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5-azide-5-fluoro-1,3-dioxane-2-one derivative and preparation method thereof

A technology of dioxocyclyl derivatives, applied in the field of preparation of vinyl azide compounds, to achieve the effects of good functional group tolerance, moderate yield and easy operation

Active Publication Date: 2020-04-24
SHANDONG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In previous studies, the retention of azide groups in the final product was rare, but ideal organic azides can be obtained through this reaction, and this research is a great challenge in the field of organic synthesis

Method used

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  • 5-azide-5-fluoro-1,3-dioxane-2-one derivative and preparation method thereof
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  • 5-azide-5-fluoro-1,3-dioxane-2-one derivative and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0084] Compound 1a (i.e. 1-(1-azidoethenyl)cyclohexyl tert-butyl carbonate (0.1336g, 0.5mmol), oxidant PIDA (0.3995g, 1.5mmol) was added to 2mL of solvent DCM, at 25°C, Py·HF (0.4956 g, 5 mmol) was added under stirring and stirring was continued until the complete consumption of vinyl azide was monitored by TLC analysis (typically 1 min). At -78° C., the suspended silica ( 15 g per 1 mmol of substrate), the resulting heterogeneous mixture was then transferred to a suspension in ethyl acetate, and the suspension was allowed to warm to room temperature. The resulting suspension was then filtered and extracted with dichloromethane (3×15 mL) for 3 times, washed 3 times with brine (3×40mL).Finally, the combined organic layer was washed with Na 2 SO 4 Drying, after removing solvent under reduced pressure, through silica gel column chromatography (eluent is V 石油醚 :V 乙酸乙酯 =10:3), the colorless oily product 2a was obtained with a yield of 96%.

Embodiment 2

[0086]Compound 1a (i.e. 1-(1-azidovinyl)cyclohexyl tert-butyl carbonate (0.1336g, 0.5mmol), oxidant PhIO (0.3301g, 1.5mmol) was added to 2mL of solvent DCM, at 25°C, Add Et with stirring 3 N. HF (0.4956 g, 5 mmol), continued stirring until complete consumption of vinyl azide was monitored by TLC analysis (typically 1 min). The silica (15 g per 1 mmol of substrate) was vigorously stirred to suspend the suspension at -78°C, then the resulting heterogeneous mixture was transferred to a suspension in ethyl acetate, which was allowed to warm to room temperature. The resulting suspension was then filtered, extracted three times with dichloromethane (3 x 15 mL) and washed once with brine (3 x 40 mL). Finally, the combined organic layers were subjected to Na 2 SO 4 Drying, after removing solvent under reduced pressure, through silica gel column chromatography (eluent is V 石油醚 :V 乙酸乙酯 =5:1), the colorless oily product 2a was obtained with a yield of 71%.

Embodiment 3

[0088] Compound 1a (i.e. 1-(1-azidoethenyl)cyclohexyl tert-butyl carbonate (0.1336g, 0.5mmol), oxidant PIFA (0.6451g, 1.5mmol) was added to 2mL of solvent DCM, at 25°C, AgF ((0.4956 g, 5 mmol) was added with stirring and stirring was continued until complete consumption of vinyl azide was monitored by TLC analysis (typically 1 min). Suspended silica was vigorously stirred at -78°C (per 1 mmol substrate 15 g)), the resulting heterogeneous mixture was then transferred to a suspension in ethyl acetate, and the suspension was allowed to warm to room temperature. The resulting suspension was then filtered and extracted with dichloromethane (3×15 mL) for 3 times, washed 3 times with brine (3×40mL).Finally, the combined organic layer was washed with Na 2 SO 4 Drying, after removing solvent under reduced pressure, through silica gel column chromatography (eluent is V 石油醚 :V 乙酸乙酯 =10:3), the colorless oily product 2a was obtained with a yield of 86%.

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Abstract

The invention belongs to the technical field of preparation of vinyl azide compounds, and relates to a 5-azide-5-fluoro-1,3-dioxane-2-one derivative and a preparation method thereof. The chemical structure of the derivative is represented by a formula (1) described in the specification, and a group described in the specification represents a cyclic alkane compound and is selected from one of C3-C10 naphthenic group, C3-C10 substituted naphthenic group and C3-C10 epoxy alkyl. The method is completed through a fluorine oxide cyclization reaction of vinyl azide, that is, a PhIF2HF reaction generated in situ by an oxidizing agent PIDA and hydrofluoride Py.HF, and is quite easy to prepare through a hydrogenation azide reaction of terminal alkyne. The method can effectively retain the azide group in the final product. These novel compounds have potential application value in organic and medicinal chemistry research.

Description

technical field [0001] The invention belongs to the technical field of preparation of vinyl azide compounds, and relates to a 5-azido-5-fluoro-1,3-dioxanyl-2-one derivative and a preparation method thereof. Background technique [0002] The information in the Background of the Invention section is only intended to increase the understanding of the general background of the present invention, and is not necessarily to be regarded as an acknowledgment or in any form to imply that the information constitutes the prior art already known to those skilled in the art. [0003] Vinyl azides are organic synthetic materials readily prepared by hydrogenation of hydrocarbons. The dramatic shift in this research field reported in the literature over the past decade has seen rapid developments in vinyl azide chemistry. Most vinyl azide-based transformations typically undergo molecular N 2 The rapid release of 2H-pyridine nitrogen and vinyl nitrogen nitride intermediates, thus providing ...

Claims

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Application Information

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IPC IPC(8): C07D319/08C07D493/10
CPCC07D319/08C07D493/10
Inventor 刘振华陈慧敏宁永泉高雯
Owner SHANDONG NORMAL UNIV
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