An optically active fluorine-containing alkyl allylamine compound and its preparation method

A technology of fluorine-containing alkyl allyl amine and fluoroalkyl allyl amine is applied in the field of fluorine-containing alkyl allyl amine compounds and preparation, and can solve the problem of α-fluoroalkyl allyl amine compounds difficulties, etc.

Active Publication Date: 2016-06-08
SHANGHAI CHEMPARTNER CO LTD
View PDF4 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Aiming at the above-mentioned technical problems in the prior art, the present invention provides an optically active fluorine-containing alkyl allyl amine compound and a preparation method. The optically active fluorine-containing alkyl allyl amine compound is The amine compound and the preparation method solve the technical problem of the difficulty in synthesizing α-fluoroalkylallylamine compounds containing quaternary carbon chiral centers in the prior art

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
  • An optically active fluorine-containing alkyl allylamine compound and its preparation method
  • An optically active fluorine-containing alkyl allylamine compound and its preparation method
  • An optically active fluorine-containing alkyl allylamine compound and its preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Under argon protection, add 1mL of anhydrous diethyl ether and unsaturated imine to the reaction tube (75.8mg, 0.25mmol), cooled to -40°C, slowly added lithium reagent dropwise Diethyl ether solution (0.75 mmol), after the dropwise addition, was returned to room temperature, stirred, and followed by TLC to complete the reaction. Add 5ml of saturated aqueous ammonium chloride solution, separate the layers, extract with ethyl acetate, and dry over anhydrous sodium sulfate. The solvent was removed by rotary evaporation, and the product was obtained by flash column chromatography 85.9 mg, 90% yield.

[0034] [α] D 20 -100.92 (c=1.29, CHCl 3 ); FT-IR (KBr, cm -1 ): ν3329, 3061, 2926, 2868, 1713, 1652, 1578, 1540, 1450, 1248, 1074, 962, 750; 1 HNMR (CDCl 3 ): δ7.67(d, J=7.3Hz, 2H), 7.46-7.22(m, 8H), 6.62(d, J=16.4Hz, 1H), 6.55(d, J=16.4Hz, 1H), 4.13 (s, 1H), 1.29(s, 9H).; 19 FNMR (CDCl 3 ): δ-73.07(s, 3F); 13 CNMR (CDCl 3 ): δ137.04, 136.46, 135.54, 129.07, 12...

Embodiment 2

[0036] Under argon protection, add 1mL of anhydrous diethyl ether and unsaturated imine to the reaction tube (75.8mg, 0.25mmol), cooled to -40°C, slowly added the prepared lithium reagent dropwise Diethyl ether solution (0.75 mmol), after the dropwise addition, was returned to room temperature, stirred, and followed by TLC to complete the reaction. Add 5ml of saturated aqueous ammonium chloride solution, separate the layers, extract with ethyl acetate, and dry over anhydrous sodium sulfate. The solvent was removed by rotary evaporation, and the product was obtained by flash column chromatography 81.1 mg, 82% yield.

[0037] [α] D 27 -145.59 (c=0.88, CHCl 3 ); FT-IR (KBr, cm -1 ): ν3372, 3253, 3061, 2960, 1713, 1652, 1506, 1449, 1364, 1153, 940, 751; 1 HNMR (400MHz, CDCl 3 )δ7.65(d, J=8.0Hz, 1H), 7.43(d, J=7.1Hz, 2H), 7.38-7.23(m, 6H), 6.81(d, J=16.3Hz, 1H), 6.50( d, J=16.3Hz, 1H), 4.01(s, 1H), 2.51(s, 3H), 1.29(s, 9H).; 19 FNMR (376MHz, CDCl 3 )δ-71.09(s, 3F); 1...

Embodiment 3

[0039] Under argon protection, add 1mL of anhydrous diethyl ether and unsaturated imine to the reaction tube (75.8mg, 0.25mmol), cooled to -40°C, slowly added the prepared lithium reagent dropwise Diethyl ether solution (0.75 mmol), after the dropwise addition, was returned to room temperature, stirred, and followed by TLC to complete the reaction. Add 5ml of saturated aqueous ammonium chloride solution, separate the layers, extract with ethyl acetate, and dry over anhydrous sodium sulfate. The solvent was removed by rotary evaporation, and the product was obtained by flash column chromatography 90 mg, yield 90%.

[0040] [α] D 27 -94.32 (c=0.97, CHCl 3 ); FT-IR (KBr, cm -1 ): ν3347, 3208, 3058, 2958, 1713, 1648, 1578, 1450, 1364, 1169, 973, 751; 1 HNMR (400MHz, CDCl 3 )δ7.50-7.42(m, 4H), 7.39-7.27(m, 4H), 7.23(d, J=7.6Hz, 1H), 6.66(d, J=16.4Hz, 1H), 6.56(d, J =16.4Hz, 1H), 4.12(s, 1H), 2.40(s, 3H), 1.31(s, 9H); 19 FNMR (376MHz, CDCl 3 )δ-72.85(s, 3F); 13 CNMR (...

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 fluoroalkyl allyl amine compound with optical activity, and also provides a preparation method of the fluoroalkyl allyl amine compound. Location selectivity addition reaction is carried out through an organic metal lithium reagent and optically pure alpha, beta-unsaturated fluoroalkyl tertiary butyl sulfinyl acyl ketone imide; and a chiral fluoroalkyl allyl amine compound which is easy to transform and derive is synthesized at high yield and excellent diastereoselectivity. According to the fluoroalkyl allyl amine compound, the required raw materials are cheap and available; the synthesis method is simple to operate; the reaction time is short; the yield and optical purity of the product are relatively high; the preparation method is a universal method for synthesizing an alpha-fluoroalkyl allyl amine compound containing a quaternary carbon chiral center, and has good application prospect.

Description

technical field [0001] The invention belongs to the field of chemical industry, and in particular relates to a fluorine-containing medicine, a pesticide intermediate and a preparation method thereof, in particular to an optically active fluorine-containing alkyl allylamine compound and a preparation method thereof. Background technique [0002] Chiral allyl amine compounds not only widely exist in natural products and bioactive molecules, but also have a wide range of applications in the field of organic synthesis as an important class of synthetic intermediates ((a) Stütz, A. Angew. Chem., Int. Ed. Engl. 1987, 26, 320. (b) Dai, C.; Stephenson, C.R.J. Org. Lett. 2010, 12, 3453. (c) Nakamura, Y.; Burke, A.M.; S.; Ziller, J.W.; Rychnovsky, S.D. Org. Lett. 2009, 12, 72. (d) Krishnan, S.; Bagdanoff, J.T.; .Soc.2008, 130, 13745.(e) Jakobsche, C.E.; Gorka, P.; Miller, S.J.Angew.Chem.Int.Ed. .). In addition, a wide variety of useful compounds can be obtained by functionalizing t...

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 & AuthorityPatents(China)
IPC IPC(8): C07C313/06C07D307/52C07C233/66C07C231/02
Inventor刘振江吴范宏刘朋
OwnerSHANGHAI CHEMPARTNER CO LTD