CN103130766A - Piperine hydrazone or acylhydrazone or sulfonyl hydrazone derivative substances and application for preparing a botanical insecticide - Google Patents
Piperine hydrazone or acylhydrazone or sulfonyl hydrazone derivative substances and application for preparing a botanical insecticide Download PDFInfo
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- CN103130766A CN103130766A CN2013100413940A CN201310041394A CN103130766A CN 103130766 A CN103130766 A CN 103130766A CN 2013100413940 A CN2013100413940 A CN 2013100413940A CN 201310041394 A CN201310041394 A CN 201310041394A CN 103130766 A CN103130766 A CN 103130766A
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Abstract
The invention relates to piperine hydrazone, acylhydrazone or sulfonyl hydrazone derivative substances and an application for preparing a botanical insecticide. The piperine hydrazone, acylhydrazone or sulfonyl hydrazone derivative substance takes the piperine hydrazone as raw materials, piperine aldehyde is obtained by means of hydrolysis, esterification, reduction and oxidation, and the piperine aldehyde is respectively reacted with replaced phenylhydrazine, the acylhydrazone and sulfonyl hydrazide. The structural formula is shown as follows. The experiment shows that the piperine hydrazone, or the acylhydrazone or the sulfonyl hydrazone derivative substances has the advantages of having good antifeedant and insecticidal activity, partly exceeds the parent piperine, wherein the insecticidal activity of some components is higher than the commercialized botanical pesticide toosendanin, and therefore the piperine hydrazone, or the acylhydrazone or the sulfonyl hydrazone derivative substances is expected to be used for preparing high-efficient, environment-friendly and low-toxic botanical insecticides.
Description
Technical field
The present invention relates to piperine hydrazone/acylhydrazone that series has insecticidal activity/sulphonyl hydrazone compounds, relate in particular to piperine hydrazone/acylhydrazone/sulphonyl hydrazone derivative and for the preparation of the application of plant insecticide.
Background technology
Piperine (Piperine) is a kind of amide derivatives alkaloid in piperaceae (Piperaceae) Piper (Piper) plant, and is anti-oxidant, antitumor because it is lived at inhibitory enzyme, and desinsection etc. are permitted many-sided biological activity and become the focus of research.
In existing document, piperine and derivative thereof are lived at inhibitory enzyme, anti-oxidant, antitumor, certain research has been done in the aspects such as desinsection: for example:
document [Li-Hua Mu, Bo Wang, Hao-Yang Ren, et al.Synthesis and inhibitory effect ofpiperine derivates on monoamine oxidase.Bioorganic﹠amp, Medicinal ChemistryLetters.2012, 22, 3343-3348.] reported piperine and synthetic acid amides thereof, ester derivative has effect and document [the Surrinder Koul that external selectivity suppresses monoamine oxidase (MAO) A and B, Jawahir L.Koul, Subhash C.Taneja, et al.Structure-Activity Relationship of Piperine and its Synthetic Analogues for theirInhibitory Potentials of Rat Hepatic Microsomal Constitutive and Inducible Cytochrome P450Activities.Bioorganic﹠amp, Medicinal Chemistry.2000,8,251-268.] reported that the derivative of piperine and amides thereof can suppress the Cytochrome P450 activity in vivo and in vitro.document [Badmaev V, M ajeed M, Prakash L.Piperine derivedfrom black pepper increases the plasma levels of coenzymeq10followingoral supplementation.J.ofNutritional Biochemistry.2000, 11(2): 109-113.] research finds that piperine has remarkable reduction superoxide-dismutase (SOD), peroxidase (CAT), Selenoperoxidase (GPX), the active function of gsh basic group transferring enzyme (GSP), reduce liver, kidney, heart, the glutathion inside concentration such as intestines, the proof piperine can reduce the cell peroxidation that high lipid food is induced.document [S.K.Reshmi, E.Sathya and P.Suganya Devi.Isolation of piperdinefrom Piper nigrumand its antiproliferative activity.African Journal of Pharmacy and Pharmacology.2010,4(8), 562-573.] reported its antiproliferative activity. document [Sunila E S, Kuttan G.Immunomodulatory and antitumor activity of Piper longum Linn and piperine.J.of Ethnopharmacology.2004,90(2-3): 339-346.] research finds that piperine obviously suppresses the growth of solid tumor in DLA cell seeding Mice Body, and the survival rate that makes the EAC mice with tumor extends to 58.8% and document [Selvendiran K by 37.3%, Prince Vijeya Singh J, Sakthis ekaran D.Invivo effect of piperine on serum and tissue glycoprotein levels in benzo(a) pyrene induced lung carcinogenesis in Swis salbino mice.Pulm Pharmacol Ther.2006,19(2): 107-111.] piperine of research discovery can suppress the lung cancer that benzene is induced.[Zheng Bin, Wang Xin, the red brightness of fiber crops. the experiment in vitro research of piperine to human hepatoma HepG2 cell's anti-tumor activity. the Chinese experimental diagnostics, 2012,16(2), 218-220.] inquire into piperine (piperine) on the propagation of people HepG2 hepatoma cell strain, kill and wound and apoptotic impact, for the treatment of liver cancer provides theoretical foundation.Document [Inder Pal Singh, Shreyans Kumar Jain, Amandeep Kaur, et al.Synthesis and Antileishmanial activity of Piperoyl-Amino Acid Conjugates.European Journal of Medicinal Chemistry.2010,45,3439-3445.] derivative of having reported piperine has active preferably to epimastigote and the amastigote of the graceful protozoon of Du Shi profit.In article with regard to the mould examination zooscopy of the best compound graceful protozoon of profit take Golden Hamster as Du Shi of two activity the activity in its body.Document [Tatiana Santana Ribeiro, Leonardo Freire-de-Lima, Jos Osvaldo Previato, et al.Toxic effects of natural piperine and its derivatives on epimastigotes and amastigotes of Trypanosoma cruzi.Bioorganic ﹠amp; Medicinal Chemistry Letters.2004,14,3555-3558.] studied natural product piperine and amino derivative thereof to the effect of schizotrypanum cruzi, be expected to therefrom seek the trypanocidal new drug of a kind of energy, cure the human diseases that is referred to as Cha Jiasi that is caused by trypanosome.document [Vanderlu cia F de Paula, Luiz C de A Barbosa, Antonio J Demuner, et al.Synthesis and insecticidal activity of new amide derivatives of piperine.Pest Manag Sci.2000, 56, 168-174.] studied the piperine amide derivatives to Ascia monuste orseis Latr, Acanthoscelides obtectus Say, Brevicoryne brassicae L, the toxic action of several insects of Protopolybia exigua DeSaus and Cornitermes cumulans Kollar.Document [Wang Jia. the research [D] of piperine to culex pipiens pallens larvae and bomyx mori cell toxicity action. Suzhou: University Of Suzhou, 2006.] reported that piperine has stronger toxic action and growth-inhibiting effect to culex pipiens pallens larvae and Sf-21 cell, can be used as the functional mass of novel pesticide.Given this, piperine and derivative thereof are being lived except inhibitory enzyme at present, anti-oxidant, outside the research of the aspect such as antitumor, also aspect the cytotoxicity of the graceful protozoon of protozoon schizotrypanum cruzi and Du Shi profit, the greedy noctuid of insect culex pipiens pallens larvae and meadow, certain research is being arranged, but piperine and derivative thereof have no report in the activity aspect mythimna separata food refusal and poisoning, therefore the synthetic of this piperine hydrazone class/acylhydrazone class/sulphonyl hydrazone analog derivative and have very strong novelty at the activity research aspect mythimna separata food refusal and poisoning.
Summary of the invention
The object of the invention is to, the piperine hydrazone/acylhydrazone/sulphonyl hydrazone analog derivative of series is provided, and provided the preparation method of these derivatives.
For realizing above-mentioned task, the present invention is achieved by following technical proposal:
Piperine hydrazone/acylhydrazone/sulphonyl hydrazone analog derivative is characterized in that, its chemical general formula is:
In formula, R is respectively:
The preparation method of above-mentioned piperine hydrazone/acylhydrazone/sulphonyl hydrazone analog derivative, it is characterized in that, obtain piperine aldehyde take piperine as raw material by hydrolysis, esterification, reduction and oxidation, then respectively with the phenylhydrazine that replaces, hydrazides, and sulfonyl hydrazide reaction, obtain serial piperine hydrazone/acylhydrazone/sulphonyl hydrazone analog derivative, specifically follow these steps to preparation:
With a certain amount of piperine aldehyde and corresponding substituted phenylhydrazines/hydrazides anhydrous alcohol solution, drip two Glacial acetic acid in backward mentioned solution, be heated to reflux, TLC follows the tracks of detection, after reaction finished, suction filtration also washed to get required sterling successively with ice dehydrated alcohol and sherwood oil.
Substituted phenylhydrazines used, hydrazides and sulfonyl hydrazide are respectively:
A, phenylhydrazine class: ortho-nitrophenyl hydrazine, paranitrophenylhydrazine, 2,3,5,6-tetrafluoro phenylhydrazine;
b, hydrazides class: acethydrazide, cyano acethydrazide, benzoyl hydrazine, to the toluyl hydrazine, between the toluyl hydrazine, adjacent toluyl hydrazine, the para hydroxybenzene formyl hydrazine, p-nitrobenzoylhydrazide, the m-nitro formyl hydrazine, to the methoxybenzoyl hydrazine, the meta-methoxy benzoyl hydrazine, 3, 4-dimethoxy benzoyl hydrazine, the O-ethoxyl formyl hydrazine, to the fluorobenzoyl hydrazine, between the fluorobenzoyl hydrazine, the m-chloro benzoyl hydrazine, adjacent chlorobenzoyl hydrazine, 2, 4, 6-trichlorobenzene formyl hydrazine, the cigarette hydrazine, the vazadrine, 2-thenoyl hydrazine, 5-chloro-2-thenoyl hydrazine, 5-bromo-2-thenoyl hydrazine,
C, sulfonyl hydrazines: benzol sulfohydrazide, p-toluene sulfonyl hydrazide, to the ethylbenzene sulfonyl hydrazide, to anisole sulfonyl hydrazide, brosyl hydrazine, m-nitro sulfonyl hydrazide, to chlorine m-nitro sulfonyl hydrazide.
According to applicant's evidence, above-mentioned piperine hydrazone/acylhydrazone/sulphonyl hydrazone analog derivative has efficiently, the insecticidal activity of low toxicity, can be used in the preparation plant insecticide.
Description of drawings
Fig. 1 and Fig. 2 are respectively hydrogen spectrum, the carbon spectrum of compound 6.
Below the embodiment that provides by accompanying drawing and contriver the present invention done further elaborate.
Embodiment
The applicant has synthesized serial new piperine hydrazone/acylhydrazone/sulfonyl hydrazines derivative, and its chemical general formula is:
In formula, R is respectively:
The preparation method of above-mentioned piperine hydrazone/acylhydrazone/sulphonyl hydrazone analog derivative obtains piperine aldehyde take piperine as raw material by hydrolysis, esterification, reduction and oxidation, then respectively with the phenylhydrazine that replaces, hydrazides, and the sulfonyl hydrazide reaction obtain.
Substituted phenylhydrazines used, hydrazides and sulfonyl hydrazide are respectively:
A, phenylhydrazine class: ortho-nitrophenyl hydrazine, paranitrophenylhydrazine, 2,3,5,6-tetrafluoro phenylhydrazine;
b, hydrazides class: acethydrazide, cyano acethydrazide, benzoyl hydrazine, to the toluyl hydrazine, between the toluyl hydrazine, adjacent toluyl hydrazine, the para hydroxybenzene formyl hydrazine, p-nitrobenzoylhydrazide, the m-nitro formyl hydrazine, to the methoxybenzoyl hydrazine, the meta-methoxy benzoyl hydrazine, 3, 4-dimethoxy benzoyl hydrazine, the O-ethoxyl formyl hydrazine, to the fluorobenzoyl hydrazine, between the fluorobenzoyl hydrazine, the m-chloro benzoyl hydrazine, adjacent chlorobenzoyl hydrazine, 2, 4, 6-trichlorobenzene formyl hydrazine, the cigarette hydrazine, the vazadrine, 2-thenoyl hydrazine, 5-chloro-2-thenoyl hydrazine, 5-bromo-2-thenoyl hydrazine,
C, sulfonyl hydrazines: benzol sulfohydrazide, p-toluene sulfonyl hydrazide, to the ethylbenzene sulfonyl hydrazide, to anisole sulfonyl hydrazide, brosyl hydrazine, m-nitro sulfonyl hydrazide, to chlorine m-nitro sulfonyl hydrazide.
The applicant has carried out insecticidal activity research to above-mentioned piperine hydrazone/acylhydrazone/sulphonyl hydrazone analog derivative.Result shows, this piperine hydrazone/acylhydrazone/sulfonyl hydrazines derivative to three age mythimna separata have stronger food refusal and cytotoxicity, can be used for preparing plant insecticide efficient, low toxicity.
Below the embodiment that the contriver provides.
Embodiment 1:
One, product: piperine acid, piperine ester, piperine alcohol, piperine aldehyde and each compound physico-chemical property of compound 1-33(see following content for details)
Two, preparation method:
Be below the synthetic route of piperine acid:
A certain amount of potassium hydroxide is dissolved in 95% ethanol, piperine is added in above-mentioned reaction solution afterwards, in oil bath after the back flow reaction certain hour, the room temperature cold filtration obtains solid, with being acid with the hydrochloric acid adjust pH after a certain amount of water dissolution, suction filtration, filter cake is with a small amount of water washing and dry required sterling.
Piperine acid physico-chemical property:
1), yellow solid, 218 ℃ of fusing points.
2), the mass spectrum of piperine acid (ESI-MS) feature:
Adopt electron spray ionisation: m/z:241.00([M+Na]
+, 100).
3), the nuclear magnetic resonance map feature of piperine acid:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 12.22(s, 1H ,-COOH), and 7.27-7.33(m, 1H), 7.23-7.24(m, 1H), 6.92-7.02(m, 4H) and, 6.06(s, 2H ,-OCH
2O-), 5.91-5.95(m, 1H);
Be below piperine ester synthesis route:
A certain amount of piperine acid is dissolved in methyl alcohol, adds the several vitriol oils in above-mentioned reaction solution, after stirring and refluxing reaction certain hour, revolve and steam desolventizing and add a certain amount of methylene dichloride dissolving in oil bath, separate to get required sterling with post after concentrating.
Piperine ester physico-chemical property:
1), faint yellow solid, 146 ℃ of fusing points.
2), the mass spectrum of piperine ester (ESI-MS) feature:
Adopt electron spray ionisation: m/z:232.90([M+H]
+, 85), 254.90([M+Na]
+, 87).
3), the nuclear magnetic resonance map of piperine ester (
1HNMR, 400MHz) feature:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1HNMR(400MHz, CDCl
3) δ: 7.38-7.44(m, 1H), 6.98-6.99(m, 1H) and, 6.90-6.92(m, 1H), 6.77-6.83(m, 2H) and, 6.66-6.73(m, 1H), 5.98(s, 2H ,-OCH
2O-), 5.93-5.96(m, 1H), 3.76(s, 3H ,-CH
3);
Be below the synthetic route of piperine alcohol:
The tetrahydrofuran solution of piperine ester slowly is added dropwise to the tetrahydrofuran (THF) of tetrahydrochysene lithium aluminium and aluminum chloride in ice-water bath in outstanding turbid night, reacts completely at this thermotonus to TLC plate detection substrate afterwards, be added to the water only reaction in reaction system.Suction filtration, filter cake methylene dichloride and methanol wash, merging filtrate separates to get required sterling with post after concentrating.
Piperine alcohol physico-chemical property:
1), faint yellow solid, fusing point 99-101 ℃.
2), the mass spectrum of piperine alcohol (ESI-MS) feature:
Adopt electron spray ionisation: m/z:226.90([M+Na]
+, 68).
3), the nuclear magnetic resonance map feature of piperine alcohol:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, CDCl
3) δ: 6.94(s, 1H), 6.81(d, 1H, J=8Hz) and, 6.74(d, 1H, J=8.0Hz), 6.59-6.64(m, 1H), 6.45-6.48(m, 1H) and, 6.35-6.40(m, 1H), 5.89-5.95(m, 3H), 4.23(d, 2H, J=5.5Hz), 1.48(s, 1H);
Be below the synthetic route of piperine aldehyde:
Piperine alcohol is dissolved in tetrahydrofuran (THF) with Manganse Dioxide, and oil bath is back to TLC and detects fully.Suction filtration is removed solid, and merging filtrate separates to get required sterling with post after concentrating.
Piperine aldehyde physico-chemical property:
1), yellow solid, 108 ℃ of fusing points.
2), the mass spectrum of piperine aldehyde (ESI-MS) feature:
Adopt electron spray ionisation: m/z:202.90([M+H]
+, 100).
3), the nuclear magnetic resonance map feature of piperine aldehyde:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, CDCl
3) δ: 9.58(d, 1H, J=8.0Hz ,-CHO), and 7.20-7.23(m, 1H), 7.03(s, 1H), 6.91-6.97(m, 2H) and, 6.80-6.85(m, 2H), 6.20-6.25(m, 1H), 6.00(s, 2H ,-OCH2O-).
Be below the synthetic route of compound 1-33:
With the phenylhydrazine/hydrazides of a certain amount of piperine aldehyde aldehyde and replacement/sulfonyl hydrazide anhydrous alcohol solution, drip two Glacial acetic acid in backward mentioned solution, be heated to reflux, TLC follows the tracks of detections, after the reaction end, gets required compound after suction filtration.
The physico-chemical property of compound 1 is as follows:
1), red solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.19(s, 0.9H, NH), 10.78(s, 0.1H, NH) and, 8.10(d, 2H, J=8.5Hz), 7.78(d, 1H, J=9.5Hz), 7.17-7.22(m, 1H) and, 6.90-7.06(m, 5H), 6.68-6.79(m, 2H), 6.46-6.51(m, 1H), 6.04(s, 2H ,-OCH
2O-);
13CNMR(125MHz, DMSO-d
6) δ: 151.51,150.61,148.41,147.84,144.97,142.08,138.67,138.11,137.70,134.93,131.77,129.01,127.54,126.79,126.64,126.43,123.19,122.59,120.82,111.64,108.97,106.03,105.79,101.69.
The physico-chemical property of compound 2 is as follows:
1), red solid, fusing point 166-168 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.08(s, 1H, NH), 8.21(d, 1H, J=9.5Hz), 8.08(d, 1H, J=8.5Hz), 7.78(d, 1H, J=8.5Hz), 7.60(t, 1H, J=7.5Hz), 7.20(s, 1H), 6.87-7.04(m, 4H), 6.73-6.78(m, 2H), 6.49-6.54(m, 1H), 6.04(s, 2H ,-OCH
2O-);
13C NMR(125MHz, DMSO-d6) δ: 148.41,148.15,147.94,141.43,139.19,136.78,135.56,131.69,131.02,128.88,127.36,126.16,122.72,118.59,116.29,108.98,105.84,101.71.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
18H
15N
3O
4([M+H]
+), 338.1135; Found, 338.1140.
The physico-chemical property of compound 3 is as follows:
1), green solid, 161 ℃ of fusing points;
2), the nuclear magnetic resonance map of this compound (
1HNMR, 500MHz) feature:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 10.27(s, 1H, NH), 7.89(d, 1H, J=9.5Hz) and, 7.14-7.21(m, 2H), 6.88-6.99(m, 3H) and, 6.62-6.69(m, 2H), 6.38-6.43(m, 1H) and, 6.03(s, 2H ,-OCH
2O-);
13C NMR(125MHz, DMSO-d
6) δ: 147.84,147.19,145.14,145.02,144.82,137.39,136.54,135.33,133.88,131.28,128.56,127.02,125.01,121.84,108.39,105.20,101.10,95.28,95.09,94.90.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
18H
12F
4N
2O
2([M+H]
+), 365.0907; Found, 365.0908.
The physico-chemical property of compound 4 is as follows:
1), faint yellow solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.18(s, 0.38H, NH), 11.06(s, 0.62H, NH), 7.79(d, 0.38H, J=9.6Hz), 7.68(d, 0.62H, J=9.6Hz), 7.18-7.21(m, 1H), 6.89-7.03(m, 3H), 6.69-6.80(m, 2H), 6.33-6.42(m, 1H), 6.03(s, 2H ,-OCH
2O-), 2.09(s, 1.86H ,-CH
3), 1.90(s, 1.14H ,-CH
3).
The physico-chemical property of compound 5 is as follows:
1), orange solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.61(s, 0.75H, NH), 11.53(s, 0.25H, NH) and, 7.82(d, 0.25H, J=9.5Hz), 7.70(d, 0.75H, J=9.5Hz), 7.20-7.25(m, 1H), 6.72-7.04(m, 5H), 6.32-6.43(m, 1H), 6.04(s, 2H ,-OCH
2O-), 4.07(s, 1.5H ,-CH
2CN), 3.76(s, 0.5H ,-CH
2CN);
13C NMR(125MHz, DMSO-d
6) δ: 164.85,159.07,150.09,148.42,148.05,147.25,141.25,140.70,136.36,136.16,131.50,128.24,128.07,127.11,122.94,122.85,116.52,116.27,108.98,105.88,101.74,25.26,24.74.
The physico-chemical property of compound 6 is as follows:
1), faint yellow solid, fusing point 214-216 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.68(s, 1H, NH), 8.14(d, 1H, J=9.5Hz), 7.88(d, 2H, J=7.5Hz), 7.57(t, 1H, J=7.0Hz), 7.50(t, 2H, J=7.0Hz), 7.23(s, 1H), 7.01-7.07(m, 1H), 6.96(d, 1H, J=8.0Hz), 6.90(d, 1H, J=7.5Hz), 6.75-6.85(m, 2H), 6.47-6.52(m, 1H), 6.05(s, 2H ,-OCH
2O-);
13C NMR(125MHz, DMSO-d6) δ: 162.75,149.62,147.85,147.44,139.85,135.41,133.32,131.58,131.02,128.34,127.47,126.70,122.26,108.39,105.30,101.14.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
19H
16N
2O
3([M+Na]
+), 343.1053; Found, 343.1054.
The physico-chemical property of compound 7 is as follows:
1), yellow solid, fusing point 233-234 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.60(s, 1H, NH), 8.13(d, 1H, J=9.6Hz), 7.79(d, 2H, J=8.0Hz), 7.31(d, 2H, J=8.0Hz), 7.23(s, 1H), 6.96-7.07(m, 2H), 6.90(d, 1H, J=8.0Hz), 6.74-6.84(m, 2H), 6.46-6.52(m, 1H), 6.04(s, 2H ,-OCH
2O-), 2.37(s, 3H ,-CH
3).
The physico-chemical property of compound 8 is as follows:
1), faint yellow solid, fusing point 212-213 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.61(s, 1H, NH), 8.13(d, 1H, J=9.5Hz), 7.67-7.70(m, 2H), 7.39-7.41(m, 2H), 7.22(s, 1H), 7.01-7.06(m, 1H), 6.96(d, 1H, J=8.0Hz), 6.90(d, 1H, J=7.5Hz), 6.75-6.84(m, 2H), 6.46-6.51(m, 1H), 6.04(s, 2H ,-OCH
2O-), 2.38(s, 3H ,-CH
3);
13C NMR(125MHz, DMSO-d
6) δ: 162.83,149.50,147.86,147.44,139.75,137.67,135.38,133.32,132.15,131.04,128.37,128,22,127.96,126.71,124.62,122.23,108.39,105.33,101.14,20.83.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
20H
18N
2O
3([M+H]
+), 335.1390; Found, 335.1385.
The physico-chemical property of compound 9 is as follows:
1), yellow solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.58(s, 0.2H, NH), 11.57(s, 0.8H, NH), 7.97(d, 0.8H, J=9.6Hz), 7.77(d, 0.2H, J=9.6Hz), 7.21-7.41(m, 5H), 6.87-7.12(m, 3H), 6.67-6.85(m, 2H), 6.44-6.50(m, 0.8H), 6.14-6.20(m, 0.2H), 6.04(s, 1.6H ,-OCH
2O-), 6.02(s, 0.4H ,-OCH
2O-), 2.35(s, 2.4H ,-CH
3), 2.21(s, 0.6H ,-CH
3).
The physico-chemical property of compound 10 is as follows:
1), faint yellow solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.47(s, 1H, NH), 10.13(s, 1H, OH) and, 8.10(d, 1H, J=9.0Hz), 7.76(d, 2H, J=8.0Hz) and, 7.22(s, 1H), 6.73-7.05(m, 7H) and, 6.45-6.50(m, 1H), 6.04(s, 2H ,-OCH
2O-);
13C NMR(125MHz, DMSO-d
6) δ: 162.36,160.52,148.68,147.85,147.38,139.25,135.09,131.06,129.52,128.54,126.77,123.75,122.19,114.87,108.39,105.27,101.13.
The physico-chemical property of compound 11 is as follows:
1), faint yellow solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.95(s, 0.9H, NH), 11.86(s, 0.1H, NH), 8.35(d, 1.8H, J=8.5Hz), 8.28(d, 0.2H, J=8.0Hz), 8.11-8.16(m, 2.8H), 7.90(d, 0.2H, J=8.0Hz), 7.23(s, 1H), 6.77-7.08(m, 5H), 6.47-6.52(m, 1H), 6.05(s, 2H ,-OCH
2O-);
13C NMR(125MHz, DMSO-d
6) δ: 161.07,150.73,149.09,147.86,147.52,140.68,138.97,135.86,130.95,129.02,128.00,126.62,123.52,122.38,108.40,105.32,101.17.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
19H
15N
3O
5([M+H]
+), 366.1084; Found, 366.1089.
The physico-chemical property of compound 12 is as follows:
1), faint yellow solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.98(s, 1H, NH), 8.72-8.73(m, 1H), 8.42-8.44(m, 1H), 8.33(d, 1H, J=8.0Hz), 8.16(d, 1H, J=9.6Hz), 7.81(t, 1H, J=8.0Hz), 7.23(d, 1H, J=1.2Hz), 6.97-7.09(m, 2H), 6.77-6.92(m, 3H), 6.47-6.54(m, 1H), 6.05(s, 2H ,-OCH
2O-).
The physico-chemical property of compound 13 is as follows:
1), faint yellow solid, fusing point 214-216 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.54(s, 1H, NH), 8.12(d, 1H, J=9.0Hz), 7.87(d, 2H, J=8.0Hz), 7.22(s, 1H), 7.00-7.05(m, 3H), 6.96(d, 1H, J=8.0Hz), 6.89(d, 1H, J=8.0Hz), 6.73-6.83(m, 2H), 6.46(t, 1H, J=9.0Hz), 6.04(s, 2H ,-OCH
2O-), 3.83(s, 3H ,-OCH
3);
13CNMR(125MHz, DMSO-d
6) δ: 162.18,161.88,149.05,147.86,147.41,139.44,135.20,131.07,129.39,128.48,126.75,125.37,122.19,113.59,108.39,105.32,101.14,55.32.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
20H
18N
2O
4([M+Na]
+), 373.1158; Found, 373.1162.
The physico-chemical property of compound 14 is as follows:
1), faint yellow solid, 106 ℃ of fusing points;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.63(s, 1H, NH), 8.13(d, 1H, J=10.0Hz), 7.41-7.47(m, 3H), 7.23(d, 1H, J=0.8Hz), 7.14(d, 1H, J=8.8Hz), 6.96-7.07(m, 2H), 6.90(d, 1H, J=8.0Hz), 6.75-6.85(m, 2H), 6.46-6.52(m, 1H), 6.05(s, 2H ,-OCH
2O-), 3.82(s, 3H ,-OCH
3).
The physico-chemical property of compound 15 is as follows:
1), yellow solid, fusing point 216-217 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.53(s, 1H, NH), 8.13(d, 1H, J=9.6Hz) and, 7.53-7.55(m, 1H), 7.46(d, 1H, J=1.6Hz), 7.23(s, 1H), 6.96-7.08(m, 3H) and, 6.90(m, 1H), 6.74-6.84(m, 2H), 6.46-6.52(m, 1H) and, 6.05(s, 2H ,-OCH
2O-), 3.83(s, 6H ,-OCH
3).
The physico-chemical property of compound 16 is as follows:
1), yellow solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.44(s, 0.15H, NH), 11.28(s, 0.75H, NH), 7.95(d, 0.8H, J=9.6Hz), 7.72(d, 0.16H, J=9.6Hz), 7.59-7.61(m, 0.81H), 7.45-7.49(m, 0.8H), 7.34-7.39(m, 0.16H), 7.19-7.23(m, 1H), 7.12(d, 1H, J=8.0Hz), 6.89-7.07(m, 4.16H), 6.66-6.85(m, 2H), 6.45-6.51(m, 0.8H), 6.14-6.20(m, 0.16H), 6.04(s, 1.6H ,-OCH
2O-), 6.02(s, 0.32H ,-OCH
2O-), 4.11-4.16(m, 1.5H), 4.00-4.05(m, 0.3H) and, 1.36(t, 2.5H, J=6.8Hz), 1.18(t, 0.5H, J=6.8Hz).
The physico-chemical property of compound 17 is as follows:
1), faint yellow solid, fusing point 220-221 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.70(s, 1H, NH), 8.12(d, 1H, J=9.6Hz), 7.95-7.98(m, 2H), 7.34(t, 2H, J=8.8Hz), 7.23(s, 1H), 6.96-7.07(m, 2H), 6.90-6.92(m, 1H), 6.75-6.87(m, 2H), 6.46-6.52(m, 1H), 6.05(s, 2H ,-OCH
2O-).
The physico-chemical property of compound 18 is as follows:
1), faint yellow solid, fusing point 216-218 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.73(s, 1H, NH), 8.13(d, 1H, J=9.6Hz), 7.68-7.75(m, 2H), 7.55-7.60(m, 1H), 7.42-7.47(m, 1H), 7.23(d, 1H, J=0.8Hz), 6.97-7.08(m, 2H), 6.72-6.92(m, 3H), 6.46-6.52(m, 1H), 6.05(s, 2H ,-OCH
2O-).
The physico-chemical property of compound 19 is as follows:
1), faint yellow solid, fusing point 226-228 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.74(s, 1H, NH), 8.13(d, 1H, J=9.5Hz), 7.93(s, 1H), 7.84(d, 1H, J=7.5Hz), 7.65(d, 1H, J=7.5Hz), 7.54(t, 1H, J=7.5Hz), 7.22(s, 1H), 7.01-7.06(m, 1H), 6.97(d, 1H, J=8.0Hz), 6.90(d, 1H, J=7.5Hz), 6.76-6.87(m, 2H), 6.47-6.52(m, 1H), 6.05(s, 2H ,-OCH
2O-);
13C NMR(125MHz, DMSO-d
6) δ: 161.30,150.20,147.87,147.49,140.26,135.65,135.32,133.16,131.41,131.00,130.38,128.15,127.18,126.66,126.32,122.30,108.40,105.35,101.16.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
19H
15ClN
2O
3([M+H]
+), 353.0687; Found, 353.0689.
The physico-chemical property of compound 20 is as follows:
1), faint yellow solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.80(s, 0.35H, NH), 11.74(s, 0.65H, NH), 7.94(d, 0.65H, J=9.5Hz), 7.76(d, 0.35H, J=10.0Hz), 7.39-7.57(m, 4H), 7.23(s, 0.65H), 7.12(s, 0.35H), 6.68-7.07(m, 5H), 6.44-6.49(m, 0.65H), 6.14-6.19(m, 0.35H), 6.02(d, 2H, J=11.5Hz ,-OCH
2O-);
13C NMR(125MHz, DMSO-d
6) δ: 168.22,162.10,149.75,147.85,147.79,147.48,147.37,146.62,140.37,139.54,135.86,135.67,135.16,135.06,131.25,130.95,130.31,130.26,129.61,129.55,129.20,128.89,128.47,127.96,127.87,127.15,126.80,126.63,126.58,122.35,122.06,108.39,105.30,105.20,101.15.
The physico-chemical property of compound 21 is as follows:
1), faint yellow solid, 186 ℃ of fusing points;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 9.45(s, 1H, NH), 7.76(d, 1H, J=9.6Hz) and, 7.61(s, 2H), 7.16(d, 1H, J=1.6Hz) and, 6.87-6.97(m, 3H), 6.55-6.65(m, 2H) and, 6.35-6.41(m, 1H), 6.03(s, 2H ,-OCH
2O-).
The physico-chemical property of compound 22 is as follows:
1), faint yellow solid, 240 ℃ of fusing points;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.89(s, 1H, NH), 8.77-8.78(m, 2H) and, 8.14(d, 1H, J=9.5Hz), 7.79-7.80(m, 2H) and, 7.24(s, 1H), 6.77-7.08(m, 5H) and, 6.47-6.52(m, 1H), 6.05(s, 2H ,-OCH
2O-);
13C NMR(125MHz, DMSO-d
6) δ: 161.77,151.39,150.77,149.98,148.45,148.11,141.30,140.93,136.46,131.52,128.55,127.19,123.45,122.96,121.97,108.98,105.91,101.75.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
18H
15N
3O
3([M+H]
+), 322.1199; Found, 322.1193.
The physico-chemical property of compound 23 is as follows:
1), faint yellow solid, 226 ℃ of fusing points;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.84(s, 1H, NH), 9.04(s, 1H), 8.75-8.76(m, 1H), 8.22(d, 1H, J=7.5Hz), 8.12(d, 1H, J=9.5Hz), 7.55(t, 1H, J=7.0Hz), 7.24(s, 1H), 6.76-7.08(m, 5H), 6.47-6.52(m, 1H), 6.05(s, 2H ,-OCH
2O-);
13C NMR(125MHz, DMSO-d
6) δ: 161.29,152.12,150.23,148.44,147.86,147.49,140.39,135.70,135.30,130.97,129.06,128.07,126.64,123.47,122.34,108.40,105.32,101.16.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
18H
15N
3O
3([M+H]
+), 322.1186; Found, 322.1188.
The physico-chemical property of compound 24 is as follows:
1), the safran solid, fusing point 204-206 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.70(s, 1H, NH), 7.87-8.12(m, 3H) and, 7.23(s, 2H), 7.01-7.06(m, 1H), 6.97(d, 1H, J=8.0Hz), 6.90(d, 1H, J=8.0Hz), 6.75-6.86(m, 2H), 6.46-6.50(m, 1H), 6.05(s, 2H ,-OCH
2O-);
13C NMR(125MHz, DMSO-d
6) δ: 157.36,149.38,147.85,147.45,145.52,139.95,139.58,138.23,135.47,134.64,134.35,131.69,131.00,128.73,128.21,128.00,127.69,126.67,122.27,108.40,105.30,101.14.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
17H
14N
2O
3S([M+H]
+), 327.0791; Found, 327.0793.
The physico-chemical property of compound 25 is as follows:
1), faint yellow solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.84(s, 0.64H, NH), 11.74(s, 0.37H, NH) and, 7.76-8.11(m, 2H), 7.20-7.24(m, 2H) and, 6.74-7.10(m, 5H), 6.44-6.56(m, 1H) and, 6.04(s, 2H ,-OCH
2O-).
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
17H
13ClN
2O
3S([M+Na]
+), 383.0234; Found, 383.0230.
The physico-chemical property of compound 26 is as follows:
1), faint yellow solid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.83(s, 0.64H, NH), 11.73(s, 0.34H, NH) and, 7.70-8.10(m, 2H), 7.20-7.40(m, 2H) and, 6.74-7.11(m, 5H), 6.44-6.57(m, 1H) and, 6.04(s, 2H ,-OCH
2O-); HRMS(ESI).
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
17H
13BrN
2O
3S([M+Na]
+), 426.9715; Found, 426.9719.
The physico-chemical property of compound 27 is as follows:
1), faint yellow solid, fusing point 157-159 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.35(s, 1H, NH), 7.81(d, 2H, J=7.5Hz) and, 7.60-7.68(m, 4H), 7.16(s, 1H) and, 6.88-6.94(m, 3H), 6.67-6.73(m, 2H) and, 6.23-6.28(m, 1H), 6.03(s, 2H ,-OCH
2O-);
13C NMR(125MHz, DMSO-d
6) δ: 149.20,147.82,147.45,139.80,138.98,135.50,132.88,130.91,129.12,127.39,126.98,126.41,122.18,108.38,105.29,101.13.
3), the high resolution mass spectrum feature of this compound:
Adopt electron spray ionisation: Calcd for C
18H
16N
2O
4S([M+H]
+), 357.0904; Found, 357.0906,
The physico-chemical property of compound 28 is as follows:
1), faint yellow solid, 172 ℃ of fusing points;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(500MHz, DMSO-d
6) δ: 11.25(s, 1H, NH), 7.69(d, 2H, J=8.0Hz) and, 7.59(d, 1H, J=9.5Hz), 7.39(d, 2H, J=7.5Hz), 7.15(s, 1H) and, 6.88-6.94(m, 3H), 6.67-6.72(m, 2H), 6.22-6.27(m, 1H), 6.03(s, 2H ,-OCH
2O-), 2.07(s, 3H ,-CH
3);
13C MR(125MHz, DMSO-d
6) δ: 149.00,147.82,147.44,143.27,139.66,136.11,135.43,130.92,129.54,127.46,127.04,126.43,122.16,108.38,105.30,101.13,20.90.
The physico-chemical property of compound 29 is as follows:
1), yellow solid, fusing point 157-158 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.29(s, 1H, NH), 7.72(d, 2H, J=8.0Hz) and, 7.60(d, 1H, J=9.6Hz), 7.43(d, 2H, J=8.4Hz), 7.16(d, 1H, J=1.6Hz) and, 6.88-6.95(m, 3H), 6.67-6.74(m, 2H), 6.22-6.29(m, 1H) and, 6.03(s, 2H ,-OCH
2O-), 2.65(q, 2H, J=7.6Hz), 1.17(t, 3H, J=7.6Hz).
The physico-chemical property of compound 30 is as follows:
1), yellow solid, fusing point 140-142 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.19(s, 1H, NH), 7.72-7.76(m, 2H) and, 7.59(d, 1H, J=9.6Hz), 7.17(d, 1H, J=1.2Hz), 7.11-7.14(m, 2H), 6.88-6.95(m, 3H), 6.67-6.74(m, 2H), 6.22-6.28(m, 1H), 6.03(s, 2H ,-OCH
2O-), 3.83(s, 3H).
The physico-chemical property of compound 31 is as follows:
1), yellow solid, fusing point 152-154 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.44(s, 1H, NH), 7.83-7.86(m, 2H) and, 7.73-7.76(m, 2H), 7.62(d, 1H, J=9.6Hz), 7.17(d, 1H, J=1.6Hz), 6.89-6.95(m, 3H), 6.69-6.77(m, 2H), 6.23-6.29(m, 1H), 6.04(s, 2H ,-OCH
2O-).
The physico-chemical property of compound 32 is as follows:
1), yellow solid, fusing point 174-176 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.64(s, 1H, NH), 8.50-8.54(m, 2H), 8.23-8.26(m, 1H), 7.92(t, 1H, J=8.0Hz), 7.65(d, 1H, J=10.0Hz), 7.17(d, 1H, J=1.2Hz), 6.88-6.96(m, 3H), 6.69-6.79(m, 2H), 6.23-6.29(m, 1H), 6.03(s, 2H ,-OCH
2O-).
The physico-chemical property of compound 33 is as follows:
1), red solid, fusing point 186-188 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterated dimethyl sulfoxide as solvent, TMS is interior mark, and wherein each peak is attributed to:
1H NMR(400MHz, DMSO-d
6) δ: 11.37(s, 0.66H, NH), 11.35(s, 0.33H, NH), 8.46(s, 0.66H), 8.42(s, 0.33H), 8.34(d, 0.66H, J=9.6Hz), 7.89-7.934(m, 1H), 7.62(d, 0.33H, J=9.6Hz), 7.22(s, 0.66H), 7.16(s, 0.33H), 6.68-7.07(m, 6H), 6.48-6.56(m, 0.66H), 6.24-6.30(m, 0.33H), 6.05(s, 1.34H ,-OCH
2O-), 6.03(s, 0.66H ,-OCH
2O-).
Embodiment 2: give birth to and survey experiment
1, for the examination insect: 3 ages are armyworm larvae in earlier stage, is provided by insectary, Xibei Univ. of Agricultural ﹠ Forest Science ﹠ Technology's public nuisance-free agricultural chemicals research centre.
2, sample and reagent:
Sample is: the compound 1-33 of Toosendanin, piperine acid, piperine ester, piperine alcohol, piperine aldehyde and embodiment preparation.Solvent is acetone, the Chengdu Long Huagongshijichang of section, analytical pure.
3, give birth to the survey method:
Adopt leaflet butterfly additive process: be culture dish bottom paving one deck filter paper of 9 centimetres at diameter, and add the water moisturizing.10 in the same sizes of every ware picking, more healthy and stronger 3 early stage in ages armyworm larvae.The compound 1-33 that takes respectively 5mg Toosendanin, piperine acid, piperine ester, piperine alcohol, piperine aldehyde and embodiment preparation adds 5ml acetone, is made into the liquid that concentration is 1mg/ml.The oat leaf is cut into the little leaf butterfly of 1 * 1 centimetre, soaked in liquid to be measured 3 seconds, feed the examination worm after drying.Take acetone solution as the blank group.10 of every processing repeat 3 times.In under room temperature (25 ℃ of left and right), humidity 65%～80%, light application time is to raise under the condition of 12 hours/12 hours.Feed with normal leaf butterfly after 48 hours until sprout wings.The food ingestion of periodic logging insect, survivor of a murder attempt's number, reveal any symptoms etc. calculate the examination worm food refusal rate of 24 hours, 48 hours and final mortality ratio according to following formula.Measurement result sees Table 1.
Food refusal rate (%)=(the average food ingestion of the average food ingestion-treatment group of control group)/(the average food ingestion of control group) * 100
Final mortality ratio (%)=(the dead number of examination worm)/(the total number of examination worm) * 100
Correct mortality ratio (%)=(processing mortality ratio-contrast mortality ratio)/(1-contrasts mortality ratio) * 100
Table 1: piperine hydrazone/acylhydrazone/sulphonyl hydrazone analog derivative 1-33 to 3 age mythimna separata the food refusal toxic effect
Conclusion:
Result shows, in the time of 34 days, the cytotoxicity of compound (2,9,17,20,31,15,16,17,20) is all higher than commercial Toosendanin, therefore be expected to for the preparation of efficiently environmental protection, the plant insecticide of low toxicity.
Claims (4)
1. piperine hydrazone/acylhydrazone/sulphonyl hydrazone analog derivative, is characterized in that, its chemical general formula is:
In formula, R is respectively:
2. the preparation method of piperine hydrazone/acylhydrazone claimed in claim 1/sulphonyl hydrazone analog derivative, it is characterized in that, by hydrolysis, esterification, reduction and oxidation obtain piperine aldehyde, then respectively with the phenylhydrazine that replaces, hydrazides, and sulfonyl hydrazide reaction, obtain serial piperine hydrazone/acylhydrazone/sulphonyl hydrazone analog derivative, specifically follow these steps to preparation:
With a certain amount of piperine aldehyde and corresponding substituted phenylhydrazines/hydrazides/sulfonyl hydrazide anhydrous alcohol solution, drip two Glacial acetic acid in backward mentioned solution, be heated to reflux, TLC follows the tracks of detection, after reaction finishes, separate to get required sterling with the preparation silica gel thin sheet after concentrating.
3. method as claimed in claim 2, is characterized in that, substituted phenylhydrazines used, hydrazides and sulfonyl hydrazide are respectively:
A, phenylhydrazine class: ortho-nitrophenyl hydrazine, paranitrophenylhydrazine, 2,3,5,6-tetrafluoro phenylhydrazine;
b, hydrazides class: acethydrazide, cyano acethydrazide, benzoyl hydrazine, to the toluyl hydrazine, between the toluyl hydrazine, adjacent toluyl hydrazine, the para hydroxybenzene formyl hydrazine, p-nitrobenzoylhydrazide, the m-nitro formyl hydrazine, to the methoxybenzoyl hydrazine, the meta-methoxy benzoyl hydrazine, 3, 4-dimethoxy benzoyl hydrazine, the O-ethoxyl formyl hydrazine, to the fluorobenzoyl hydrazine, between the fluorobenzoyl hydrazine, the m-chloro benzoyl hydrazine, adjacent chlorobenzoyl hydrazine, 2, 4, 6-trichlorobenzene formyl hydrazine, the cigarette hydrazine, the vazadrine, 2-thenoyl hydrazine, 5-chloro-2-thenoyl hydrazine, 5-bromo-2-thenoyl hydrazine,
C, sulfonyl hydrazines: benzol sulfohydrazide, p-toluene sulfonyl hydrazide, to the ethylbenzene sulfonyl hydrazide, to anisole sulfonyl hydrazide, brosyl hydrazine, m-nitro sulfonyl hydrazide, to chlorine m-nitro sulfonyl hydrazide.
4. piperine hydrazone/acylhydrazone claimed in claim 1/sulphonyl hydrazone analog derivative is for the preparation of the application of plant insecticide.
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| CN104592209A (en) * | 2015-01-21 | 2015-05-06 | 华东师范大学 | Piperine-class novel derivative as well as preparation method and application thereof |
| CN107892685A (en) * | 2017-10-26 | 2018-04-10 | 西北农林科技大学 | Pipering analog derivative, preparation method and its application for preparing plant insecticide |
| CN110003160A (en) * | 2019-05-14 | 2019-07-12 | 贵州中医药大学 | A kind of Osthole hydrazone class/acylhydrazone class/sulphur acylhydrazone and preparation method thereof and application |
| CN110627692A (en) * | 2019-10-14 | 2019-12-31 | 河南科技大学 | Paeonol benzenesulfonylhydrazone and derivative thereof, preparation method of paeonol benzenesulfonylhydrazone and derivative thereof, botanical insecticide and application of botanical insecticide |
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| CN110627692B (en) * | 2019-10-14 | 2021-09-24 | 河南科技大学 | Paeonol benzenesulfonylhydrazone and derivative thereof, preparation method of paeonol benzenesulfonylhydrazone and derivative thereof, botanical insecticide and application of botanical insecticide |
| CN114621160A (en) * | 2022-03-29 | 2022-06-14 | 西北农林科技大学 | Piperine oxime ester derivative, preparation and application |
| CN114621160B (en) * | 2022-03-29 | 2024-04-16 | 西北农林科技大学 | Piperine oxime ester derivative, preparation and application |
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