CN110437191A - 13- amino Xanthatin analog derivative and its preparation method and application - Google Patents

13- amino Xanthatin analog derivative and its preparation method and application Download PDF

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CN110437191A
CN110437191A CN201910754845.2A CN201910754845A CN110437191A CN 110437191 A CN110437191 A CN 110437191A CN 201910754845 A CN201910754845 A CN 201910754845A CN 110437191 A CN110437191 A CN 110437191A
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xanthatin
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CN110437191B (en
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郅晓燕
李婷
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Shanxi Agricultural University
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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Abstract

The present invention provides a kind of 13- amino Xanthatin analog derivative, chemical general formula are as follows:Preparation method is that Xanthatin and secondary amine carry out the outer Michael addition reaction of ring and be made.The present invention has synthesized serial new 13- amino Xanthatin analog derivative, which has stronger cytotoxicity to diamondback moth；There is certain inhibiting effect to the spore germination of tomato early blight bacterium, Beancurd sheet reaping hook germ, botrytis cinerea and cucumber anthracnose.Therefore it can be used for preparing efficient, less toxic plant insecticide and bacteriostatic agent.

Description

13- amino Xanthatin analog derivative and its preparation method and application
Technical field
The present invention relates to Xanthatin analog derivative technical field more particularly to 13- amino Xanthatin analog derivative and its systems Preparation Method and application.
Background technique
Xanthatin (Xanthatin) is one of composite family (Compositae) Xanthium (Xanthium L.) plant times Sesquiterpene lactone compounds, it is anti-inflammatory because it is antitumor, desinsection and antibacterial etc. permitted various bioactivity and become research Focus.
To Xanthatin and its derivative in antitumor, anticancer in existing literature, anti-inflammatory, antiulcer inhibits enzyme activity, desinsection and It is antibacterial etc. to have done certain research: document [Geng Ya-di, Zhang Lei, Wang Guo-Yu, et al.Xanthatin mediates G2/M cell cycle arrest,autophagy and apoptosis via ROS/ XIAP signaling in human colon cancer cells[J].Natural product research,2018: 1-5.] discovery Xanthatin can inhibit and mediate mankind's Apoptosis of Colon Cancer Cells and autophagy, and be studied its mechanism.With And document [Shi Tian-Lu, Zhang Lei, Cheng Qi-Yao, et al.Xanthatin induces apoptosis by activating endoplasmic reticulum stress in hepatoma cells[J].European Journal of pharmacology, 2019,843:1-11.] study the form for finding that Xanthatin can cause 3 kinds of liver cancer cells It learns and changes and reduce cell survival rate.And document [Shen Mei, Zhou Xue-Zhi, Ye Lei, et al.Xanthatin inhibits corneal neovascularization by inhibiting the VEGFR2-mediated STAT3/ PI3K/Akt signaling pathway[J].International journal of molecular medicine, 2018,42:769-778.] report Xanthatin and inhibit corneal neovascularization and inflammation protective effect in model of alkali burned Mechanism.Therefore, Xanthatin can be used for developing the new drug of one kind to treat Corneal Alkali Burns.Document [Hiromasa Yokoe, Kentaro Noboru,Yuki Manabe,et al.Enantioselective synthesis of 8-epi- xanthatin and biological evaluation of xanthanolides and their derivatives [J] .Chemical&Pharmaceutical Bulletin, 2012,60:1340-1342.] confirm that Xanthatin can inhibit Drosophila larvae growth.Document [the structural modification and its insecticidal activity assay of Meng Xueying, Shen Huimin Siberian cocklebur extract Xanthatin [J] Gansu Agriculture University journal, 2015,50:102-112] research of Xanthatin structural modification is learnt, to Xanthatin structure Its insecticidal activity to Tetranychus urticae and mythimna separata can be improved in transformation.Document [E.Ginesta-Peris, F.J.Garcia- Breijo,E.Primo-Yufera.Antimicrobial activity of xanthatin from Xanthium Spinosum L. [J] Letters in Applied Microbiology.1994,18,206-208.] to the antibacterial of Xanthatin Activity finds that it is inhibited to bacillus and staphylococcus after being probed into, and has to anthrax-bacilus preferable anti- Control effect.Document [Dipanwita Saha, Ramashish Kumar, S.Ghosh, et al.Control of foliar diseases of tea with Xanthium strumarium leaf extract[J].Industrial Crops and Products, 2012,37:376-382.] have found that Xanthatin has inhibiting effect to tea tree brown spot, graywall.
In consideration of it, Xanthatin and its derivative desinsection and antibacterial etc. are ground in antitumor, anti-inflammatory, antiulcer at present Study carefully, but the work of Xanthatin and its derivative in terms of diamondback moth poisoning and various plants pathogen fungus spore germination inhibition Journal of Sex Research has not been reported.
Summary of the invention
The object of the present invention is to provide Michael's addition type 13- amino Xanthatin analog derivatives outside the new ring of series, and Give the preparation method of derivative.It is proved according to test, 13- amino Xanthatin analog derivative has desinsection efficiently, less toxic And bacteriostatic activity, it can be used in preparing plant insecticide and bacteriostatic agent.
To realize above-mentioned task, the present invention is achieved by following technical measures:
13- amino Xanthatin analog derivative, chemical general formula are as follows:
R in chemical general formula is respectively as follows:
The preparation method of above-mentioned Xanthatin analog derivative carries out Michael outside ring with secondary amine as raw material using Xanthatin and adds At reaction, serial 13- amino Xanthatin analog derivative is obtained.
Specifically follow these steps to prepare:
A certain amount of Xanthatin is dissolved with corresponding secondary amine with methanol, is stirred to react under room temperature or oil bath, TLC Reaction solution is concentrated under reduced pressure to the end of reacting for tracing detection, and preparation silica gel thin sheet chromatographic isolation obtains required target product.
The present invention has synthesized serial new 13- amino Xanthatin analog derivative, which has diamondback moth There is stronger cytotoxicity；To tomato early blight bacterium, Beancurd sheet reaping hook germ, the spore of botrytis cinerea and cucumber anthracnose Sprouting has certain inhibiting effect.Therefore it can be used for preparing efficient, less toxic plant insecticide and bacteriostatic agent.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of compound 9；
Fig. 2 is the nuclear magnetic resonance spectroscopy of compound 14；
Fig. 3 is the nuclear magnetic resonance spectroscopy of compound 16.
Specific embodiment
The embodiment provided below by way of attached drawing and inventor is elaborated further the present invention.
Embodiment 1:
The following are the synthetic routes of compound 1-20:
A certain amount of Xanthatin and secondary amine are dissolved with methanol, are stirred to react under room temperature or oil bath later, TLC tracking Detection, to the end of reacting, reaction solution is concentrated under reduced pressure, and preparation silica gel thin sheet chromatographic isolation obtains required target product.
The number of compound 1-20 is corresponded with the number of the R in chemical general formula (1)-(20) respectively.
The physicochemical property of compound 1 is as follows:
1) weak yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C17H26NO3([M+H]+)292.1913,found 292.1917。
The physicochemical property of compound 2 is as follows:
1) white solid, 50.7-51.4 DEG C of fusing point；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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 (CH2CH3 )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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C19H30NO3([M+H]+)320.2226,found 320.2225。
The physicochemical property of compound 3 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C22H34NO3([M+H]+)360.2539,found 360.2534。
The physicochemical property of compound 4 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C19H28NO3([M+H]+)318.2069,found 318.2072。
The physicochemical property of compound 5 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C21H32NO3([M+H]+)346.2382,found 346.2388。
The physicochemical property of compound 6 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C21H32NO3([M+H]+)346.2382,found 346.2380。
The physicochemical property of compound 7 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C21H32NO3([M+H]+)346.2382,found 346.2388。
The physicochemical property of compound 8 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C22H34NO3([M+H]+)360.2539,found 360.2541。
The physicochemical property of compound 9 is as follows:
1) amorphous powder, 41.9-43.4 DEG C of fusing point；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C26H34NO3([M+H]+)408.2539,found 408.2541。
Fig. 1 is the nuclear magnetic resonance spectroscopy of compound 9.
The physicochemical property of compound 10 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C27H36NO3([M+H]+)422.2695,found 422.2695。
The physicochemical property of compound 11 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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,-OCH3 ),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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C22H32NO5([M+H]+)390.2280,found 390.2281。
The physicochemical property of compound 12 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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 ,-CH2 CH3),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 ,-CH2CH3 ), 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C23H34NO5([M+H]+)404.2437,found 404.2443。
The physicochemical property of compound 13 is as follows:
1) white solid, 152.3-153.1 DEG C of fusing point；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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,-CH2 OCH2 -),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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C19H28NO4([M+H]+)334.2018,found 334.2014。
The physicochemical property of compound 14 is as follows:
1) white solid, 176.7-177.7 DEG C of fusing point；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C19H27NO3SNa([M+Na]+)372.1609,found 372.1605。
Fig. 2 is the nuclear magnetic resonance spectroscopy of compound 14.
The physicochemical property of compound 15 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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)COCH3 ),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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C21H31N2O4([M+H]+)375.2284,found 375.2291。
The physicochemical property of compound 16 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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 ,-OCH2 CH3),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 ,-OCH2CH3 ), 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C22H33N2O5([M+H]+)405.2389,found 405.2387。
Fig. 3 is the nuclear magnetic resonance spectroscopy of compound 16.
The physicochemical property of compound 17 is as follows:
1) amorphous powder, 63.8-66.4 DEG C of fusing point；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C25H33N2O3([M+H]+)409.2491,found 409.2493。
The physicochemical property of compound 18 is as follows:
1) white solid, 61.5-62.8 DEG C of fusing point；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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,PhCH3 ),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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C26H35N2O3([M+H]+)423.2648,found 423.2648。
The physicochemical property of compound 19 is as follows:
1) white solid, 64.4-65.7 DEG C of fusing point；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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,-OCH3 ),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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C26H35N2O4([M+H]+)439.2597,found 439.2602。
The physicochemical property of compound 20 is as follows:
1) yellow liquid；
2) the nuclear magnetic resonance figures spectrum signature of the compound:
Using deuterated chloroform as solvent, TMS is internal standard, wherein each peak belongs to are 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, CH3OCH2 CH2-),3.35(s,3H,CH3 OCH2CH2-),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) the high resolution mass spectrum feature of the compound:
Using electrospray ionisation: Calcd for C22H35N2O4([M+H]+)391.2597,found 391.2599。
Embodiment 2:
Insecticidal activity test:
1, for trying insect: 2 latter stage in age diamondback moth (Plutella xylostella) larvas.
2, sample and reagent: Xanthatin analog derivative 1-20 and positive control drug prepared by raw material Xanthatin, embodiment Agent toosendanin (> 98%)；Solvent is acetone (analysis is pure).
3, sod cultivation:
It uses leaflet dish additive process: spreading one layer of filter paper in diameter for the culture dish bottom of 9cm, and add water moisturizing.Every ware is chosen Take 20 2 in the same size, more healthy and stronger latter stage in age diamondback moth larvaes.Suitable toosendanin, Xanthatin and implementation are weighed respectively Acetone is added in the compound 1-20 of example preparation, is made into the medical fluid that concentration is 20mg/ml.Chinese cabbage leaf is cut into the leaflet of 1 × 1cm Dish takes 2 μ L medical fluids to be measured to be uniformly applied to blade surface with micro intravenous drip tolerance, and test worm is fed after drying.Using acetone as blank pair According to group.Every processing 20, is repeated 3 times.In temperature is at 25 ± 1 DEG C, humidity 65%~80%, light application time are 12h/12h's Under the conditions of raise.Normal leaf dish is fed after 48h until pupating.Survivor of a murder attempt's number of periodic logging test worm, performance symptom etc., according to following Formula -1 and formula -2 calculate feed normal leaf dish rise test worm for 24 hours, the death rate of 48h and 72h.Measurement result is shown in Table 1.The death rate (%)=(test worm death number)/(test worm total number) × 100 (formula -1)
Corrected mortality (%)=(processing group average mortality-control group average mortality)/(1- control group Mean Death Rate) × 100 (formula -2)
Stomach poison activity of the Xanthatin analog derivative 1-20 of the invention of table 1 to diamondback moth larvae
Conclusion:
The result shows that compound 6,8,13 and 16 prepared by the present invention after feeding diamondback moth larvae for 24 hours when school The positive death rate has been higher than or close to commercialization insecticide toosendanin, has shown stronger stomach poison activity；In 72h, compound 6- The cytotoxicity of 8,13 and 16 pairs of diamondback moths is also above positive control medicament toosendanin.Therefore, Xanthatin class of the invention is spread out Biology is expected to be used for preparation efficiently, less toxic plant insecticide.
Embodiment 3:
Antibacterial activity test:
1, for trying pathogen: tomato early blight bacterium (Alternaria solani), Beancurd sheet reaping hook germ (Fusarium Solani), botrytis cinerea (Botrytis cinerea), cucumber anthracnose (Colletotrichum Orbiculare), is provided by Agricultural University Of Shanxi's plant pathology laboratory
2, sample and reagent:
Sample are as follows: Xanthatin analog derivative 1-20 and positive control medicament phenylate prepared by raw material Xanthatin, embodiment Methyl cyclic-azole (98%) and hymexazol (99%)；Solvent is DMSO (chromatographically pure), and emulsifier is Tween-80 (excellent pure grade).
3, sod cultivation:
Using inhibition spore germination method:
(1) preparation of spore suspension: sterile water is added on having cultivated the good bacterial strain flat board for producing spore, is existed with oese Media surface gently rubs, and then filters out mycelia and culture medium with double gauze.It is added in spore suspension appropriate sterile Water, stirring.It observes under 100 power microscopes, is advisable with 30-40, every visual field spore.The spore suspension prepared is by 0.5% (v/ V) glucose solution is added in ratio.
(2) 1mg/ml medicament mother liquor is prepared: sample to be tested is accurately weighed with a ten thousandth electronic balance, after being dissolved with DMSO Required concentration is diluted to 0.1% Tween-80 aqueous solution.According to agent activity, 5-7 series mass concentration is set, it is organic The final content of solvent is no more than 2%.
(3) it chemicals treatment: with liquid-transfering gun from low concentration to high concentration, successively draws medical fluid and is added in test tube, then draw The spore suspension that same volume prepares keeps medical fluid and spore suspension mixed in equal amounts uniform.It is drawn with liquid-transfering gun above-mentioned mixed It closes 30 μ L of liquid to drip on glass slide, then be put in the culture dish with shallow seated groundwater, capping is trained in the incubator of preference temperature It supports, every processing is repeated 3 times, and is set the processing without medicament and made blank control.
(4) when blank control spore germination rate reaches 90% or more, each processing spore germination feelings observation statistics: are checked Condition.Every processing is each to repeat random observation 3 or more the visuals field, and investigation spore sum is no less than 300, records sprouting number and spore respectively Sub- sum.The short radius that spore germination length is greater than spore is considered as sprouting.The spore germination of each processing group is calculated according to formula -3 Rate, while using the correction inhibition of germination of each processing group of the calculating of formula -4, and each processing is calculated with Excel software IC50.Measurement result is shown in Table 2.
Spore germination rate (%)=(sprouting spore count)/(statistics spore sum) × 100 (formula -3)；
Correction inhibition of germination (%)=(control group be averaged spore germination rate-processing group be averaged spore germination rate)/ (control group be averaged spore germination rate) × 100 (formula -4).
The Xanthatin class compound 1-20 of the invention of table 2 is to the spore germination inhibitory effect for trying strain
Conclusion:
The result shows that compound 1,2,7 and 8 prepared by the present invention, to tomato early blight bacterium, Beancurd sheet reaping hook germ, tomato The bacteriostatic activity of ash arrhizus bacteria is all higher than the antibacterial agent difenoconazole of commercialization, and wherein most is also above hymexazol.In addition, The inhibition of germination of 1,2 and 8 pair of tomato early blight bacterium of compound has been more than two kinds of comparison medicaments；Compound 1-8 and chemical combination Object 11 and 12 is above hymexazol and difenoconazole to the bacteriostatic activity of Beancurd sheet reaping hook germ；Compound 2,7,8 and chemical combination Object 12 is higher than two kinds of positive control medicaments to the bacteriostatic activity of botrytis cinerea, and especially compound 12 is to botrytis cinerea The IC of spore50Value has been even up to 23.10 μ g.mL-1, show strong inhibiting effect；3,10 and 11 pairs of cucumber charcoals of compound The bacteriostatic activity of subcutaneous ulcer germ is higher than hymexazol.So the 13- amino Xanthatin analog derivative that the present invention designs is expected to be used for preparing Efficiently, environmentally friendly novel plant based bacteriostat.

Claims (5)

1.13- amino Xanthatin analog derivative, which is characterized in that chemical general formula are as follows:
R in chemical general formula is one kind below:
2. the preparation method of 13- amino Xanthatin analog derivative described in claim 1, which is characterized in that Xanthatin and second level Amine carries out the outer Michael addition reaction of ring, obtains serial 13- amino Xanthatin analog derivative.
3. the preparation method of 13- amino Xanthatin analog derivative as claimed in claim 2, which comprises the following steps:
Xanthatin is dissolved with corresponding secondary amine with methanol, is stirred to react under room temperature or oil bath；
Reaction solution is concentrated under reduced pressure to the end of reacting for TLC tracing detection, and preparation silica gel thin sheet chromatographic isolation obtains required mesh Mark product.
4. the preparation method of 13- amino Xanthatin analog derivative described in claim 2 or 3, which is characterized in that the second level Amine is following one kind:
A, morpholine class: morpholine, thiomorpholine；
B, piperidines: pipecoline, 3- methyl piperidine, 4- methyl piperidine, 3,5- lupetidine, 4- Phenylpiperidine, 4- benzyl Phenylpiperidines, 4- piperidine methyl formate, ethyl nipecotate；
C, piperazines: N- acetylpiperazine, N- piperazinecarboxylic acid ethyl ester, 1-php, 1- (3- aminomethyl phenyl) piperazine, 1- (3- first Phenyl) piperazine, 1- (2- methoxy ethyl) piperazine.
D, other: 40% dimethylamine agueous solution, diethylamine, N-methylcyclohexylamine, pyrrolidines.
5. the application of 13- amino Xanthatin analog derivative described in claim 1, which is characterized in that be used to prepare plant source and kill Worm agent or bacteriostatic agent.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110452204A (en) * 2019-08-16 2019-11-15 山西农业大学 Xanthatin thioether class and imines analog derivative and its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110452204A (en) * 2019-08-16 2019-11-15 山西农业大学 Xanthatin thioether class and imines analog derivative and its preparation method and application
CN110452204B (en) * 2019-08-16 2021-03-12 山西农业大学 Xanthatin thioether and imine derivatives, and preparation method and application thereof

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