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

New synthetic method of carane aldehyde acid lactone, caronic acid, caronic anhydride and key intermediates thereof

A technology of carolic acid lactone and synthesis method, which is applied in chemical instruments and methods, preparation of carboxylic acid by oxidation, preparation of oxygen-containing compounds, etc., can solve problems such as large amount of acetone usage, dangerous operation, increased production cost, etc., and achieve easy Industrialized production, high production safety and mild conditions

Active Publication Date: 2013-03-06
ABA CHEM NANTONG
View PDF3 Cites 11 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

A large amount of potassium permanganate is used as an oxidant in the subsequent oxidation reaction, which is dangerous to operate and may cause a fire, and at the same time, a large amount of manganese-containing residues are generated to pollute the environment
At the same time, the amount of acetone used in the oxidation reaction is very large, and it cannot be used in this reaction after recovery, which greatly increases the production cost

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
  • New synthetic method of carane aldehyde acid lactone, caronic acid, caronic anhydride and key intermediates thereof
  • New synthetic method of carane aldehyde acid lactone, caronic acid, caronic anhydride and key intermediates thereof
  • New synthetic method of carane aldehyde acid lactone, caronic acid, caronic anhydride and key intermediates thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1a

[0056] Preparation of Intermediate IIIa:

[0057]

[0058] Add intermediate la (54g) in the reaction flask, copper catalyst (the catalyst is the complex of cuprous trifluoromethanesulfonate and benzonitrile 1:1) (0.5g), dichloroethane 200ml, heat up to 60-65 ℃. A solution of 48 g of ethyl diazoacetate II dissolved in 100 ml of dichloroethane was added dropwise to the system, and the drop was completed while maintaining an internal temperature of 60-85°C. Stirring was continued for 30 minutes after dropping. Distilled under reduced pressure, collected fractions at 117-120°C / 1kPa to obtain 60g of intermediate IIIa.

[0059] Trans IIIa NMR:

[0060] 1 HNMR δ4.18(dd, J=12, 7Hz 1H), 4.13(m, 2H), 4.00(dd, J=12, 8Hz, 1H), 2.07(s, 3H), 1.73(ddd, J=8, 7, 5.5Hz, 1H), 1.43(d, J=5.5Hz, 1H), 1.27(s, 3H), 1.26(t, J=7Hz, 3H), 1.19(s, 3H)

[0061] Cis IIIa NMR:

[0062] 1 HNMR: δ4.50(dd, J=12, 7Hz, 1H), 4.39(dd, J=12, 8Hz, 1H), 4.11(m, 2H), 2.06(s, 3H), 1.60(d, J= 9Hz, 1H), 1.44(d...

Embodiment 1b

[0064] Preparation of Intermediate IIIb:

[0065]

[0066] Operation is the same as example Ia: wherein catalyzer is the complex compound that is cuprous trifluoromethanesulfonate and benzonitrile 1: 1, and the weight ratio of catalyzer and raw material Ib is 0.01, and the mol ratio of raw material Ib and ethyl diazoacetate II is 1:1.5.

[0067] Trans IIIb NMR:

[0068] 1 HNMR: δ4.12 (m, 2H), 3.74 (dd, J=11, 6Hz, 1H), 3.53 (dd, J=11, 8Hz, 1H), 1.66 (ddd, J=8, 6, 5.5Hz, 1H), 1.33(d, J=5Hz, 1H), 1.26(t, J=7Hz, 3H), 1.23(s, 3H), 1.18(s, 3H), 0.10(s, 9H)

[0069] Cis IIIb NMR:

[0070] 1 HNMR: δ4.08(m, 2H), 3.91(dd, J=6.5, 2.5Hz, 2H), 1.52(d, J=9Hz, 1H), 1.40(ddd, J=9, 6.52.5Hz, 1H) , 1.25(s, 3H), 1.25(t, J=7Hz, 3H), 1.18(s, 3H), 0.10(s, 9H)

Embodiment 1c

[0072] Preparation of Intermediate IIIc:

[0073]

[0074] Operation is the same as example Ia: wherein catalyzer is the complex compound of cuprous trifluoromethanesulfonate and benzonitrile 1: 1, and the weight ratio of catalyzer and raw material Ic is 0.01, and the mol ratio of raw material Ic and ethyl diazoacetate II is 1 : 1.5.

[0075] Trans IIIc NMR:

[0076] 1 HNMR: δ4.12 (m, 2H), 3.77 (dd, J=11, 6Hz, 1H), 3.55 (dd, J=11, 8Hz, 1H), 1.63 (ddd, J=9, 6, 5Hz, 1H ), 1.35(d, J=5Hz, 1H), 1.24(t, J=7Hz, 3H), 1.22(s, 3H), 1.18(s, 3H), 0.89(s, 9H), 0.06(s, 3H ), 0, 05(s, 3H)

[0077] Cis IIIc NMR:

[0078] 1 HNMR: δ4.08(m, 2H), 3.96(dd, J=11, 7Hz, 1H), 3.90(dd, J=11, 6.5Hz, 1H), 1.52(d, J=9Hz, 1H), 1.40 (ddd, J=9, 7, 6.5Hz, 1H), 1.25(s, 3H), 1.25(t, J=7Hz, 3H), 1.18(s, 3H), 0.89(s, 9H), 0.06(s , 3H), 0.05(s, 3H)

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 invention relates to a new synthetic method of carane aldehyde acid lactone, caronic acid, caronic anhydride and key intermediates thereof. The method comprises using hydroxy protected isoamyl alcohol as initial materials, performing an addition of a double bond to generate a key intermediate with a three-membered ring, hydrolyzing ethyl ester and protective groups, and then controlling oxidation conditions to obtain the carane aldehyde acid lactone and the caronic acid respectively. The method has advantages of mild condition, high production security, easy industrial production, no metal residues, and no other waste liquid, waste residue and exhaust gas that pollut the environment, and can effectively reduce cost.

Description

technical field [0001] The invention relates to a new synthesis method of caronic acid lactone, caronic acid, caronic anhydride and key intermediates thereof. Background technique [0002] Caronaldehydic acid hemiacetal is an important intermediate in the production of deltamethrin (molecular formula) which is the most toxic among the pyrethroid insecticides. It is widely used in the fields of pesticides and medicine, and its molecular formula is as follows. [0003] [0004] Carronolactone [0005] [0006] deltamethrin [0007] Carronic acid is the raw material for the production of the important intermediate carronic anhydride of the hepatitis C protease inhibitor boceprevir, and is also widely used in pesticides and other organic synthesis fields. Their chemical formulas are as follows: [0008] [0009] Caronic acid Caronic anhydride [0010] [0011] The general synthetic route of carvalolactone at present is as follows: [0012] [0013] This route ...

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
IPC IPC(8): C07C62/02C07C51/16C07C27/02C07C61/04C07D307/93
CPCY02P20/55
Inventor 秦东光张五军孙婧李倩张平康立涛
Owner ABA CHEM NANTONG
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