,53.09,49.21,44.58,36.30,34.45,34.13,30.61,28.99,28.79,27.72,21.83,18.57.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C21H32NO3([M+H]+)346.2382,found 346.2388。
The physicochemical properties of compound 8 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.26(d,J＝9.0Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.28-4.32(m,1H,8-H),2.97-3.02(m,2H,9-H and 10-H),2.76-2.79(m,2H),2.69(d,J＝7.0Hz,1H),2.53-2.57(m,2H),2.32-2.35(m,1H,6-H),2.29(s,3H,15-H),2.13-2.19(m,1H,6-H),1.85-1.90(m,1H,11-H),1.61-1.75(m,5H),1.42-1.46(m,1H),1.16(d,J＝6.5Hz,3H,14-H),0.86(d,J＝7.0Hz,6H),0.49-0.56(m,1H)；13C NMR(125MHz,CDCl3)δ:198.55,177.23,148.72,144.42,139.90,124.40,81.31,63.28,60.61,58.02,49.38,44.50,42.00,36.30,31.28,30.99,29.00,28.81,27.78,19.64,19.48,18.57.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C22H34NO3([M+H]+)360.2539,found 360.2541。
The physicochemical properties of compound 9 are as follows:
1) amorphous powder, melting point 41.9-43.4 deg.C;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.29-7.32(m,2H,Ar-H),7.19-7.23(m,3H,Ar-H),7.10(d,J＝16.0Hz,1H,2-H),6.30(d,J＝9.0Hz,1H,5-H),6.20(d,J＝16.0Hz,1H,3-H),4.30-4.34(m,1H,8-H),2.99-3.04(m,3H),2.92(d,J＝10.0Hz,1H),2.87(d,J＝12.5Hz,1H,13-H),2.58-2.66(m,2H),2.49-2.53(m,1H),2.34-2.36(m,1H,6-H),2.30(s,3H,15-H),2.16-2.24(m,2H),2.07-2.11(m,1H,6-H),1.90-1.96(m,1H,11-H),1.82-1.86(m,2H),1.68-1.77(m,3H),1.17(d,J＝6.0Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.55,177.19,148.69,146.14,144.48,139.69,128.42,126.79,126.20,124.50,81.35,57.91,56.00,53.49,49.12,44.71,42.31,36.31,33.51,33.31,29.01,28.82,27.74,18.59.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C26H34NO3([M+H]+)408.2539,found 408.2541。
FIG. 1 is a NMR spectrum of Compound 9.
The physicochemical properties of compound 10 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.26-7.29(m,2H,Ar-H),7.17-7.20(m,1H,Ar-H),7.14(d,J＝6.5Hz,2H,Ar-H),7.09(d,J＝16.0Hz,1H,2-H),6.27(d,J＝8.5Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.27-4.31(m,1H,8-H),3.02-3.05(m,1H,9-H),2.95-3.01(m,1H,10-H),2.81-2.84(m,1H),2.74-2.78(m,2H),2.49-2.56(m,4H),2.31-2.34(m,1H,6-H),2.29(s,3H,15-H),2.12-2.17(m,1H,6-H),2.03-2.07(m,1H),1.85-1.91(m,2H),1.70-1.75(m,1H,9-H),1.62(d,J＝11.5Hz,2H),1.52(brs,1H),1.21-1.28(m,2H),1.16(d,J＝6.5Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.54,177.19,148.71,144.43,140.40,139.81,129.07,128.19,125.83,124.43,81.31,57.95,55.53,53.05,49.16,44.63,43.14,37.76,36.30,32.41,32.03,29.00,28.80,27.76,18.58。
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C27H36NO3([M+H]+)422.2695,found 422.2695。
The physicochemical properties of compound 11 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.26(d,J＝9.0Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.28-4.33(m,1H,8-H),3.68(s,3H,-OC 3H),3.02-3.07(m,1H,9-H),2.93-2.98(m,1H,10-H),2.87(d,J＝9.5Hz,1H),2.76-2.81(m,2H),2.54-2.62(m,2H),2.32-2.35(m,1H,6-H),2.30(s,4H,15-H),2.14-2.19(m,2H),1.99-2.04(m,1H),1.86-1.91(m,3H),1.68-1.75(m,3H),1.16(d,J＝6.5Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.58,177.04,175.52,148.68,144.49,139.57,124.56,81.36,57.72,54.47,52.32,51.69,49.06,44.65,40.83,36.29,28.99,28.76,28.45,28.13,27.69,18.57.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C22H32NO5([M+H]+)390.2280,found 390.2281。
The physicochemical properties of compound 12 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.07(d,J＝16.0Hz,1H,2-H),6.25(d,J＝8.5Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.28-4.32(m,1H,8-H),4.14(q,J＝6.0Hz,2H,-C 2HCH3),3.02-3.07(m,1H,9-H),2.88-2.96(m,2H),2.85(d,J＝11.0Hz,1H,13-H),2.56-2.60(m,3H),2.40-2.44(m,1H),2.32-2.35(m,1H,6-H),2.29(s,3H,15-H),2.07-2.22(m,3H),1.87-1.93(m,2H),1.71-1.75(m,2H),1.53(brs,2H),1.26(t,J＝6.0Hz,3H,-CH2C 3H),1.16(d,J＝6.5Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.54,176.99,173.92,148.63,144.49,139.65,124.46,81.33,60.39,57.78,54.71,53.37,49.38,48.98,44.62,36.28,29.00,28.78,27.79,26.54,24.41,18.57,14.25.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C23H34NO5([M+H]+)404.2437,found 404.2443。
The physicochemical properties of compound 13 are as follows:
1) white solid, melting point 152.3-153.1 deg.C;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.27(dd,J＝9.0,3.5Hz,1H,5-H),6.20(d,J＝16.0Hz,1H,3-H),4.29-4.34(m,1H,8-H),3.66-3.72(m,4H,-C 2HOC 2H-),3.02-3.08(m,1H,9-H),2.92-2.98(m,1H,10-H),2.84(dd,J＝13.0,4.0Hz,1H,13-H),2.64(dd,J＝13.0,7.5Hz,1H,13-H),2.51-2.57(m,3H),2.42-2.44(m,2H),2.33-2.37(m,1H,6-H),2.29(s,3H,15-H),2.15-2.21(m,1H,6-H),1.89-1.97(m,1H,11-H),1.71-1.77(m,1H,9-H),1.17(d,J＝7.5Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.48,176.85,148.51,144.62,139.26,124.57,81.34,66.89,57.78,54.08,48.85,44.52,36.29,29.03,28.74,27.82,18.58.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C19H28NO4([M+H]+)334.2018,found 334.2014。
The physicochemical properties of compound 14 are as follows:
1) white solid, melting point 176.7-177.7 ℃;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.25(d,J＝9.0Hz,1H,5-H),6.20(d,J＝16.0Hz,1H,3-H),4.29-4.33(m,1H,8-H),3.02-3.08(m,1H,9-H),2.86-2.93(m,2H),2.76-2.81(m,2H),2.68-2.71(m,2H),2.58-2.65(m,5H),2.52-2.54(m,1H),2.33-2.35(m,1H,6-H),2.30(s,3H,15-H),2.14-2.20(m,1H,6-H),1.86-1.93(m,1H,11-H),1.70-1.75(m,1H,9-H),1.17(d,J＝6.5Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.51,176.88,148.50,144.63,139.21,124.57,81.32,57.91 55.52,48.71,44.89,36.27,28.99,28.76,27.88,27.81,18.56.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C19H27NO3SNa([M+Na]+)372.1609,found 372.1605。
FIG. 2 is a NMR spectrum of Compound 14.
The physicochemical properties of compound 15 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.25(d,J＝8.5Hz,1H,5-H),6.21(d,J＝16.0Hz,1H,3-H),4.31-4.35(m,1H,8-H),3.69-3.71(m,1H),3.45-3.50(m,3H),3.03-3.09(m,1H,9-H),2.87-2.92(m,1H,10-H),2.84(d,1H,J＝13.0Hz,13-H),2.65-2.67(m,1H),2.49-2.56(m,4H),2.34-2.37(m,2H),2.30(s,3H,15-H),2.17-2.22(m,1H,6-H),2.08(s,3H,(N)COC 3H),1.90-1.96(m,1H,11-H),1.71-1.76(m,1H,9-H),1.17(d,J＝5.5Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.47,176.71,168.96,148.39,144.69,138.97,124.59,81.35,56.96,53.78,53.22,48.63,46.15,44.90,41.29,36.24,29.00,28.68,27.84,21.30,18.55.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C21H31N2O4([M+H]+)375.2284,found 375.2291。
The physicochemical properties of compound 16 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.25(d,J＝8.5Hz,1H,5-H),6.20(d,J＝16.0Hz,1H,3-H),4.30-4.34(m,1H,8-H),4.15(q,J＝7.0Hz,2H,-OC 2HCH3),3.45(s,4H),3.03-3.07(m,1H,9-H),2.90-2.95(m,1H,10-H),2.84(d,J＝13.0Hz,1H,13-H),2.63-2.67(m,1H,13-H),2.48-2.54(m,3H),2.34-2.40(m,3H),2.30(s,3H,15-H),2.16-2.21(m,1H,6-H),1.89-1.95(m,1H,11-H),1.71-1.76(m,1H,9-H),1.27(t,J＝7.0Hz,3H,-OCH2C 3H),1.17(d,J＝6.5Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.52,176.78,155.46,148.48,144.62,139.16,124.57,81.34,61.41,57.32,53.32,48.83,44.72,43.54,36.24,28.97,28.71,27.80,18.55,14.66.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C22H33N2O5([M+H]+)405.2389,found 405.2387。
FIG. 3 is a NMR hydrogen spectrum of Compound 16.
The physicochemical properties of compound 17 are as follows:
1) amorphous powder, melting point 63.8-66.4 ℃;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.26-7.28(m,2H,Ar-H),7.07(d,J＝16.0Hz,1H,2-H),6.93(d,J＝7.5Hz,2H,Ar-H),6.85-6.87(m,1H,Ar-H),6.25(d,J＝9.0Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.31-4.35(m,1H,8-H),3.18(brs,4H),3.03-3.06(m,1H,9-H),2.97-3.02(m,1H,10-H),2.90(d,1H,J＝13.0Hz,13-H),2.67-2.71(m,3H),2.57-2.60(m,3H),2.34-2.36(m,1H,6-H),2.29(s,3H,15-H),2.16-2.21(m,1H,6-H),1.91-1.98(m,1H,11-H),1.72-1.76(m,1H,9-H),1.17(d,J＝6.5Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.59,176.97,151.21,148.62,144.58,139.46,129.15,124.57,119.87,116.08,81.40,57.51,53.61,49.13,49.06,44.64,36.31,29.01,28.81,27.80,18.61.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C25H33N2O3([M+H]+)409.2491,found 409.2493。
The physicochemical properties of compound 18 are as follows:
1) white solid, melting point 61.5-62.8 deg.C;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.13-7.17(m,1H,Ar-H),7.07(d,J＝16.0Hz,1H,2-H),6.68-6.74(m,3H,Ar-H),6.25(d,J＝8.5Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.31-4.35(m,1H,8-H),3.17(brs,4H),2.97-3.04(m,2H,9-H and10-H),2.90(d,J＝12.5Hz,1H,13-H),2.66-2.71(m,3H),2.56-2.61(m,3H),2.34-2.36(m,1H,6-H),2.31(s,3H,PhC 3H),2.29(s,3H,15-H),2.16-2.21(m,1H,6-H),1.91-1.97(m,1H,11-H),1.71-1.76(m,1H,9-H),1.17(d,J＝6.0Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.53,176.91,151.23,148.57,144.54,139.40,138.80,128.95,124.53,120.78,116.94,113.22,81.37,57.46,53.60,49.18,49.03,44.57,36.27,28.98,28.77,27.75,21.76,18.56.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C26H35N2O3([M+H]+)423.2648,found 423.2648。
The physicochemical properties of compound 19 are as follows:
1) white solid, melting point 64.4-65.7 deg.C;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.15-7.18(m,1H,Ar-H),7.07(d,J＝16.0Hz,1H,2-H),6.54(d,J＝7.5Hz,1H,Ar-H),6.45(s,1H,Ar-H),6.43(d,J＝7.5Hz,1H,Ar-H),6.25(d,J＝8.5Hz,1H,5-H),6.19(d,J＝16.0Hz,1H,3-H),4.30-4.35(m,1H,8-H),3.79(s,3H,-OC 3H),3.17(brs,4H),3.03-3.07(m,1H,9-H),2.96-3.01(m,1H,10-H),2.90(d,J＝13.0Hz,1H,13-H),2.65-2.71(m,3H),2.58(brs,3H),2.34-2.36(m,1H,6-H),2.29(s,3H,15-H),2.16-2.21(m,1H,6-H),1.93-1.97(m,1H,11-H),1.71-1.76(m,1H,9-H),1.17(d,J＝6.0Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.54,176.91,160.59,152.57,148.57,144.56,139.38,129.80,124.56,108.84,104.54,102.54,81.37,57.46,55.19,53.54,49.03,44.62,36.29,28.99,28.78,27.75,18.57.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C26H35N2O4([M+H]+)439.2597,found 439.2602。
The physicochemical properties of compound 20 are as follows:
1) a yellow liquid;
2) nuclear magnetic resonance spectrum characteristics of the compound:
using deuterated chloroform as a solvent and TMS as an internal standard, wherein the attribution of each peak is as follows:1H NMR(500MHz,CDCl3)δ:7.08(d,J＝16.0Hz,1H,2-H),6.26(d,J＝8.5Hz,1H,5-H),6.20(d,J＝16.0Hz,1H,3-H),4.28-4.32(m,1H,8-H),3.53(t,J＝7.0Hz,2H,CH3OC 2HCH2-),3.35(s,3H,C 3HOCH2CH2-),3.02-3.07(m,1H,9-H),2.94-2.99(m,1H,10-H),2.85(d,J＝13.0Hz,1H,13-H),2.58-2.63(m,4H),2.48-2.54(m,8H),2.33-2.35(m,1H,6-H),2.29(s,3H,15-H),2.12-2.18(m,1H,6-H),1.87-1.93(m,1H,11-H),1.70-1.75(m,1H,9-H),1.17(d,J＝6.5Hz,3H,14-H)；13C NMR(125MHz,CDCl3)δ:198.54,176.99,148.63,144.51,139.57,124.47,81.31,70.19,58.91,57.85,57.47,53.53,49.05,44.52,36.29,29.00,28.77,27.79,18.58.
3) high resolution mass spectral characteristics of the compound:
electrospray ionization is adopted: calcd for C22H35N2O4([M+H]+)391.2597,found 391.2599。
Example 2:
and (3) insecticidal activity test:
1. test insects: terminal diamondback moth (Plutella xylostella) larvae at 2 years old.
2. Sample and reagent: 1-20 parts of xanthatin derivatives prepared in the embodiment and a positive control medicament toosendanin (98%); the solvent was acetone (analytical grade).
3. The bioassay method comprises the following steps:
a leaflet dish addition method is adopted: a layer of filter paper is laid on the bottom of a culture dish with the diameter of 9cm, and water is added for moisturizing. 20 robust 2-year-old terminal diamondback moth larvae with consistent size are picked from each dish. Proper amounts of toosendanin, xanthatin and the compounds 1-20 prepared in the examples are respectively weighed and added with acetone to prepare liquid medicine with the concentration of 20 mg/ml. Cutting Chinese cabbage into small discs of 1 × 1cm, taking 2 μ L of liquid medicine to be tested with a micro dropper, uniformly coating on the surface of the leaf, air drying, and feeding for testing insects. Acetone was used as a blank control. Repeat 3 times for each 20 treatments. Feeding the seeds under the conditions that the temperature is 25 +/-1 ℃, the humidity is 65-80% and the illumination time is 12h/12 h. After 48h, the normal leaf disks are fed until pupation occurs. The number of live mouths, expression symptoms and the like of the test insects are recorded regularly, and the mortality rates of the test insects after being fed to normal leaf disks for 24h, 48h and 72h are calculated according to the following formula-1 and formula-2. The results are shown in Table 1. Mortality (%) - (number of test insect deaths)/(total number of test insects) × 100 (formula-1)
Corrected mortality (%) - (treatment group average mortality-control group average mortality)/(1-control group average mortality) × 100 (formula-2)
TABLE 1 Gastrotoxicity Activity of Xanthintin derivatives 1-20 of the invention against Plutella xylostella larvae
Figure BDA0002168418690000131
And (4) conclusion:
the results show that the corrected mortality rate of the compounds 6, 8, 13 and 16 prepared by the method is higher than or close to that of the commercial pesticide toosendanin 24 hours after the feeding of the plutella xylostella larvae is finished, and the compounds show stronger stomach toxicity activity; at 72h, the poisoning activity of the compounds 6-8, 13 and 16 on diamond back moths is higher than that of the positive control medicament toosendanin. Therefore, the xanthatin derivative is expected to be used for preparing efficient and low-toxicity botanical insecticides.
Example 3:
and (3) antibacterial activity test:
1. pathogenic bacteria to be tested: tomato early blight (Alternaria solani), Fusarium solani (Fusarium solani), Botrytis cinerea (Botrytis cinerea) and cucumber Colletotrichum orbiculosum (Colletotrichum orbicular) provided by the plant pathology laboratory of Shanxi university of agriculture.
2. Sample and reagent:
the samples were: raw materials of xanthatin, 1-20 parts of xanthatin derivatives prepared in the embodiment, and positive control medicaments of difenoconazole (98%) and hymexazol (99%); the solvent is DMSO (chromatographic purity), and the emulsifier is Tween-80 (superior grade purity).
3. The bioassay method comprises the following steps:
adopting a method for inhibiting spore germination:
(1) preparation of spore suspension: adding sterile water on a strain plate cultured to produce spores, lightly rubbing the surface of a culture medium by using an inoculating loop, and filtering hyphae and the culture medium by using double-layer gauze. Sterile water is added to the spore suspension and the mixture is stirred. Preferably 30-40 spores per field of view, for 100-fold microscopic observation. The prepared spore suspension was added to the glucose solution at a ratio of 0.5% (v/v).
(2) Preparing 1mg/ml medicament mother liquor: accurately weighing a sample to be detected by a ten-thousandth electronic balance, dissolving the sample by DMSO, and diluting the dissolved sample by 0.1% Tween-80 aqueous solution to the required concentration. According to the activity of the medicament, 5-7 series of mass concentrations are set, and the final content of the organic solvent is not more than 2%.
(3) Medicament treatment: and (3) sequentially sucking the liquid medicine from low concentration to high concentration by using a pipette, adding the liquid medicine into the test tube, sucking the prepared spore suspension with the same volume, and uniformly mixing the liquid medicine and the spore suspension in equal quantity. The mixture was pipetted 30. mu.L onto a glass slide and placed in a petri dish with shallow water and incubated in an incubator at the appropriate temperature, 3 replicates per treatment and a blank with no agent.
(4) And (4) observation and statistics: when the germination rate of the blank control spores reaches over 90 percent, the germination condition of each treated spore is checked. Randomly observing more than 3 visual fields in each treatment, investigating the total number of spores to be not less than 300, and recording the germination number and the total number of spores respectively. Germination is considered to be a germination in which the spore germination length is greater than the short radius of the spore. Calculating spore germination rate of each treatment group according to formula-3, calculating corrected spore germination inhibition rate of each treatment group according to formula-4, and calculating IC of each treatment group by using Excel software50. The results are shown in Table 2.
Spore germination rate (%) ═ (number of germinated spores)/(total number of statistical spores) × 100 (formula-3);
corrected spore germination inhibition (%) was ═ (average spore germination rate of control group-average spore germination rate of treatment group)/(average spore germination rate of control group) × 100 (formula-4).
TABLE 2 Xanthin compounds 1-20 of the present invention have inhibitory effects on spore germination of test strains
Figure BDA0002168418690000141
Figure BDA0002168418690000151
And (4) conclusion:
the results show that the bacteriostatic activity of the compounds 1, 2, 7 and 8 prepared by the invention on early blight of tomato, fusarium solani and botrytis cinerea is higher than that of the commercialized antibacterial agent difenoconazole, and most of the bacteriostatic activity is higher than that of hymexazol. In addition, the spore germination inhibition rate of the compounds 1, 2 and 8 on the tomato early blight bacteria exceeds that of two control medicaments; the bacteriostatic activity of the compounds 1-8 and the compounds 11 and 12 on fusarium solani is higher than that of hymexazol and difenoconazole; the bacteriostatic activity of the compounds 2, 7, 8 and 12 on botrytis cinerea is higher than that of two positive control medicaments, especially the IC of the compound 12 on botrytis cinerea spores50The value even reaches 23.10 mug.mL-1Exhibit strong inhibitory action; the bacteriostatic activity of the compounds 3, 10 and 11 on cucumber colletotrichum is higher than that of hymexazol. Therefore, the 13-amino xanthatin derivative designed by the invention is expected to be used for preparing efficient and environment-friendly novel plant-source bacteriostatic agents.

Claims (5)

1.13-amino xanthatin derivatives, characterized by the chemical general formula:
Figure FDA0002168418680000011
r in the chemical formula is one of the following:
Figure FDA0002168418680000012
2. the process for the preparation of 13-amino xanthatin derivatives according to claim 1, wherein xanthatin is reacted with a secondary amine by exoMichael reaction to obtain the series of 13-amino xanthatin derivatives.
3. The process for preparing a 13-amino xanthatin derivative according to claim 2, comprising the steps of:
dissolving xanthatin and corresponding secondary amine with methanol, and stirring at room temperature or in oil bath for reaction;
and (3) tracking and detecting by TLC, after the reaction is finished, concentrating the reaction solution under reduced pressure, and performing chromatographic separation on a prepared silica gel thin plate to obtain the required target product.
4. A process for the preparation of a 13-amino xanthatin derivative according to claim 2 or 3, characterized in that the secondary amine is one of the following:
a. morpholines: morpholine, thiomorpholine;
b. piperidines: 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 3, 5-dimethylpiperidine, 4-phenylpiperidine, 4-benzylpiperidine, methyl 4-piperidinecarboxylate and ethyl 3-piperidinecarboxylate;
c. piperazines: n-acetylpiperazine, ethyl N-piperazinecarboxylate, 1-phenylpiperazine, 1- (3-methylphenyl) piperazine, 1- (3-methoxyphenyl) piperazine, 1- (2-methoxyethyl) piperazine;
d. and others: 40% dimethylamine aqueous solution, diethylamine, N-methylcyclohexylamine, and pyrrolidine.
5. The use of the 13-amino xanthatin derivative according to claim 1 for preparing a botanical pesticide or bacteriostatic agent.
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