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Preparation method of ortho-diazido compound

An azide and compound technology, which is applied in the field of preparation of ortho-bis-azide compounds and achieves the effects of mild conditions and simple post-processing

Inactive Publication Date: 2017-03-01
SHANGHAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Among the reported bisazide reactions, some require the use of sodium azide, a highly toxic and explosive metal azide, some require the use of highly iodine azide reagents that are not available in the market and are complex to prepare, and some use expensive Therefore, it is necessary to develop a novel olefin diazide reaction using safe and cheap reagents, catalysts and solvents under mild conditions

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Embodiment 1: add catalyzer manganese acetate (Mn(OAc) in the reaction tube of 15 milliliters 3 • 2H 2 O, 2.4 mg, 0.009 mmol, 3% mol), plus styrene (34.3 microliters, 0.3 mmol, 1.0 equivalent), the oil pump is vacuumed, nitrogen is filled, and the gas is repeatedly pumped twice, and the reaction tube is Add 2 ml of dichloromethane, add tert-butyl peroxybenzoate (70.0 μl, 0.375 mmol, 1.25 equiv), add azidotrimethylsilane (TMSN 3 , 98.0 microliters, 0.75 mmoles, 2.5 equivalents), stirred for 12 hours under nitrogen atmosphere, dichloromethane was evaporated by rotary evaporation, and then direct column chromatography (ether / petroleum ether = 1 / 60) to obtain the product 50.3 mg, total yield 88%.

[0019] : 1 H NMR (500 MHz, Chloroform- d ) δ 7.46 – 7.30 (m, 5H),4.68 (dd, J = 8.4, 4.8 Hz, 1H), 3.51 (dd, J = 13.0, 8.5 Hz, 1H), 3.44 (dd, J = 12.5, 4.5 Hz, 1H)

Embodiment 2

[0020] Embodiment 2: add catalyzer manganese acetate (Mn(OAc) in the reaction tube of 15 milliliters 3 • 2H 2 O, 4.0 mg, 0.015 mmol, 5% mol), the oil pump was evacuated, filled with nitrogen, and the air was repeatedly pumped twice, and 2 ml of dichloromethane was added to the reaction tube, followed by 4-fluorostyrene (35.8 μl , 0.3 mmol, 1.0 equivalent), plus tert-butyl peroxybenzoate (84.0 microliters, 0.45 mmol, 1.5 equivalent), plus azidotrimethylsilane (TMSN 3 , 118 microliters, 0.9 mmol, 3.0 equivalents), stirred for 12 hours under nitrogen atmosphere, dichloromethane was removed by rotary evaporation, and then directly column chromatography (ether / petroleum ether = 1 / 60) to obtain the product 56.0 mg, total yield 91%.

[0021] : 1 H NMR (500 MHz, Chloroform- d ) δ 7.36 – 7.28 (m,2H), 7.15 – 7.06 (m, 2H), 4.66 (dd, J = 8.2, 5.0 Hz, 1H), 3.49 (dd, J = 12.7,8.1 Hz, 1H), 3.42 (dd, J = 12.8, 5.0 Hz, 1H).

Embodiment 3

[0022] Embodiment 3: add catalyzer manganese acetate (Mn(OAc) in the reaction tube of 15 milliliters 3 • 2H 2 O, 4.0 mg, 0.015 mmol, 5% mol), the oil pump was evacuated, nitrogen was filled, and the air was repeatedly pumped twice, and 2 ml of dichloromethane was added to the reaction tube, followed by 4-acetoxystyrene (48.7 mg, 0.3 mmol, 1.0 equiv), plus tert-butyl peroxybenzoate (84.0 microliters, 0.45 mmol, 1.5 equiv), plus azidotrimethylsilane (TMSN 3 , 118 μl, 0.9 mmol, 3.0 equivalents), stirred for 12 hours under nitrogen atmosphere, added 2 ml of saturated sodium bicarbonate solution, stirred for 30 minutes to remove benzoic acid, extracted with dichloromethane, dried, and evaporated to remove solvent II Chloromethane, the solvent dichloromethane was evaporated by rotary evaporation, and then direct column chromatography ( ) was obtained to obtain the product 65.1 mg, total yield 88%.

[0023] : 1 H NMR (500 MHz, Chloroform- d ) δ 7.40 – 7.33 (m,2H), 7.20 – 7.13...

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Abstract

The invention relates to a preparation method of an ortho-diazido compound. The method comprises the following specific steps: dissolving a manganese salt catalyst, an olefin compound, a peroxide oxidizing agent and azidotrimethyl silane in a solvent under the protection of inert gas according to the molar ratio of 0.01-3.0: 1.0:1.0-2.0, reacting at the temperature of minus 30 to minus 100 DEG C for 6-24 h, and carrying out separation and purification to obtain a diazido compound. According to the method, raw materials used are cheap and easily available, peroxide used as an industrial raw material is used as an oxidizing agent, and cheap and stable manganese is used as a catalyst so as to obtain the diazido compound. The purchased solvent is directly used for the reaction. The solvent used is a commonly-used cheap solvent without any special treatment. The reaction condition is mild, and aftertreatment is simple. The preparation method is suitable for industrial production.

Description

technical field [0001] The invention relates to a method for preparing an ortho-position bis-azide compound by olefin bis-azidation. Background technique [0002] Organic azide compound is an important and widely used organic chemical building block and synthetic intermediate. It also has a kind of application in material science. At the same time, many organic compounds containing azide groups have good biological activities. Olefin azidation reaction is one of the effective methods to introduce azide groups into organic molecules, including hydroazidation reaction of alkenes, oxidative azidation reaction, azidation arylation reaction, double azidation and other methods , in which the diazide reaction of alkenes can conveniently introduce two adjacent azide groups into the molecule at the same time, resulting in an important class of diazide compounds. [0003] Among the reported bisazide reactions, some require the use of sodium azide, a highly toxic and explosive metal a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C247/10C07C247/12C07C247/04C07C247/14
CPCC07C247/10C07C247/04C07C247/12C07C247/14
Inventor 郝健陈运荣康恺赵丹薇万文蒋海珍胡青阳
Owner SHANGHAI UNIV
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