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Method for synthesizing allyl azide derivative

A derivative, allyl technology, applied in the field of synthesizing allyl azide derivatives, can solve the problems of low reaction yield, explosiveness, increased cost, etc., and achieves cheap and easy-to-obtain raw materials, simple synthesis steps, and reaction conditions. mild effect

Active Publication Date: 2020-05-22
SOUTHWEST UNIVERSITY FOR NATIONALITIES
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the disadvantage of this method is that a series of allyl compounds need to be pre-synthesized, which increases the steps of synthesizing the target product and virtually increases the cost of the reaction, which is not in line with the development direction of green chemistry.
Bugarin's group recently reported the nonmetal-induced intermolecular tandem reaction of terminal allenes and azides to construct allyl azide derivatives. The disadvantage of this method is that the reaction yield is low, and the substrate is explosive Sodium nitride, not conducive to large-scale production applications
The Toast and Munoz research group reported the use of gold to catalyze the intermolecular cascade reaction of allenes and trimethylsilyl azide to construct allyl azide derivatives. Important significance, but the regioselectivity of the reaction is not good due to the different reaction sites of allenes

Method used

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  • Method for synthesizing allyl azide derivative
  • Method for synthesizing allyl azide derivative
  • Method for synthesizing allyl azide derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] In a 25mL reaction tube, add aniline allene (28.5mg, 0.1mmol), ferrous chloride (2.5mg, 0.02mmol), azidotrimethylsilane (17.3mg, 0.15mmol), add 2mL of dichloromethane , stirred and refluxed at 40°C for 26 hours until the raw material allenamine was consumed, then the mixture was concentrated under reduced pressure and purified by chromatographic column (petroleum ether / ethyl acetate=20 / 1) to obtain a yellow solid product (30.9 mg, yield: 95%).

[0024] The structural formula of the obtained compound is as follows:

[0025]

[0026] m p 81.4-82.3℃; IR (neat) 3610, 2932, 2108, 1661, 1587, 1489, 1409, 743cm -1 ; 1 HNMR (400MHz, CDCl 3 )δ7.55(d, J=8.0Hz, 2H), 7.38–7.36(m, 3H), 7.31(d, J=12.4Hz, 1H), 7.27(d, J=2.6Hz, 2H), 6.96( d,J=6.3Hz,2H),4.40(dt,J=14.7,7.5Hz,1H),3.70(d,J=7.4Hz,2H),2.44(s,3H). 13 C NMR (100MHz, CDCl 3 )δ144.29, 135.81, 135.24, 134.30, 130.03, 129.71, 129.66, 129.34, 127.49, 103.09, 51.00, 21.64. HRMS (ESI) m / z calcd for C 16 h 17 N 4 o 2 S +...

Embodiment 2

[0028] In a 25mL reaction tube, add p-fluoroaniline (30.3mg, 0.1mmol), ferrous chloride (2.5mg, 0.02mmol), azidotrimethylsilane (17.3mg, 0.15mmol), add 2mL di Chloromethane, stirred and refluxed at 40°C for 40 hours until the raw material allenamine was consumed, then the mixture was concentrated under reduced pressure and purified by chromatography (petroleum ether / ethyl acetate=20 / 1) to obtain a white solid product (33.6mg, produced The rate is 97%). The structural formula of the obtained compound is as follows:

[0029]

[0030] m p 92.7-93.8℃; IR (neat) 3691, 2935, 2378, 2110, 1662, 1549, 1371, 744cm -1 , 1 HNMR (400MHz, CDCl 3 )δ7.52(d, J=8.0Hz, 2H), 7.28(s, 2H), 7.27(d, J=9.2Hz, 1H), 7.04(t, J=8.3Hz, 2H), 6.92(s, 2H), 4.38(dt, J=13.8, 7.4Hz, 1H), 3.69(d, J=7.2Hz, 2H), 2.42(s, 3H). 13 C NMR (100MHz, CDCl 3 )δ162.70(d, J=248.7Hz), 144.52, 134.90, 134.21, 131.93(d, J=8.9Hz), 131.59(d, J=3.2Hz), 129.81, 127.47, 116.76(d, J=22.7 Hz), 103.18, 50.89, 21.65. HRMS (ESI)...

Embodiment 3

[0032] Add p-methylaniline allene (30mg, 0.1mmol), ferrous chloride (2.5mg, 0.02mmol), azidotrimethylsilane (17.3mg, 0.15mmol) into a 25mL reaction tube, add 2mL di Chloromethane, stirred and refluxed at 40°C for 40 hours until the raw material allenamine was consumed, then the mixture was concentrated under reduced pressure and purified by chromatography (petroleum ether / ethyl acetate=20 / 1) to obtain a yellow solid product (33.4mg, produced The rate is 98%). The structural formula of the obtained compound is as follows:

[0033]

[0034] m p 83.4-84.8℃; IR (neat) 3463, 2935, 2377, 2112, 1661, 1370, 1172, 744cm -1 , 1 HNMR (400MHz, CDCl 3)δ7.61(d, J=7.4Hz, 2H), 7.35(d, J=17.2Hz, 1H), 7.32(s, 2H), 7.21(d, J=7.5Hz, 2H), 6.88(d, J=7.5Hz, 2H), 4.46(dt, J=13.6, 7.3Hz, 1H), 3.75(d, J=7.2Hz, 2H), 2.49(s, 3H), 2.41(s, 3H). 13 C NMR (100MHz, CDCl 3 )δ144.19,139.46,135.35,134.41,133.04,130.32,129.68,127.49,122.38,102.93,51.01,21.63,21.24.HRMS(ESI)m / zcalcd for C 17 h 19 N 4 o...

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Abstract

The invention discloses a method for synthesizing an allyl azide derivative. The method comprises the step of inducing an allene amine compound with a structure as shown in a formula (I) which is described in the specification to react with azidotrimethylsilane with a structure as shown in a formula (II) which is described in the specification by using an iron reagent in an organic solvent so as to synthesize the allyl azide derivative with a structure as shown in a formula (III) which is described in the specification. In the formulas, the substituent group R<1> is an aryl group, a benzyl group or an alkyl group; and the substituent R<2> is a p-toluenesulfonyl group, an acetyl group or a methanesulfonyl group.

Description

technical field [0001] The invention relates to the technical field of organic chemistry, in particular to a method for synthesizing allyl azide derivatives. Background technique [0002] Organic azide derivatives, as a class of compounds containing azide functional groups, are widely used in organic synthesis, such as the construction of triazole derivatives by click reaction. In addition, compounds containing azide functional groups exhibit good biological activities, such as anti-HIV, anti-inflammatory, antibacterial and anti-myeloma activities. Compared with general azides, allyl azides exhibit more specific reactivity. For example, it is used as a precursor for the synthesis of compounds such as amines, cyanides, and allyltriazoles. Due to its good application value, many synthetic methods have been developed in recent years. [0003] The traditional method of synthesizing allyl azide is through allyl substituted compounds and azide compounds, such as allyl alcohol, ...

Claims

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Application Information

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IPC IPC(8): C07C303/40C07C311/21C07C311/18C07C311/05C07C247/08C07D263/22
CPCC07C303/40C07C247/08C07D263/22C07C311/21C07C311/18C07C311/05
Inventor 李肖肖赵志刚刘兴利刘永春
Owner SOUTHWEST UNIVERSITY FOR NATIONALITIES
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