Unlock instant, AI-driven research and patent intelligence for your innovation.

Preparation method of chiral fluoroalkyl ternary carbocyclic compound

A technology of fluoroalkyl ternary and fluoroalkyl cyclopropene, which is applied in the field of preparation of chiral fluoroalkyl ternary carbocyclic compounds, and can solve the problems of high explosiveness, limited preparation, purification, storage and use, and inapplicability to industrial applications, etc. question

Inactive Publication Date: 2021-09-14
NORTHEAST NORMAL UNIVERSITY
View PDF6 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, fluoroalkyldiazomethane has high volatility, high toxicity and high explosiveness, which greatly limits its preparation, purification, storage and use
Therefore, the current methods for preparing chiral fluoroalkylcyclopropene and fluoroalkylcyclopropane have great safety hazards and are not suitable for large-scale industrial applications.

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
  • Preparation method of chiral fluoroalkyl ternary carbocyclic compound
  • Preparation method of chiral fluoroalkyl ternary carbocyclic compound
  • Preparation method of chiral fluoroalkyl ternary carbocyclic compound

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0042] The invention provides a preparation method of a chiral fluoroalkyl three-membered carbocyclic compound, comprising the following steps:

[0043] When the chiral fluoroalkyl three-membered carbocyclic compound is a chiral fluoroalkyl cyclopropene compound:

[0044] The fluoroalkylsulfonylhydrazone derivative of the structure shown in formula I, the alkyne derivative of the structure shown in formula II, the first chiral metal catalyst, the first alkali compound and the first organic solvent are mixed, and the first [2 +1] cycloaddition reaction to obtain a chiral fluoroalkyl cyclopropene compound having a structure shown in formula III;

[0045] When the chiral fluoroalkyl three-membered carbocyclic compound is a chiral fluoroalkyl cyclopropane compound:

[0046] Mix the fluoroalkylsulfonylhydrazone derivative of the structure shown in formula I, the alkene derivative of the structure shown in formula IV, the second chiral metal catalyst, the second alkali compound and...

Embodiment 1

[0096]

[0097] Under nitrogen condition, o-trifluoromethylbenzenesulfonyl hydrazide (30mmol) and ketone compound trifluoromethylacetophenone (30mmol) were dissolved in 40mL ethyl acetate (EA), then boron trifluoride diethyl ether ( 45mmol), the resulting material was reacted overnight in an oil bath at 40°C, after the reaction, 40mL of saturated aqueous sodium chloride solution (mass concentration of 1.33g / mL) was added to the resulting product, extracted with EA, and the resulting extract was treated with sulfuric acid After drying over magnesium and concentrating under reduced pressure, the resulting product was subjected to silica gel column chromatography to obtain trifluoromethylbenzenesulfonylhydrazone 1a;

[0098] Under nitrogen conditions, the trifluoromethylbenzenesulfonylhydrazone 1a (39.6mg, 0.1mmol), phenylacetylene 2a (20mg, 0.2mmol) and the commercially available chiral metal catalyst Rh 2 (R-BTPCP) 4 (2mg, relative to 1a, 1mol%), DIPEA (33μl, 0.2mmol) and 3...

Embodiment 2

[0104]

[0105] Under nitrogen, trifluoromethylbenzenesulfonylhydrazone 1a (39.6mg, 0.1mmol), styrene 2b (21mg, 0.2mmol), chiral metal catalyst Rh 2 (R-PTAD) 4 (2mg, 1mol%), DIPEA (33μl, 0.2mmol), and 3mL of toluene were added to a 10mL reaction flask, and stirred at room temperature for 12h. After the reaction, the resulting product was filtered with diatomaceous earth, and the resulting filtrate was concentrated under reduced pressure. After separation by analysis, compound 3b (25.4 mg, yield 97%) was obtained as a colorless oily substance.

[0106] characterize

[0107] The compound 3b prepared in embodiment 2 is carried out NMR characterization, and the obtained spectrograms are respectively shown in Figure 4~6 ; The resulting characterization data are:

[0108] 1 H-NMR (600MHz, CDCl 3 )δ7.21-7.18(m,1H),7.16-7.12(m,4H),7.10-7.06(m,3H),6.79-6.76(m,2H),2.84(dd,J=7.0Hz,J= 9.6Hz,1H),1.87(dd,J=6.0Hz,J=9.6Hz,1H),1.69-1.66(m,1H). 13 C-NMR (150MHz, CDCl 3 )δ135.6, 132....

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 provides a preparation method of a chiral fluoroalkyl ternary carbocyclic compound, and belongs to the technical field of organic synthesis. According to the method, a fluoroalkyl sulfonyl hydrazone derivative is used as a raw material, under the alkaline condition, the fluoroalkyl sulfonyl hydrazone derivative is subjected to in-situ decomposition, so that the fluoroalkyl diazo compound is generated in situ, and the generated fluoroalkyl diazo compound is subjected to asymmetric [2+1] cycloaddition reaction with an alkyne derivative or an olefin derivative to realize conversion of the fluoroalkyl diazo compound. The method can be operated by a one-pot method, does not need a special feeding device or manual dripping operation, has the characteristics of simplicity in operation, safety, mildness and suitability for large-scale application, and solves the problem that dangerous reagents need to be operated in the existing method.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a preparation method of a chiral fluoroalkyl three-membered carbocyclic compound. Background technique [0002] Chiral fluoroalkyl-substituted three-membered carbocyclic compounds, as an important class of organic structural units, often appear in a variety of drug candidates and agricultural organic molecules. Their unique spatial structure, electronic properties, and optical activity also make them often used as functional group substitutes in the core structures of various analgesics, insecticides, and antibiotics to improve their biological activities. At the same time, the existence of high strain tension also makes this kind of compound become a kind of highly active chiral synthon widely used in organic synthesis. [0003] The [2+1] asymmetric cycloaddition reaction of fluoroalkylcarbenes with alkynes and alkenes is the most convenient and direct method for the ...

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): C07C22/08C07C17/272C07C41/30C07C43/225
CPCC07C17/272C07C41/30C07C2601/02C07C2601/08C07B2200/07C07C22/08C07C43/225
Inventor 毕锡和张欣宇
Owner NORTHEAST NORMAL UNIVERSITY