Cyclic bis-peroxides, methods of synthesis and use in the preparation of alkyl bifunctional compounds

Abstract

Cyclic bis-peroxide, synthetic method and application thereof in preparation of alkyl bifunctional compound; cyclic bis-peroxide is prepared by using cycloalkanone as raw material, oxidizing into bis-peroxide alcohol under catalysis of hydrogen peroxide and proton acid, and alcohol hydroxyl is protected by acyl chloride and other protective agents; alkyl bifunctional compound is prepared under mild conditions by using trifluoromethanesulfonic acid ferrous as catalyst and TMSN3 as-N3 source, including but not limited to double azidation, double halogenation, double boronization, double phosphorization and double thiocyanate esterification; the application greatly widens the synthesis range of bifunctional alkane molecule, improves the synthesis efficiency, simplifies the synthesis process and reduces the synthesis pollution; a novel, green and efficient path is provided for synthesis of alkyl bifunctional compound, and the category of energetic material preparation technology is widened.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of energetic materials, and particularly relates to cyclic bis-peroxides, a synthesis method and application thereof in the preparation of alkyl bifunctional compounds. BACKGROUND

[0002] Energetic materials are a kind of high-performance, high-efficiency and high-reliability materials, which have wide application prospects in military, aerospace, petroleum, chemical industry, automobile, electronics, construction and other fields. With the progress of science and technology and the diversification of people's needs, the application field of energetic materials is also expanding. In the field of new energy, energetic materials can be used for energy storage and power generation, etc.; in the field of environmental protection, they can be used for harmless treatment of waste and pollutants, etc.

[0003] Azido group (-N3) is a functional group with strong reactivity. It can decompose under certain conditions and release a large amount of energy. This structural feature makes alkyl bis-azido compounds an important class of energetic materials. Alkyl bis-azido compounds have high energy density and can be used as high-energy fuels. In the combustion process, the nitrogen and other gases produced by the decomposition of azido groups can provide a large amount of heat energy, thereby propelling the flight of rockets or other aircraft. In addition, in the field of energetic adhesives, alkyl bis-azido compounds also play an important role. They can be used as components of adhesives to improve the strength and heat resistance of adhesives.

[0004] The industrial preparation methods of alkyl bisazide compounds mainly include two kinds: catalytic azidation method and dibromide synthesis method. The catalytic azidation method refers to the preparation of bisazide compounds by reacting a compound containing a carbon-carbon double bond with an azide reagent (NaN3) in the presence of a catalyst and a free radical initiator (acyl peroxide, hydroperoxide, dialkyl peroxide). For example, the patent application No. 201711026558.7 discloses a preparation method of bisazide compounds. In the presence of a copper-containing catalyst, an iron catalyst or a triflate anion metal catalyst and a free radical initiator (benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, etc.), the desired bisazide compound is prepared by reacting raw materials including a compound containing a carbon-carbon double bond and an azide reagent. However, this method needs to be carried out under specific temperature, pressure and catalyst conditions, which are difficult to control accurately, thereby affecting the purity and yield of the product, and the types of compounds containing carbon-carbon double bonds are limited, which restricts the expansion of the types of alkyl bisazide compounds. In addition, manganese salt catalysts can also convert olefin compounds into alkyl bisazide compounds in the presence of peroxide such as hydrogen peroxide and benzoyl peroxide. However, this method usually requires low-temperature reaction, which increases the energy consumption and cost in the production process, and at the same time, low-temperature reaction may also lead to a decrease in reaction rate, thereby affecting the production efficiency. The dibromide synthesis method refers to the synthesis of alkyl bisazide by azidation reaction of corresponding bromohydrocarbon with azide reagent. In the synthesis process, the reaction conditions need to be strictly controlled to ensure the purity and yield of the product, and the types of dibromoalkyl compounds are less, which limits the diversity of alkyl bisazide compounds. SUMMARY

[0005] In view of the technical problems existing in the preparation of existing alkyl bifunctional compounds, especially alkyl bisazide compounds, the present application provides a cyclic bisperoxide, a synthesis method and its application in the preparation of alkyl bifunctional compounds, develops a new method for continuous generation of carbon radicals, and efficiently obtains a series of bisazide compounds containing alkyl chains with long or short length by using a high-yield metal catalyst. The present application greatly enriches the synthesis method of alkyl bifunctional compounds, especially alkyl bisazide compounds, has the advantages of low catalyst cost, simple and rapid preparation process, and easy industrial production, etc.

[0006] To achieve the above purpose, the technical scheme adopted by the present application is:

[0007] The chemical formula of the cyclic bisperoxide is: R represents an aryl group, a n-propyl group, a t-butyl group, an ethyl ester group, an alcohol hydroxyl group, a halogen atom, a cyano group or a trifluoromethyl group; n represents 0-10.

[0008] The synthesis method of the cyclic bisperoxide has the following synthesis circuit:

[0009]

[0010] wherein R includes aryl, n-propyl, t-butyl, ethyl ester, alcohol hydroxyl, halogen, cyano or trifluoromethyl; n represents 0-10; R 1 including acetyl, chloroacetyl, benzoyl, p-fluorobenzoyl, m-fluorobenzoyl, m-chlorobenzoyl, trimethylsilyl, triethylsilyl or triphenylsilyl.

[0011] The synthesis method is specifically as follows: mixing A mmol of hydrogen peroxide, B mmol of cycloalkanone and C mmol of H2SO4 in D mL of ethanol, stirring for 1-12 h to convert into E mmol of cycloalkyl diperoxy alcohol; wherein A:B=(4-8):1; B:C=(5-10):1; B:D=(1-2):1; subsequently, dissolving the cycloalkyl diperoxy alcohol in F mL of dichloromethane, adding G mL of n-hexane, then adding H mmol of base, and dropping I mmol of acyl chloride or chlorosilane at-30℃ to prepare the diperoxy compound after reaction for 30-50 min; wherein E:F=(1-2):1; E:G=1:(10-20); E:H=1:(2-3); E:I=1:(2-3).

[0012] The cycloalkanone is selected from one of cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclododecanone, cyclopentadecanone, 4-phenylcyclohexanone, 4-methylcyclohexanone, 4,4-difluorocyclohexanone, 4-ethylcyclohexanone, 4-propylcyclohexanone, 2-phenylcyclohexanone, adamantone, 2,2-dimethylcyclopentanone, and 2-indanone.

[0013] The base is pyridine, DMAP, triethylamine, sodium carbonate, sodium hydroxide or cesium carbonate.

[0014] The acyl chloride is selected from one of benzoyl chloride, p-fluorobenzoyl chloride, m-fluorobenzoyl chloride, o-fluorobenzoyl chloride, pentafluorobenzoyl chloride, acetyl chloride, chloroacetyl chloride.

[0015] The chlorosilane includes trimethylchlorosilane (TMSCl), triethylchlorosilane (TESCl) or t-butyldimethylchlorosilane (TBSCl).

[0016] The application of the cyclic diperoxy compound in the preparation of an alkyl bifunctional compound comprises mixing J mmol of trimethylsilyl azide TMSN3, TMSNCS or MgCl2, K mmol of catalyst and E mmol of diperoxy compound in L mL of ethyl acetate or acetonitrile solvent, then heating to 50℃±5℃ under the protection of inert gas to prepare the target diazide compound; wherein E:J=1:(2-3); E:K=(10-20):1; E:L=1:(5-10).

[0017] The catalyst is a transition metal, including Fe(OTf)2, FeCl2, FeBr2, Fe(acac)2, Fe(OAc)2, Fe(OTs)2, CuOTf, CuCl, Cu(CH3CN)4PF6, Cu(OAc)2, CuI, CuBr, CuSO4, NiCl2, Ni(OTf)2, NiBr2, Ni(acac)2, Ni(OAc)2, PdCl2, Pd(OAc)2, RuCl2, Co(dppe)Cl2, Co(Ph3P)2Cl2, CoI2, CoBr2, Co(acac)3, Co(acac)2, Co(OAc)2 or CoCl2.

[0018] The inert gas includes nitrogen or helium.

[0019] The reaction time after heating to 50℃±5℃ is 3-6h.

[0020] Compared with the prior art, the present application has the following advantages:

[0021] 1. The present application mainly uses inexpensive and various cycloalkanones as raw materials, which are oxidized to diperoxy alcohols under the catalysis of hydrogen peroxide and protonic acid, and the alcohol hydroxyl groups are protected by acyl chloride and other protective agents, thereby improving the activity of the substrate and rapidly preparing diperoxy compounds. The diperoxy compounds prepared by the present application have good stability and can be stored and used for a long time in an environment of-20℃. The raw materials for preparation are cycloalkanone, hydrogen peroxide and acyl chloride, which have low cost and good atom economy.

[0022] 2. The diperoxy compounds prepared by the present application are then used as catalysts for the preparation of alkyl bifunctional compounds, especially alkyl bisazide compounds, under mild conditions by using TMSN3 as a source of-N3. Compared with the existing catalytic azidation method of olefins or the synthesis method of dibromide, alkyl bisazide can realize 1,n bifunctionalization of the alkyl chain under mild conditions through two consecutive catalytic processes of transition metals, including bisazidation, bis-thiocyanate and bis-halogenation. In addition, it is found that it is suitable for the late-stage modification of complex natural products, amino acids and drugs, and asymmetric bifunctionalization of the alkyl chain is feasible. Compared with the traditional method, the present application widens the substrate range, improves the synthesis efficiency, simplifies the synthesis process and reduces the synthesis pollution.

[0023] In summary, the present application prepares alkyl bifunctional compounds under mild conditions catalyzed by a yield metal (such as ferrous triflate), and compared with the existing catalytic azidation method, the preparation method of the present application has the advantages of wide substrate synthesis range, good functional group tolerance (ester group, amide, alkenyl group, halogen atom, etc.), mild reaction condition, high reaction efficiency, etc. It has wide application in organic synthesis, including but not limited to double azidation, double halogenation, double boronation, double phosphonation and double thiocyanation, which greatly widens the synthesis range of bifunctional alkane molecules. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The nuclear magnetic spectrum of the double peroxy compound A of Example 1 is shown in the following figure, wherein, Figure 1 (A) in the figure is a hydrogen spectrum, Figure 1 (B) in the figure is a carbon spectrum.

[0025] Figure 2 The nuclear magnetic spectrum of the double peroxy compound B of Example 2 is shown in the following figure, wherein, Figure 2 (A) in the figure is a hydrogen spectrum, Figure 2 (B) in the figure is a carbon spectrum.

[0026] Figure 3 The nuclear magnetic spectrum of the double peroxy compound C of Example 3 is shown in the following figure, wherein, Figure 3 (A) in the figure is a hydrogen spectrum, Figure 3 (B) in the figure is a carbon spectrum.

[0027] Figure 4 The nuclear magnetic spectrum of the double peroxy compound D of Example 4 is shown in the following figure, wherein, Figure 4 (A) in the figure is a hydrogen spectrum, Figure 4 (B) in the figure is a carbon spectrum.

[0028] Figure 5 The nuclear magnetic spectrum of the double peroxy compound E of Example 5 is shown in the following figure, wherein, Figure 5 (A) in the figure is a hydrogen spectrum, Figure 5 (B) in the figure is a carbon spectrum.

[0029] Figure 6 The nuclear magnetic spectrum of the product 1 alkyl double azide compound of Example 1 is shown in the following figure, wherein, Figure 6 (A) in the figure is a hydrogen spectrum, Figure 6 (B) in the figure is a carbon spectrum.

[0030] Figure 7 The nuclear magnetic spectrum of the product 2 alkyl double azide compound of Example 2 is shown in the following figure, wherein, Figure 7 (A) in the figure is a hydrogen spectrum, Figure 7 (B) in the figure is a carbon spectrum.

[0031] Figure 8The NMR spectrum of the product 3-alkyl bisazide compound from Example 3 is shown below. Figure 8 (A) in the spectrum is the proton spectrum. Figure 8 (B) in the figure represents the carbon spectrum.

[0032] Figure 9 The NMR spectrum of the product 4-alkyl bisazide compound from Example 4 is shown below. Figure 9 (A) in the spectrum is the proton spectrum. Figure 9 (B) in the figure represents the carbon spectrum.

[0033] Figure 10 The NMR spectrum of the product 5-alkyl bisazide compound from Example 5 is shown below. Figure 10 (A) in the spectrum is the proton spectrum. Figure 10 (B) in the figure represents the carbon spectrum.

[0034] Figure 11 The NMR spectrum of product 6 from Example 6 is shown below. Figure 11 (A) in the spectrum is the proton spectrum. Figure 11 (B) in the figure represents the carbon spectrum.

[0035] Figure 12 The NMR spectrum of product 7 from Example 7 is shown below. Figure 12 (A) in the spectrum is the proton spectrum. Figure 12 (B) in the figure represents the carbon spectrum. Detailed Implementation

[0036] The preparation method of the present invention will be described in detail below with reference to the accompanying drawings and the following sets of embodiments, but this should not be construed as limiting the scope of protection of the present invention.

[0037] It should be noted that, unless otherwise specified, the operations used in the implementation methods, such as mixing and filtering, are all conventional operations in the art.

[0038] The pharmaceuticals and reagents used in the following examples were all commercially available analytical grade.

[0039] Example 1

[0040] 1. The novel double peroxide compound A provided in this embodiment is: 2-chloroethane-1-peroxyacid-1-[(2-chloroacetyl)peroxy]-4-phenylcyclohexyl ester.

[0041]

[0042] 2. The steps for synthesizing double peroxide compound A.

[0043]

[0044] In a 100 mL round bottom flask with a magnet, 10 mmol of 4-phenylcyclohexanone was first added, followed by 5-10 mL of ethanol solvent, 40-80 mmol of hydrogen peroxide was added during stirring, 1-2 mmol of H2SO4 was added dropwise, 50-100 mL of saturated sodium chloride aqueous solution was added after stirring for 12 h, extracted with dichloromethane for three times, and then quickly obtained by column chromatography (ethyl acetate: petroleum ether = 1:10); then 7.5 mmol of the synthesized bis-peroxide alcohol was dissolved in 4-8 mL of dichloromethane, and 75-150 mL of n-hexane was added, cooled to -30°C in a low-temperature cold trap, then pyridine (15-23 mmol) was added to the mixture, and chloroacetyl chloride (15-23 mmol) was added dropwise while stirring, and the low-temperature reaction was carried out for 30 min; after the reaction was completed, the reaction liquid was filtered through a Buchner funnel, and the residue was washed with n-hexane, and the filtrate was vacuum concentrated (temperature below 30°C), and column chromatography was quickly separated to obtain (dichloromethane: petroleum ether = 1:2, total yield of two-step synthesis 41%).

[0045] Referring to Figure 1 The nuclear magnetic spectrum of 2-chloroethane-1-peroxoic acid-1-[(2-chloroacetyl)peroxy]-4-phenylcyclohexyl ester A is illustrated in the figure:

[0046] 1 H NMR (400 MHz, CDCl3) δ 7.34-7.28 (m, 2H), 7.25-7.19 (m, 3H), 4.12 (s, 2H), 4.10 (s, 2H), 2.66-2.59 (m, 1H), 2.51-2.41 (m, 2H), 1.93-1.75 (m, 6H);

[0047] 13 C NMR (100 MHz, CDCl3) δ 164.4, 112.9, 46.9, 38.0 37.9, 32.2, 30.0, 27.4, 23.1 ppm;

[0048] 3. Application of bis-peroxide compound A in the preparation of alkyl bifunctional compounds, specifically in the preparation of alkyl bis-azide compounds, more specifically in the preparation of (1,5-diazidopentan-3-yl) benzene 1.

[0049]

[0050] In a 100 mL reaction tube equipped with a magnetic, the catalyst Fe(OTf)2(5 mmol%, 53 mg) was added, then the tube was evacuated and backfilled with nitrogen (three times); subsequently, a solution of bis-peroxide A (3.0 mmol, 1100 mg) and TMSN3 (9.0 mmol, 1000 mg) in EA (30.0 mL) was added via syringe; the reaction mixture was stirred at 50 °C for 3 h; after the end of the reaction, the reaction mixture was concentrated under vacuum and purified by flash chromatography on silica gel (PE:DCM = 5:1) to give the product (1,5-diazidopentan-3-yl)benzene as a colorless transparent oil (yield 62%, 427 mg).

[0051] The separation yield of this case of the application by column chromatography was 62%. Reference is made to the NMR spectra of (1,5-diazidopentan-3-yl)benzene 1 illustrated in the figures: Figure 6 From the figures, the NMR spectra of (1,5-diazidopentan-3-yl)benzene 1 are illustrated:

[0052] 1 H NMR (400 MHz, CDC13) δ 7.35-7.31 (m, 2H), 7.26-7.22 (m, 1H), 7.16-7.14 (m, 2H), 3.20-3.13 (m, 2H), 3.07-3.00 (m, 2H), 2.84-2.77 (m, 1H), 1.97-1.86 (m, 4H);

[0053] 13 C NMR (100 MHz, CDC13) δ 142.1, 128.9, 127.5, 127.0, 49.3, 40.2, 35.6 ppm;

[0054] Example 2

[0055] 1. This example provides the synthesis of the novel bis-peroxide B, 2-chloroethane-1- peroxy acid-2-[(2-chloroacetyl)peroxy]-2,3-dihydro-1H-inden-2-yl ester.

[0056]

[0057] 2. Synthesis steps of bis-peroxide B

[0058]

[0059] In a 100 mL round bottom flask with a magnetic stirrer, 10 mmol of 2-indanone was first added, followed by 5-10 mL of ethanol solvent, 40-80 mmol of hydrogen peroxide was added during stirring, 1-2 mmol of H2SO4 was added dropwise, 50-100 mL of saturated sodium chloride aqueous solution was added after stirring for 12 h, extracted with dichloromethane three times, and then quickly obtained by column chromatography (ethyl acetate: petroleum ether = 1:10); then 6.0 mmol of the synthesized bis-peroxide alcohol was dissolved in 3-6 mL of dichloromethane, and n-hexane (60-120 mL) was added, cooled to -30°C in a low-temperature cold trap, then pyridine (12-18 mmol) was added to the mixture, and chloroacetyl chloride (12-18 mmol) was added dropwise while stirring, and the low-temperature reaction was carried out for 30 min; after the reaction was completed, the reaction liquid was filtered with a Buchner funnel, and the residue was washed with n-hexane, and the filtrate was vacuum concentrated (temperature below 30°C), and column chromatography was used for rapid separation (dichloromethane: petroleum ether = 1:2, total yield of two-step synthesis 49%).

[0060] Reference Figure 2 The nuclear magnetic resonance spectrum of 2-chloroethane-1-peroxoic acid-2-[(2-chloroacetyl)peroxy]-2,3-dihydro-1H-inden-2-yl ester B is illustrated in the figure:

[0061] 1 H NMR (400 MHz, CDCl3) δ 7.25-7.19 (m, 4H), 4.12 (s, 4H), 3.51 (m, 4H);

[0062] 13 C NMR (100 MHz, CDCl3) δ 164.1, 137.2, 127.6, 124.8, 121.4, 39.8, 37.9 ppm;

[0063] 3. Application of bis-peroxide compound A in the preparation of alkyl bifunctional compounds, specifically in the preparation of alkyl bis-azide compounds, more specifically in the preparation of 1,2-bis(azidomethyl)benzene 2.

[0064]

[0065] In a 100 mL reaction tube equipped with a magnetic, the catalyst Fe(OTf)2(5 mmol%, 53 mg) was added, then the tube was evacuated and backfilled with nitrogen (three times); subsequently, a solution of bis-peroxide B (3.0 mmol, 1000 mg) and TMSN3(9.0 mmol, 1000 mg) in EA (30.0 mL) was added via syringe; the reaction mixture was stirred at 50 °C for 3 h; after that, the reaction mixture was concentrated in vacuo and purified by flash chromatography on silica gel (PE:DCM = 5:1) to give the product 1,2-bis(azidomethyl)benzene as a colorless transparent oil (yield 46%, 258 mg).

[0066] The separation yield of this case of the application by column chromatography was 46%. Reference is made to Figure 7 The NMR spectrum of 1,2-bis(azidomethyl)benzene 2 is illustrated in the figure:

[0067] 1 H NMR (400 MHz, CDC13) δ 7.41-7.35 (m, 4H), 4.44 (s, 4H);

[0068] 13 C NMR (100 MHz, CDC13) δ 133.8, 130.1, 129.0, 52.2 ppm;

[0069] Examples 3-5

[0070] The cyclic bis-peroxides were prepared according to the same procedure as in Examples 1 and 2, as shown in the table below:

[0071] Example 6

[0072] 1. This example provides the synthesis procedure of the novel bis-peroxide compound A, 2-chloroethane-1- peroxy acid-1-[(2-chloroacetyl)peroxy]-4-phenylcyclohexyl ester.

[0073]

[0074] 2. The synthesis procedure of bis-peroxide compound A is identical to Example 1.

[0075] 3. The application of bis-peroxide compound A in the preparation of alkyl bifunctional compounds, specifically in the preparation of alkyl bis-thiocyanate compounds, more specifically in the preparation of [5-(cyanothio)-3- phenylpentyl]sulfanecarbonitrile 6:

[0076]

[0077] In a 100 mL reaction tube equipped with a magnetic, the catalyst Fe(OTf)2(5 mmol%, 53 mg) was added, then the tube was evacuated and backfilled with nitrogen (three times); subsequently, a solution of bis-peroxide A (3.0 mmol, 1100 mg) and TMSNCS (9.0 mmol, 1200 mg) in EA (30.0 mL) was added via syringe; the reaction mixture was stirred at 50 °C for 3 h; after the end of the reaction, the reaction mixture was concentrated under vacuum and purified by flash chromatography on silica gel (PE:EA = 5:1). The product was obtained as a colorless transparent oil (yield 69%, 487 mg).

[0078] The separation yield of this case of the application by column chromatography was 69%. Refer to Figure 11 The NMR spectrum of (1,5-diazidopentan-3-yl)benzene 6 is illustrated in the figure:

[0079] 1 H NMR (400 MHz, CDC13) δ 7.37-7.33 (m, 2H), 7.29-7.25 (m, 1H), 7.16-7.15 (m, 2H), 2.96-2.88 (m, 1H), 2.84-2.77 (m, 2H), 2.68-2.61 (m, 2H), 2.24-2.13 (m, 4H);

[0080] 13 C NMR (100 MHz, CDC13) δ 140.3, 129.4, 127.7, 127.4, 111.8, 42.7, 36.4, 31.6 ppm;

[0081] Example 7

[0082] 1. This example provides the synthesis steps of the new bis-peroxide A, 2-chloroethane-1- peroxy acid-1-[(2-chloroacetyl)peroxy]-4-phenylcyclohexyl ester.

[0083]

[0084] 2. The synthesis steps of bis-peroxide A are identical to those of Example 1.

[0085] 3. The application of bis-peroxide A in the preparation of alkyl bifunctional compounds, specifically in the preparation of (1,5-dichloropentan-3-yl)benzene 7:

[0086]

[0087] In a 100 mL reaction tube equipped with a magnetic bar, the catalyst CuOTf (20 mmol%, 127 mg) was added, then the tube was evacuated and backfilled with nitrogen (three times); subsequently, a solution of bis-peroxide A (3.0 mmol, 1100 mg) and MgCl2(9.0 mmol, 855 mg) mixed in CH3CN (30.0 mL) was added via syringe; the reaction mixture was stirred at 50 °C for 3 h; after the end of the reaction, the reaction mixture was concentrated under vacuum and purified by flash chromatography on silica gel (PE:DCM = 5:1) to give the product as a colorless transparent oil (yield 60%, 388 mg).

[0088] The separation yield of this case of the application by column chromatography was 60%. Reference is made to Figure 12 The NMR spectrum of (1,5-dichloropent-3-yl)benzene 7 is illustrated in the figure:

[0089] 1 H NMR (400 MHz, CDC13) δ 7.35-7.30 (m, 2H), 7.25-7.23 (m, 1H), 7.20-7.17 (m, 2H), 3.44-3.37 (m, 2H), 3.27-3.21 (m, 2H), 3.12-3.05 (m, 1H), 2.16-2.02 (m, 4H);

[0090] 13 C NMR (100 MHz, CDC13) δ 141.7, 128.8, 127.7, 127.0, 42.7, 40.1, 39.1 ppm;

[0091] General applicability of the bis-azidation reaction

[0092] With reference to Examples 1 to 5, by studying the size of the different cyclic ketones, from five-membered cyclic ketones to fifteen-membered cyclic ketones, starting materials corresponding to the respective bis-azidoalkyl (products 8-10) were obtained, all with moderate to good yields. In addition, thienyl heterocycles (product 11), alkenyl groups (product 12), ester groups (products 11-12) were compatible.

[0093]

[0094] The above examples have described the application in detail, the purpose of which is to enable those skilled in the art to understand the content of the application and implement it, and it cannot therefore limit the protection scope of the application, any equivalent changes or modifications made in accordance with the spirit and principle of the application should be covered within the protection scope of the application.

Claims

1. A cyclic bis-peroxide characterized in that, having the chemical formula: specifically selected from 2. The method of synthesis of cyclic bis-peroxides according to claim 1, wherein, The synthetic line is as follows:

3. The method of synthesis of cyclic bis-peroxides according to claim 2, wherein, The synthetic method is as follows: A mmol of hydrogen peroxide, B mmol of cycloalkanone, and C mmol of H2SO4 are mixed in D mL of ethanol, and stirred for 1-12 h to convert into E mmol of cycloalkyl diperoxy alcohol; A:B=(4-8):1; B:C=(5-10):1; B:D=(1-2):1; then, the cycloalkyl diperoxy alcohol is dissolved in F mL of dichloromethane, G mL of n-hexane is added, then H mmol of base is added, Immol of chloroacetyl chloride is added dropwise at-30℃, and the reaction is carried out for 30-50 min to prepare the diperoxy compound; E:F=(1-2):1; E:G=1:(10-20); E:H=1:(2-3); E:I=1:(2-3).

4. The method of synthesis of cyclic bis-peroxides according to claim 3, wherein, The base is pyridine, DMAP, triethylamine, sodium carbonate, sodium hydroxide, or cesium carbonate.

5. Use of the cyclic bis-peroxide according to claim 1 in the preparation of an alkyl difunctional compound, characterized in that, J mmol of TMSN3, TMSNCS, or MgCl2, K mmol of catalyst, and E mmol of cyclic diperoxy compound are mixed uniformly in L mL of ethyl acetate or acetonitrile solvent, then heated to 50℃±5℃ under the protection of inert gas to react, to prepare an alkyl bifunctional compound; E:J=1:(2-3); E:K=(10-20):1; E:L=1:(5-10). The catalyst is Fe(OTf)2 or CuOTf.

6. Use of the cyclic bis-peroxide according to claim 5 in the preparation of an alkyl difunctional compound, characterized in that, The inert gas includes nitrogen or helium. The reaction time after heating to 50℃±5℃ is 3-6 h.

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