CN110105188A - A kind of double cage hydrocarbon compounds and its preparation method and application - Google Patents

A kind of double cage hydrocarbon compounds and its preparation method and application Download PDF

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CN110105188A
CN110105188A CN201910463606.1A CN201910463606A CN110105188A CN 110105188 A CN110105188 A CN 110105188A CN 201910463606 A CN201910463606 A CN 201910463606A CN 110105188 A CN110105188 A CN 110105188A
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formula
diels
compound
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addition reaction
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石义军
刘雪静
韩迎
闫鹏
别福升
曹晗
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Southern Shandong Coal Chemical Industry Engineering Institute For Research And Technology Of Shandong Province
Zaozhuang University
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Southern Shandong Coal Chemical Industry Engineering Institute For Research And Technology Of Shandong Province
Zaozhuang University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
    • C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
    • C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
    • C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
    • C07C49/643—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having three rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/92—Systems containing at least three condensed rings with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/93—Spiro compounds
    • C07C2603/94—Spiro compounds containing "free" spiro atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels

Abstract

The present invention provides a kind of double cage hydrocarbon compounds and its preparation method and application, has the structure as shown in following formula (I) or formula (II):Wherein, isomers, R are H or cycloalkane each other for formula (I) and formula (II), wherein when R is cycloalkane, are spirally connected with formula (I) or formula (II).Such compound density is in 1.4g/cm3More than, volume combustion calorific value is greater than 52MJ/L, and has good thermal stability, is excellent high Density Hydrocarbon Fuels, can be applied to aerospace field.

Description

A kind of double cage hydrocarbon compounds and its preparation method and application
Technical field
The present invention relates to organic synthesis fields, and in particular to a kind of double cage hydrocarbon compounds and its preparation method and application.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art Art.
Cage hydrocarbon compound can be divided into single cage hydrocarbon compound and double cage hydrocarbon compounds according to the number of its cage hydrocarbon, for single cage The research of hydrocarbon compound, is just concerned since 1964, because Eaton et al. completed the conjunction of cubane in 1964 for the first time At；But it is just fewer for the research of double cage hydrocarbon compounds, because the synthesis of double cage hydrocarbon compounds is more complicated and double cage hydrocarbonylations are closed The type of object is also fewer, so being seldom concerned.Cage hydrocarbon compound is very widely used, concentrates on two big fields, can make It is applied to aerospace field for high Density Hydrocarbon Fuels, the drug component that also can be used as treatment disease is applied to field of medicaments.
High Density Hydrocarbon Fuels are a kind of novel synthetic fuels, are used primarily in the propellant of aerospace craft.With The fast development of mankind's aerospace industry, it is also higher and higher to the performance requirement of fuel, not only there is high density, but also to have height Volume combustion calorific value, ensure that carry more fuel in the narrow engine fuel tank of aircraft in this way, to reach The faster speed of a ship or plane and farther voyage.The density of the polycyclic HC fuel of high density used at present is in 1.0g/cm3Left and right, body Product combustion heat value is in 40MJ/L or so.With the continuous development of aerospace craft, high density cage HC fuel is constantly studied to be closed At coming out, compared with polycyclic HC fuel, there is higher density and higher volume combustion calorific value, density generally all to exist for it 1.0g/cm3More than, volume combustion calorific value is above 40MJ/L, is more preferably high-density propellant.
Design and synthesis for cage hydrocarbon compound, single cage hydrocarbon compound type reported in the literature is more, mainly has cube Alkane, single homocubane, basket alkane and PCUD (five rings [5.4.0.02,6.03,10.05,9] hendecane).1964, Eaton and Cole were first It is secondary to have synthesized cubane.1966, Hoover et al. synthesized single homocubane for the first time.1966, Masamune and Dauben Et al. synthesized basket alkane for the first time.1970, Hoover et al. synthesized PCUD again for the first time.Marchand looks for another way within 1974, Using 1,4-benzoquinone and cyclopentadiene as initial feed, three steps are the PCUD for having synthesized high yield.And setting for double cage hydrocarbon compounds Meter and synthesis, reported in the literature less, PCUD dimerizing olefins body is to study most commonly used double cage hydrocarbon, PCUD dimerizing olefins at present Body was synthesized in 1988 by Marchand et al. for the first time, but inventors have found that its complex synthetic route, low yield are unsuitable big Amount synthesizes, and needs to complete the connection of double caged skeleton structures in synthetic route using McMurry coupling reaction, this makes double cages The synthesis cost of hydrocarbon compound greatly improves, and is not suitable for large-scale production.
Summary of the invention
Therefore, the purpose of the present invention is to provide a kind of novel double cage hydrocarbon compounds, shown in structure such as formula (I), formula (II), And the method for preparing double cage hydrocarbon compounds is provided, and prepare the intermediate compound of formula (III) of double cage hydrocarbon compounds Or formula (IV) and double cage hydrocarbon compounds are preparing high Density Hydrocarbon Fuels or as high Density Hydrocarbon Fuels in aerospace The application in field.The compound of the present invention density is in 1.4g/cm3More than, volume combustion calorific value is all larger than 52MJ/L, and has There is good thermal stability, is excellent high Density Hydrocarbon Fuels, can be applied to aerospace field.
Wherein, R is that hydrogen or cycloalkane are spirally connected when the R is cycloalkane with main structure with spiral shell carbon atom.
Of the present invention to be spirally connected, when referring to that R is cycloalkane, cycloalkane and ring where it share a carbon atom (i.e. spiral shell carbon Atom), form the loop coil for sharing a spiral shell carbon atom.
Specifically, the present invention has technical solution as follows:
In the first aspect of the present invention, the present invention provides a kind of double cage hydrocarbon compounds, have such as following formula (I) or formula (II) structure shown in:
Wherein, isomers, R are H or cycloalkane each other for formula (I) and formula (II), wherein when R is cycloalkane, with formula (I) Or formula (II) is spirally connected with spiral shell carbon atom.
In certain embodiments of the present invention, the formula (I) or formula (II) compound are selected from flowering structure:
Wherein, compound HV-1 and compound HV-2 isomers each other, compound HV-3 and compound HV-4 isomery each other Body.
Compound HV-1 and HV-2 of the present invention is crystal, and crystal structure figure is as depicted in figs. 1 and 2, crystallography Information is as shown in table 1, table 2:
The crystallographic data of compound HV-1 is as shown in table 1:
The crystallographic data of compound HV-2 is as shown in table 2:
Wherein, the density of compound HV-1, HV-2, HV-3 and HV-4 is in 1g/cm3More than, reach as high as 1.5g/cm3With On, volume combustion calorific value is all larger than 52MJ/L, reaches as high as 55MJ/L, and fusing point has good thermostabilization at 260 DEG C or more Property, it can be used as high density cage HC fuel for aerospace field.
In the second aspect of the present invention, the present invention provides a kind of methods for preparing above-mentioned double cage hydrocarbon compounds comprising: 2,2'- diphenoquinone withDiels-Alder addition reaction is carried out in organic solvent, obtains Diels-Alder addition reaction Then product carries out [2+2] illumination cycloaddition reaction under high-voltage ultraviolet mercury lamp or sunlight irradiation respectively；Wherein, R is as above Defined in text；When R is non-hydrogen, it is spirally connected with cyclopentadiene.
In embodiments of the present invention, the Diels-Alder addition reaction product has formula (III) or formula (IV) institute Show structure, R is as hereinbefore defined:
Wherein, formula (III) and formula (IV) isomers each other.
In certain embodiments of the present invention, in the Diels-Alder addition reaction, 2,2'- diphenoquinones with Molar ratio 1:1.8-1:6.
In certain embodiments of the present invention, the Diels-Alder addition reaction carries out in organic solvent, described Organic solvent is selected from one of tetrahydrofuran, ethyl acetate, methylene chloride, methanol, ethyl alcohol, chloroform and acetone or a variety of.
In certain embodiments of the present invention, the reaction temperature of the Diels-Alder addition reaction is -30 DEG C -0 ℃。
In certain embodiments of the present invention, the Diels-Alder addition reaction include: by 2,2'- diphenoquinone with1:1.8-1:6 feeds intake in molar ratio, and reaction temperature is controlled at -30 DEG C -0 DEG C, is stirred continuously in organic solvent anti- It answers 2-6 hours, after reaction, organic solvent is concentrated, faint yellow solid is obtained, after faint yellow solid carries out column chromatography Respectively obtain Diels-Alder addition reaction product formula (III) and formula (IV)；Wherein, R is as hereinbefore defined.
In certain embodiments of the present invention, when R is H, in the Diels-Alder addition reaction, 2,2'- diphenoquinones Molar ratio with cyclopentadiene is 1:2-1:5, preferably 1:4-1:5.
In certain embodiments of the present invention, in the Diels-Alder addition reaction, 2,2'- diphenoquinones and ring penta When two alkene reactions, reaction temperature is -20 DEG C~-5 DEG C.
In certain embodiments of the present invention, when R is cyclopropane, in the Diels-Alder addition reaction, 2,2'- The molar ratio of diphenoquinone and spiral shell [2,4] -4,6- heptadiene is 1:2-1:4, preferably 1:2-1:3.
In certain embodiments of the present invention, in the Diels-Alder addition reaction, 2,2'- diphenoquinones and spiral shell [2, 4] when -4,6- heptadiene reacts, reaction temperature is -30 DEG C~-10 DEG C.
In some embodiments of the present invention, the Diels-Alder addition reaction product is selected from flowering structure:
Wherein, compound D-A-1 and compound D-A-2 isomers each other, compound D-A-3 and compound D-A-4 are each other Isomers.
In certain embodiments of the present invention, described [2+2] the illumination cycloaddition reaction includes by Diels-Alder addition Reaction product is dissolved in solvent respectively, is stirred continuously and is irradiated under high-voltage ultraviolet mercury lamp or sunlight, subtracts after reaction Pressure, which filters, can be obtained [2+2] illumination cycloaddition reaction product i.e. formula (I) or formula (II) compound.
In certain embodiments of the present invention, in [2+2] illumination cycloaddition reaction, the solvent be selected from acetone, toluene, One of benzene, methylene chloride and ethyl acetate are a variety of.
In certain embodiments of the present invention, in [2+2] illumination cycloaddition reaction, the reaction time is 1-5 hours.
In some embodiments of the present invention, compound HV-1 and compound HV-2 isomers each other, can be by such as Lower reaction route is prepared:
In some embodiments of the present invention, compound HV-3 and compound HV-4 isomers each other, can be by such as Lower reaction route is prepared:
In the third aspect of the present invention, the present invention provides the compounds of structure shown in formula (III) or formula (IV):
Wherein, R is for example as hereinbefore defined.
In some embodiments of the present invention, formula (III) or formula (IV) compound are selected from flowering structure:
Formula (III) or formula (IV) and the preparation method of compound D-A-1, D-A-2, D-A-3, D-A-4 institute for example above It states.
In the fourth aspect of the present invention, the present invention provides above-mentioned formulas (III) or formula (IV) compound to exist as intermediate Prepare the application in formula (I) or formula (II) compound；Wherein, the formula (I) or formula (II) compound are as hereinbefore defined.Its Preparation method is as noted before.
In the fifth aspect of the invention, the present invention also provides above-mentioned formulas (I) or formula (II) compound in preparation high density In HC fuel application or as high Density Hydrocarbon Fuels aerospace field application.
The density of the polycyclic HC fuel of high density in the prior art is in 1.0g/cm3Left and right, volume combustion calorific value exist 40MJ/L or so.The density of cubane is in 1.29g/cm3, combustion heat value is in 59MJ/L or so, but angle between C-C in its structure It is 90 °, there is very high tension energy, the complex and yield of synthesis is extremely low, seldom uses as fuel.PUCD be research compared with More single cage hydrocarbon, density is in 1.23g/cm3, volume combustion calorific value is 51MJ/L, but its volatility with higher, limitation Its application in fuel area.Existing double cage hydrocarbon compounds such as PCUD dimerizing olefins body, density is in 1.2g/ cm3Left and right, volume combustion calorific value is in 49MJ/L or so, for example spiral shell PUCD dimer its density is in 1.226g/cm3Left and right, volume combustion The higher reachable 53MJ/L of value is heated, but synthetic route is excessively cumbersome, more demanding to reaction condition, synthesis cost is excessively high, and It is not suitable as fuel use of large-scale production.And the density of the compound of the present invention HV-1, HV-2, HV-3 and HV-4 exist 1.4g/cm3More than, it is excellent high density hydrocarbon that volume combustion calorific value, which is all larger than 52MJ/L, and has good thermal stability Class A fuel A can be applied to aerospace field.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.Hereinafter, coming in conjunction with attached drawing detailed Describe bright embodiment of the present invention in detail, in which:
Fig. 1 is the X-ray crystal structure figure of compound HV-1.
Fig. 2 is the X-ray crystal structure figure of compound HV-2.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip Part or according to the normal condition proposed by manufacturer.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art Justice is identical.In addition, any method similar to or equal to what is recorded and material can be applied to the method for the present invention.Wen Zhong The preferred implement methods and materials are for illustrative purposes only.
Embodiment 1
The preparation of D-A-1 and D-A-2
Diels-Alder addition reaction: successively by the 2,2'- diphenoquinone of 1.00g (4.67mmol) and 30ml methylene chloride It is added in 100mL round-bottomed flask, reaction system is that freshly prepd ring penta is slowly added dropwise under ice salt bath (- 10 DEG C) in yellow turbid Diene (1.6ml, 19.36mmol), the reaction was continued 4 hours, and system becomes yellow transparent liquid from yellow turbid.After solution concentration Column chromatography is carried out, obtains 0.51g (1.47mmol) faint yellow solid D-A-1, yield 31% first；Continue column to chromatograph to obtain 0.46g (1.33mmol) faint yellow solid D-A-2, yield 28%.
D-A-1 fusing point: 162-164 DEG C of1H NMR(400MHz,CDCl3) δ 6.43 (s, 2H), 6.21 (dd, J=5.4, 2.9Hz, 2H), 6.05 (dd, J=5.5,2.9Hz, 2H), 3.52 (s, 4H), 3.37-3.23 (m, 4H), 1.58-1.52 (m, 2H), 1.43 (d, J=8.8Hz, 2H)13C NMR(101MHz,CDCl3)δ197.47,195.86,147.25,138.91, 134.87,134.07,48.48,48.09,47.85,47.75.HRMS(ESI):C22H18O4[M+Na]+calcd,369.11028； found,369.10995.
D-A-2 fusing point: 158-160 DEG C of1H NMR(400MHz,CDCl3)δ6.44(s,2H),6.25-6.17(m,2H), 6.07 (dd, J=5.2,2.3Hz, 2H), 3.52 (s, 4H), 3.31 (ddd, J=23.3,8.9,3.8Hz, 4H), 1.55 (d, J= 8.8Hz, 2H), 1.43 (d, J=8.7Hz, 2H)13C NMR(101MHz,CDCl3)δ197.47,195.98,147.45, 138.76,134.93,134.14,48.55,48.13,47.78,47.64,47.54.HRMS(ESI):C22H18O4[M+Na]+ calcd,369.11028；found,369.10960.
Under the same terms, the molar ratio of 2,2'- diphenoquinone and cyclopentadiene is become into 1:5, reaction temperature becomes -20 DEG C When, the yield of D-A-1 and D-A-2 can promote 20% or so respectively.
The preparation of HV-1
[2+2] illumination cycloaddition reaction: being added 0.51g (1.47mmol) D-A-1 being prepared in quartz reactor, Nitrogen protection is used after vacuum nitrogen gas 3 times.30ml ethyl acetate is added under nitrogen protection, be stirred continuously makes D-A-1 at room temperature Dissolution, solution is light yellow transparent solution.Condensing unit is opened, is carried out at room temperature with 400W high-voltage ultraviolet mercury lamp (or sunlight) Irradiation 2 hours stops illumination.Solution becomes colourless by yellow, and a large amount of white precipitates are precipitated, and depressurizes and takes out after cooling down at room temperature Filter, with a small amount of ethyl acetate rinse filter cake, obtains white solid powder.Column chromatography is carried out after filtrate concentration, finally merges filter cake The white solid chromatographed with column, is obtained 0.46g (1.33mmol) HV-1, and the density of yield 90%, HV-1 is 1.468g/cm3, for volume combustion calorific value in 52MJ/L or more, fusing point is 310-313 DEG C, has good thermal stability.
HV-1 fusing point: 310-313 DEG C of1H NMR(400MHz,CDCl3) δ 3.15 (d, J=6.2Hz, 2H), 2.99 (d, J= 28.5Hz, 6H), 2.71 (d, J=11.6Hz, 6H), 2.03 (d, J=11.3Hz, 2H), 1.89 (d, J=11.3Hz, 2H)13C NMR(101MHz,CDCl3)δ211.85,210.54,55.17,55.08,52.36,46.26,44.72,44.14,42.50, 40.88,37.47.HRMS(EI):C22H18O4[M]+calcd,346.1205；found,346.1212.
Wherein, the crystallographic data of compound HV-1 is as shown in table 1:
The preparation of HV-2
[2+2] illumination cycloaddition reaction: 0.46g (1.33mmol) D-A-2, vacuum nitrogen filling are added in quartz reactor Nitrogen protection is used after gas 3 times.30ml ethyl acetate is added under nitrogen protection, be stirred continuously dissolves D-A-2 at room temperature, and solution is Light yellow transparent solution.Condensing unit is opened, is irradiated 2 hours with 400W high-voltage ultraviolet mercury lamp (or sunlight) at room temperature, Stop illumination.A large amount of white precipitates are precipitated, depressurizes and filters after cooling down at room temperature, with a small amount of ethyl acetate rinse filter cake, obtain white Color solid powder.Column chromatography is carried out after filtrate concentration, the final white solid for merging filter cake and column and chromatographing is obtained 0.40g (1.16mmol) HV-2, yield 87%.The density of HV-2 is 1.516g/cm3, volume combustion calorific value 52MJ/L with On, fusing point is 306-309 DEG C, has good thermal stability.
HV-2 fusing point: 306-309 DEG C of1H NMR(400MHz,CD2Cl2)δ3.22-3.04(m,2H),3.03-2.73(m, 6H), 2.62 (s, 4H), 2.40 (s, 2H), 1.96 (d, J=11.2Hz, 2H), 1.82 (d, J=11.2Hz, 2H)13C NMR (101MHz,CDCl3)δ210.66,209.57,54.00,53.73,50.81,45.69,43.23,42.85,40.56,39.85, 36.54.HRMS(EI):C22H18O4[M]+calcd,346.1205；found,346.1206.
Wherein, the crystallographic data of compound HV-2 is as shown in table 2:
Embodiment 2
The preparation of D-A-3 and D-A-4
It prepares in the same manner as shown in Example 1, wherein 2,2'- diphenoquinones rub with spiral shell [2,4] -4,6- heptadiene You are 1:2.5, and reaction temperature is -20 DEG C, are reacted 4 hours, the yield that the yield of D-A-3 is 33%, D-A-4 is 30%.
The preparation of double cage hydrocarbon compound HV-3 and HV-4 according to cage hydrocarbon compound HV-1 and HV-2 double in embodiment 1 preparation Method obtains, and specific characterize data is as follows:
D-A-3 fusing point: 163-165 DEG C of1H NMR(400MHz,CDCl3)δ6.48(s,2H),6.33-6.23(m,2H), 6.19-6.08 (m, 2H), 3.48 (ddd, J=19.9,8.5,3.8Hz, 4H), 2.90 (s, 4H), 0.66-0.56 (m, 4H), 0.55-0.44(m,4H).13C NMR(101MHz,CDCl3)δ197.30,195.70,147.51,139.14,134.92, 134.18,52.66,52.57,49.37,48.94,43.71,6.97,5.94.HRMS(ESI):C26H22O4[M+Na]+calcd, 421.14103；found,421.14098.
D-A-4 fusing point: 156-158 DEG C of1H NMR(400MHz,CDCl3)δ6.48(s,2H),6.33-6.27(m,2H), 6.20-6.15(m,2H),3.56-3.42(m,4H),2.97-2.79(m,4H),0.69-0.56(m,4H),0.54-0.43(m, 4H).13C NMR(101MHz,CDCl3)δ198.36,196.86,148.78,140.03,136.02,135.24,53.57, 53.47,50.46,50.01,44.70,7.98,6.99.HRMS(ESI):C26H22O4[M+Na]+calcd,421.14103； found,421.14103.
HV-3 fusing point: 260-262 DEG C of1H NMR(400MHz,CDCl3) δ 3.31 (dd, J=13.9,6.2Hz, 2H), 3.19-3.05 (m, 2H), 2.93 (s, 4H), 2.79 (d, J=6.2Hz, 2H), 2.38 (s, 2H), 2.32-2.23 (m, 2H), 0.77-0.56(m,8H).13C NMR(101MHz,CDCl3)δ211.87,210.52,55.63,55.56,53.11,50.34, 49.68,46.95,42.72,37.70,37.50,5.50,4.05.HRMS(EI):C26H22O4[M]+calcd,398.1518； found,398.1527.
HV-4 fusing point: 318-320 DEG C of1H NMR(400MHz,CDCl3)δ3.48-3.34(m,2H),3.24(s,2H), 3.00-2.85(m,4H),2.43(s,2H),2.29-2.15(m,4H),0.77-0.56(m,8H).13C NMR(101MHz, CDCl3)δ210.65,209.48,54.48,54.18,51.50,48.86,48.45,46.36,40.77,36.77,36.52, 4.43,3.06.HRMS(EI):C26H22O4[M]+calcd,398.1518；found,398.1522.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of double cage hydrocarbon compounds have the structure as shown in following formula (I) or formula (II):
Wherein, isomers, R are H or cycloalkane each other for formula (I) and formula (II), wherein when R is cycloalkane, with formula (I) or formula (II) it is spirally connected.
2. compound according to claim 1, which is characterized in that formula (I) or formula (II) compound are selected from flowering structure:
3. the method for preparing double cage hydrocarbon compounds described in claim 1 comprising: 2,2'- diphenoquinones withIn organic solvent Middle progress Diels-Alder addition reaction, obtains Diels-Alder addition reaction product, then in high-voltage ultraviolet mercury lamp or [2+2] illumination cycloaddition reaction is carried out respectively under sunlight irradiation；Wherein, R is as shown in claims 1 or 2；When R is non-hydrogen When, it is spirally connected with cyclopentadiene.
4. according to the method described in claim 3, it is characterized in that, the Diels-Alder addition reaction product has formula (III) or structure shown in formula (IV), R is as shown in claims 1 or 2:
Preferably, in the Diels-Alder addition reaction, 2,2'- diphenoquinones withMolar ratio 1:1.8-1:6；
Preferably, the Diels-Alder addition reaction carries out in organic solvent, the organic solvent be selected from tetrahydrofuran, One of ethyl acetate, methylene chloride, methanol, ethyl alcohol, chloroform and acetone are a variety of；
Preferably, the reaction temperature of the Diels-Alder addition reaction is -30 DEG C -0 DEG C；
Preferably, the Diels-Alder addition reaction include: by 2,2'- diphenoquinone withIn molar ratio 1:1.8-1:6 into Row feeds intake, and reaction temperature is controlled at -30 DEG C -0 DEG C, is stirred continuously reaction 2-6 hours in organic solvent, after reaction, right Organic solvent is concentrated, and yellow solid is obtained, and yellow solid respectively obtains Diels-Alder addition reaction after carrying out column chromatography Product formula (III) and formula (IV)；Wherein, R is as shown in claims 1 or 2.
5. the method according to claim 3 or 4, which is characterized in that when R is H, in the Diels-Alder addition reaction, The molar ratio of 2,2'- diphenoquinone and cyclopentadiene is 1:2-1:5；
Preferably, in the Diels-Alder addition reaction, when R is cyclopropane, 2,2'- diphenoquinones and spiral shell [2,4] -4,6- heptan The molar ratio of diene is 1:2-1:4；
Preferably, in the Diels-Alder addition reaction, when 2,2'- diphenoquinones are reacted with cyclopentadiene, reaction temperature be- 20 DEG C~-5 DEG C；
Preferably, in the Diels-Alder addition reaction, when 2,2'- diphenoquinones and spiral shell [2,4] -4,6- heptadiene react, instead Answering temperature is -30 DEG C~-10 DEG C.
6. according to the method described in claim 5, it is characterized in that, the Diels-Alder addition reaction product is selected from following Structure:
7. according to the method described in claim 3, it is characterized in that, [2+2] the illumination cycloaddition reaction includes by Diels- Alder addition reaction product is dissolved in solvent respectively, is stirred continuously and is irradiated under high-voltage ultraviolet mercury lamp or sunlight, reaction After decompression filter [2+2] illumination cycloaddition reaction product i.e. formula (I) or formula (II) compound can be obtained；
Preferably, in [2+2] illumination cycloaddition reaction, the solvent is selected from acetone, toluene, benzene, methylene chloride and ethyl acetate One of or it is a variety of；
Preferably, in [2+2] illumination cycloaddition reaction, the reaction time is 1-5 hours.
8. compound, with structure shown in formula (III) or formula (IV):
Wherein, R is as shown in claims 1 or 2；
Preferably, formula (III) or formula (IV) compound are selected from flowering structure:
9. application of the compound described in claim 8 as intermediate in preparation formula (I) or formula (II) compound；Its In, the formula (I) or formula (II) compound are as described in claims 1 or 2.
10. the application in preparation high Density Hydrocarbon Fuels of formula (I) or formula (II) compound exists as high Density Hydrocarbon Fuels The application of aerospace field.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114437837A (en) * 2020-10-30 2022-05-06 中国石油化工股份有限公司 Fuel composition and application thereof
CN114478179A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Cage-shaped hydrocarbon with spiro structure and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114478179A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Cage-shaped hydrocarbon with spiro structure and preparation method and application thereof
CN114437837A (en) * 2020-10-30 2022-05-06 中国石油化工股份有限公司 Fuel composition and application thereof
CN114437837B (en) * 2020-10-30 2023-11-10 中国石油化工股份有限公司 Fuel composition and application thereof

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