CN1178633A - Crowndaisy chrysanthemum extract compound, preparing method and use thereof - Google Patents
Crowndaisy chrysanthemum extract compound, preparing method and use thereof Download PDFInfo
- Publication number
- CN1178633A CN1178633A CN 97106696 CN97106696A CN1178633A CN 1178633 A CN1178633 A CN 1178633A CN 97106696 CN97106696 CN 97106696 CN 97106696 A CN97106696 A CN 97106696A CN 1178633 A CN1178633 A CN 1178633A
- Authority
- CN
- China
- Prior art keywords
- compound
- furans
- chrysanthemum extract
- alkyl
- extract compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 81
- 244000067456 Chrysanthemum coronarium Species 0.000 title claims abstract description 40
- 239000000284 extract Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 11
- 235000007871 Chrysanthemum coronarium Nutrition 0.000 title abstract description 21
- 235000007516 Chrysanthemum Nutrition 0.000 title abstract description 15
- 244000189548 Chrysanthemum x morifolium Species 0.000 title abstract 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 furans diol compound Chemical class 0.000 claims description 25
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 235000015134 garland chrysanthemum Nutrition 0.000 claims description 19
- 150000002240 furans Chemical class 0.000 claims description 18
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 17
- 230000001887 anti-feedant effect Effects 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 6
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000007848 Bronsted acid Substances 0.000 claims description 4
- 238000007171 acid catalysis Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
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- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical group [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 150000001639 boron compounds Chemical class 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 125000003003 spiro group Chemical group 0.000 abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000001766 physiological effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 30
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
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- 238000005984 hydrogenation reaction Methods 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 241000723353 Chrysanthemum Species 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 13
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 11
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 6
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- 239000012153 distilled water Substances 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 description 1
- 150000002084 enol ethers Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- 208000037805 labour Diseases 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- NHOIBRJOQAYBJT-IMGVWCFESA-N nimbin Chemical compound C=1([C@@H]2C[C@H]3O[C@H]4[C@](C3=C2C)(C)[C@@H]([C@]2(C(=O)C=C[C@](C)([C@@H]2[C@H]4OC(C)=O)C(=O)OC)C)CC(=O)OC)C=COC=1 NHOIBRJOQAYBJT-IMGVWCFESA-N 0.000 description 1
- ZQIYJHBQRBBBRZ-UHFFFAOYSA-N nimbin Natural products COC(=O)CC1C2C(C(OC(=O)C)C3OC4CC(C(=C4C13C)C)c5cocc5)C(C)(C=CC2=O)C(=O)OC ZQIYJHBQRBBBRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- VNMDYSSJFJFEQI-UHFFFAOYSA-N penta-1,3-diyne Chemical compound CC#CC#C VNMDYSSJFJFEQI-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003016 pheromone Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 150000008300 phosphoramidites Chemical class 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000014860 sensory perception of taste Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to dioxa spiro crowndaisy chrysanthemum extract compound synthesized with furan alcohol or butanol through simple path. The said compound has the physiological activity of rejecting eating and thus is one compound with pest-resisting activity and suitable for commercial production.
Description
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 interrelated data, be used for the investment of agrochemistry aspect every year above 4,000,000,000 dollars in the world wide, and expense wherein over half is used for insecticide, but still have every year the crops about 15% to eat loss in vain because of raising of insect, the influence that causes thus is especially serious in developing country of the third world.How world population prevents damage by disease and insect with phenomenal growth in 10 years of future, increases crop yield, satisfies population growth's needs, has become a very urgent problem.
The protection of current crops mainly depends on the application of phosphoramidite chemical insecticide, though these compounds are very effective, but shortcoming also is conspicuous, because these compounds seldom have selectivity, insect 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 insecticide just can reach the harmful purpose of going out, and so caused vicious circle, and its direct result is to destroy the ecological balance, 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 on the agricultural product for a long time, and 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 plant species of occurring in nature has been showed colourful damage by disease and insect hedge to us, and the bioactive molecule 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 noticeable 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 inhibitor or sense of taste repellant (Munakadta, K.; Appl.Chem., 1975,42,57), Van professor Beek of Dutch agriculture university has summed up the advantage of desirable anti-feedant in detail: 1. plant-less toxicity; 2. to the mankind, animal, beneficial insect and other biological avirulence; 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 extermination of disease and insect pest; 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 control efficiency 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 anti-feedant 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 active component can not satisfy the demands, could obtain some products because will change a lot of labours owing to content is low, and in separation 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 (CN 931124449-4) to have following chemical formula A or B:
A furans formula crowndaisy chrysantheins 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 withdraw 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 known method (Org.Shy.Coll III, 425) be prepared into furylacrylic acid, again with Raney nickel reduce the furans propionic acid, get the furans propyl alcohol through lithium aluminium hydride reduction, continue and the butyl lithium effect gets 5-position lithium compound, in same reaction bulb, 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 anti-feedant to the research and development 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 cycle compound 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-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
Or
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 withdraw group.Electron donating group such as OCH
3, OC
2H
5, Cl, Br, electron withdraw 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 
R
1=
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-hexadiine 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 initiation 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 butyl lithium and unsaturated aldehydes or ketones
React the furans diol compound,
Productive rate: R=H R
1=p-Cl
70% R=Ph, R
1=Ph 65%R=H R
1=p-Br
69%R=H R
1=
62% can be described as furans formula crowndaisy chrysantheins again like thing.Specifically 2-furans propyl alcohol or butanols and contain butyl lithium 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 butyl lithium also is to help reaction.For increasing lithium salts solvability in solvent, add complexing agent usually, as tetramethylethylenediamine, carry out to add fast response.The mol ratio of alcohol or butanols and complexing agent can be 1 in the furans: 1-0.001.
Compound 2 can also be protected with acetyl group; 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, promptly obtained compound 5, and the mol ratio of 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 bicarbonate 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 Bronsted acid, silica gel, ion exchange resin or Louis (Lewis) acid catalysis and generate Garland chrysanthemum extract compounds in aforesaid compound 4
Described Bronsted acid is inorganic acid, disulfate, dihydric 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, complex 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 solven according to different catalyzer, as benzene,toluene,xylene, cycloalkane, alkane, pyridine, ethyl acetate, acetone, carrene, chloroform, carbon tetrachloride, acetate, oxolane, acetonitrile, dimethyl formamide, chloroform, carrene, carbon tetrachloride etc.
The cyclodehydration reaction temperature can be room temperature to reflux temperature, heat usually and carry out helping to add fast response.
The dehydration catalyst amount, 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 working as R=H in the compound 4, R
1=
The time, directly carry out silica gel column chromatography, relatively can realize transforming under the temperate condition, but productive rate is lower.And with catalysis under p-methyl benzenesulfonic acid pyridiniujm (be called for short PPTs) the non-polar solven room temperature, productive rate is 85%.The Lewis acid catalysis also can obtain satisfactory result, as sulfuric acid ketone,
To reflux temperature, conversion yield is 92% to iron sulfate etc. in non-polar solven and room temperature, partly the results are shown in Table shown in 1.
Table 1. furans glycol catalytic cyclization reaction and productive rate product dehydration-cyclisation conditions productive rate (%)
The HCl/ non-polar solven, room temperature 74.5
Silica gel chromatograph 25
PPTs/ toluene, room temperature 85
CuSO
45H
2O/ non-polar solven 92
70 ℃
CuSO
45H
2The O/ non-polar solven
70 ℃ 97
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 acetylization; 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 sulphate 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-two chloro-2-butine are at DMSO-H
2Obtain 1 through the KOH processing in the O system, the 3-diacetylene (L.Brandsma, in " Preparative Acetylenic Chemistry ", 2nd td., Elsvier, Amsterdam, 1988,179.).
1, the 3-diacetylene is handled through butyl lithium 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
2Oii) .CuSO
45H
2O, toluene, 60-70 ℃, 22% compound 12 is sloughed protecting group without separating direct cyclisation, has only obtained final products 14 with 22% productive rate,
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 oxidized 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 hydrogen.Catalyst amount 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, absolute ethyl alcohol is made solvent, and compound 8-3 is carried out catalytic hydrogenation reaction, and we have successfully obtained the analog of complete this little molecule 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, by the amount of control hydrogenation, we have obtained compound 15-1 with 81% productive rate.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, R
1=
During n=1, no matter under 1/200 concentration or 1/400 concentration to the diamond-back moth antifeedant activity apparently higher than margosine 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.
Molten boiling point is not calibrated among the embodiment, infrared spectrum is by Shimadazu IR-440, Perkin-Elmer 983 or Digilab FTIR type determination of infrared spectroscopy, and nuclear magnetic resonnance is by Varian EM-360A, EM-390 or AMX-300, AMX-600 type nmr determination.Mass spectrum is measured by HP-5989A or VG Quattro GC/MS/MS type mass spectrograph, and high resolution mass spectrum is by Finnigan MAT type Instrument measuring, and elementary analysis is measured by Institute of Analysis of this institute.
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 on silica gel H (400 order) or neutral alumina (300 order), thin-layer chromatography adopts aqueous sulfuric acid (ammonium molybdate and the sulfuric acid of ammonium molybdate, the weight ratio of water: 1: 1: 15) sprays back 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 ℃ drips 7.8mL (1.6M) n-BuLi-hexane solution down, be chilled to-78 ℃ behind the stirring at room 2-3hr, slowly drip the THF solution of benzaldehyde 1.06g (10mmol),-78 ℃ were stirred after 4 hours, slowly rise to stirred overnight at room temperature, saturated NH4Cl solution cancellation reaction, ethyl acetate extraction (15mL * 4), saturated common salt water washing, anhydrous sodium sulfate drying, column chromatography gets product 840mg, productive rate 72%, be recrystallized the graininess crystal.
mp：62-63℃.
IR(film)：3352，3064，3031，2945，2880，1603，1558，1494，1452；
1H-NMR(600MHz，CD
3COCD
3)7.4(2H，d，J＝7.2Hz)，7.31(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，-O
H)，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)；
HR MS (m/z): calculated 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 (4.1mmol) furans propyl alcohol and 1.49g (8.2mmol) benzophenone react the 750mg product, productive rate 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，-O
H)，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) piperonal 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 propane diols, 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 the raw material elimination, filter, filter residue washs with ether, merge organic facies and concentrate the neutral alumina column chromatography, obtain 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: calculated 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 enforcement 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, 5.45. embodiment 8 furans butanols synthetic:
5.73g furans butyric acid (37.9mmol) is dissolved in the mixture that the 40mL absolute ether slowly adds 1.75g aluminium lithium hydrogen and 60mL ether, after making system be slight boiling condition to dropwise, refluxes 2 hours, adds suitable quantity of water and decomposes unnecessary LiAlH
4, add the mixed liquor that 20g oxalic acid 6mL hydrochloric acid and water are made into again, tell the ether layer, water layer is with extracted by ether (30mL * 3), the water washing of combined ether layer saturated common salt, anhydrous sodium sulfate drying concentrates, and 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=7.3Hz), 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) the BuLi hexane solution, after the stirring at room 4 hours, be chilled to-78 ℃, THF (20ml) solution-78 a ℃ following reaction that adds the 1.54g thiophenecarboxaldehyde slowly rose to room temperature after 4 hours, stirring is spent the night, saturated NH
4Cl solution cancellation reaction, ethyl acetate extraction.Anhydrous sodium sulfate drying concentrates, silica gel 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)：7.29(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，-O
H)，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 (1.86mmol) that adds 11.4g (112mmol) down of 14mL 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), respectively with water and saturated common salt water washing, after anhydrous sodium sulfate drying concentrated, crude product was with silica gel column chromatography (P: E=25: 1) again, get product 1.407g, productive rate 84%.Embodiment 11 compound 6-1's is synthetic:
Slowly drop among the DMF of 0.63g (8.6mmol) 1.30g phosphorus oxychloride (8.5mmol) is dissolved under 0 ℃ of the 4.3ml carrene, equality of temperature stirred 0.5 hour.1.29g being dissolved in the 9ml carrene, furans butanols ethyl ester (8.0mmol) slowly drops in the above-mentioned reaction system, rise to room temperature, stir after three hours, add 30ml saturated sodium carbonate solution and 30ml carrene and tell organic layer, organic facies is washed with the 30ml saturated nacl aqueous solution, anhydrous sodium sulfate drying, vacuum concentration silica gel column chromatography (PE: EA=7: 1) get product 0.94g, productive rate 91%.
Rf=03 (PE: EA=7: 1) embodiment 12 compounds 10 is synthetic:
0.46g1 3-pentadiine (7.1mmol) is dissolved in the anhydrous THF of 10mL, adds 1.07mLTMEDA (11mmol), is chilled to-78 ℃, N
2Protection down; the hexane solution-78 that drips 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.Organic facies is with the saturated common salt water washing, and anhydrous sodium sulfate drying concentrates, and thick product is with silica gel column chromatography (PE: EA=6: 1,2: the 1+0.5% triethylamine), get the product of 741mg product and 84mg deacetylate, gross production rate 68.5%.
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; Measured value 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, 60 ℃ were stirred 12 hours down, boil off methyl alcohol, water layer is with ethyl acetate extraction (20mL * 3), saturated common salt water washing, anhydrous sodium sulfate drying concentrates, silica gel column chromatography (P: E=1.5: 1 ,+0.4% triethylamine) get 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 (0.34mmol) 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, removing by filter the copper sulphate filter residue washs with amount of ethyl acetate, merging organic facies concentrates, neutral alumina column chromatography (PE: EA=50: 1) get product 68mg, productive rate 92%.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(600MHz，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
140
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), 30min adds and stirs after 3 hours, adds the saturated NH of 10mL
4Cl solution cancellation reaction, ethyl acetate extraction, organic facies is with the saturated common salt water washing; Anhydrous sodium sulfate drying concentrates, and thick product is 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(2Hs)，4.08(4H，t，J＝6.4Hz)，3.15(2H，s，-O
H)，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 generates
The result is as shown in the table.
Synthesizing of embodiment 17 compounds 14:
| ??8-13 | ?R 1＝p-CH 3OC 6H 4?R＝p-CH 3OC 6H 4?n＝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)，3.97(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％ |
| ??8-14 | ?R 1＝p-CH 3OC 6H 4?R＝p-CH 3OC 6H 4?n＝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％ |
| ??8-16 | ?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 5?R＝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％ |
| ??8-18 | ?R 1＝C 6H 5?R＝PhC≡C- ?n＝2 | ??3093，3060 ??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)， ??1.85～1.61(5H，m). | ??C：84.05 ??H：6.14 | ??84.11 ??6.14 | ??328(M +) | ??91％ |
150mg raw material (0.34mmol) is dissolved in 10mL methyl alcohol, adds 2mL water, the 500mg saleratus, 50 ℃ were stirred 24 hours down, and TLC follows the tracks of and shows that raw material disappears, and boils off methyl alcohol, water layer is with ethyl acetate extraction (20mL * 3), saturated common salt water washing, anhydrous sodium sulfate drying; Concentrate and to boil off that solvent adds 5ml toluene and 84mg (0.34mmol) anhydrous cupric sulfate stirs after 2 hours for 50 ℃, the elimination solid concentrates the neutral alumina column chromatography and gets product 24mg, productive rate 22%.
1H NMR (CD
3COCD
3, 300MHz): 6.73-6.31 (4H organizes doublet more, J=5.5-5.6Hz), 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).
HRMS (m/z): calculated value C
20H
18O
4:; Measured value: the selective hydrogenation of the two keys of 322.1219. embodiment 18 compound 8-3:
216mg 8-3 (1mmol) is dissolved in the 20ml absolute ethyl alcohol, adds palladium-carbon of 21mg 10%, 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)。
Elementary analysis calculated value: C, 77.75% H, 7.47%; Measured value C, 77.74% H, 7.67%.Embodiment 19 compound 15-1 hydrogenations:
100mg 15-1 (0.46mmol) is dissolved in the 10ml absolute ethyl alcohol, and atmospheric hydrogenation stops hydrogenation under palladium-carbon room temperature of adding 10mg 10% to the hydrogen that absorbs monovalent, 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) is dissolved in palladium-carbon that the 10ml absolute ethyl alcohol adds 15mg5%, and atmospheric hydrogenation stops hydrogenation under the room temperature to the hydrogen that absorbs monovalent, remove by filter palladium carbon, filtrate si-enriched plastic column chromatography (P: E=40: 1), get 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:
100mg 15-2 (0.38mmol) is dissolved in palladium-carbon that the 5ml absolute ethyl alcohol adds 10mg5%, and atmospheric hydrogenation spends the night under the room temperature, removes by filter palladium carbon, filtrate si-enriched plastic column chromatography (P: E=40: 1), get product 73mg, productive rate 72%.
IR(film)：2978，2882，1608，1504，1490，1443，1346，1249.
1H?NMR(CD
3COCD
3，300MHz)：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; Measured value: C, 68.90.H, 7.37. embodiment 22
Will
1mmpl 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 adds a small amount of distilled water insulation with filter paper in the glass culture dish of diameter 9cm.Wild cabbage or cabbage heart leaf are broken into the circular blade of diameter 2cm with the device that fans the air, for the concentration of test agent with acetone diluted to 0.5%, blade put into dry after acetone diluted liquid soaks, the contrast blade soaks with acetone, and every ware is put into 6 in blade, 10 of diamond-back moths, culture dish is inserted in the constant temperature insectary (25 ± 2 ℃, RH 70%) check result after 24 hours, get the every processing of food area with LI-3000 type leaf area analyzer 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 analog thereof the antifeedant activity to diamond-back moth.
Table IV crowndaisy chrysanthemum element and analog thereof are to the antifeedant activity of diamond-back moth
Claims (9)
1. Garland chrysanthemum extract compounds is characterized in that having following molecular formula:
Wherein
=singly-bound or two key, n=1 or 2, R=H, C
2-14Unsaturated alkyl or heterocyclic radical, R=H, C
2-14Insatiable hunger alkyl or heterocycle, R
1=C
2-14Unsaturated alkyl or heterocycle, described heterocycle is
Or
Base, R
2=C
1-4Alkyl or benzyl, described C
2-14Unsaturated alkyl be aryl, unsaturated alkyl, unsaturated alkyl is thiazolinyl R
3CH=CH or alkynyl R
4CH ≡ CH, aryl be PhX, XPhCH=CH,
XPhY, Ph, R
3=C
1-5Alkyl, thiazolinyl, alkynyl or phenyl, R
4=C
1-5Alkyl, thiazolinyl, alkynyl, phenyl or
X or Y=H, electron donating group or electron withdraw group, electron donating group are OCH
3, OC
2H
5, Cl, Br, electron withdraw group is NO
2, CN, the XY=methylene-dioxy
In the molecular formula R=H, n=1 and
During=two key, remove R
1=naphthyl, PhCl, PhBr, XPhY, X and Y ≠ H and R
4=
Outward, R ≠ H.
2. Garland chrysanthemum extract compounds as claimed in claim 1 is characterized in that having following molecular formula
Wherein R, R
1Described with the n implication with claim 1.
3. Garland chrysanthemum extract compounds as claimed in claim 1 is characterized in that having following molecular formula
Or
4. Garland chrysanthemum extract compounds as claimed in claim 1 is characterized in that having following molecular formula
Or
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 butyl lithium and unsaturated aldehydes or ketones
React the furans diol compound
(2) furans propyl alcohol or butanols with acetyl group protect acetylate, obtain the furans acetylate of 2-formaldehyde again through Vilsmier-Hack reaction, after the reaction of alkynyl anion, deacetylation gets the furans diol compound again
N=1 or 2
(3) cyclization takes place with Bronsted acid, silica gel, ion exchange resin or Louis acid catalysis dehydration with room temperature in the furans diol compound with above-mentioned (1) and (2) to reflux temperature in solvent, and furans diol compound and Bronsted acid or lewis acidic mol ratio are 1: 0.1-50.
(4) with (3) product logical hydrogen under the Pd-C catalyst.
7. preparation method as claimed in claim 6 is characterized in that described lewis acid is cupric salt, trivalent iron salt, silver salt, complex salt or boron compound.
8. preparation method as claimed in claim 7 is characterized in that described mantoquita is CuSO
4, CuSO
43H
2O, CuSO
45H
2O, Cu (Otf)
2Or Cu (OSO
2CF
3)
2, described molysite is 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, described silver salt is AgClO
4, described complex salt is a florisil, described boride is BF
3(OC
2H
5)
2
9. purposes as claim 1 or 6 described Garland chrysanthemum extract compounds is characterized in that having the compound of antifeedant activity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106696A CN1067397C (en) | 1997-11-04 | 1997-11-04 | Crowndaisy chrysanthemum extract compound, preparing method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106696A CN1067397C (en) | 1997-11-04 | 1997-11-04 | Crowndaisy chrysanthemum extract compound, preparing method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1178633A true CN1178633A (en) | 1998-04-15 |
| CN1067397C CN1067397C (en) | 2001-06-20 |
Family
ID=5168912
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106696A Expired - Fee Related CN1067397C (en) | 1997-11-04 | 1997-11-04 | Crowndaisy chrysanthemum extract compound, preparing method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1067397C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675339A (en) * | 2012-04-27 | 2012-09-19 | 华南理工大学 | Screw epoxidation indole heterocyclic compound as well as synthetic method and purpose thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060165C (en) * | 1993-05-24 | 2001-01-03 | 中国科学院上海有机化学研究所 | Crowndaisy chrysantheins compound |
-
1997
- 1997-11-04 CN CN97106696A patent/CN1067397C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675339A (en) * | 2012-04-27 | 2012-09-19 | 华南理工大学 | Screw epoxidation indole heterocyclic compound as well as synthetic method and purpose thereof |
| CN102675339B (en) * | 2012-04-27 | 2014-06-11 | 华南理工大学 | Screw epoxidation indole heterocyclic compound as well as synthetic method and purpose thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1067397C (en) | 2001-06-20 |
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