CN1067397C

CN1067397C - Crowndaisy chrysanthemum extract compound, preparing method and use thereof

Info

Publication number: CN1067397C
Application number: CN97106696A
Authority: CN
Inventors: 吴毓林; 高阳; 徐汉虹
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 1997-11-04
Filing date: 1997-11-04
Publication date: 2001-06-20
Anticipated expiration: 2017-11-04
Also published as: CN1178633A

Abstract

The present invention relates to a dioxa spiro chrysanthemum coronarium prime compound having an unsaturated side chain. The present invention has a molecular formula (the right formula), wherein R=the unsaturated alkyl or heterocycle of H or C2-14, and R<1>= the unsaturated alkyl and heterocycle of C2-14. The dioxa spiro chrysanthemum coronarium prime compound is synthesized by furan alcohol or butanol through a simple way. The compound has aphagia physiological activity and is a compound which has anti-insect activity and is suitable for industrial production.

Description

A kind of Garland chrysanthemum extract compounds, preparation method and its usage

The present invention relates to a kind of Garland chrysanthemum extract compounds, preparation method and be used for the purposes of antifeedant for insect with dioxo spiro ring structure of unsaturated terminal chain

Add up according to pertinent data, the investment that is used for the agrochemistry aspect in the world wide every year surpasses 4,000,000,000 dollars and expense wherein over half is used for sterilant but annually still have the farm crop about 15% to run off in vain because of the food of raising of insect, and the influence that causes thus is especially serious in developing country of the third world.How world population prevents disease and pest with phenomenal growth in 10 years of future, increases crop yield, and the needs that satisfy the population growth have become a very urgent problem.

The protection of current farm crop mainly depends on the application of phosphoramidite chemical sterilant, though these compounds are very effective but shortcoming also is conspicuous, because these compounds seldom have selectivity insect are had large-scale lethality, usually when killing off the insect pests, the insect of other kind also is unable to escape misfortune, comprising the natural enemy of these insects.And after insect developed immunity to drugs to agricultural chemicals, the dosage that then needs to strengthen sterilant just can reach the harmful purpose of going out, and so caused vicious cycle, and its direct result is to destroy the eubiosis, causes environmental pollution.Synthetic pesticide generally is difficult to decompose, and also is difficult to by the crop absorption metabolism, and residual agricultural chemicals is trapped in for a long time on the agricultural-food human body and livestock are also caused very big harm.In order to address these problems, just need the new prevention and elimination of disease and pests method of exploitation.

Each kind of plant of occurring in nature has been showed colourful disease and pest hedge to us, and the bioactive molecules of seeking new prevention and elimination of disease and pests for us provides abundant source, and wherein the research and development of antifeedant for insect are especially prominent over past ten years.Antifeedant for insect is meant and hinders the insect feed, rather than the chemical substance that insect is directly killed, and insect usually remains in around the food refusal source, and until because of hungry dead, it also can be called raises food hold back agent or sense of taste repellent (Munakadta, K.; Appl.Chem., 1975,42,57), Van professor Beek of Dutch agriculture university has summed up the advantage of desirable antifeedant in detail: 1. plant-less toxicity; 2. to human animal, beneficial insect and other biological nontoxicity; 3. stop insect as much as possible to invade food; 4. these pest species are optionally shown toxicity; 5. when low-down concentration, still has activity; 6. lasting medicine; 7. not toxigenicity or peculiar smell metabolite; 8. can be by plant absorbing and metabolism; 9. easy application cheap and easy to get; 10. do not conflict mutually with the additive method of the prevention and control of plant diseases, pest control; 11. do not change taste, the size and appearance of product; 12. insect is developed immunity to drugs; 13. can storage-stable.For a kind of compound, even only satisfied some above-mentioned requirement, it still has using value, because it can use to reach than single means prevention effect widely with other crop pest control methods are common.

Current, it mainly is owing to do not reach requirement that the application of antifeedant for insect is restricted, and is difficult to usually obtain in a large number.Most natural antifeedant for insect complex structures are difficult to synthesize easily, and extract antifeedant because its content is low from occurring in nature, and investment is big, unpractical often (S.V.Ley, P.L.Toogod, Chemistry in Britain, 1990,31.).

Crowndaisy chrysanthemum has another name called crowndaisy chrysanthemum, is composite family Chrysanthemum vegetable formal name Chrysantheum segetum L. (Composetae), is the common vegetables of spring and autumn in the south of the lower reaches of the Yangtze River, and crowndaisy chrysanthemum has unique perfume, is not subjected to general insect infestations.We wish and can seek non-harmful natural antifeedant for insect from crowndaisy chrysanthemum one class food plant, by the analysis to the crowndaisy chrysanthemum derived essential oil, isolate a kind of compound 1-Z and 1-E with obvious antifeedant activity, Chinese popular name called after crowndaisy chrysanthemum element (Z.H.Wu, J.Wang, J.C.Li, Y.Z.Chen, A.J.Yu, Z.R.Feng, J.Shen, Y.L.Wu, P.F.Guo, Y.L.Wang, Natural Product R﹠amp; D (China)), this is the spiro ketal enol ether compound that has a long-chain conjugation alkynes side chain of a structure uniqueness.

The crowndaisy chrysanthemum element is expected to be used for crop disease and pest resisting and crop, might develop into a class novel pesticide.But from natural crowndaisy chrysanthemum element, separate to such an extent that activeconstituents can not satisfy the demands, could obtain some products because will change a lot of labours owing to content is low, and in sepn process, its active constituent mutability, as pass through synthetic work, also can further improve its activity, so Wu Yulin etc. provided once Crowndaisy chrysantheins compound (CN931124449-4) to have following chemical formula A or B;

A furans formula crowndaisy chrysantheins is like thing B volution formula crowndaisy chrysantheins like R in the thing formula be unsaturated alkyl as

R ¹CH=CH; R ²CH ≡ CH; Heterocycle as

X is H; Electron donating group such as OCH ₃OC ₂H ₅Electron-withdrawing group such as NO ₂CNR ¹Be alkyl, preferential C _1-5R ²Be alkyl; Thiazolinyl; Alkynyl; The three is preferential Heterocycle as

The synthetic method system of this Garland chrysanthemum extract compounds adopts furfural cheap and easy to get to make raw material, press currently known methods (Org.Shy.Coll III, 425) be prepared into furfuracrylic acid, again with Raney nickel reduce the furans propionic acid, get the furans propyl alcohol through lithium aluminium hydride reduction, continue and the butyllithium effect gets 5-position lithium compound, in same reaction flask, react again with unsaturated aldehyde, get final product a class furans formula crowndaisy chrysantheins like thing, acid treatment can cyclisation get volution formula crowndaisy chrysantheins like thing.We wish further by the novel antifeedant to the researchdevelopment one class high-efficiency low-toxicity of Garland chrysanthemum extract compounds thus.

The purpose of this invention is to provide a kind of new Garland chrysanthemum extract compounds, is a kind of dioxo spiro cyclic cpds with unsaturated terminal chain.

Another object of the present invention provides the method for the above-mentioned Garland chrysanthemum extract compounds of preparation.

Purpose of the present invention also provides the purposes of this class Garland chrysanthemum extract compounds.

Garland chrysanthemum extract compounds of the present invention has following molecular formula,

, n=1 or 2 wherein,

Singly-bound one or two key=, R=H, unsaturated alkyl or heterocyclic radical, R ¹Be unsaturated alkyl or heterocyclic radical.Described unsaturated alkyl can be C _2-14The insatiable hunger alkyl, as R ³CH=CH, R ⁴CH ≡ CH can be aryl or substituted aryl, as PhX, XPhCH=CH, XPhY or Ph; Described heterocyclic radical is

Base, wherein R ³=C _1-5Alkyl, thiazolinyl, alkynyl or phenyl, R ⁴=C _1-5Alkyl, thiazolinyl, alkynyl, phenyl or , R ²=C _1-4Alkyl or benzyl.X or Y=H, electron donating group or electron-withdrawing group.Electron donating group such as OCH ₃, OC ₂H ₅, Cl, Br, electron-withdrawing group such as NO ₂, CN etc., XY can also be a methylene-dioxy In this molecule when n=1 and When being two key, remove R ⁴ Among PhBr, PhCl or the XPhY beyond X and the Y ≠ H, R ≠ H.In other words, compound of the present invention can be

During R ≠ H,

X and Y ≠ H; Br or

Anti-synthesis analysis shows that the precursor of compound 1 can have two route of synthesis, article one, can directly be cut to furans propanol compounds and 2,4-hexadiyne aldehyde, another can be cut to 1, the furtural compound that 3-pentadiine and 5-alkyl replace, but final all can be by the 2-furans propyl alcohol of easy preparation as starting raw material.So compound of the present invention can be made by following several method.With molecular formula be

2 2-furans propyl alcohol or butanols are raw material, with known method and butyllithium and unsaturated aldehydes or ketones React the furans diol compound, Productive rate:

Can be described as furans formula crowndaisy chrysantheins again like thing.Specifically 2-furans propyl alcohol or butanols and contain butyllithium polar solvent and

Unsaturated aldehydes or ketones reacted 1-5 hour down to-78 ℃ in room temperature.Three's mol ratio is followed successively by 1: 1-1000: 0.8-10.Adding more unsaturated aldehydes or ketones and butyllithium also is to help reaction.For increasing lithium salts solubleness in solvent, add complexing agent usually, as Tetramethyl Ethylene Diamine, carry out to add fast response.The mol ratio of furans propyl alcohol or butanols and complexing agent can be 1: 1-0.001.

Compound 2 can also be protected with ethanoyl; obtain acetylate 5, again through Vismier-Hack reaction (P.Deshong, R.E.Waltermire; H.L.Ammon; J.Am.Chem.Soc., 1988,110; 1901.); produce compound 6, compound 6 and the reaction of alkynyl negatively electronization compound obtain compound 7 and a small amount of 4,7 again deacetylation change into compound 4-1.

Specifically, compound 2 reacted 1-10 hour to room temperature in 0 ℃ in the polar solvent that contains 4-(N, N-dimethyl amido) pyridine (abbreviation DMAP) with aceticanhydride, and the mol ratio that promptly obtains compound 5, compound 2, aceticanhydride and DMAP is 1: 1-5: 0.1-1.Compound 5 and phosphorus oxychloride are in polar solvent, and-10 ℃ were reacted 0.5-5 hour to room temperature, generated compound 6, and compound 5 is 1 with the phosphorus oxychloride mol ratio: 0.8-5.Compound 6 is 1 with alkynyl negatively electronization compound mol ratio: 0.5-1000, in solvent and 0 ℃ to the room temperature reaction promptly generated compound 7 and a small amount of compound 4 in 0.5 to 10 hour.The monovalence metal carbonate or the supercarbonate of compound 7 and 0.1-20 times of mol ratio, in polar solvent, room temperature to reflux temperature reacted 1-20 hour down, converted compound 4 to.

Cyclization can take place with protonic acid, silica gel, ion exchange resin or Louis (Lewis) acid catalysis and generate Garland chrysanthemum extract compounds in aforesaid compound 4

Described protonic acid is mineral acid, hydrosulfate, dihydrogen phosphate such as HCl, H ₂SO ₄, H ₃PO ₄, KHSO ₄, NaHSO ₄, KH ₂PO ₄, NaH ₂PO ₄Deng, described Lewis acid is mantoquita, molysite, silver salt, composite salt and boride, as CuSO ₄, CuSO ₄3H ₂O, CuSO ₄5H ₂O, Cu (OSO ₂CF ₃) ₂, FeCl ₃, Fe ₂(SO ₄) ₃3H ₂O, Fe ₂(SO ₄) ₃6H ₂O, Fe ₂(SO ₄) ₃9H ₂O, Fe ₂(SO ₄) ₃12H ₂O, Fe wherein ₂(SO ₄) ₃3H ₂O and Fe ₂(SO ₄) ₃6H ₂More common, the AgClO of O ₄, florisil, BF ₃(OC ₂H ₅) ₂Deng.

The cyclodehydration reaction can be selected polarity or non-polar solvent according to different catalyzer, as benzene,toluene,xylene, naphthenic hydrocarbon, alkane, pyridine, ethyl acetate, acetone, methylene dichloride, chloroform, tetracol phenixin, acetate, tetrahydrofuran (THF), acetonitrile, dimethyl formamide, chloroform, methylene dichloride, tetracol phenixin etc.

The cyclodehydration temperature of reaction can be room temperature to reflux temperature, heat usually and carry out helping to add fast response.

The dehydration reaction catalyst levels, being generally described furans diol compound and catalyst molar ratio is 1: 0.01-50 because catalyzer is inexpensive, also is to help reaction so adopt more catalyzer, recommends mol ratio to be followed successively by 1: 0.5-1., as R=H in the compound 4,

The time, directly carrying out silica gel column chromatography, relatively can realize transforming under the mild conditions.But productive rate is lower.And with catalysis under tosic acid pyridinium salt (be called for short PPTs) the non-polar solvent room temperature, productive rate is 85%.The Lewis acid catalysis also can obtain satisfactory result, as blue vitriol, To reflux temperature, conversion yield is 92% to ferric sulfate etc. in non-polar solvent and room temperature, partly the results are shown in Table shown in 1.

Table 1. furans glycol catalytic cyclization reaction and productive rate

Reagent and condition: ⅰ) Ac ₂O, pyridine, DMAP, 84%.ⅱ)POCl ₃，DMF，91％ⅲ)Pentadiyne，BuLi，69％。ⅳ), KHCO ₃, MeOH-H ₂O, 90%, ⅴ) CuSO ₄5H ₂O, toluene, 70 ℃, 92%

2-position furans butanols is through acetylize; the Vilsmier-Hack reaction obtains compound; compound 9 and 1; the reaction of 3-pentadiine obtains compound 10 with 69% productive rate; 10 slough protecting group obtains compound 11 with 90% productive rate; handle two mixture of isomers that obtained compound 8-2 at last with 92% productive rate through copper sulfate again; analyze from nuclear magnetic spectrum; the ratio of two isomer is 8-2Z/8-2E=2: 1; the selectivity of 1Z slightly improved when the synthetic crowndaisy chrysanthemum of the selectivity ratios of 8-2Z isomer was plain, and this compound also has and fragrance like the crowndaisy chrysantheins.

1,4-dioxy-2-butyne is at DMSO-H ₂Obtain 1 through the KOH processing in the O system, the 3-diacetylene (L.Brandsma, in " Preparative " Acetyienic Chemistry " 2nd td, EIsvier, Amsterdam, 1988,179).

1, the 3-diacetylene is handled through butyllithium and is slowly dropped to then in the THF solution of furan compound 6 (n=1), yet because 1, the 3-diacetylene is a gas, is difficult to control on amount, and we only obtain required product 12 with 13% productive rate.

Reagent and condition: ⅰ) .a, BuLi, b.33,13%; ⅱ) KHCO ₃, MeOHH ₂O11) .CuSO ₄5H ₂O, toluene, 80-70 ℃, 22% compound 12 is sloughed protecting group and has only been obtained the finished product 14 with 22% productive rate without separating direct cyclisation,

Garland chrysanthemum extract compounds 8 of the present invention, alternative hydrogenation.In polar solvent, when moles of hydrogen hydrogenation such as using, two keys in the furan nucleus can be hydrogenated to singly-bound, further the two keys of the enol ether that hydrogenation can be other with furan nucleus further be hydrogenated to singly-bound.Also can directly above-mentioned two two keys be reduced into the singly-bound compound.Usually adopt Pd-C to make catalyzer, directly the method for logical oxygen.Catalyst levels is generally 0.01-1.

When above-mentioned hydrogenation, R and R ¹During for unsaturated aromatic hydrocarbon, changing effect is more apparent

Work, as under the room temperature with Pd-C as catalyzer, dehydrated alcohol is made solvent, and compound 8-3 is carried out catalytic hydrogenation reaction, and we have successfully obtained the analogue of complete this small molecules spiro ketal insect pheromone of hydrogenation products compound 16-1 with 59% productive rate as a result. Choose appropriate reaction conditions, reaction can be controlled at and have only on the common ring two keys to be hydrogenated the spiro ketal enol ether compound of this step with the class formation uniqueness shown in a large amount of synthetic compound 15-1, we have obtained compound 15-1 with 81% productive rate the amount by the control hydrogenation.Compound 15-1 is carried out same hydrotreatment, and the hydrogen of the monovalent of 15-1 absorption as a result obtains compound 16-1 with 70% productive rate.

With compound 23 be substrate we obtained compound 14-2 and 15-2 with similar result.

The crowndaisy chrysanthemum element has antifeedant activity, and Garland chrysanthemum extract compounds of the present invention is because of having similar structures, so infer to have similar activity.As work as R=H,

During n=1, no matter under 1/200 concentration or 1/400 concentration to the small cabbage moth antifeedant activity apparently higher than Kuliansu commodity Magoson (containing nimbin 0.3%), cabbage caterpillar has been shown very high antifeedant activity, this compound aromatic ring structure will show stable chemical property, has industrial actual application prospect.

Garland chrysanthemum extract compounds of the present invention not only raw material is easy to get, and synthetic route is simple and easy, and productive rate is higher, and presents the food refusal physiologically active, is a kind of agricultural chemicals with good prospect.

To help further to understand the present invention by following embodiment, but not limit content of the present invention.

The molten not calibrated infrared spectra of boiling point is by Shimadazu IR-440 among the embodiment, Perkin-Elmer 983 or Digilab FTIR type determination of infrared spectroscopy nucleus magnetic resonance are by Varian EM-360A, EM-390 or AMX-300, AMX-600 type nmr determination.Mass spectrum is measured high resolution mass spectrum by HP-5989A or VG Quattro GC/MS/MS type mass spectrograph and is measured by Institute of Analysis of this institute by the ultimate analysis of Finnigan MAT type Instrument measuring.

The reagent purifying is with reference to Purification of Laboratory Chemicals; D.D.Perrin, W.L.F.Armarego and D.R.Perrin Eds.; Pergamon Press:Oxford, 1980.Rapid column chromatography all carries out aqueous sulfuric acid (ammonium molybdate and the sulfuric acid that thin-layer chromatography adopts ammonium molybdate on silica gel H (400 order) or neutral alumina (300 order), the weight ratio of water: 1: 1: 15) sprays the post-heating colour developing, perhaps adopt the colour developing of potassium permanganate solution and iodine cylinder.Embodiment 1: compound 4-3's is synthetic

0.63g (5.0mmol) furans propyl alcohol (5.5mmol) is dissolved in the 10mL anhydrous polar solvent, add 1.8mLTMEDA (11.8mmol), 0 ℃ is chilled to-78 ℃ behind dropping 7.8mL (1.6M) the n-BuLi-hexane solution stirring at room 2-3hr down, slowly drip the THF solution of phenyl aldehyde 1.06g (10mmol),-78 ℃ of stirrings slowly rise to the saturated NH4Cl solution of stirred overnight at room temperature cancellation reaction ethyl acetate extraction (15mL * 4) after 4 hours, saturated common salt water washing anhydrous sodium sulfate drying column chromatography gets product 840mg, productive rate 72%, recrystallization get the particulate state crystal.

mp：?62-63℃

IR(film)：3352,3064,3031,2945,2880,1603,1558,1494,1452；

¹H-NMR(600MHz,CD ₃COCD ₃)7.42(2H,d,J=7.2Hz),731(2H,m),7,24(1H,m),5.95(1H,d,J=2.6Hz),5.93(1H,d,J=2.6Hz),5.70(1H,s),3.53(2H,t,J=6.3Hz),3.21(2H,s,-OH),2.61(2H,t,J=7.5Hz),1.76(2H,m)ppm；

MS(m/z)232(M ⁺,?40),215(182),214(77),197(35),183(1000,173(42),105(73),77(47)；

HRMS (m/z): juice calculation value C ₁₄H ₁₆O ₃: 232.1099; Measured value: 232.1126. embodiment 2 compound 4-4's is synthetic:

According to embodiment 1 noted earlier, 0.517g (4.1mmo1) furans propyl alcohol and 1.49g (8.2mmol) benzophenone react 750mg product yield 59%

mp：99.5-100℃；

IR(KBr)：3356,3184,3061,3036,2937,1599,1585,1548,1493,1447；

¹H?NMR(300MHz,CD ₃COCD ₃)：7.24-7.36(10H,m)，5.98(1H,m)，5.81(1H,d,J=3.2Hz)，3.54(2H,t,J=6.3Hz),3.17(1H,s,-OH),3.14(1H,s,-OH),2.64(2H,t,J=7.5Hz),1.78(2H,tt,J=6.3Hz,7.5Hz)ppm；

MS(m/z)：308(M ⁺,15),291(87),290(83),259(29),231(57),105(100)；

Analysis calculated value C ₂₀H ₂₀O ₃: C, 77.90; H, 6.54; Measured value: C, 77.82; H, 6.54. embodiment 3 compound 4-2's is synthetic:

According to typical operation one noted earlier, 0.96g (7.5mmol) furans propyl alcohol and 2.25g (15.0mmol) piperonylaldehyde react 1.29g product yield 62%.

IR(film)：3420,2591,2893,1604,1559,1503,1488,1444；

¹H?NMR(600MHz,CD ₃COCD ₃)：6.93(1H,s,),6.88(1H,d?J=7.3Hz),6.77(1H,d,J=7.9Hz),5.98(1H,d?J=2.5Hz),5.94(3H,m),5.62(1H,s),3.54(2H,t,J=6.3Hz),3.27(2H,s,-OH),2.61(2H,t,J=7,5Hz),1.77(2H,tt,J=6.5Hz,7.4Hz)ppm；

MS (m/z): 276 (M ⁺, 9), 259 (31), 258 (100), 241 (6), 230 (38), 227 (47), 174 (28) 149 (29); HR MS: calculated value C ₁₅H ₁₄O ₄(M ⁺-H ₂O): 258.0892; Measured value: 258 0879. embodiment 4

As described in the embodiment 1, unsaturated aldehyde or reactive ketone with different make the furans propylene glycol, and be as shown in the table with furans propyl alcohol or butanols.

Embodiment 5 compound 8-4's is synthetic:

70 ℃ of following 200mg compound 4-3 (0.86mmol) heat 40-80 ℃ through the equimolar cupric sulfate pentahydrate of 1-2 in 100ml toluene, stirred 1-5 hour, TLC shows that raw material elimination filtration filter residue merges organic phase with the ether washing and concentrates the neutral alumina column chromatography, obtains product 179mg, productive rate 97%.

IR(film)：3086,3022,2984,?2981,1653,1594,1492,1449,

¹H?NMR(300MHz,C ₆D ₆)：7.88(2H,m),7.31(2H,m),7.11(1H,m),5.96(1H,d,J=5.5Hz),5.72(1H,dd,J=0.7Hz,5.6Hz),5.34(1H,s),4.00(1H,m),3.67(1H,m),2.00-1.88(2H,m),1.62-1.46(2H,m)ppm；

MS(m/z)：215(M ⁺+1,29),214(M ⁺,58),184(25),172(13),158(17),127(21),115(100),53(86)；

HR MS: juice calculation value C ₁₄H ₁₄O ₂: 214.0994; Measured value 214.0955. embodiment 6 compound 8-4's is synthetic:

Obtain product 273mg, productive rate 97% according to 4,60 ℃ of following 300mg compound 4-4 of embodiment noted earlier (0.97mmol) cupric sulfate pentahydrate processing through equivalent in toluene.

mp：143.5-144.5℃；

IR(KBr)：3060,3030,2990,2880,1627,1595,1585,1491,1442；

¹H?NMR(300MHz,C ₆D ₆)：7.80(2H,m),7.28-7.05(8H,m),6.23(1H,d,J=5.6Hz),5.72(1H,d,J=5.6Hz),398(1H,m),3,67(1H,dd,J=7.6Hz,15.2Hz),2.00-1.87(2H,m)，1.69-1.47(2H,m)ppm；

MS(m/z)：291(M ⁺+1,24),290(M ⁺,100),272(15),262(48),206(56),191(29),165(40)；

Calculated value C ₂₀H ₁₈O ₂: C, 82.73; H, 6.25; Measured value C, 82.79; H, 6.24. embodiment 7 compound 8-1's is synthetic:

Obtain product 240mg, productive rate 92% according to 4,80 ℃ of following 278mg compounds 15 of embodiment noted earlier (1.0mmol) cupric sulfate pentahydrate processing through equivalent in toluene.

mp：92-93℃；

IR(KBr)：3080,2898,1655,1586,1504,1484,1442；

¹H?NMR(300MHz,C ₆D ₆)：7.78(1H,s),7.10(1H,dd,J=1.0Hz,8.0Hz),6.79(1H,d,J=8.1Hz),5.95(1H,d,J=5.5Hz),5.69(1H,d,J=5.5Hz),5.35(2H,d,J=3.7Hz),5.27(1H,s),3.92(1H,m),3.63(1H,m),1.93-1.82(2H,m),1.69-1.44(2H,m)ppm；

MS(m/z)：259(M ⁺1),258(M ⁺,100),230(26),216(4),188(5),174(17),144(10),116(10),115(10)；

Calculated value C ₁₅H ₁₄O ₄: C, 69.77; H, 5.46; Measured value C, 69.77; H, 545. embodiment, 8 furans butanols synthetic:

5.73g furans butyric acid (37.9mmol) is dissolved in and makes system be slight boiling condition in the mixture that the 40mL anhydrous diethyl ether slowly adds 1.75g aluminium lithium hydrogen and 60mL ether to dropwise the back and refluxed 2 hours, add suitable quantity of water and decompose unnecessary LiAlH ₄, adding the mixed solution that 20g oxalic acid 6mL hydrochloric acid and water is made into again and tell ether layer water layer with ether extraction (30mL * 3), combined ether layer saturated common salt water washing anhydrous sodium sulfate drying evaporating column chromatography gets furans butanols product 3.75g, productive rate 79%.

¹H NMR (CCl4,90MHz): 7.22 (1H, s), 6.19 (1H, d, J=3.5Hz), 5.90 (1H, d, J=3.5Hz), 3.56 (2H, t, J=5.7Hz), 2.64 (2H, t, J=73Hz), 1.62 (4H, m) ppm embodiment 9 compound 4-8's is synthetic:

0.966g furans butanols (6.9mmol) is dissolved in 40mL THF, add 2.37mL (15.8mmol) TMEDA, 0 ℃ drips 6.8mL (2.3M down, 15.8mmol) BuLi hexane solution stirring at room after 4 hours, be chilled to-78 ℃, (20ml) solution-78 ℃ following reaction that adds the 1.54g thiophenecarboxaldehyde slowly rose to stirred overnight at room temperature, saturated NH after 4 hours ₄Cl solution cancellation reaction, ethyl acetate extraction anhydrous sodium sulfate drying si-enriched plastic column chromatography (PE: EA=2: the 1+0.5% triethylamine) get product 1.24g, productive rate 71%.

IR(film)：3407,2945,1650,1580,

¹H?NMR(600MHz,CD ₃COCD ₃)：729(1H,dd,J=1.2Hz,5.0Hz),?6.93(1H,m),6.90(1H,dd,J=3.5Hz,5.0Hz),6.07(1H,d,J=3.0Hz),5.92(1H,d,J=3.0Hz),5.91(1H,s),3.48(2H,t,J=6.4Hz),3.17(2H,s,-OH),2.54(2H,t,J=7.6Hz),1.61(2H,m),1.49(2H,m)ppm；

MS(m/z)：235(M ⁺+1-H ₂O,18),234(M ⁺-H ₂O,100),178(19),176(39),150(21),124(26)；

Calculated value C ₁₃H ₁₆O ₃S:C, 61.88; H, 6.39; S, 12.71; Measured value C, 61.92; H, 6.47; S, 13.20. embodiment 10 compound 8-5's is synthetic:

According to embodiment 4 noted earlier, 70-80 ℃ of following 445mg compound 30 (1.76mmol) cupric sulfate pentahydrate processing through equivalent in toluene obtains product 400mg, productive rate 97%.

IR(film)：3098,2945,2877,16459,1582,1648,1244；

¹H-NMR(600MHz,C ₆D ₆)：7.27(1H,d,J=3.4Hz)，7.22(1H,d,J=5.1Hz)，7.05(1H,dd,J=3.4Hz，5.1Hz),6.08(1H,d,J=5.6Hz),6.02(1H,d,J=5.6Hz)，5.82(1H,s),4.47(1H,m),3.91(1H,m),2.35(1H,m),1.85-1.66(5H,m)ppm；

MS(m/z)：234(M ⁺,100),217(4),189(13),176(27),150(15),123(19)；

Calculated value C ₁₃H ₁₄O ₂S:C, 66.64; H, 6.02; S, 13.68; Measured value: C, 66.64; H, 6.26; S, 13.66. embodiment 11 compound 5-2's is synthetic:

129g (92mmol) furans butanols is dissolved in 0 ℃ of acetic anhydride and 0.233g DMAP (1.86mmo1) that adds 11.4g (112 mmol) down of 1.4mL pyridine, stirred 8 hours under the room temperature, add the dilution of 50ml ether, earlier respectively with water and copper/saturated copper sulphate solution washing (10ml * 2), concentrate the back crude product with silica gel column chromatography (P: E=25: 1) with water and saturated common salt water washing anhydrous sodium sulfate drying respectively again, get product 1.407g, productive rate 84%.Embodiment 11 compound 6-1's is synthetic:

1.30g being dissolved under 0 ℃ of the 4.3ml methylene dichloride, phosphorus oxychloride (8.5mmol) slowly drops among the DMF of 0.63g (8.6mmo1), equality of temperature stirred 0.5 hour, 1.29g being dissolved in the 9ml methylene dichloride, furans butanols ethyl ester (8.0mmol) slowly drops in the above-mentioned reaction system, rise to stirring at room add after three hours 30ml saturated sodium carbonate solution and 30ml methylene dichloride tell the organic layer organic phase with 30ml saturated nacl aqueous solution washing anhydrous sodium sulfate drying vacuum concentration silica gel column chromatography (PE: EA=7: 1) product 0.94g, productive rate 91%.

Rf=0.3 (PE: EA=7: 1) embodiment 12 compounds 10 is synthetic:

0.46g1 3-pentadiine (7.1mmo1) is dissolved in the anhydrous THF of 10mL, adds 1.07mL TMEDA (11mmo1), is chilled to-78 ℃, N ₂The hexane solution-78 that protection drips down 3.1mL (2.3M) n-BuLi ℃ stirs down and to rise to after 30 minutes in the THF solution that slowly drops to 0.94g (4.5mmol) substituted furan alditol under 0 ℃ of the room temperature (20ml); added in 30 minutes to stir and spend the night, add the saturated NH of 10mL ₄Cl solution cancellation reaction; ethyl acetate extraction has and severally concentrates thick product with silica gel column chromatography (PE: EA=6: 1 with saturated common salt water washing anhydrous sodium sulfate drying; 2: the 1+0.5% triethylamine), get the product overall yield 68.5% of 741mg product and 84mg deacetylate.

IR(film,cm ^-1)：3421,2954,2260,2237,1734,1557,1508,1434,1246；

¹H?NMR(600MHz,CD ₃COCD ₃)：6.28(1H,d,J=2.8Hz)，6.03(1H,d,J=2.7Hz),?5.44(1H,s),4.06(2H,t,J=6.0Hz),3.19(1H,s,-OH),2.64(2H,m),1.99(3H,s),1.94(3H,d,J=0.7Hz),1.68(4H,m)ppm；

MS(m/z)：275(M ⁺+1,6),274(M ⁺,32),257(45),196(48),169(54),115(57),91)59),43(100)；

Calculated value C ₁₆H ₁₈O ₄: C, 70.06; H, 6.61; Actually be worth; C, 70.12; H, 6.75). synthesizing of embodiment 13 compounds 11:

150mg raw material (0.55mmol) is dissolved in 10mL methyl alcohol and adds 2mL water, the 560mg saleratus stirred 12 hours down for 60 ℃, boil off methyl alcohol, water layer is with ethyl acetate extraction (20mL * 3), saturated common salt water washing anhydrous sodium sulfate drying si-enriched plastic column chromatography (P: E=1.5: 1, + 0.4% triethylamine) gets product 114mg, productive rate 90%.

mp：78-80℃；

IR(KBr,cm ^-1)：3408,3300,2948,2872,2235,2138,1581,1509,1438,1370；

¹H?NMR(600MHz,CD ₃COCD ₃)：6.41(1H,d,J=2.8Hz),6.15(1H,d,J=2.4Hz),5.58(1H,s)3.69(2H,t,J=6.3Hz),3.34(2H,s,-OH),2.75(2H,t,J=7.2Hz),2.08(3H,s),1.83(2H,m),1.71(2H,m)ppm；

MS(m/z)：215(M ⁺-OH,31),214(M ⁺-H ₂O,100),199(9),185(28),169(19),156(38),129),115(25)；

Anal. calculated value C ₁₄H ₁₆O ₃: C, 72.39; H, 6.94; Measured value: C, 72.33; H, 6.92. embodiment 14 compound 8-2's is synthetic:

80mg raw material 51 (0.34mmo1) is dissolved in the following 100mg (0.4mmol) of adding of 10ml toluene stirring cupric sulfate pentahydrate and is heated to 75 ℃ of stirrings 2 hours, TLC shows that raw material disappears, remove by filter the copper sulfate filter residue and merge the concentrated neutral alumina column chromatography of organic phase (PE: EA=50: 1) get product 68mg, productive rate 92% with the amount of ethyl acetate washing.Nmr analysis shows that the ratio of two isomer is Z/E=2: 1.

IR(film,cm ^-1)：3095,3047,2948,2882,2231,2138,1631,1581,1441；

¹H?NMR(600M?Hz,C ₆D ₆)：

2-E：6.50(1H,d,J=5.5Hz),5.76(1H,d,J=5.6Hz),5.17(1H,s),4.01-3.84(2H,m),1.86-1.70(2H,m),1.49(3H,s),1.47-1.31(4H,m)ppm；

2-Z：5.75(1H,d,J=5.3Hz),5.57(1H,d,J=5.6Hz),4.52(1H,s),4.01-3.84(2H,m),1.86-1.70(2H,m),1.43(3H,s),1.47-1.31(4H,m)ppm；

MS(m/z)：215(M ⁺+1,21),214(M ⁺,100),199(9),185(29),171(21),156(41),143(12),129(22)；

HRMS (m/z): calculated value C ₁₄H ₁₄O ₂: 214.0994, measured value: 214.1017. embodiment 15 compounds 12 synthetic:

Under-78 ℃, to above-mentioned condensation 1, the hexane solution-78 that slowly drips 7mL (2.5M) n-BuLi among the anhydrous THF of 3-diacetylene ℃ stirs down and to rise to behind the 30min in the THF solution that slowly drops to 1.00g (5.1mmol) substituted furan alditol under 0 ℃ of the room temperature (20ml), and 30min adds to stir and adds the saturated NH of 10mL after 3 hours ₄Cl solution cancellation reaction, ethyl acetate extraction, organic phase are with the saturated common salt water washing, and anhydrous sodium sulfate drying concentrates thick product with silica gel column chromatography (PE: EA=2: 1 ,+0.5% triethylamine), get product 150mg, productive rate 13.3%.

IR(film)：3410,2961,1737,1718,1557,1434,1368,1248；

¹H?NMR(CD ₃COCD ₃,300MHz)：6.32(2H,d,J=3.2Hz),6.06(2H,dd,J=0.8Hz,3.3Hz),5.51(2H,s),4.08(4H,t,J=6.4Hz),3.15(2H,s,-OH),2.70(4H,t,J=7.4Hz),1.99(6H,s),1.95(4H,m)ppm.

MS(m/z)：442(M ⁺,8.0),424(M ⁺-H ₂O,100),406(18.7),382(24.8),364(47.8),277(43.7),247(74.6),235(53.5),155(74.6).

Calculated value C ₂₄H ₂₆O ₈: C, 65.15.H, 5.92; Measured value: C, 64.90.H, 5.97. embodiment 16 The furans glycol is perhaps used micro-HCl acidifying catalysis by the silicagel column column chromatography, or uses Cu++ Louis acid catalysis method as described in embodiment 15, and cyclodehydration is given birth to , the result is as shown in the table.

8.13	R ¹=p-CH ₃OC ₆H ₄R=p-CH ₃OC ₆H ₄n=1	3085,2895 1626,1606 1583,1463	7,84(2H,d,J=7.0Hz),7.72(2H,d,J=7-3Hz), 7.11(2H,d,J=7.0Hz),6.99(2H,d,J=7-3Hz), 6.25(1H,d,J=5.7Hz),5.72(1H,d,J=5.7Hz), 3.67(1H,m),3.9(1H,m), 2.00-1.87(2H,m),1.65-1.45(2H,m).	C:75.37 H:6.03	75.40 6.33	350(M ⁺)	97％
8.13	R ¹=p-CH ₃OC ₆H ₄R=p-CH ₃OC ₆H ₄n=1	3085,2895 1626,1606 1583,1463		C:75.37 H:6.03	75.40 6.33	350(M ⁺)	97％	8.14	R ¹=p-CH ₃OC ₆H ₄R=p-CH ₃OC ₆H ₄n=2	3085,2895 1626,1606 1581,1460	7.84(2H,d,J=7.1Hz),7.70(2H,d,J=7.0Hz), 7.09(2H,d,J=7.1Hz),7.01(2H,d,J=7.0Hz), 6.20(1H,d,J=5.6Hz),6.08(1H,d,J=5.6Hz), 4.47(1H,m),4.00(1H,m),2.39(1H,m), 1.90-1.65(5H,m)．	C:75.58 H:6.77	75.79 6.64	364(M ⁺)	91％
8.15	R ¹=PhC≡C- R=PhC≡C－ n=1	3095,3052 2192,1619 1582,1485	7.73-7.67(4H,m),7.27-7.17(6H,m), 6.50(1H,d,J=5.6Hz),5.95(2H,d,J=5.6Hz), 4.15(1H,m),3.80(1H,m),2.07(2H,m), 1.76-1.63(2H,m).	C:85.11 H:5.37	85.17 5.37	338(M ⁺)	91％	8.14	R ¹=p-CH ₃OC ₆H ₄R=p-CH ₃OC ₆H ₄n=2	3085,2895 1626,1606 1581,1460		C:75.58 H:6.77	75.79 6.64	364(M ⁺)	91％
8.15	R ¹=PhC≡C- R=PhC≡C－ n=1	3095,3052 2192,1619 1582,1485		C:85.11 H:5.37	85.17 5.37	338(M ⁺)	91％	8-16	R ¹=PhC≡C- R=PhC≡C- n=2	3095,3050 2195,1618 1581,1486	7.74-7.67(4H,m),7.27-7.15(6H,m), 6.47(1H,d,J=5.6Hz),6.00(1H,d,J=5.5Hz), 4.49(1H,m),4．01(1H,m),2.37(1H,m), 1.87-1.60(5H,m)．	C:85.25 H:5.70	85.19 5.72	352(m ⁺)	93％
8.17	R ¹=C ₆H ₅R=PhC≡C- n=1	3095,3060 2192,1617 1582,1485	7.80-7.67(4H,m),7.28-7.05(6H,m), 6.34(1H,d,J=5.6Hz),5.90(1H,d,J=5.6Hz), 4.15(1H,m),3.79(1H,m),2.04(2H,m), 1.77-1.65(2H,m)．	C:84.14 H:5.73	84.04 5.77	314(m ⁺)	95％	8-16	R ¹=PhC≡C- R=PhC≡C- n=2	3095,3050 2195,1618 1581,1486		C:85.25 H:5.70	85.19 5.72	352(m ⁺)	93％
8.17	R ¹=C ₆H ₅R=PhC≡C- n=1	3095,3060 2192,1617 1582,1485		C:84.14 H:5.73	84.04 5.77	314(m ⁺)	95％	8.18	R ¹=C ₆H ₅R=PhC≡C- n=2	30913,3060 2193,1615 1582,1487	7.80-7.67(4H,m),7,25-7.05(6H,m), 6.30(1H,d,J=5.6Hz),6.07(1H,d,J=5.6Hz), 4.47(1H,m),4.00(1H,m),2.39(1H,m), 1.35-1.61(5H,m)．	C:84.05 H:6.14	84.11 6.14	328(M ⁺)	91％

Synthesizing of embodiment 17 compounds 14:

150mg raw material (0.34mmol) is dissolved in 10mL methyl alcohol and adds 2mL water, the 500mg saleratus stirred 24 hours down for 50 ℃, TLC tracing display raw material disappears and boils off the methyl alcohol water layer with ethyl acetate extraction (20mL * 3), saturated common salt water washing anhydrous sodium sulfate drying concentrates and to boil off solvent and add 50 ℃ of 5ml toluene and 84mg (0.34mmol) anhydrous cupric sulfates and stir that elimination solids-enriched neutral alumina column chromatography gets product 24mg, productive rate 22% after 2 hours.

¹H NMR (CD ₃COCD ₃, 300MHz): 6.73-6.31 (4H organizes doublet J=5.5-5.6Hz more), 4.99-4.79 (2H, 3 singlets), 4.13-3.92 (4H, m), 2.21-1.96 (8H, m) ppm

MS?(m/z)：322(M ⁺,10.9),277(4.92),239(3.7),219(5.5),195(5.2),149(18.4),111(28.9),57(100.0).

HR MS (m/z): calculated value C ₂₀H ₈O ₄:; The selective hydrogenation of the two keys of measured value 322.1219. embodiment 18 compound 8-3:

216mg 8-3 (1mmol) is dissolved in the 20ml dehydrated alcohol, adds palladium-carbon of 21mg10%, and atmospheric hydrogenation removes by filter palladium carbon to the hydrogen that absorbs monovalent under the room temperature, and filtrate concentrates, the silica gel silicon layer analyse product 15-1 177mg, productive rate 81%.

IR：3056,2987,2891,1673,1596,1493,1448,1362：

¹H?NMR(CD ₃COCD ₃,600Hz)：7.37(2H,d,J=7.2Hz),7.12(2H,m),6.90(2H,m),5.06(1H,m),3.87(1H,m),3.80(1H,m),2.77(1H,m),2.60(1H,m)2.13～1.92(6H,m)ppm。

MS(m/z)：217(34.6,M ⁺+1),216(100,M ⁺),199(7.3),97(85.5)。

Ultimate analysis calculated value: C, 77.75%H, 7.47%; Measured value C, 77.74%H, 7.67%.Embodiment 19 compound 15-1 hydrogenations:

100mg15-1 (0.46mmol) is dissolved under palladium-carbon room temperature that the 10ml dehydrated alcohol adds 10mg10% atmospheric hydrogenation to be stopped hydrogenation to the hydrogen that absorbs monovalent and removes by filter palladium carbon filtrate concentrating, and silica gel column chromatography gets product 16-171mg, productive rate 70%.Embodiment 20 compound 15-2 selective hydrogenations:

210mg (0.81mmol) be dissolved under palladium-carbon room temperature that the 10ml dehydrated alcohol adds 15mg5% atmospheric hydrogenation stop to the hydrogen that absorbs monovalent hydrogenation remove by filter palladium carbon filtrate si-enriched plastic column chromatography (P: E=40: 1), product 150mg, productive rate 71%.

IR(film)：2895,1671,1597,1503,1488,1443,1349,1247.

¹H?NMR(CD ₃COCD ₃,300MHz)：7.20(1H,d,J=1.6Hz),6.85-6.68(2H,m),5.90(2H,s),5.12(1H,d,J=1.2Hz),4.00-3.87(2H,m),2.88(1H,m),2.66(1H,m),2.23-2.02(6H,m)ppm

MS(m/z)：261(22.1,M ⁺+1),260(100,M ⁺),147(16.3),135(17.0),119(9.1),97(82.3).

HR MS (m/z): calculated value C ₁₅H ₁₆O ₄:; Measured value 260.1043. embodiment 21 compound 15-2 hydrogenations:

100mg15-2 (0.38mmol) is dissolved in that atmospheric hydrogenation spends the night under palladium-carbon room temperature that the 5ml dehydrated alcohol adds 10mg5%, remove by filter palladium carbon filtrate si-enriched plastic column chromatography (P: E=40: 1), product 73mg, productive rate 72%.

IR(film)：2978,2882,1608,1504,1490,1443,1346,1249.

¹H?NMR(CD ₃COCD ₃,300?MHz)：6.78-6.66(3H,m),5.92(2H,s),4.10(1H,m),3.88-3.74(2H,m),2.85-2.58(2H,m),2.11-1.72(8H,m)ppm

MS (m/z): 262 (12.1, M ⁺), 220 (5.5), 171 (6.9), 135 (44.4), 127 (100.0), 97 (12.6), 85 (27.2). calculated value C ₁₅H ₁₈O ₄: C, 68.69.H, 6.92; Actual measurement is straight; C, 68.90.H, 7.37. embodiment 22 will 1mmol is dissolved in the 10-20ml anhydrous polar solvent, adds palladium-carbon of 50-30mg 5%.Normal pressure feeds hydrogen down.Filter, concentrate, obtain hydride through column chromatography, as shown in the table.

The test of embodiment 23 antifeedant activities

Adopt non-selective active testing method, pad is with filter paper in the glass culture dish of diameter 9cm, add a small amount of distilled water insulation, wild cabbage or cabbage heart leaf are broken into the circular blade of diameter 2cm with the device that fans the air, supplying test agent with the concentration of acetone diluted to 0.5% blade to be put into dries after acetone diluted liquid soaks, the contrast blade soaks with acetone, every ware is put into 6 in blade, 10 of small cabbage moths, with culture dish insert the constant temperature insectary (25 ± 2 ℃, RH70%) in, check result after 24 hours, get the every processing of food area with L1-3000 type leaf area determinator mensuration and repeat 5 times, calculate as follows and soak percentage.

The food refusal rate=(contrast is got food blade area-processing and is got food blade area contrast and get food blade area * 100% table IV and listed crowndaisy chrysanthemum element and analogue thereof the antifeedant activity to small cabbage moth

Table IV crowndaisy chrysanthemum element and analogue thereof are to the antifeedant activity of small cabbage moth

Claims

1. Garland chrysanthemum extract compounds is characterized in that having following chemical formula:

In the chemical formula==singly-bound or two key, n=1 or 2, R=H or R ¹, R ¹=PhX, XPhCH=CH, naphthalene, XphY, Ph, R ³CH=CH, R ⁴CH=C, Wherein, R ³=C _1-5Alkyl, C _1-5Thiazolinyl, C _1-5Alkynyl or phenyl,

R ⁴=C _1-5Alkyl, C _1-5Thiazolinyl, C _1-5Alkynyl, phenyl or

R ²=C _1-4Alkyl or benzyl, X or Y=H, electron donating group or electron-withdrawing group, XY=methylene-dioxy

Electron donating group is OCH ₃, OC ₂H ₅, Cl or Br,

Electron-withdrawing group is NO ₂Or CN, in the above-mentioned chemical formula when==when the condition of two keys and n=1, R=H possesses simultaneously, R ¹ ^≠Ph ^-, CH ₃Oph ^-, C ₂H ₅Oph ^-, NO ₂Ph ^-, CNph ^-, phCH=CH ^-, CH ₃OphCH=CH ^-, C ₂H ₅OphCH=CH ^-, NO ₂PhCH=CH ^-, CNphCH=CH ^-, C _1-5The ethene that replaces of alkyl or ethynyl, C _1-5Ethene or the ethynyl and the C of alkenyl substituted _1-5The ethene or the ethynyl of alkynyl substituted.

2. Garland chrysanthemum extract compounds as claimed in claim 1 is characterized in that having following molecular formula

Wherein R, R ¹Described with the implication of n with claim 1.

3. Garland chrysanthemum extract compounds as claimed in claim 1 is characterized in that having following molecular formula

4. Garland chrysanthemum extract compounds as claimed in claim 1 is characterized in that having following molecular formula N=1 or 2.

5. Garland chrysanthemum extract compounds as claimed in claim 1 is characterized in that having following molecular formula , n=1 or 2.

6. the preparation method of Garland chrysanthemum extract compounds as claimed in claim 1 is characterized in that with following (1) and (3), (2) and (3), and (1), (2) and (4), or four kinds of methods of (2), (3) and (4):

(1) furans propyl alcohol or butanols and butyllithium and unsaturated aldehydes or ketones RCOR1 react the furans diol compound

(2) furans propyl alcohol or butanols with ethanoyl protect acetylate, obtain 2-formaldehyde through Vilsmier-Hack reaction again and get the furans acetylate, after the reaction of alkynyl negative ion, deacetylation gets the furans diol compound again

N=1 or 2,

(3) above-mentioned (1) and (2) is got the furans diol compound and in solvent, to reflux temperature, cyclization takes place with protonic acid, silica gel, ion exchange resin or Louis acid catalysis dehydration with room temperature, furans diol compound and protonic acid or lewis acidic mol ratio are 1: 0.1-50, (4) are with product logical hydrogen under the Pd-C catalyst of (3).

7. the preparation method of Garland chrysanthemum extract compounds as claimed in claim 6 is characterized in that described Lewis acid is cupric salt, trivalent iron salt, silver salt, composite salt or boron compound.

8. the preparation method of Garland chrysanthemum extract compounds as claimed in claim 7 is characterized in that described mantoquita is CuSO ₄Or its hydrate, described molysite is FeCl ₃Or the hydrate of ferric sulfate, described silver salt is AgClO ₄, described composite salt is a florisil, described boride is BF ₃(OC ₂H ₅) ₂

9. the purposes of a Garland chrysanthemum extract compounds as claimed in claim 1 is characterized in that being used for preparation and has the active agricultural chemicals of insect antifeedant.