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13-thioether substituted pleocidin derivative and preparation method thereof

A technology for spinosyn and derivatives, applied in the field of 13-thioether-substituted spinosyn derivatives and its preparation, can solve the problems of unreported insecticidal and acaricidal activities, and achieve high reaction yield and mild reaction conditions Effect

Active Publication Date: 2013-03-20
HUNAN CHEM RES INST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there is no report on the preparation method and insecticidal and acaricidal activity of the 13-sulfide substituted spinosad derivatives

Method used

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  • 13-thioether substituted pleocidin derivative and preparation method thereof
  • 13-thioether substituted pleocidin derivative and preparation method thereof
  • 13-thioether substituted pleocidin derivative and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0020] Example 1. Compound HNPC-X1001, i.e. 13-(2-hydroxyl) ethylthio-13,14-dihydro-spinosyn A synthesis

[0021]

[0022] Take 1 mL each of ether and acetone to make a mixed solution, place it in a 25 mL three-necked flask, add 100 mg of spinosyn A (0.136 mmol, 1.0 eq), and stir until completely dissolved. Add 50mg of anhydrous potassium carbonate (0.36mmol, 2.6eq) to the above solution at room temperature, and stir to form a white cloudy solution. Add 10 μl of mercaptoethanol to the above solution under nitrogen protection. Spinosad basically disappeared after 48 hours of reaction at room temperature, forming a large polar point (visible after iodine fumigation). Stop the reaction, spin off the solvent under reduced pressure, add 5 mL of saturated potassium carbonate aqueous solution, extract with 10 mL×3 ethyl acetate, combine the organic layers, dry over anhydrous sodium sulfate, and spin off the solvent under reduced pressure to obtain 70 mg of a white solid. After p...

example 2

[0023] Example 2. The compound HNPC-X1002 is the synthesis of 13-(2-acetoxy)ethylthio-13,14-dihydro-spinosyn A

[0024]

[0025] Take 100mg (0.124mmol, 1.0eq) of compound 1 into a 5mL dry single-necked bottle, add 3mL of anhydrous chloroform, and stir until completely dissolved. Add 80μl of triethylamine (0.496mmol, 4.0eq) to the above solution, stir well and then add 40μl of acetyl chloride (0.496mmol, 4.0eq). Transfer to an oil bath and heat to reflux. After the reaction was complete, cool to room temperature, add 2 mL of water, extract with 5 mL of chloroform x 3, combine the chloroform layers, dry and filter over anhydrous sodium sulfate, and spin off the solvent under reduced pressure to obtain a white solid. After column separation with ethyl acetate:methanol=20:1, 66 mg of white viscous solid was obtained, with a yield of 63%. 1 H NMR (400MHz, CDCl 3 ):δ5.88(d,1H),5.79(d,1H),4.85(s,1H),4.80(m,1H),4.40(d,1H),4.31(m,1H),4.10(m, 2H),3.73(m,2H),3.67(s,1H),3.40-3.60(m...

example 3

[0026] Example 3. Compound HNPC-X1003, namely the synthesis of 13-(2-benzoyloxy)ethylthio-13,14-dihydro-spinosyn A

[0027]

[0028] Take 50mg (0.062mmol, 1.0eq) of compound 1 into a 10mL dry single-necked bottle, add 3mL of anhydrous chloroform, and stir until completely dissolved. Add 17 μl of triethylamine (0.124 mmol, 2.0 eq) to the above solution, stir well and then add 15 μl of benzoyl chloride (0.124 mmol, 2.0 eq). Transfer to an oil bath and heat to reflux. After the reaction was complete, cool to room temperature, add 2 mL of water, extract with 5 mL of chloroform x 3, combine the chloroform layers, dry over anhydrous sodium sulfate, and spin off the solvent under reduced pressure to obtain a white viscous liquid. The column was passed through ethyl acetate to obtain 35 mg of a colorless viscous solid with a yield of 63%. 1 H NMR (400MHz, CDCl 3 ):δ8.06(d,J=7.2Hz,1H),7.54-7.60(m,1H),7.50(d,J=8.0Hz,2H),5.88(d,J=9.6Hz,1H),5.79 (d,J=9.6Hz,1H),4.77-4.90(m,2H),4.45-...

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Abstract

The invention discloses a 13-thioether substituted pleocidin derivative which is represented by a general formula (I) shown in the specification and has an insecticide and acarid-killing activity, and a preparation method thereof. The compound with the general formula (I) is obtained by a chemical synthesis method from natural pleocidin or a pleocidin derivative prepared by a semi-synthesis method as a raw material. The synthesis method disclosed by the invention comprises a 13-Michael reaction, an acylation reaction and an esterification reaction. The compound with the general formula (I) has good activity on various pests and acarids on crops. The compound with the general formula (I) is prepared into an acid addition salt by using a standard salt preparation technology to be used for crop protection.

Description

technical field [0001] The invention relates to a 13-sulfide substituted spinosyn derivative with insecticidal and acaricidal activities and a preparation method thereof. Background technique [0002] Spinosyns are secondary metabolites of soil actinomycete Saccharopolyspora spinosa after aerobic fermentation in culture medium. Spinosyn is a macrocyclic lactone compound, which contains a four-nuclear ring system with multiple chiral carbons. The 9-hydroxyl and 17-hydroxyl groups on the macrocycle are respectively linked to two different six-membered sugars, and the 17-position is linked to is an amino sugar, and at the 9-position is a rhamnose. The tetranuclear ring system consists of a 5,6,5-cis-trans-trans-tricyclic ring system fused to a twelve-membered macrocyclic lactone, which contains an α,β-unsaturated ketone and an independent double bond. When the 6-position of the ring is replaced by hydrogen, it is spinosyn A, which accounts for 85-90% of the mixture; when the ...

Claims

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Application Information

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IPC IPC(8): C07H17/08C07H1/00A01N43/22A01N43/40A01P7/04A01P7/02
Inventor 欧晓明刘苏友裴晖马大友李明刘丽君王希中易正华白建军喻快
Owner HUNAN CHEM RES INST
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