CN106467475A - The preparation method of ortho position double azido compound - Google Patents

The preparation method of ortho position double azido compound Download PDF

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CN106467475A
CN106467475A CN201610739098.1A CN201610739098A CN106467475A CN 106467475 A CN106467475 A CN 106467475A CN 201610739098 A CN201610739098 A CN 201610739098A CN 106467475 A CN106467475 A CN 106467475A
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manganese
acid
plus
preparation
equivalents
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郝健
陈运荣
康恺
赵丹薇
万文
蒋海珍
胡青阳
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C247/08—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being unsaturated
    • C07C247/10—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being unsaturated and containing rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C247/04—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C247/12—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/14—Compounds containing azido groups with azido groups bound to carbon atoms of rings other than six-membered aromatic rings

Abstract

The present invention relates to a kind of preparation method of ortho position double azido compound.The concretely comprising the following steps of the method：Under inert gas shielding, manganese saline catalyst, alkenes compounds, per-type oxidizer and azidotrimethylsilane are pressed 0.01～3.0:1.0:1.0～2.0 mol ratio is dissolved in solvent, reacts 6～24 hours, separated purification obtains double azido compound at a temperature of -30～-100 DEG C.Method used in the present invention utilizes raw material cheap and easy to get, with the peroxide as the raw material of industry as oxidant, cheaply stable manganese is catalyst, obtain two-fold compound, directly using buying the solvent of coming, the solvent of use is conventional cheap solvent for reaction, need not any different process, the mild condition of reaction, post processing simple it is adaptable to commercial production.

Description

The preparation method of ortho position double azido compound
Technical field
The present invention relates to a kind of preparation method being obtained ortho position double azido compound by the two-fold nitridation of alkene.
Background technology
Organic azide is a kind of important widely used organic chemistry building block and synthetic intermediate, and it is in material Also have in science and plant and will apply, the Organic substance simultaneously much containing azido group has good biological activity.Alkene azido reaction It is to introduce one of effective ways of azido group in organic molecule, anti-including the hydrogen azido reaction of alkene, oxidation Azide Should, Azide arylation reaction, the method such as two-fold nitridation, the wherein two-fold nitridation reaction of alkene can be easily simultaneously to intramolecular Introduce two adjacent azido groups, obtain the important double azido compound of a class.
At present it has been reported that two-fold nitridation reaction in, some need using this high toxicity of Hydrazoic acid,sodium salt and volatile Metal azide, some need to buy and prepare the high iodine azide reagent of complexity using market, and some are using costliness Catalyst, thus the reagent cheap using safety of necessary development, the new olefin of the mild condition of catalysts and solvents Two-fold nitridation reaction.
Content of the invention
An object of the present invention is to provide a kind of preparation method of ortho position double azido compound.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of preparation method of double azido compound is it is characterised in that the concretely comprising the following steps of the method：Under inert gas shielding, Manganese saline catalyst, alkenes compounds, per-type oxidizer and azidotrimethylsilane are pressed 0.01～3.0: 1.0 :1.0～2.0 mol ratio is dissolved in solvent, reacts 6～24 hours, separated purification obtains at a temperature of -30～100 DEG C Double azido compound；
Above-mentioned manganese salt is manganese sulfate, manganese carboxylate, manganese chloride, Manganese dibromide., manganese iodide, manganese nitrate or Manganese perchlorate.
The carboxylate radical of above-mentioned manganese carboxylate come from formic acid, acetic acid, propanoic acid, butanoic acid, valeric acid, cyclopenta acid, cyclohexyl acid, Suberyl acid.
Above-mentioned per-type oxidizer is：Di-t-butyl peroxide, cumyl peroxide, perbenzoic acid uncle Butyl ester, benzoyl peroxide, tert-butyl hydroperoxide, peracetic acid, Perpropionic Acid, Perbutyric Acid, perbenzoic acid, 3- chlorine Benzoyl hydroperoxide, acetyl peroxide, peroxidating propionyl or peroxidating butyryl.
Above-mentioned organic solvent is dichloromethane, ether, acetonitrile, ethyl acetate, toluene, oxolane, acetone, tert-pentyl alcohol Or the tert-butyl alcohol.
Above-mentioned olefin(e) compound is：Straight chain, side chain or cyclic olefin.
Above-mentioned cyclic olefin is：、、、、Or.
The structural formula of above-mentioned straight chain or linear alkene is：, the knot of described straight chain or linear alkene Structure formula is：, wherein, R, R ' and R ' ' be hydrogen,、、、、、、、、Or R, R ' and R ' ' connects into saturated cyclic structure, and wherein n is 3 to 7 integer, R1For the conventional substituted radical in organic chemistry, such as methyl, Ethyl, propyl group, butyl, halogen, cyano group, nitro, methoxyl group or acetoxyl group.
When the alkene being used is cyclic olefin, described cyclic olefin is、、 、、Or；
In the present invention, described cyclic olefin isWhen, the structure of the double azido compound of reaction gained is；Described cyclic olefin isWhen, the structure of the double azido compound of reaction gained is；Described cyclic olefin isWhen, the structure of the double azido compound of reaction gained is；Described cyclic olefin isWhen, the double azido compound of reaction gained Structure is；Described cyclic olefin isWhen, react the two-fold of gained The structure of nitrogen compound is；Described cyclic olefin isWhen, react gained The structure of double azido compound be.
Method used in the present invention utilizes raw material cheap and easy to get, using the peroxide as the raw material of industry for oxidation Agent, cheaply stable manganese is catalyst, obtains two-fold compound, the solvent that reaction is directly come, the solvent of use using purchase Conventional cheap solvent, need not any different process, the mild condition of reaction, post processing simple it is adaptable to commercial production.
Specific embodiment
Further illustrate the present invention below by the mode of embodiment, but therefore do not limit the present invention to described reality Apply among a scope.The experimental technique of unreceipted actual conditions in example below, conventionally and condition, or according to Catalogue selects.
Embodiment 1：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 2.4 milligrams, 0.009 MM, 3% mole）, then plus styrene（34.3 microlitres, 0.3 mM, 1.0 equivalents）, oil pump evacuation, inflated with nitrogen, instead Substitute gas 2 times again, in reaction tube plus 2 milliliters of dichloromethane, plus peroxidized t-butyl perbenzoate（70.0 microlitres, 0.375 mmoles You, 1.25 equivalents）, plus azidotrimethylsilane（TMSN3, 98.0 microlitres, 0.75 mM, 2.5 equivalents）, in nitrogen atmosphere Lower stirring 12 hours, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product50.3 milligrams, total recovery 88%.
:1H 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：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 4- fluorobenzene ethene（35.8 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 milli Mole, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen atmosphere Lower stirring 12 hours, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product56.0 milligrams, total recovery 91%.
:1H 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：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 4- acetoxy-styrene（48.7 milligrams, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitre, 0.45 mM, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen Atmosphere encloses lower stirring 12 hours, plus 2 milliliters of saturated sodium bicarbonate solutions, and stirring removes benzoic acid in 30 minutes, and dichloromethane extracts After be dried, revolving boils off methylene chloride, and revolving boils off methylene chloride, then direct column chromatography（）, obtain product65.1 milligrams, total recovery 88%.
:1H NMR (500 MHz, Chloroform-d) δ 7.40 – 7.33 (m, 2H), 7.20 – 7.13 (m, 2H), 4.70 (dd,J= 8.4, 4.7 Hz, 1H), 3.51 (dd,J= 12.8, 8.4 Hz, 1H), 3.45 (dd,J= 12.8, 4.7 Hz, 1H), 2.33 (s, 3H).
Embodiment 4：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 4- methoxyl group base styrene（40.4 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitre, 0.45 mM, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen Atmosphere encloses lower stirring 12 hours, and revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/20）, obtain To product58.8 milligrams, total recovery 90%.
:1H NMR (500 MHz, Chloroform-d) δ 7.32 – 7.25 (m, 2H), 7.00 – 6.93 (m, 2H), 4.65 (dd,J= 8.3, 5.0 Hz, 1H), 3.85 (s, 3H), 3.51 (dd,J= 12.7, 8.3 Hz, 1H), 3.43 (dd,J= 12.7, 5.0 Hz, 1H).
Embodiment 5：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 2,5- dimethyl styrene（43.9 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitre, 0.45 mM, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen Atmosphere encloses lower stirring 12 hours, and revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain To product61.5 milligrams, total recovery 95%.
:1H NMR (500 MHz, Chloroform-d) δ 7.21 (d,J= 1.7 Hz, 1H), 7.17 – 7.08 (m, 2H), 4.93 (dd,J= 8.9, 4.4 Hz, 1H), 3.53 (dd,J= 12.8, 8.9 Hz, 1H), 3.42 (dd,J= 12.8, 4.4 Hz, 1H), 2.39 (s, 3H), 2.37 (s, 3H).
Embodiment 6：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 4- t-butyl styrene（55.0 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitre, 0.45 mM, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen Atmosphere encloses lower stirring 12 hours, and revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain To product66.1 milligrams, total recovery 90%.
:1H NMR (500 MHz, Chloroform-d) δ 7.50 – 7.43 (m, 2H), 7.29 (m, 2H), 4.68 (dd,J= 8.6, 4.7 Hz, 1H), 3.53 (dd,J= 12.8, 8.5 Hz, 1H), 3.46 (dd,J= 12.7, 4.7 Hz, 1H), 1.36 (s, 9H).
Embodiment 7：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 4- methyl styrene（39.5 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 MM, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in blanket of nitrogen Enclose lower stirring 12 hours, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, produced Thing49.8 milligrams, total recovery 82%.
:1H NMR (500 MHz, Chloroform-d) δ 7.27 – 7.21 (m, 4H), 4.67 (dd,J= 8.4, 4.9 Hz, 1H), 3.52 (dd,J= 12.7, 8.4 Hz, 1H), 3.45 (dd,J= 12.7, 4.9 Hz, 1H), 2.40 (s, 3H).
Embodiment 8：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 4- chlorostyrene（36.0 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 milli Mole, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen atmosphere Lower stirring 12 hours, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product55.9 milligrams, total recovery 84%.
:1H NMR (500 MHz, Chloroform-d) δ 7.42 – 7.36 (m, 2H), 7.31 – 7.24 (m, 2H), 4.65 (dd,J= 8.1, 5.0 Hz, 1H), 3.49 (dd,J= 12.8, 8.0 Hz, 1H), 3.43 (dd,J= 12.7, 5.0 Hz, 1H).
Embodiment 9：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 4- bromstyrol（39.2 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 milli Mole, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen atmosphere Lower stirring 12 hours, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product72.0 milligrams, total recovery 90%.
:1H NMR (500 MHz, Chloroform-d) δ 7.61 – 7.54 (m, 2H), 7.27 – 7.21 (m, 2H), 4.67 (dd,J= 8.0, 5.0 Hz, 1H), 3.51 (dd,J= 12.8, 8.1 Hz, 1H), 3.45 (dd,J= 12.8, 5.0 Hz, 1H).
Embodiment 10：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus Anti-form-1,2- stilbene（54.0 milligrams, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitre, 0.45 mM, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen Atmosphere encloses lower stirring 12 hours, and revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/20）, obtain To productWithTotally 70.0 milligrams, total recovery 88%, trans product/cis-product= 2.0/1.0.
:1H NMR (500 MHz, Chloroform-d) δ 7.46 – 7.38 (m, 2H), 7.34 – 7.25 (m, 6H), 7.14 – 7.06 (m, 2H), 4.67 (s, 2H).
:1H NMR (500 MHz, Chloroform-d) δ 7.46 – 7.38 (m, 2H), 7.34 – 7.25 (m, 6H), 7.14 – 7.06 (m, 2H), 4.72 (s, 2H).
Embodiment 11：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 2.4 milligrams, 0.009 milli Mole, 3% mole）, 4- nitrostyrolene（44.7 milligrams, 0.3 mM, 1.0 equivalents）, oil pump evacuation, inflated with nitrogen, instead Substitute gas 2 times again, in reaction tube plus 2 milliliters of dichloromethane, plus peroxidized t-butyl perbenzoate（70.0 microlitres, 0.375 mmoles You, 1.25 equivalents）, plus azidotrimethylsilane（TMSN3,98.0 microlitres, 0.75 mM, 2.5 equivalents）, in nitrogen atmosphere Lower stirring 12 hours, plus 2 milliliters of saturated sodium bicarbonate solutions, stirring removes benzoic acid for 30 minutes, is dried after dichloromethane extraction, Revolving boils off methylene chloride, and revolving boils off methylene chloride, then direct column chromatography (ethyl acetate/petroleum ether=1/ 20), obtain product63.5 milligrams, yield 89%.
：1H NMR (500 MHz, Chloroform-d) δ 8.30 (d,J= 8.8 Hz, 2H), 7.57 (d,J= 8.7 Hz, 2H), 4.82 (dd,J= 7.4, 5.4 Hz, 1H), 3.65 – 3.47 (m, 2H).
Embodiment 12：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus Cyclo-octene（38.8 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 mM, 1.5 equivalent）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, stir under nitrogen atmosphere 12 hours, revolving boiled off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product46.1 milligrams, total recovery 79%, trans product/cis-product=4.4/1.
:1H NMR (500 MHz, Chloroform-d) δ 3.57 – 3.48 (m, 2H), 2.00 – 1.35 (m, 12H).
:1H NMR (500 MHz, Chloroform-d) δ 3.79 – 3.73 (m, 2H), 2.00 – 1.35 (m, 12H).
Embodiment 13：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plusα- methyl styrene（39.0 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 MM, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in blanket of nitrogen Enclose lower stirring 12 hours, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, produced Thing56.3 milligrams, total recovery 93%.
:1H NMR (500 MHz, Chloroform-d) δ 7.51 – 7.41 (m, 4H), 7.41 – 7.35 (m, 1H), 3.52 (d,J= 12.5 Hz, 1H), 3.43 (d,J= 12.6 Hz, 1H), 1.80 (s, 3H).
Embodiment 14：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus Indenes（35.0 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 mM, 1.5 Equivalent）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, stirring 12 is little under nitrogen atmosphere When, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product49.9 milligrams, total recovery 83%.
:1H NMR (500 MHz, Chloroform-d) δ 7.43 – 7.31 (m, 3H), 7.31 – 7.26 (m, 1H), 4.80 (d,J= 5.6 Hz, 1H), 4.20 (dd,J= 6.9, 5.6 Hz, 1H), 3.38 (dd,J= 16.0, 7.3 Hz, 1H), 2.97 (dd,J= 16.0, 6.6 Hz, 1H).
Embodiment 15：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 1,2- dihydronaphthalene（39.1 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 milli Mole, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen atmosphere Lower stirring 12 hours, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product52.0 milligrams, total recovery 81%.
:1H NMR (500 MHz, Chloroform-d) δ 7.44 – 7.37 (m, 1H), 7.35 – 7.25 (m, 2H), 7.18 (m, 1H), 4.46 (d,J= 6.6 Hz, 1H), 3.90 (m, 1H), 3.03 – 2.84 (m, 2H), 2.28 (m, 1H), 2.07 – 1.93 (m, 1H).
Embodiment 16：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 3- phenylpropen（39.5 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 milli Mole, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen atmosphere Lower stirring 12 hours, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product45.5 milligrams, total recovery 75%.
:1H NMR (500 MHz, Chloroform-d) δ 7.36 (m, 2H), 7.33 – 7.29 (m, 1H), 7.27 – 7.22 (m, 2H), 3.75 (m, 1H), 3.43 (dd,J= 12.7, 4.0 Hz, 1H), 3.32 (dd,J= 12.7, 6.9 Hz, 1H), 2.91 (d,J= 7.0 Hz, 2H).
Embodiment 17：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, oil pump evacuation, inflated with nitrogen, repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, then plus 1-decene（56.7 microlitres, 0.3 mM, 1.0 equivalents）, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 mM, 1.5 equivalent）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, stir under nitrogen atmosphere 12 hours, revolving boiled off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product53.2 milligrams, total recovery 79%.
:1H NMR (500 MHz, Chloroform-d) δ 3.49 – 3.42 (m, 1H), 3.38 (dd,J= 12.7, 4.0 Hz, 1H), 3.31 (dd,J= 12.6, 7.4 Hz, 1H), 1.58 – 1.49 (m, 2H), 1.50 – 1.19 (m, 12H), 0.88 (t,J= 7.0 Hz, 3H).
Embodiment 18：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 4.0 milligrams, 0.015 milli Mole, 5% mole）, then plus methyl cinnamate（48.6 milligrams, 0.3 mM, 1.0 equivalents）, oil pump evacuation, inflated with nitrogen, Repeatedly substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, plus peroxidized t-butyl perbenzoate（84.0 microlitres, 0.45 milli Mole, 1.5 equivalents）, plus azidotrimethylsilane（TMSN3, 118 microlitres, 0.9 mM, 3.0 equivalents）, in nitrogen atmosphere Lower stirring 12 hours, plus 2 milliliters of saturated sodium bicarbonate solutions, stirring removes benzoic acid for 30 minutes, is dried after dichloromethane extraction, Revolving boils off methylene chloride, then direct column chromatography（Ethyl acetate/petroleum ether=10/1）, obtain product25.1 milligrams, yield 34%,40.0 milligrams, yield 54%, total recovery 88%.
：1H NMR (500 MHz, Chloroform-d) δ 7.49 – 7.36 (m, 5H), 5.08 (d,J= 5.8 Hz, 1H), 4.05 (d,J= 5.8 Hz, 1H), 3.77 (s, 3H).
：1H NMR (500 MHz, Chloroform-d) δ 7.50 – 7.37 (m, 5H), 4.93 (d,J= 8.0 Hz, 1H), 4.13 (d, J = 8.1 Hz, 1H), 3.85 (s, 3H).
Embodiment 19：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn (OAc) 3 2H2O, 2.4 milligrams, 0.009 milli Mole, 3% mole）, 1- vinyl naphthalene（44.4 microlitres, 0.3 mM, 1.0 equivalents）, oil pump evacuation, inflated with nitrogen, repeatedly Substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, plus peroxidized t-butyl perbenzoate（70.0 microlitres, 0.375 mmoles You, 1.25 equivalents）, plus azidotrimethylsilane（TMSN3,98.0 microlitres, 0.75 mM, 2.5 equivalents）, in nitrogen atmosphere Lower stirring 12 hours, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product64.7 milligrams, yield 91%.
：1H NMR (500 MHz, Chloroform-d) δ 8.06 (d,J= 8.4 Hz, 1H), 7.93 (dd,J= 20.2, 8.1 Hz, 2H), 7.69 – 7.50 (m, 4H), 5.49 (dd,J= 8.0, 4.9 Hz, 1H), 3.74 – 3.60 (m, 2H).
Embodiment 20：Catalyst acetic acid manganese is added in 15 milliliters of reaction tube（Mn(OAc)3•2H2O, 2.4 milligrams, 0.009 milli Mole, 3% mole）, 2- vinyl naphthalene（46.2 milligrams, 0.3 mM, 1.0 equivalents）, oil pump evacuation, inflated with nitrogen, repeatedly Substitute gas 2 times, in reaction tube plus 2 milliliters of dichloromethane, plus peroxidized t-butyl perbenzoate（70.0 microlitres, 0.375 mmoles You, 1.25 equivalents）, plus azidotrimethylsilane（TMSN3,98.0 microlitres, 0.75 mM, 2.5 equivalents）, in nitrogen atmosphere Lower stirring 12 hours, revolving boils off methylene chloride, then direct column chromatography（Ether/petroleum ether=1/60）, obtain product63.5 milligrams, yield 89%.
：1H NMR (500 MHz, Chloroform-d) δ 7.98 – 7.80 (m, 4H), 7.61 – 7.51 (m, 2H), 7.46 (dd,J= 8.5, 1.8 Hz, 1H), 4.87 (dd,J= 8.4, 4.9 Hz, 1H), 3.63 (dd,J= 12.8, 8.4 Hz, 1H), 3.56 (dd,J= 12.8, 4.8 Hz, 1H).

Claims (8)

1. a kind of preparation method of double azido compound is it is characterised in that the concretely comprising the following steps of the method：In inert gas shielding Under, manganese saline catalyst, alkenes compounds, per-type oxidizer and azidotrimethylsilane are pressed 0.01～3.0: 1.0 :1.0～2.0 mol ratio is dissolved in solvent, reacts 6～24 hours, separated purification at a temperature of -30～100 DEG C Obtain double azido compound.
2. the preparation method of two-fold nitride according to claim 1 is it is characterised in that described manganese salt is manganese sulfate, carboxylic Sour manganese, manganese chloride, Manganese dibromide., manganese iodide, manganese nitrate or Manganese perchlorate.
3. the preparation method of described two-fold nitride according to claim 2 is it is characterised in that described manganese carboxylate Carboxylate radical comes from formic acid, acetic acid, propanoic acid, butanoic acid, valeric acid, cyclopenta acid, cyclohexyl acid or suberyl acid.
4. the preparation method of two-fold nitride according to claim 1 is it is characterised in that described peroxide aoxidizes Agent is：Di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, benzoyl peroxide, t-butyl peroxy Change hydrogen, peracetic acid, Perpropionic Acid, Perbutyric Acid, perbenzoic acid, 3- chloroperoxybenzoic acid, acetyl peroxide, peroxidating Propionyl or peroxidating butyryl.
5. the preparation method of two-fold nitride according to claim 1 is it is characterised in that described organic solvent is dichloro Methane, ether, acetonitrile, ethyl acetate, toluene, oxolane, acetone, tert-pentyl alcohol or the tert-butyl alcohol.
6. the preparation method of double azido compound according to claim 1 is it is characterised in that described olefin(e) compound For：Straight chain, side chain or cyclic olefin.
7. the preparation method of double azido compound according to claim 6 is it is characterised in that described cyclic olefin is：、、、、Or.
8. the preparation method of double azido compound according to claim 6 is it is characterised in that described straight chain or straight chain alkene The structural formula of hydrocarbon is：, wherein, R, R ' and R ' ' be hydrogen,、、、、、、、、Or R, R ' and R ' ' connects into saturated cyclic structure, and wherein n is 3 to 7 integer, R1For the conventional substituted radical in organic chemistry, such as methyl, Ethyl, propyl group, butyl, halogen, cyano group, nitro, methoxyl group or acetoxyl group.
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