Preparation method of ortho-diazido compound

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of an ortho-diazide compound. The preparation method comprises the following steps: under an oxygen-free condition, dissolving an olefin compound, trimethylsilyl azide, an iron salt catalyst and alkyl hydroperoxide in a solvent according to a molar ratio of 1: (2-4): (0.01-0.05): 1, reacting at room temperature for 20-30 hours, and separating and purifying to obtain the product. The ortho-diazide compounds obtained by the method have various types, can be directly used, and also can be used for further preparing o-diamine compounds; the raw materials adopted by the method are simple, cheap and easy to obtain, the reaction condition is mild, the reaction operation and post-treatment are simple, the production cost can be greatly reduced, and the production efficiency can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing an ortho-bisazide compound. Background Art

[0002] Organic azides have a wide range of applications in chemical biology, medicinal chemistry, and organic synthetic chemistry. Due to the various applications of 1,2-bisazide, the bisazidation reaction is a hot topic of research. At the same time, ortho-bisazide compounds, as precursors of ortho-diamines, can be effectively converted into ortho-diamines, and ortho-diamines are common structural fragments in many drug-related molecules and ligands of metal catalytic systems, such as Tamiflu for the treatment of influenza, biotin, Chlorpromazine for the treatment of mental illness, and Jacobsen ligands.

[0003] In recent years, the preparation of ortho-bisazide compounds often requires expensive high-valent iodine derivatives or peroxide esters, and many of these methods require complex ligands and high requirements for reaction conditions, which limits the application of ortho-bisazide compounds. How to achieve efficient preparation of ortho-bisazide compounds using cheap and readily available raw materials under mild conditions has become a technical problem that needs to be solved urgently. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention provides a method for preparing an ortho-bisazide compound. The ortho-bisazide compounds obtained by the method are of various types and can be used directly or further prepared into ortho-diamine compounds; the raw materials used in the method are simple, cheap and easily available, the reaction conditions are mild, the reaction operation and post-treatment are simple, and the production cost can be greatly reduced and the production efficiency can be improved.

[0005] The present invention adopts the following technical solutions:

[0006] The present invention provides a method for preparing an ortho-bisazide compound represented by formula (I) or formula (II), comprising: under anaerobic conditions, dissolving a compound represented by formula (Ia), trimethylsilyl azide, an iron salt catalyst, and alkyl hydroperoxide in a molar ratio of 1:2-4:0.01-0.05:1 in a solvent, reacting at room temperature for 20-30 hours, and separating and purifying to obtain an ortho-bisazide compound represented by formula (I); or,

[0007] Under anaerobic conditions, the compound represented by formula (IIa), trimethylsilyl azide, an iron salt catalyst, and alkyl hydroperoxide are dissolved in a solvent in a molar ratio of 1:2-4:0.01-0.05:1, reacted at room temperature for 20-30 hours, and separated and purified to obtain an ortho-bisazide compound represented by formula (II);

[0008]

[0009] Wherein, R is one of a substituted or unsubstituted C6-C30 monocyclic aromatic hydrocarbon group, a substituted or unsubstituted C6-C30 condensed aromatic hydrocarbon group, an estrone group, a C1-C20 alkyl group, a phthalimide group, an N-alkyl-N-phenylcarboxamide group, a naphthoxy C2-C6 alkanoyl group, an N-alkylphthalimide group, and a C8-C20 ester group; the substitution is substituted by 1-3 substituents selected from alkyl, alkoxy, alkoxycarbonyl, haloalkyl, cyano, and halogen;

[0010] R 1 is hydrogen or C1-C3 alkyl;

[0011] R 2 is one of hydrogen, C1-C3 alkyl, and C6-C30 monocyclic aromatic hydrocarbon group;

[0012] n is an integer of 1 to 3.

[0013] In some embodiments, R is one of phenyl, naphthyl, p-tert-butylphenyl, p-methoxyphenyl, methoxycarbonylphenyl, p-trifluoromethylphenyl, p-cyanophenyl, m-methylphenyl, m-bromophenyl, o-methylphenyl, p-bromophenyl, mesitylene, estrone, C1-C15 alkyl, benzoate, phthalimide, N-methyl-N-phenylformamide, benzyl, 1-naphthyloxyacetyl, ethyl benzoate, N-propylphthalimide, and propyl benzoate.

[0014] In some embodiments, R 1 It is hydrogen or methyl.

[0015] In some embodiments, R 2 It is one of hydrogen, methyl and phenyl.

[0016] In some embodiments, the compound represented by formula (Ia) is one of 2-vinylnaphthalene, 1-vinylnaphthalene, styrene, p-tert-butylstyrene, p-methoxystyrene, methyl p-vinylbenzoate, p-trifluoromethylstyrene, p-cyanostyrene, p-bromostyrene, 3-bromostyrene, 3-methylstyrene, 2-methylstyrene, 2,4,6-trimethylstyrene, α-methylstyrene, β-methylstyrene, 1,2-stilbene, vinylestrol, N-vinylphthalimide, vinyl benzoate, N-methyl-N-phenyl allylamide, 1-tridecene, 3-phenylprop-1-ene, naphthyl-2-propenebutyrate, but-1-en-4-yl benzoate, N-(5-pent-1-ene)phthalimide, and hex-2-en-6-yl benzoate.

[0017] In some embodiments, the iron salt catalyst is one of ferrous trifluoromethanesulfonate, ferric chloride, ferrous chloride, and ferrous acetate.

[0018] In some embodiments, the alkyl hydroperoxide is a tertiary C4-C6 alkyl hydroperoxide.

[0019] In some embodiments, the solvent is one of 1,2-dichloroethane, dichloromethane, and acetonitrile.

[0020] In some embodiments, the reaction is followed until complete using thin layer chromatography.

[0021] In some embodiments, separation and purification includes: extracting after mixing the reaction solution with a diluent and an extractant, separating the organic phase, removing the solvent from the organic phase, and subjecting the organic phase from which the solvent has been removed to column chromatography.

[0022] In some embodiments, the diluent is a saturated carbonate solution, and the extractant is one of an ester solvent, an ether solvent, and a halogenated alkane solvent.

[0023] The beneficial effects of the present invention are:

[0024] 1. The preparation method provided by the present invention adopts an olefin compound with a structure represented by formula (Ia) or formula (IIa) and trimethylsilyl azide, an iron salt catalyst, and alkyl hydroperoxide as raw materials and performs a suitable molar ratio, and is matched with suitable reaction conditions, so as to realize the iron-catalyzed and ligand-free efficient preparation of ortho-bisazide compounds under mild conditions using cheap and readily available raw materials.

[0025] 2. The preparation method provided by the present invention uses olefin compounds as starting materials. The raw materials are easily available and of various types. The products obtained therefrom are of various types and can be used directly or for other further reactions.

[0026] 3. The preparation method provided by the present invention does not require the use of precious metal reagents and ligands, but only uses a catalytic amount of a cheap and readily available iron salt catalyst, has a high raw material utilization rate, a high product yield, and almost no by-products, which is conducive to purification after the reaction is completed.

[0027] 4. The preparation method provided by the present invention has mild reaction conditions, simple reaction operation and post-treatment process, stable and controllable reaction process, high catalytic efficiency, greatly reduces the amount of reagents used and the generation and emission of reaction waste, and is suitable for large-scale production. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] Example 1: Preparation of 2-(1,2-diazideethyl)naphthalene

[0030]

[0031] Using 2-vinylnaphthalene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0032] (1) Add 2-vinylnaphthalene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 2-(1,2-diazideethyl)naphthalene (yield 88%).

[0033] (2) Add 2-vinylnaphthalene (0.2 mmol), FeCl 3 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 2-(1,2-diazideethyl)naphthalene (yield 86%).

[0034] (3) Add 2-vinylnaphthalene (0.2 mmol), FeCl 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 2-(1,2-diazideethyl)naphthalene (yield 70%).

[0035] (4) Add 2-vinylnaphthalene (0.2 mmol), Fe(OAc) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 2-(1,2-diazideethyl)naphthalene (yield 80%).

[0036] The analytical data of the product are as follows: 1H NMR (600 MHz, CDCl3) δ7.91 (d, J = 8.4 Hz, 1H), 7.89-7.84 (m, 2H), 7.81 (s, 1H), 7.56-7.49 (m, 2H), 7.43 (dd, J = 8.4, 1.8 Hz, 1H), 4.85 (dd, J = 8.4, 4.8 Hz, 1H), 3.64-3.50 (m, 2H); 13C NMR (150 MHz, CDCl3) δ133.7, 133.5, 133.2, 129.2, 128.1, 127.8, 126.8, 126.6, 124.0, 65.8, 55.9; HRMS m / z [M+HN 4 ] + calculated for C 12 H 11 N 2 + :183.0917,found:183.0916.

[0037] Example 2: Preparation of 1-(1,2-diazideethyl)naphthalene

[0038]

[0039] Using 1-vinylnaphthalene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0040] Add 1-vinylnaphthalene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), under nitrogen protection, stirred at room temperature for 24 hours. Saturated NaHCO3 solution and ethyl acetate were added to the reaction solution for extraction, the organic phase was subjected to a rotary evaporator to remove the solvent, and column chromatography was performed to obtain the bisazido compound 1-(1,2-diazideethyl)naphthalene (yield 71%).

[0041] The analytical data of the product are as follows:1 H-NMR (600MHz, CDCl 3 )δ8.03(d,J=8.4Hz,1H),7.93(d,J=8.4Hz,1H),7.89(d,J=8.4Hz,1H),7.67-7.47(m,4H),5.47(dd,J=7.8,4.8Hz,1H),3.70-3.60(m,2H); 13 C-NMR (150 MHz, CDCl 3 )δ134.0,131.9,130.3,129.6,129.4,127.0,126.2,125.4,125.0,122.3,62.8,55.6; HRMS m / z[M+H] + calculated for C 12 H 11 N 6 + :239.1038,found:239.1040.

[0042] Example 3: Preparation of 1,2-diazideethylbenzene

[0043]

[0044] Using styrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0045] Styrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), under nitrogen protection, stirred at room temperature for 24 hours. Saturated NaHCO3 solution and ethyl acetate were added to the reaction solution for extraction, the organic phase was subjected to a rotary evaporator to remove the solvent, and column chromatography was performed to obtain the bisazido compound 1,2-diazideethylbenzene (yield 75%).

[0046] The analytical data of the product are as follows: 1 HNMR (600MHz, CDCl 3 )δ7.42(t,J=8.4Hz,2H),7.38(t,J=8.4Hz,1H),7.34(t,J=6.6Hz,2H),4.68(dd,J=8.4,4.8Hz,1H),3.55-3.40(m,2H); 13 C NMR (150 MHz, CDCl 3 )δ136.4,129.1,129.1,127.0,65.5,56.0; HRMS m / z[M+H]+ calculated for C 8 H 9 N 6 + :189.0883,found:189.0884.

[0047] Example 4: Preparation of 1-tert-butyl-4-(1,2-diazideethyl)benzene

[0048]

[0049] Using tert-butylstyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0050] Add 4-tert-butylstyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 1-tert-butyl-4-(1,2-diazideethyl)benzene (yield 80%).

[0051] The analytical data of the product are as follows: 1 HNMR (600MHz, CDCl 3 )δ7.42(d,J=7.8Hz,2H),7.25(d,J=8.4Hz,2H),4.65(dd,J=8.4,4.8Hz,1H),3.55-3.37(m,2H),1.32(s,9H); 13 CNMR (150MHz, CDCl 3 )δ152.2,133.3,126.7,126.0,65.3,56.0,34.7,31.3; HRMS m / z[M+HN 4 ] + calculated for C 12 H 17 N 2 + :189.1386,found:189.1385.

[0052] Example 5: Preparation of 1-(1,2-diazideethyl)-4-methoxybenzene

[0053]

[0054] Using p-methoxystyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0055] Add p-methoxystyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 1-(1,2-diazideethyl)-4-methoxybenzene (yield 84%).

[0056] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3 )δ7.25(d,J=9Hz,2H),6.93(d,J=8.4Hz,2H),4.62(dd,J=8.4,5.4Hz,1H),3.82(s,3H),3.51-3.36(m,2H); 13 C NMR (150 MHz, CDCl 3 )δ160.0,128.3,114.4,65.00,55.8,55.3; HRMS m / z[M+H] + calculated for C 9 H 11 N 6 O + :219.0989,found:219.0986.

[0057] Example 6: Preparation of methyl 4-(1,2-diazideethyl)benzoate

[0058]

[0059] Using methyl p-vinylbenzoate and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0060] In the Schlenk tube, methyl p-vinylbenzoate (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazido compound 4-(1,2-diazideethyl)benzoic acid methyl ester (yield 90%).

[0061] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3 )δ8.08(d,J=8.4Hz,2H),7.41(d,J=8.4Hz,2H),4.73(dd,J=7.8,4.8Hz,1H),3.91(s,3H),3.55-3.43(m,2H); 13 C NMR (150 MHz, CDCl 3 )δ166.4,141.3,130.8,130.4,127.0,65.1,55.9,52.3; HRMS m / z[M+H] + calculated for C 10 H 11 N 6 O 2 + :247.0938,found:247.0936.

[0062] Example 7: Preparation of 1-(1,2-diazideethyl)-4-trifluoromethylbenzene

[0063]

[0064] Using trifluoromethylstyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0065] In the Schlenk tube, add trifluoromethylstyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 1-(1,2-diazideethyl)-4-trifluoromethylbenzene (yield 92%).

[0066] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3 )δ7.69(d,J=7.8Hz,2H),7.48(d,J=8.4Hz,2H),4.75(dd,J=7.8,4.8Hz,1H),3.55-3.42(m,2H);13 C NMR (150 MHz, CDCl 3 )δ140.4,131.2(q,J=32.4Hz),127.4,126.1(q,J=3.3Hz),123.8(d,J=270.7Hz),64.9,55.9; HRMS m / z[M+H] + calculated for C 9 H 8 F 3 N 6 + :257.0757,found:257.0758.

[0067] Example 8: Preparation of 4-(1,2-diazideethyl)benzonitrile

[0068]

[0069] Using p-cyanostyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0070] Add p-cyanostyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 4-(1,2-diazideethyl)benzonitrile (yield 71%).

[0071] The analytical data of the product are as follows: 1 HNMR (600MHz, CDCl 3 )δ7.71(d,J=8.4Hz,2H),7.47(d,J=8.4Hz,2H),4.74(dd,J=7.2,5.4Hz,1H),3.55-3.42(m,2H); 13 CNMR (150MHz, CDCl 3 )δ141.7,132.9,127.8,118.2,113.0,64.77,55.8; HRMS m / z[M+H] + calculated for C 9 H 8 N 7 + :214.0836,found:214.0835.

[0072] Example 9: Preparation of 1-bromo-4-(1,2-diazideethyl)benzene

[0073]

[0074] Using p-bromostyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0075] Add p-bromostyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 1-bromo-4-(1,2-diazideethyl)benzene (yield 75%).

[0076] The analytical data of the product are as follows: 1 HNMR (600MHz, CDCl 3 )δ7.55(d,J=8.4Hz,2H),7.27(d,J=8.4Hz,2H),4.64(dd,J=8.4,5.4Hz,1H),3.51-3.40(m,2H); 13 CNMR (150MHz, CDCl 3 )δ135.4,132.3,128.6,123.1,64.9,55.8; HRMS m / z[M+HN 4 ] + calculated for C 8 H 8 Bn 2 + :210.9865,found:210.9865.

[0077] Example 10: Preparation of 1-bromo-3-(1,2-diazideethyl)benzene

[0078]

[0079] Using 3-bromostyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0080] Add 3-bromostyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3(4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 1-bromo-3-(1,2-diazideethyl)benzene (yield 88%).

[0081] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3 )δ7.60-7.45(m,2H),7.32-7.24(m,2H),4.63(dd,J=7.8,4.8Hz,1H),3.52-3.40(m,2H); 13 C NMR (150 MHz, CDCl 3 )δ138.7,132.2,130.7,130.1,125.5,123.2,64.9,55.9; HRMS m / z[M+HN 4 ] + calculated for C 8 H 8 Bn 2 + :210.9865,found:210.9865.

[0082] Example 11: Preparation of 1-(1,2-diazideethyl)-3-methylbenzene

[0083]

[0084] Using 3-methylstyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0085] Add 3-methylstyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 1-(1,2-diazideethyl)-3-methylbenzene (yield 78%).

[0086] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3)δ7.30(t,J=7.2Hz,1H),7.19(d,J=7.8Hz,1H),7.13(d,J=8.4Hz,2H),4.64(dd,J=8.4,4.8Hz,1H),3.54-3.40(m,2H),2.39(s,3H); 13 C NMR (150 MHz, CDCl 3 )δ135.4,134.5,131.1,128.8,126.8,126.5,62.1,55.2,19.2; HRMS m / z[M+H] + calculated for C 9 H 11 N 6 + :203.1040,found:203.1038.

[0087] Example 12: Preparation of 1-(1,2-diazideethyl)-2-methylbenzene

[0088]

[0089] Using 2-methylstyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0090] Add 2-methylstyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 1-(1,2-diazideethyl)-2-methylbenzene (yield 81%).

[0091] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3 )δ7.37-7.35(m,1H),7.28-7.20(m,3H),4.92(dd,J=9,4.2Hz,1H),3.52-3.37(m,2H),2.38(s,3H); 13 CNMR (150MHz, CDCl 3 )δ139.0,136.3,129.9,129.0,127.6,124.0,65.6,56.0,21.5; HRMS m / z[M+H] +calculated for C 9 H 11 N 6 + :203.1040,found:203.1040.

[0092] Example 13: Preparation of 2-(1,2-diazideethyl)-1,3,5-trimethylbenzene

[0093]

[0094] Using 2,4,6-trimethylstyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0095] Add 2,4,6-trimethylstyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 2-(1,2-diazideethyl)-1,3,5-trimethylbenzene (yield 92%).

[0096] The analytical data of the product are as follows: 1 HNMR (600MHz, CDCl 3 )δ6.88(s,2H),5.18(d,J=3.6Hz,1H),3.70(t,J=10.8Hz,1H),3.35(d,J=9.0Hz,1H),2.41(s,6H),2.27(s,3H); 13 C NMR (150 MHz, CDCl 3 )δ138.3,136.7,130.6,129.1,62.1,53.4,20.8,20.7; HRMS m / z[M+H] + calculated for C 11 H 15 N 6 + :231.1353,found:231.1352.

[0097] Example 14: Preparation of (1,2-diazidepropane-2-yl)benzene

[0098]

[0099] Using α-methylstyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0100] Add α-methylstyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazido compound (1,2-diazidepropane-2-yl)benzene (yield 61%).

[0101] The analytical data of the product are as follows: 1H NMR (600MHz, CDCl 3 )δ7.50-7.39(m,4H),7.35(d,J=7.2Hz,1H),3.52-3.38(m,2H),1.77(s,3H); 13C NMR(150MHz, CDCl 3 )δ140.6,128.9,128.3,125.8,66.6,61.0,22.3; HRMS m / z[M+Na] + calculated for C 9 H 10 N 6 Na + :225.0859,found:225.0857.

[0102] Example 15: Preparation of (1,2-diazidepropane-1-yl)benzene

[0103]

[0104] Using β-methylstyrene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0105] Add β-methylstyrene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazido compound (1,2-diazidepropane-1-yl)benzene (yield 82%).

[0106] The analytical data of the product are as follows: 1H NMR (600MHz, CDCl 3 )δ7.46-7.40(m,2H),7.40-7.36(m,1H),7.35-7.28(m,2H),4.53(d,J=6.0Hz,0.57H),4.37(d ,J=7.8Hz,0.43H),1.26(d,J=6.6Hz,1.85H),1.11(d,J=6.6Hz,1.35H),;13CNMR(150MHz,CDCl 3 )δ136.2,136.0,128.9,128.8,128.8,127.5,70.7,69.6,61.5,61.0,16.7,15.0; HRMS m / z[M+H] + calculated for C 9 H 11 N 6 + :203.1040,found:203.1036.

[0107] Example 16: Preparation of 1,2-diazide-1,2-diphenylethane

[0108]

[0109] Using 1,2-phenylethylene and trimethylsilane as raw materials, the reaction steps are as follows:

[0110] Add 1,2-stilbene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazido compound 1,2-diazide-1,2-diphenylethane (yield 93%).

[0111] The analytical data of the product are as follows: 1H NMR (600 MHz, CDCl3) δ7.40-7.32 (m, 2H), 7.30-7.04 (m, 8H), 4.68 (s, 0.66H), 4.63 (s, 1.34H); 13C NMR (150 MHz, CDCl3) δ135.9, 135.8, 129.0, 128.8, 128.7, 128.6, 128.0, 127.7, 70.8, 69.7; HRMS m / z [M+H] +calculated for C 14 H 13 N 6 + :265.1196,found:265.1194.

[0112] Example 17: Preparation of 1,2-diazide-2,3-dihydro-1H-indene

[0113]

[0114] Using indene and trimethylsilane azide as raw materials, the reaction steps are as follows:

[0115] Indene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain the bisazido compound 1,2-diazide-2,3-dihydro-1H-indene (yield 88%).

[0116] The analytical data of the product are as follows: 1H NMR (600 MHz, CDCl3) δ7.38 (d, J = 6.6 Hz, 1H), 7.36-7.29 (m, 2H), 7.26 (d, J = 6.6 Hz, 1H), 4.77 (d, J = 5.4 Hz, 1H), 4.17 (q, J = 6.6 Hz, 1H), 3.37 (dd, J = 16.2, 6.6 Hz, 1H), 2.96 (dd, J = 15.6, 6.6 Hz, 1H); 13C NMR (150 MHz, CDCl3) δ139.1, 137.8, 129.5, 127.8, 125.2, 124.6, 70.3, 67.7, 36.1; HRMS m / z [M+H] + calculated for C 9 H 9 N 6 + :201.0883,found:201.0887.

[0117] Example 18: Preparation of (8R,9S,13S,14S)-3-(1,2-diazideethyl)-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phenanthrene-17-one

[0118]

[0119] Using vinylestrol and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0120] Add vinylestradiol (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound (8R,9S,13S,14S)-3-(1,2-diazideethyl)-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phenanthrene-17-one (yield 65%).

[0121] The analytical data of the product are as follows: 1 H-NMR (600MHz, CDCl 3 )δ7.33(d,J=8.4Hz,1H),7.10(d,J=8.4Hz,1H),7.05(s,1H),4.61(dd,J=7.8,4.8 Hz,1H),3.51(dd,J=12.6,8.6Hz,1H),3.44(dd,J=12.6,4.8Hz,1H),2.96-2.90(m ,2H),2.53(dd,J=19.2,8.4Hz,1H),2.45-2.40(m,1H),2.34-2.28(m,1H),2.20-2 .11(m,1H),2.10-2.00(m,2H),2.00-1.94(m,1H),1.68-1.42(m,6H),0.92(s,3H); 13 C-NMR (CDCl 3 ,150MHz)δ220.8,140.8,137.4,133.7,127.6,127.5,126.1,124.3,,65.3, 55.9,50.5,48.0,44.4,38.0,35.8,31.6,29.4,26.4,25.6,21.6,13.8; HRMS m / z[M+H] + calculated for C 20 H 25 N 6 O + :365.2084,found:365.2083.

[0122] Example 19: Preparation of (2-(1,2-diazideethyl)isoindole-1,3-dione

[0123]

[0124] Using N-vinylphthalimide and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0125] In a Schlenk tube, add N-vinylphthalimide (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 2-(1,2-diazideethyl)isoindole-1,3-dione (yield 76%).

[0126] The analytical data of the product are as follows: 7.95-7.89 (m, 2H), 7.83-7.78 (m, 2H), 5.68 (t, J = 7.2 Hz, 1H), 4.07-3.97 (m, 2H); 13 C NMR (150 MHz, CDCl 3 )δ167.0,134.9,131.3,124.1,65.2,50.6.HRMS m / z[M+HN 4 ] + calculated for C 10 H 8 N 3 O 2 + :202.0611,found:202.0610.

[0127] Example 20: Preparation of 1,2-diazideethyl benzoate

[0128]

[0129] Using vinyl benzoate and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0130] Add vinyl benzoate (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3(4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain the bis-azide compound 1,2-diazide ethyl benzoate (yield 70%).

[0131] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3 )δ8.09(d,J=7.8Hz,2H),7.63(t,J=7.2Hz,1H),7.49(t,J=7.8Hz,2H),6.25(t,J=4.8Hz,1H),3.58-3.50(m,2H); 13 C NMR (150 MHz, CDCl 3 )δ165.7,134.1,130.1,128.7,128.4,83.9,52.9; HRMS m / z[M+H] + calculated for C 9 H 9 N 6 O 2 + :233.0781,found:233.0786.

[0132] Example 21: Preparation of 2,3-diazide-N-methyl-N-phenylpropionamide

[0133]

[0134] Using N-methyl-N-phenylallylamide and trimethylsilane as raw materials, the reaction steps are as follows:

[0135] In a Schlenk tube, add N-methyl-N-phenylallylamide (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazido compound 2,3-diazide-N-methyl-N-phenylpropionamide (yield 71%).

[0136] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3)δ7.45(t,J=7.8Hz,2H),7.32(t,J=7.2Hz,1H),7.30-7.24(m,2H),3.70-3.40(m,2H),3.28(s,3H),1.46(s,3H); 13 C NMR (150 MHz, CDCl 3 )δ169.7,143.4,129.7,128.2,127.3,67.0,59.0,41.1,21.4; HRMS m / z[M+H] + calculated for C 11 H 14 N 7 O + :260.1254,found:260.1253.

[0137] Example 22: Preparation of 1,2-diazolidine

[0138]

[0139] Using 1-tridecene and trimethylsilane as raw materials, the reaction steps are as follows:

[0140] Add 1-tridecene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain the bisazide compound 1,2-tridecanediazide (yield 62%).

[0141] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3 )δ3.49-3.49(m,1H),3.40-3.27(m,2H),1.55(q,J=7.8Hz,2H),1.36-1.20(m,18H),0.88(t,J=7.2Hz,3H); 13 C NMR (150 MHz, CDCl 3 )δ62.1,54.8,31.9,31.8,29.7,29.6,29.5,29.4,29.3,25.9,22.7,14.1; HRMS m / z[M+HN 4 ] + calculated for C13 H 27 N 2 + :211.2169,found:211.2168.

[0142] Example 23: Preparation of (2,3-diazidepropyl)benzene

[0143]

[0144] Using 3-phenylprop-1-ene and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0145] In a Schlenk tube, add 3-phenylprop-1-ene (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazido compound (2,3-diazidepropyl)benzene (yield 61%).

[0146] The analytical data of the product are as follows: 1H NMR (600 MHz, CDCl3) δ7.34 (t, J = 7.2 Hz, 2H), 7.28 (t, J = 7.2 Hz, 1H), 7.22 (d, J = 7.2 Hz, 2H), 3.75-3.69 (m, 1H), 3.41 (dd, J = 12.6, 4.2 Hz, 1H), 3.31 (dd, J = 12.6, 6.6 Hz, 1H), 2.88 (d, J = 7.2 Hz, 2H); 13C NMR (150 MHz, CDCl3) δ136.3, 129.3, 128.8, 127.2, 62.9, 53.9, 38.0; HRMS m / z [M+H] + calculated for C 9 H 11 N 6 + :203.1040,found:203.1039.

[0147] Example 24: Preparation of 2-naphthyl 3,4-diazide butyrate

[0148]

[0149] Using 1-propenebutyric acid naphthalene-2-yl ester and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0150] In a Schlenk tube, 1-propenebutyric acid naphthalen-2-yl ester (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound, 3,4-naphthyl diazide butyrate (yield 50%).

[0151] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3 )δ7.87(d,J=9.0Hz,2H),7.82(d,J=8.4Hz,1H),7.59(d,J=2.4Hz,1H),7.54-7.46(m,2H ),7.26(dd,J=8.4,2.4Hz,1H),4.20-4.10(m,1H),3.58-3.50(m,2H),2.94-2.82(m,2H); 13 CNMR (101MHz, CDCl 3 )δ168.8,147.9,133.7,131.6,129.7,127.8,127.7,126.8,126.0,120.7,118.5,58.05,54.2,36.9; HRMS m / z[M+H] + calculated for C 14 H 13 N 6 + :297.1095,found:297.1096.

[0152] Example 25: Preparation of 3,4-benzoic acid diazide butyl ester

[0153]

[0154] Using benzoic acid but-1-en-4-yl ester and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0155] In a Schlenk tube, add benzoic acid but-1-en-4-yl ester (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain the bisazide compound 3,4-benzoic acid diazidobutyl ester (yield 61%).

[0156] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3 )δ8.04(d,J=7.2Hz,2H),7.58(t,J=7.2Hz,1H),7.46(t,J=7.8Hz,2H),4.54-4.40(m,2H),3.7 8-3.68(m,1H),3.51(dd,J=12.6,4.2Hz,1H),3.44(dd,J=12.6,7.2Hz,1H),2.10-1.88(m,2H); 13 C NMR (150 MHz, CDCl 3 )δ166.4,133.3,129.8,129.6,128.5,61.1,59.2,54.9,31.1; HRMS m / z[M+H] + calculated for C 11 H 13 N 6 O 2 + :261.1095,found:261.1094.

[0157] Example 26: Preparation of 2-(4,5-diazidene)isoindole-1,3-dione

[0158]

[0159] Using N-(5-pent-1-enyl)phthalimide and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0160] In a Schlenk tube, N-(5-pent-1-enyl)phthalimide (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 2-(4,5-diazidoenyl)isoindole-1,3-dione (yield 58%).

[0161] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl3 )δ7.87-7.82(m,2H),7.75-7.70(m,2H),3.72(t,J=7.2Hz,2H),3.57-3.53(m,1H),3.41(dd,J=12.6 ,3.6Hz,1H),3.40(dd,J=12.6,7.2Hz,1H),1.92-1.83(m,1H),1.82-1.72(m,1H)1.60-1.51(m,2H). 13 C NMR (150 MHz, CDCl 3 )δ168.4,134.1,132.0,123.3,61.5,54.8,37.2,29.1,25.1.HRMS m / z[M+HN 4 ] + calculated for C 13 H 14 N 3 O 2 + :244.1081,found:244.1079.

[0162] Example 27: Preparation of 4,5-diazidehexylbenzoate

[0163]

[0164] Using benzoic acid hex-2-en-6-yl ester and trimethylsilyl azide as raw materials, the reaction steps are as follows:

[0165] In a Schlenk tube, add hex-2-en-6-yl benzoate (0.2 mmol), Fe(OTf) 2 (2mol%),TMSN 3 (4 equivalents), TBHP (1 equivalent) and acetonitrile (2 mL), stirred at room temperature for 24 hours under nitrogen protection. Saturated NaHCO 3 The solution was extracted with ethyl acetate, the organic phase was subjected to a rotary evaporator to remove the solvent, and the mixture was separated by column chromatography to obtain a bisazide compound 4,5-diazidehexylbenzoate (yield 52%).

[0166] The analytical data of the product are as follows: 1 H NMR (600 MHz, CDCl 3)δ8.04(d,J=8.4Hz,2H),7.57(t,J=7.2Hz,1H),7.45(t,J=7.8Hz,2H),4.41-4.32(m,2H),3.63-3.55(m,1H),3.41 -3.35(m,1H),2.06-1.96(m,1H),1.90-1.81(m,1H),1.78-1.70(m,1H),1.67-1.60(m,1H),1.34(d,J=6.6Hz,3H); 13 C NMR (150 MHz, CDCl 3 )δ166.6,133.1,130.1,129.6,128.4,66.0,64.2,60.3,27.5,25.7,14.8; HRMS m / z[M+H] + calculated for C 13 H 17 N 6 O 2 + :289.1408,found:289.1409.

[0167] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

Claims

1. A method for preparing an ortho-bisazide compound represented by formula (I) or formula (II), characterized in that: The preparation method comprises: Under anaerobic conditions, the compound represented by formula (Ia), trimethylsilyl azide, iron salt catalyst, and alkyl hydroperoxide are dissolved in a solvent in a molar ratio of 1:2-4:0.01-0.05:1, reacted at room temperature for 20-30 hours, and separated and purified to obtain an ortho-bisazide compound represented by formula (I); or, Under anaerobic conditions, the compound represented by formula (IIa), trimethylsilyl azide, an iron salt catalyst, and alkyl hydroperoxide are dissolved in a solvent in a molar ratio of 1:2-4:0.01-0.05:1, reacted at room temperature for 20-30 hours, and separated and purified to obtain an ortho-bisazide compound represented by formula (II); Wherein, R is one of a substituted or unsubstituted C6-C30 monocyclic aromatic hydrocarbon group, a substituted or unsubstituted C6-C30 condensed aromatic hydrocarbon group, an estrone group, a C1-C20 alkyl group, a phthalimide group, an N-alkyl-N-phenylcarboxamide group, a naphthoxy C2-C6 alkanoyl group, an N-alkylphthalimide group, and a C8-C20 ester group; the substitution is substituted by 1-3 substituents selected from alkyl, alkoxy, alkoxycarbonyl, haloalkyl, cyano, and halogen; R 1 is hydrogen or C1-C3 alkyl; R 2 is one of hydrogen, C1-C3 alkyl, and C6-C30 monocyclic aromatic hydrocarbon group; n is an integer of 1 to 3.

2. The preparation method according to claim 1, characterized in that: The R is one of phenyl, naphthyl, p-tert-butylphenyl, p-methoxyphenyl, methoxycarbonylphenyl, p-trifluoromethylphenyl, p-cyanophenyl, m-methylphenyl, m-bromophenyl, o-methylphenyl, p-bromophenyl, mesitylene, estrone, C1-C15 alkyl, benzoate, phthalimide, N-methyl-N-phenylformamide, benzyl, 1-naphthyloxyacetyl, ethyl benzoate, N-propylphthalimide, and propyl benzoate.

3. The preparation method according to claim 1, characterized in that: The R 1 It is hydrogen or methyl.

4. The preparation method according to claim 1, characterized in that: The R 2 It is one of hydrogen, methyl and phenyl.

5. The preparation method according to claim 1, characterized in that: The compound represented by the formula (Ia) is one of 2-vinylnaphthalene, 1-vinylnaphthalene, styrene, p-tert-butylstyrene, p-methoxystyrene, methyl p-vinylbenzoate, p-trifluoromethylstyrene, p-cyanostyrene, p-bromostyrene, 3-bromostyrene, 3-methylstyrene, 2-methylstyrene, 2,4,6-trimethylstyrene, α-methylstyrene, β-methylstyrene, 1,2-stilbene, vinylestrol, N-vinylphthalimide, vinyl benzoate, N-methyl-N-phenyl allylamide, 1-tridecene, 3-phenylprop-1-ene, naphthyl-2-propenebutyrate, but-1-en-4-yl benzoate, N-(5-pent-1-ene)phthalimide, and hex-2-en-6-yl benzoate.

6. The preparation method according to claim 1, characterized in that: The iron salt catalyst is one of ferrous trifluoromethanesulfonate, ferric chloride, ferrous chloride and ferrous acetate.

7. The preparation method according to claim 1, characterized in that: The alkyl hydroperoxide is a tertiary C4-C6 alkyl hydroperoxide.

8. The preparation method according to claim 1, characterized in that: The solvent is one of 1,2-dichloroethane, dichloromethane and acetonitrile.

9. The preparation method according to claim 1, characterized in that: The separation and purification comprises: extracting after mixing the reaction solution with a diluent and an extractant, separating the organic phase, removing the solvent from the organic phase, and separating the organic phase from which the solvent has been removed by column chromatography.

10. The preparation method according to claim 9, characterized in that: The diluent is a saturated carbonate solution, and the extractant is one of an ester solvent, an ether solvent, and a halogenated alkane solvent.

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