CN105601484A - (6S)-(-)-6-bromoisolongifolenone and synthetic method and application thereof - Google Patents

(6S)-(-)-6-bromoisolongifolenone and synthetic method and application thereof Download PDF

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Publication number
CN105601484A
CN105601484A CN201510791195.0A CN201510791195A CN105601484A CN 105601484 A CN105601484 A CN 105601484A CN 201510791195 A CN201510791195 A CN 201510791195A CN 105601484 A CN105601484 A CN 105601484A
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Prior art keywords
isolongifolenone
bromine
synthetic method
solvent
bromoisolongifolenone
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CN201510791195.0A
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CN105601484B (en
Inventor
杨益琴
丁志斌
王石发
徐徐
徐海军
杨金来
芮坚
曹晓琴
王芸芸
王忠龙
杨丽娟
张齐
孙楠
谷文
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Nanjing Forestry University
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Nanjing Forestry University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
    • C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
    • C07C49/643—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having three rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses (6S)-(-)-6-bromoisolongifolenone and a synthetic method and an application thereof. The synthetic method comprises the steps: taking isolongifolenone and copper bromide, and carrying out a bromination reaction in a solvent system, to obtain (6S)-(-)-6-bromoisolongifolenone. A natural renewable resource longifolene derivative-isolongifolenone is used as the raw material, and (6S)-(-)-6-bromoisolongifolenone is prepared through the stereoselectivity reaction; the compound has good selective toxic killing effect on tinocallis kahawaluokalani kirkaldy, and when the concentration of the compound is 50 mg/L, the fatality rate of the tinocallis kahawaluokalani kirkaldy is as high as 82.2%. Therefore, the compound as an insecticide has the characteristics of high efficiency, environmental protection, convenient use, simple synthetic route and low cost, is expected to be used as a novel insecticide for use, and has wide application in eliminating the tinocallis kahawaluokalani kirkaldy especially when used as a specific insecticide.

Description

(6S)-(-)-6-bromine Isolongifolenone and synthetic method and application
Technical field
The invention belongs to technical field of organic synthesis, relate to (6S)-(-)-6-bromine Isolongifolenone and synthetic method thereof andApplication.
Background technology
The long spot aphid of crape myrtle has another name called crape myrtle sour jujube tail aphid, belongs to Homoptera, Aphidoidea, spot Aphidiadae. Distribution China Beijing,The ground such as Shanghai, Jiangsu, Zhejiang, Taiwan. Host, except crape myrtle, have not been reported. To the harm of crape myrtle every yearOccur, the full spire reverse side of normal lid, makes young sprout distortion, and tender leaf is crispaturaed, uneven, and affect bud and form, andInflorescence is shortened, even, without flower, also can bring out sooty mould simultaneously, viral disease spreads disease.
Control to the long spot aphid of crape myrtle has several different methods, such as gardening is prevented and treated: in conjunction with pruning, remove disease worm winterBranch, thin and weak branch and overstocked branch, to reduce the aphid ovum of surviving the winter, the economic environmental protection of this method, but it is low to prevent and treat efficiency; MedicamentControl: the large emergence period sprays with 5000～10000 times of 25% Diaclodens, 10% imidacloprid wettable powder 2000Times, or 100 times of liquid of 50% Folithion missible oil, 1000 times of 40% omethoate emulsifiable solutions and 80% DDVP breast100 times of liquid of oil etc., this method can effectively kill off the insect pests, but DDVP can produce poisoning, and easy " burning leaf ", and thiopheneAlthough worm piperazine effective, harmless, its complex synthetic route, cost is higher; Biological control: protection utilize ladybug,The natural enemies such as Chrysopa, this method environmental protection, but can cause biological chain disorder, and be difficult to promote.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of the present invention is to provide one to there is handCompound (6S)-(-)-6-bromine Isolongifolenone of property. Another object of the present invention is to provide a kind of above-mentioned(6S) preparation method of-(-)-6-bromine Isolongifolenone, different with the oxidation product of natural reproducible resource isolonglifoleneThe ketenes that comes into leaves is raw material, carries out bromo-reaction with copper bromide, obtains (6S)-(-)-6-bromine Isolongifolenone. ThisThe bright application that also has an object that above-mentioned (6S)-(-)-6-bromine Isolongifolenone is provided.
Technical scheme, in order to realize foregoing invention object, the technical solution used in the present invention is:
(6S)-(-)-6-bromine Isolongifolenone, the structural formula of this compound is:
The synthetic method of described (6S)-(-)-6-bromine Isolongifolenone: get Isolongifolenone and copper bromide at solventIn system, carry out bromo-reaction, obtain (6S)-(-)-6-bromine Isolongifolenone.
The synthetic method of described (6S)-(-)-6-bromine Isolongifolenone, is characterized in that, comprises the following steps:
1) Isolongifolenone, copper bromide and solvent are added successively and be furnished with agitator, thermometer and reflux condensation modeIn the there-necked flask of device, back flow reaction under nitrogen protection, follows the tracks of and detects until Isolongifolenone transforms with GCAfter reaching 95%, rate stops reaction;
2) reactant liquor is after distillating recovering solvent, then adds distilled water, is extracted with ethyl acetate extractBe washed with distilled water to again neutrality, then use saturated common salt water washing; Organic phase is anhydrated point with anhydrous sodium sulfate drying;Concentration and recovery solvent after filtration removal drier, obtains (6S)-(-)-6-bromine Isolongifolenone crude product;
3) (6S)-(-)-6-bromine Isolongifolenone crude product is recrystallized in methanol solvate, obtains water white transparency(6S)-(-)-6-bromine Isolongifolenone crystal.
Described solvent is alcohols, ester class, aromatic hydrocarbons, nitrile solvents. Be preferably methyl alcohol, ethanol, isopropyl alcohol,The tert-butyl alcohol, ethyl acetate, toluene, acetonitrile. Most preferably be methyl alcohol, ethanol.
Described (6S)-(-)-6-bromine Isolongifolenone is in the application of preparing in pesticide. Described worm is that crape myrtle is longSpot aphid.
Beneficial effect: compared with prior art, the present invention utilize the derivative of natural reproducible resource longifolene-Isolongifolenone is raw material, reacts make (6S)-(-)-6-bromine Isolongifolenone by stereoselectivity; This chemical combinationThing has well selective toxic action to the long spot aphid of crape myrtle, and in the time that its concentration is 50mg/L, crape myrtle is longThe fatal rate of spot aphid is up to 82.2%. Therefore this compound has efficiently, environmental protection, conveniently makes as pesticideWith etc. feature, and synthetic route is simple, with low cost, is expected to use as novel pesticide, especially as speciallyOne insects agent is possessing application widely aspect the long spot aphid of dissipation crape myrtle.
Brief description of the drawings
Fig. 1 is the variation of variable concentrations (6S)-(-)-6-bromine Isolongifolenone to the long spot aphid of crape myrtle toxicity testGraph of a relation.
Specific implementation method
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
In the 100mL there-necked flask of being furnished with thermometer, agitator and reflux condenser, add successively6.54g (0.03mol) Isolongifolenone, ethanol 60mL and 13.44g (0.06mol) copper bromide, is heated to the temperature that refluxesDegree reaction 3h left and right to Isolongifolenone conversion ratio reaches more than 95% (GC tracking and testing). Question response liquid cooling butTo room temperature, add 100mL ethyl acetate dilution, remove accessory substance cuprous bromide with 3 × 200mL water,Organic phase is washed to neutrality with saturated common salt, through anhydrous Na2SO4After being dried, filtering, concentrating, obtain yellow liquidBody crude product, then be recrystallized with 10mL methyl alcohol, 7.75g colourless transparent crystal (6S)-(-)-6-bromine obtained differentThe ketenes that comes into leaves, productive rate is 87.0%.
Product characterizes: 91.7～92.6 DEG C of fusing points;(c＝1mg/mL，CHCl3)；GC-MS(70eV)m/z(％)：296(M+,60),281(7),255(56),240(10),217(48),203(9),189(20),175(100),161(30),145(36),119(27),105(29),91(45),69(21),55(15)；FT-IR(KBr)ν/cm-1：2961(νasC-H,CH3),2875(νsC-H,CH2),1670(vC＝O),1642(νC＝C),1460(τC-H,CH2),1384(τC-H,CH3),1264(νsC-H,CH2)；1HNMR(300MHz,CDCl3)δ：1.09(s,3H),1.12(s,3H),1.17(s,3H),1.25(s,3H),1.46(d,J＝9.93Hz,2H),1.64(t,J＝12.30Hz,2H),1.77(m,J＝8.49Hz,2H),1.96(m,J＝10.86Hz,1H),4.01(s,1H),5.76 (s, 1H). Compound (6S)-(-)-6-bromine Isolongifolenone with chirality, structural formula is:
Embodiment 2
Get (6S)-(-)-6-bromine Isolongifolenone, be mixed with the mother liquor of high concentration with acetone, when Primary Screening Test, useThe 0.1%TritonX-100 aqueous solution is diluted to 200mg/L, uses 0.1%TritonX-100 water when virulence line is measuredSolution dilution becomes needed series concentration gradient, by the cabbage leaf dish of diameter 5cm respectively in above-mentioned liquidSoak 10s, after taking out, naturally dry to without open fire, taking the 0.1%TritonX-100 aqueous solution as contrast. To dryLeaf butterfly put into the plastic culture dish of diameter 6.5cm, access of the same size 3 mid-term in age diamondback moth larvae10. Test is processed 3 times and is repeated. It is that 25 ± 1 DEG C, photoperiod are 16h:8 that diamondback moth after treatment is put into temperatureIn the constant incubator of h (L:D), cultivate, connect check result after worm 48h. When inspection, touch polypide with writing brush,Taking larva can not the coordinated movement of various economic factors as death standard. As shown in Figure 1. Result shows, compound is to the long spot aphid of crape myrtleThere is very strong toxicity action, and its concentration is while being 50mg/L, the death rate of the long spot aphid of crape myrtle up to82.2％。

Claims (8)

1. (6S)-(-)-6-bromine Isolongifolenone, is characterized in that, the structural formula of this compound is:
2. the synthetic method of (6S)-(-)-6-bromine Isolongifolenone claimed in claim 1, is characterized in that: getIsolongifolenone and copper bromide carry out bromo-reaction in dicyandiamide solution, obtain (6S)-(-)-6-bromine Isolongifolenone.
3. the synthetic method of (6S)-(-)-6-bromine Isolongifolenone according to claim 2, is characterized in that,Comprise the following steps:
1) Isolongifolenone, copper bromide and solvent are added successively and be furnished with agitator, thermometer and reflux condensation modeIn the there-necked flask of device, back flow reaction under nitrogen protection, follows the tracks of and detects until Isolongifolenone transforms with GCAfter reaching 95%, rate stops reaction;
2) reactant liquor is after distillating recovering solvent, then adds distilled water, is extracted with ethyl acetate extractBe washed with distilled water to again neutrality, then use saturated common salt water washing; Organic phase is anhydrated point with anhydrous sodium sulfate drying;Concentration and recovery solvent after filtration removal drier, obtains (6S)-(-)-6-bromine Isolongifolenone crude product;
3) (6S)-(-)-6-bromine Isolongifolenone crude product is recrystallized in methanol solvate, obtains water white transparency(6S)-(-)-6-bromine Isolongifolenone crystal.
4. according to the synthetic method of (6S)-(-)-6-bromine Isolongifolenone described in claim 2 or 3, its featureBe, described solvent is alcohols, ester class, aromatic hydrocarbons, nitrile solvents.
5. the synthetic method of (6S)-(-)-6-bromine Isolongifolenone according to claim 4, is characterized in that,Described solvent is methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, ethyl acetate, toluene, acetonitrile.
6. the synthetic method of (6S)-(-)-6-bromine Isolongifolenone according to claim 4, is characterized in that,Described solvent is methyl alcohol, ethanol.
7. (6S)-(-)-6-bromine Isolongifolenone claimed in claim 1 is in the application of preparing in pesticide.
8. application according to claim 7, described worm is the long spot aphid of crape myrtle.
CN201510791195.0A 2015-11-17 2015-11-17 (6S) () 6 bromine Isolongifolenone and its synthetic method and application Expired - Fee Related CN105601484B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101801901A (en) * 2007-07-13 2010-08-11 美国农业部 Use Isolongifolene ketone and/or the arthropodan method of Isolongifolene keto analog repellent
CN103951566A (en) * 2014-04-30 2014-07-30 南京林业大学 N-alkyl-1,2,3,4,5,6-hexahydro-1,1,5,5-tetramethyl-7H-2,4 alpha-methanonaphthalene-7-amine compound as well as synthetic method and application thereof
CN104892543A (en) * 2015-06-03 2015-09-09 南京林业大学 Thiazole compounds, as well as synthesis method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101801901A (en) * 2007-07-13 2010-08-11 美国农业部 Use Isolongifolene ketone and/or the arthropodan method of Isolongifolene keto analog repellent
CN103951566A (en) * 2014-04-30 2014-07-30 南京林业大学 N-alkyl-1,2,3,4,5,6-hexahydro-1,1,5,5-tetramethyl-7H-2,4 alpha-methanonaphthalene-7-amine compound as well as synthetic method and application thereof
CN104892543A (en) * 2015-06-03 2015-09-09 南京林业大学 Thiazole compounds, as well as synthesis method and application thereof

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Title
丁志彬等: "手性a-溴代异长叶烯酮的合成研究", 《林产化学与工业》 *
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