CN105601484B - (6S) () 6 bromine Isolongifolenone and its synthetic method and application - Google Patents

Abstract

The invention discloses a kind of (6S) () 6 bromine Isolongifolenone and its synthetic method and application, the synthetic method is：Take Isolongifolenone to carry out bromo-reaction in dicyandiamide solution with copper bromide, obtain (6S) () 6 bromine Isolongifolenone.The present invention is raw material using derivative-Isolongifolenone of natural reproducible resource longifolene, and (6S) () 6 bromine Isolongifolenone is made by Stereoselective reaction；The compound has selective toxic action well to the long spot aphid of crape myrtle, and when its concentration is 50mg/L, the fatal rate of the long spot aphid of crape myrtle is up to 82.2%.Therefore the features such as compound has efficient, environmental protection, convenient use as insecticide, and synthetic route is simple, it is with low cost, it is expected to use as novel pesticide, possesses especially as selectivity insecticide in terms of the long spot aphid of dissipation crape myrtle and be widely applied.

Description

(6S)-(-)-6-bromoisolongifolenone and its synthesis method and application

technical field

The invention belongs to the technical field of organic synthesis, and relates to (6S)-(-)-6-bromoisolongifolenone and its synthesis method and application.

Background technique

The crape myrtle aphid, also known as the crape myrtle acanthus, belongs to the order Homoptera, Aphidoidea, and Aphididae. Distributed in Beijing, Shanghai, Jiangsu, Zhejiang, Taiwan and other places in China. Except for crape myrtle, the host has not been reported yet. The damage to crape myrtle occurs every year, often covering the reverse side of young leaves, twisting new shoots, shrinking young leaves, unevenness, affecting the formation of flower buds, shortening inflorescences, or even having no flowers. virus disease.

There are many methods for the prevention and control of Lagerstroemia aphid, such as horticultural control: combining pruning in winter, removing diseased and insect branches, thin branches and over-dense branches to reduce overwintering aphid eggs. This method is economical and environmentally friendly, but the control efficiency is low; chemical control : Spray 25% thiamethoxam 5000-10000 times, 10% imidacloprid WP 2000 times, or 50% fenitrothion EC 100 times, 40% omethoate EC 1000 times and 80% dichlorvos EC 100 times liquid, etc., this method can effectively kill pests, but dichlorvos will cause phytotoxicity, and it is easy to "burn leaves". Although thiamethoxam is efficient and harmless, its synthesis route is complicated and the cost is high; biological control: protection Using natural enemies such as ladybugs and lacewings, this method is green and environmentally friendly, but it will cause disorder in the biological chain and is difficult to promote.

Contents of the invention

Purpose of the invention: In view of the deficiencies in the prior art, the purpose of the present invention is to provide a chiral compound (6S)-(-)-6-bromoisolongenone. Another object of the present invention is to provide a method for preparing the above-mentioned (6S)-(-)-6-bromoisolongifolenone, which uses the oxidation product of isolongifolene, a natural renewable resource, as a raw material , and copper bromide for bromination reaction to obtain (6S)-(-)-6-bromoisolongifolenone. Another object of the present invention is to provide the application of the above-mentioned (6S)-(-)-6-bromoisolongenone.

Technical scheme, in order to realize above-mentioned purpose of the invention, the technical scheme that the present invention adopts is:

(6S)-(-)-6-bromoisolongifolenone, the structural formula of the compound is:

The synthetic method of described (6S)-(-)-6-bromoisolongifolenone: take isolongifolenone and copper bromide to carry out bromination reaction in a solvent system to obtain (6S)-(-) -6-Bromoisolongenone.

The synthetic method of described (6S)-(-)-6-bromoisolongenone, is characterized in that, comprises the following steps:

1) Add isolongifolenone, copper bromide and solvent in sequence to a three-neck flask equipped with a stirrer, a thermometer and a reflux condenser, reflux reaction under nitrogen protection, and track and detect with GC until the conversion rate of isolongifolenone Stop reaction after reaching 95%;

2) After the reaction solution is distilled to recover the solvent, distilled water is added, extracted with ethyl acetate, the extract is washed with distilled water until neutral, and then washed with saturated saline; the organic phase is dried with anhydrous sodium sulfate to remove water; filtered to remove Concentrating and recovering the solvent after desiccant to obtain the crude product of (6S)-(-)-6-bromoisolongifolenone;

3) The crude product of (6S)-(-)-6-bromoisolongifolenone was recrystallized in methanol solvent to obtain colorless and transparent crystals of (6S)-(-)-6-bromoisolongifolenone .

Described solvent is alcohols, esters, aromatic hydrocarbons, nitrile solvents. Preferred are methanol, ethanol, isopropanol, tert-butanol, ethyl acetate, toluene, acetonitrile. Most preferred are methanol and ethanol.

The application of the (6S)-(-)-6-bromoisolongenone in the preparation of pesticides. Described worm is crape myrtle aphid.

Beneficial effect: Compared with the prior art, the present invention uses isolongifolene, a derivative of longifolene, a natural renewable resource, as a raw material to prepare (6S)-(-)-6-bromo through stereoselective reaction Isopalenone: This compound has a good selective poisoning effect on Lagerstroemia aphids, and when its concentration is 50mg/L, the lethality rate of Lagerstroemia aphids is as high as 82.2%. Therefore, this compound has the characteristics of high efficiency, environmental protection, and convenient use as an insecticide, and the synthetic route is simple, and the cost is low. It is expected to be used as a new type of insecticide, especially as a specific insecticide. Wide range of applications.

Description of drawings

Fig. 1 is a diagram showing the change relationship of different concentrations of (6S)-(-)-6-bromoisolongenone in determining the toxicity of Lagerstroemia versicolor aphids.

Specific implementation method

The present invention will be further described below in conjunction with specific embodiments.

Example 1

In a 100mL three-necked flask equipped with a thermometer, a stirrer and a reflux condenser, add 6.54g (0.03mol) of isolongifolenone, 60mL of ethanol and 13.44g (0.06mol) of copper bromide, and heat to reflux temperature for 3 hours From about to iso-longifolenone, the conversion rate reaches over 95% (GC tracking test). After the reaction solution was cooled to room temperature, add 100mL ethyl acetate to dilute, remove the by-product cuprous bromide with 3×200mL water, wash the organic phase with saturated brine until neutral, dry over anhydrous Na ₂ SO ₄ , filter and concentrate Afterwards, the yellow liquid crude product was obtained, which was recrystallized with 10 mL of methanol to obtain 7.75 g of colorless and transparent crystals of (6S)-(-)-6-bromoisolongenone with a yield of 87.0%.

Product characterization: melting point 91.7～92.6℃; (c=1 mg/mL, CHCl ₃ ); 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 (ν _asC-H , CH ₃ ), 2875 (ν _sC-H , CH ₂ ), 1670 (v _C=O ), 1642 (ν _C=C ), 1460 (τ _CH , CH ₂ ), 1384 (τ _CH , CH ₃ ), 1264 (ν _sC-H , CH ₂ ); ¹ H NMR (300MHz, CDCl ₃ ) 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). The chiral compound (6S)-(-)-6-bromoisolongifolenone has the structural formula:

Example 2

Get (6S)-(-)-6-bromoisolongifolenone, prepare a high-concentration mother solution with acetone, and dilute it to 200mg/L with 0.1% Triton X-100 aqueous solution during the preliminary screening test. Dilute with 0.1% Triton X-100 aqueous solution to form the required series of concentration gradients, soak cabbage leaf discs with a diameter of 5 cm in the above-mentioned medicinal solution for 10 seconds, take them out, and dry them naturally until there is no clear water, then add 0.1% Triton X- 100 aqueous solution as a control. Put the dried leaf butterfly into a plastic petri dish with a diameter of 6.5 cm, and insert 10 mid-3rd instar diamondback moth larvae of the same size. Experimental treatments were repeated 3 times. The treated Plutella xylostella were cultured in a constant temperature incubator with a temperature of 25±1°C and a photoperiod of 16h:8h (L:D), and the results were checked 48 hours after inoculation. During the inspection, lightly touch the worm body with a brush, and the standard of death is the inability of the larva to coordinate movement. As shown in Figure 1. The results showed that the compounds had a strong toxic effect on the Lagerstroemia versicolor aphid, and when the concentration was 50mg/L, the death rate of the Lagerstroemia versicolor was as high as 82.2%.

Claims (7)

1. (1. 6S)-(-) -6- bromine Isolongifolenones, it is characterised in that the structural formula of the compound is：
2. 2. the synthetic method of (6S)-(-) -6- bromine Isolongifolenones described in claim 1, it is characterised in that：Take isolonglifolene Ketone carries out bromo-reaction with copper bromide in dicyandiamide solution, obtains (6S)-(-) -6- bromine Isolongifolenones；Comprise the following steps：

   1) Isolongifolenone, copper bromide and solvent are sequentially added to three mouthfuls of burnings equipped with agitator, thermometer and reflux condenser In bottle, back flow reaction, stops reaction with GC tracing detections after Isolongifolenone conversion ratio reaches 95% under nitrogen protection；

   2) reaction solution adds distilled water, is extracted with ethyl acetate after being distilled to recover solvent, and extract is again with distillation washing Wash to neutrality, then use saturated common salt water washing；Organic phase removes moisture with anhydrous sodium sulfate drying；Filtering removed and concentrated after drier Recycling design, obtains (6S)-(-) -6- bromine Isolongifolenone crude products；

   3) (6S)-(-) -6- bromines Isolongifolenone crude product is recrystallized in methanol solvate, obtain (6S) of water white transparency - (-) -6- bromine Isolongifolenone crystal.
3. 3. the synthetic method of (6S)-(-) -6- bromine Isolongifolenones according to claim 2, it is characterised in that described Solvent is alcohols, esters, aromatic hydrocarbons, nitrile solvents.
4. 4. the synthetic method of (6S)-(-) -6- bromine Isolongifolenones according to claim 3, it is characterised in that described Solvent is methanol, ethanol, isopropanol, the tert-butyl alcohol, ethyl acetate, toluene, acetonitrile.
5. 5. the synthetic method of (6S)-(-) -6- bromine Isolongifolenones according to claim 3, it is characterised in that described Solvent is methanol, ethanol.
6. 6. application of (6S)-(-) -6- bromine Isolongifolenones in insecticide is prepared described in claim 1.
7. 7. application according to claim 6, described worm is the long spot aphid of crape myrtle.