Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

(6S)-6-methyl-2-ketone derivant, synthesizing method and use in synthesis of (S)-methoprene

A technology of methoprene and derivatives, which is applied in the field of -6-methyl-2-one derivatives and achieves the effects of high yield, short steps and easy operation

Inactive Publication Date: 2008-03-05
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
View PDF3 Cites 6 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] At present, there are many methods for synthesizing Hydroprene, but the report of synthetic (S)-Hydroprene is less (J. ofNature Compounds, 2001, 37, 140)

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • (6S)-6-methyl-2-ketone derivant, synthesizing method and use in synthesis of (S)-methoprene
  • (6S)-6-methyl-2-ketone derivant, synthesizing method and use in synthesis of (S)-methoprene
  • (6S)-6-methyl-2-ketone derivant, synthesizing method and use in synthesis of (S)-methoprene

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] The synthesis of embodiment 1 (R)-5-bromo-4-methylpentanoic acid methyl ester (2)

[0037]

[0038] In a 500mL three-necked bottle, dissolve 50g of the crude product lactone 1 in 200mL of anhydrous methanol. Pass dry HBr gas under stirring, and keep white mist in the bottle. After reacting at room temperature for 16 hours, it was detected by TLC that the raw material disappeared, and the flow of HBr gas was stopped. The solution was spin-dried under reduced pressure, the residue was extracted with ether (4×100mL), and the organic phase was washed with saturated NaHCO 3 Solution (2×80 mL), washed with saturated brine (2×50 mL), dried over anhydrous sodium sulfate, and spin-dried under reduced pressure. Distilled under reduced pressure, 28.54 g of compound 2 was collected as a 52°C-54°C / 60Pa fraction, with a weight yield of 56%. [α] D 25 2.16 (c1.1, CH 3 Cl) 1 H NMR (300MHz, CDCl 3 ): δ3.68(s, 3H), 3.36-3.39(m, 2H), 2.35(t, 2H, J=7.5Hz), 1.75-1.90(m, 2H), 1.52-...

Embodiment 2

[0039] Synthesis of Example 2 Compound 3

[0040]

[0041] Add 360mg (15mmol) of magnesium chips into a 50mL three-necked bottle, vacuum-fill with nitrogen three times, and then add 4mL of anhydrous THF. 1.2 mL (1.51 g, 10 mmol) of isopentyl bromide was dissolved in 6 mL of anhydrous THF, and added dropwise to the above reaction flask. First add 10 drops dropwise and stir. After the reaction is triggered, continue to add dropwise, keep the reaction system slightly hot, continue stirring for 1 hour after the drop is complete, and let it stand for use.

[0042] Another 50mL three-neck bottle was taken and vacuum filled with nitrogen three times. Compound 2 (0.418g, 2.0mmol) was dissolved in 5mL of anhydrous THF, and 0.1mL of 1.0M Li 2 CuCl 4 Tetrahydrofuran solution, 0.96 mL NMP (991 mg, 10.0 mmol). At room temperature, 2.5 mL (2.5 mmol) of the above-prepared Grignard reagent was added dropwise, and after 3 hours of reaction, TLC detected that the raw material disappeared...

Embodiment 3

[0043] Synthesis of Example 3 Compound 4

[0044]

[0045] Lithium aluminum hydride (0.711g, 18.7mmol) was suspended in 20mL of anhydrous ether, and the ether solution (20mL) of 3 (3.12g, 15.6mmol) was added dropwise to the above system at 0°C. After the dropwise addition, it was raised to room temperature and reacted for 3 hours, and TLC detected that the reaction was complete. The reaction was carefully quenched with sodium sulfate containing crystal water until a loose solid was produced, which was filtered with suction and washed several times with diethyl ether. Spin-dried under reduced pressure, followed by flash column chromatography to obtain 42.58 g of a colorless oily substance with a yield of 96%. [α] D 26 -2.12 (c0.99, CHCl 3 ); 1 H NMR (CDCl 3 , 300Mz) δ: 3.63(t, J=6.6Hz, 2H), 1.67~1.09(m, 12H), 1.36(br s, 1H), 0.90~0.85(m, 9H); 13 C NMR (CDCl 3 , 75MHz) δ: 63.4, 39.3, 37.2, 32.9, 32.6, 30.2, 27.9, 24.7, 22.7, 22.6, 19.6; IR (film) v: 3328, 2956, 2929, ...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The present invention provides one kind of (6S)-6-methyl-2-ketone derivatives in novel structure. The (6S)-6-methyl-2-ketone derivatives may prepared with (4R)-methyl caprolactone obtained easily from steroid sapogenin oxidizing and degrading waste as material, and may be applied in synthesizing optical pure (S)-ethyl methoprene. The present invention can raise the utilization rate of steroid sapogenin, reduce environmental pollution, prepare thioketal compounds in the structure as shown and expand the application range of steroid sapogenin oxidizing and degrading waste.

Description

technical field [0001] The invention relates to a class of (6S)-6-methyl-2-ketone derivatives, which can be conveniently prepared from small segment lactones obtained by the degradation of steroidal sapogenins, and these compounds can be used to synthesize optically pure Methoprene (S)-Hydroprene. Using the method of the invention to synthesize (S)-Hydroprene has shorter steps than the existing literature methods, simple and convenient operation and high yield. technical background [0002] Methoprene (hydroprene, (E, E)-3,7,11-trimethyl-2,4-dodecenoic acid ethyl ester) is a kind of drug developed by Zoecon Biopharmaceutical Company in the United States. Effective insect growth regulators (Insect Growth Regulators, IGRs) with juvenile hormone activity (Juvenile Hormone Analog, Juvenile Hormone Analog, referred to as JHA), the agent is effective against tobacco budworm, Aedes aegypti, and greater wax moth. All have good control effect (J.Agric.Food Chem.1976,24,207). This ...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): C07D339/08C07C49/17C07C309/66C07C309/73C07C69/587C07C67/30
Inventor 田伟生王子坤许启海
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com