Hydrocarbon containing three-membered rings, preparation method and application

Abstract

The invention provides a hydrocarbon containing a three-membered ring, the molecular formula of the hydrocarbon containing the three-membered ring is C18H30, and the structural formula of the hydrocarbon containing the three-membered ring is shown in the specification, the density of the hydrocarbon containing the three-membered ring is 0.9845 g / cm < 3 >, the mass calorific value is 42.938 MJ / kg, the freezing point is less than-60 DEG C, the kinematic viscosity at 20 DEG C is 4.90 mm < 2 > / s, the kinematic viscosity at-20 DEG C is 14.30 mm < 2 > / s, and the volume calorific value is 42.272 MJ / L, the mass calorific value of the hydrocarbon containing the three-membered ring is higher than that of gasoline, RP-3 and other active fuels, and the hydrocarbon containing the three-membered ring can be used as a novel fuel and can also be used as an additive of gasoline, diesel oil, aviation kerosene and other typical fuels.

Description

Technical Field

[0001] This invention belongs to the field of hydrocarbon fuel technology, and relates to a hydrocarbon containing a three-membered ring, its preparation method, and its application. Background Technology

[0002] Currently, liquid hydrocarbon fuels are widely used in aerospace engines. The performance of an aircraft largely depends on the properties of the fuel, with key properties being its density and volumetric calorific value. Extensive research has been conducted both domestically and internationally on hydrocarbon fuel synthesis, including the synthesis of high-performance fuels such as JP-10 using cyclopentadiene as a raw material through hydrogenation, polymerization, and other methods; and the synthesis of tetracyclic hydrocarbons [7.4.0.0] using indene as a raw material. 2.7 .1 3.6 High-performance fuels include tetradecane.

[0003] The aforementioned artificially synthesized high-density fuels all use five- or six-membered ring polyolefins as raw materials. Increasing the number of rings will reduce the hydrogen content in hydrocarbon molecules, resulting in a decrease in the mass calorific value of the fuel and an need to improve its performance. Introducing a three-membered ring structure into the fuel molecule can solve this problem to some extent. There is a lack of liquid hydrocarbon fuels with the corresponding structure in the current technology, which urgently needs to be improved. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a hydrocarbon containing a three-membered ring, a preparation method and an application, so as to solve the technical problem that the performance of liquid hydrocarbon fuels in the existing technology needs to be further improved.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A hydrocarbon containing a three-membered ring, the molecular formula of which is C0. 18 H 30 The structural formula is as follows: .

[0006] The present invention also has the following technical features: Specifically, the density of the hydrocarbon is 0.9845 g / cm³. 3 It has a calorific value of 42.938 MJ / kg, a freezing point < -60 °C, and a kinematic viscosity of 4.90 mm at 20 °C. 2 / s, kinematic viscosity at -20 °C is 14.30 mm. 2 / s, with a volumetric calorific value of 42.272 MJ / L.

[0007] This invention also protects a method for preparing a hydrocarbon containing a three-membered ring, the method comprising the following steps: Step 1: Add the prescribed amount of strong base and a crown ether compatible with the strong base to an appropriate amount of organic solution to obtain solution A; Step 2: Add the prescribed amounts of strong base and crown ether to mixed solution A to obtain mixed solution B; Step 3: Add the prescribed amount of haloform dropwise to mixed solution B, and then perform separation and chromatographic chromatography to obtain gemdichlorocyclopropane intermediate; Step 4: Dissolve the geminal dichlorocyclopropane intermediate obtained in Step 3 in an ultra-dry solvent, add lithium aluminum hydride under a water bath condition of -5 to 0℃, and heat to (55-65)℃ for dehalogenation reaction. After the reaction is completed, the hydrocarbon containing three-membered rings is obtained by quenching, washing and phase separation, rotary evaporation of oil phase, purification and chromatography.

[0008] Furthermore, the aforementioned β- The molar ratio of bisabolene, strong base, crown ether, haloform and lithium aluminum hydride is 1: (9~15):(0.1~0.3):(9~15):(18~27).

[0009] Furthermore, the organic solvent mentioned in step 1 is selected from any one of dichloromethane, tetrahydrofuran, chloroform, and 1,2-dichloroethane.

[0010] Furthermore, the ultra-dry solvent mentioned in step 4 is selected from any one or more of ultra-dry tetrahydrofuran, ultra-dry diethylene glycol dimethyl ether, ultra-dry diethyl ether, and ultra-dry methyl tert-butyl ether.

[0011] Furthermore, the strong base includes potassium hydroxide and sodium hydroxide.

[0012] This invention also protects the use of hydrocarbons containing three-membered rings as fuels or fuel additives, wherein the fuels in the additives include gasoline, diesel, aviation kerosene and high-energy fuel HD-01.

[0013] Furthermore, when used as a fuel additive, the amount of the hydrocarbon containing three-membered rings added is 0.1% to 40% of the fuel mass.

[0014] Compared with the prior art, the present invention has the following technical effects: (1) The hydrocarbons containing three-membered rings provided by the present invention have excellent properties such as low freezing point and viscosity and high mass calorific value.

[0015] (2) The hydrocarbons containing three-membered rings provided by the present invention can be used as new fuels, or as additives for typical fuels such as gasoline, diesel and aviation kerosene.

[0016] (3) The preparation method provided by the present invention is simple and easy to implement, providing new ideas and directions for the synthesis of new generation hydrocarbon fuels, and providing ideas and guidance for the design of subsequent new fuels. Attached Figure Description

[0017] Figure 1 The 1H NMR spectrum of 7,7-dichloro-4-(2,2-dichloro-1-(2-(2,2-dichloro-3,3-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane obtained in Example 1; Figure 2 Carbon spectrum of 7,7-dichloro-4-(2,2-dichloro-1-(2-(2,2-dichloro-3,3-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane obtained in Example 1; Figure 3 The 1H NMR spectrum of 4-(1-(2-(2,2-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane; Figure 4 The carbon spectrum of 4-(1-(2-(2,2-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane; Figure 5 High-resolution mass spectra of 7,7-dichloro-4-(2,2-dichloro-1-(2-(2,2-dichloro-3,3-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane; Figure 6 High-resolution mass spectra of 4-(1-(2-(2,2-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane (I); Figure 7 High-resolution mass spectrometry (HMS / MS) of 4-(1-(2-(2,2-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane.

[0018] The specific content of the present invention will be further explained in detail below with reference to the embodiments. Detailed Implementation

[0019] It should be noted that, unless otherwise specified, all raw materials in this invention are known in the prior art, such as... β- Bisabolene is produced using existing technologies known to... β- Bisabolene.

[0020] The concept of this invention is that geminal dihalocarbenes exhibit high reactivity with polymethyl-substituted point-rich olefins. Excess halogen is then removed via a dehalogenation reaction to construct a cyclopropane structure, thus solving the current problem of the difficulty in cyclopropanating polysubstituted olefins. This method allows for the construction of more high-energy-density fuel components, providing more options for fuel formulation.

[0021] The hydrocarbon containing a three-membered ring of the present invention has the molecular formula C0. 18 H 30 The structural formula is: .

[0022] The compound is named 4-(1-(2-(2,2-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane.

[0023] In this invention, the testing instruments used for the structure include: Nuclear magnetic resonance: The nuclear magnetic resonance (NMR) was performed using an AVANCE AV500 NMR spectrometer from Bruker GmbH, Germany.

[0024] High-resolution mass spectrometry: High-resolution mass spectrometry was performed using a Thermo Fisher QExactive mass spectrometer from Thermo Fisher Scientific, Inc., USA.

[0025] The methods and equipment used in the performance testing are as follows: Fuel density: Measured using a DMA 4100 M densitometer.

[0026] Kinematic viscosity: Measured using a SYP1003-7 petroleum product kinematic viscosity meter.

[0027] Freezing point: The freezing point of jet fuel was determined using a BSY-181 jet fuel freezing point tester, in accordance with the method for determining the freezing point of jet fuel (GB 2430-81).

[0028] Mass calorific value: According to the provisions of GB / T384-1981(1988) "Determination of calorific value of petroleum products", the oxygen bomb calorimetry method is used for determination.

[0029] The following are specific embodiments of the present invention. It should be noted that the present invention is not limited to the following specific embodiments. All equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.

[0030] Example 1: Following the above technical solution, this embodiment provides a method for preparing a hydrocarbon containing a three-membered ring. The synthetic route for the hydrocarbon containing a three-membered ring, namely 4-(1-(2-(2,2-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane, is as follows: .

[0031] The method specifically includes the following steps: Step 1: Add 45 mmol of potassium hydroxide solid and 1.5 mmol of 18-crown ether-6 to dichloromethane (18 mL) to obtain mixed solution A; Step 2: Add 5 mmol of β-bisabolene to mixed solution A to obtain mixed solution B; Step 3: Add 45 mmol of the prescribed amount of chloroform dropwise to mixed solution B, then heat the resulting mixture to 35°C and maintain this temperature for 8 hours; after the reaction solution is separated into layers by aqueous solution, the organic phase is washed several times with deionized water and dried with anhydrous magnesium sulfate, and the solvent is removed by rotary evaporation; purified by column chromatography, the gemdichlorocyclopropane intermediate (bisabolene gemdichlorocyclization product) is obtained. Step 4: Dissolve 5 mmol of the gemdichlorocyclopropane intermediate (bisabolene gemdichlorocyclization product) obtained in Step 3 in 135 mL of ultra-dry tetrahydrofuran. Add 90 mmol of lithium aluminum hydride powder and stir for 30 minutes in a 0°C water bath. Maintain the reaction temperature at 60°C for dehalogenation until the halogen is completely removed. After the halogen is completely removed, quench the reaction with ethyl acetate in an ice-water bath. Slowly add 15% sodium hydroxide to dissolve the insoluble matter. After phase separation, collect the oil phase and wash it several times with deionized water. Remove the solvent by rotary evaporation. Finally, obtain the target product by multi-column chromatography.

[0032] Structural assessment: IR (KBr, cm -1 ): 1 H NMR (500 MHz, Chloroform- d ) δ 2.06 – 1.85 (m, 1H), 1.84 – 1.69 (m,1H), 1.57 – 1.41 (m, 3H), 1.36 (d, J = 1.7 Hz, 1H), 1.34 – 1.24 (m, 4H), 1.20(ddd, J = 10.2, 8.0, 5.3 Hz, 3H), 1.11 – 0.93 (m, 11H), 0.93 – 0.80 (m, 1H), 0.74 (td, J = 9.2, 8.6, 3.6 Hz, 2H), 0.43 – 0.35 (m, 1H), 0.31 (dt, J = 9.1, 4.4Hz, 2H), 0.28 – 0.20 (m, 3H), 0.20 – 0.10 (m, 3H), 0.08 (t, J= 4.8 Hz, 1H), -0.18 (t, J = 4.5 Hz, 1H). 13 C NMR (126 MHz, Chloroform- d ) δ 40.10, 35.96, 35.94,35.29, 35.16, 35.12, 32.07, 31.96, 31.93, 29.87, 28.44, 28.31, 28.06, 27.83,27.50, 27.29, 27.23, 27.20, 27.17, 27.15, 27.08, 26.85, 26.73, 25.20, 25.19,24.68, 24.54, 23.02, 22.98, 22.79, 22.77, 22.15, 20.83, 20.02, 19.80, 19.78, 19.67, 18.47, 18.32, 18.10, 16.21, 15.52, 14.76, 14.74, 10.09, 10.07, 10.05, 10.03, 9.66, 9.58, 9.54, 9.51. The highest mass-to-charge ratios (m / z) observed in the HRMS (EI) mass spectrometry were 231 and 232, which can be attributed to the quasi-molecular ion peak [M−14]⁺. This indicates that the molecular weight of the compound is 246 (246 – 14 = 232), presumably corresponding to the target molecular product.

[0033] The results of NMR and high-resolution mass spectrometry analysis show that the product obtained in this embodiment is the target product of the present invention: 4-(1-(2-(2,2-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane.

[0034] Performance testing: The density of the hydrocarbon obtained in this embodiment was measured to be 0.9845 g / cm³. 3 It has a calorific value of 42.938 MJ / kg, a freezing point < -60 °C, and a kinematic viscosity of 4.90 mm at 20 °C. 2 / s, kinematic viscosity at -20 °C is 14.30 mm. 2 / s, with a volumetric calorific value of 42.272 MJ / L.

[0035] Because the product prepared in this embodiment has excellent properties such as low freezing point, low viscosity and high calorific value, and its calorific value is higher than that of gasoline, RP-3 and other existing fuels, the hydrocarbon containing three-membered rings provided by this invention can be used as a new type of fuel, or as an additive for typical fuels such as gasoline, diesel and aviation kerosene. When used as a fuel additive, the amount of hydrocarbon containing three-membered rings added is 0.1% to 40% of the fuel mass.

[0036] Example 2: This embodiment provides a method for preparing a hydrocarbon containing a three-membered ring. The preparation method and steps used in this embodiment are the same as those in Example 1, except that the haloform used in this embodiment is bromoform, and the ultra-dry solvent and reaction conditions in step 4 are different. Step 4 specifically includes: dissolving 5 mmol of the gem-dichlorocyclopropane intermediate (bisabolene gem-dichloro cyclization product) obtained in step 3 in 90 mL of ultra-dry tetrahydrofuran, adding 90 mmol of lithium aluminum hydride powder under 0°C water bath conditions and stirring for 30 minutes, then maintaining the reaction system temperature at 55°C for dehalogenation reaction until the halogen is completely removed. After the halogen is completely removed, the reaction is quenched with ethyl acetate in an ice-water bath, and the insoluble matter is dissolved by slowly adding 15% sodium hydroxide. After phase separation, the oil phase is collected and washed several times with deionized water, the solvent is removed by rotary evaporation, and finally the target product is obtained by multi-column chromatography.

[0037] Upon testing, the product obtained in this embodiment is the target product of the present invention: 4-(1-(2-(2,2-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane.

[0038] Example 3: This embodiment provides a method for preparing a hydrocarbon containing a three-membered ring. Steps 1-3 of this method are the same as those disclosed in Example 1. The difference is that step 4 specifically includes: dissolving 40 mmol of the gem-dichlorocyclopropane intermediate (bisabolene gem-dichloro cyclization product) obtained in step 3 in 720 mL of ultra-dry tetrahydrofuran; adding 720 mmol of lithium aluminum hydride powder and stirring for 30 minutes under 0°C water bath conditions; maintaining the reaction system temperature at 60°C for dehalogenation reaction until the halogen is completely removed; quenching the reaction with ethyl acetate in an ice-water bath after halogen removal; slowly adding 15% sodium hydroxide to dissolve the insoluble matter; collecting the oil phase after phase separation and washing it several times with deionized water; removing the solvent by rotary evaporation; and finally obtaining the target product by multi-column chromatography.

[0039] Upon testing, the product obtained in this embodiment is the target product of the present invention: 4-(1-(2-(2,2-dimethylcyclopropyl)ethyl)cyclopropyl)-1-methylbicyclo[4.1.0]heptane.

[0040] The specific technical features described in the above embodiments can be combined in any suitable manner without contradiction, as long as they do not violate the spirit of the present invention, and should also be regarded as the content disclosed by the present invention.

Claims

1. A hydrocarbon containing a three-membered ring, characterized in that, The molecular formula of this hydrocarbon containing a three-membered ring is C3. 18 H 30 The structural formula is as follows: 。 2. The hydrocarbon containing a three-membered ring as described in claim 1, characterized in that, The density of the hydrocarbon containing the three-membered ring is 0.9845 g / cm³. 3 It has a calorific value of 42.938 MJ / kg, a freezing point < -60 °C, and a kinematic viscosity of 4.90 mm at 20 °C. 2 / s, kinematic viscosity at -20 °C is 14.30 mm. 2 / s, with a volumetric calorific value of 42.272 MJ / L.

3. The method for preparing a hydrocarbon containing a three-membered ring as described in claim 1 or claim 2, characterized in that, The method includes the following steps: Step 1: Add the prescribed amount of strong base and crown ether to an appropriate amount of organic solution to obtain solution A; Step 2: Add the prescribed amount to mixed solution A. β -Bisatolen, to obtain mixed solution B; Step 3: Add the prescribed amount of haloform dropwise to mixed solution B, and then perform separation and chromatographic chromatography to obtain gemdichlorocyclopropane intermediate; Step 4: Dissolve the geminal dichlorocyclopropane intermediate obtained in Step 3 in an ultra-dry solvent, and add lithium aluminum hydride under a water bath condition of -5 to 0℃; raise the temperature to 55 to 65℃ to carry out a dehalogenation reaction; after the reaction is completed, quench, wash and separate the phases, evaporate the oil phase, purify and chromatographically to obtain hydrocarbons containing three-membered rings.

4. The preparation method according to claim 3, characterized in that, The β- The molar ratio of bisabolene, strong base, crown ether, haloform and lithium aluminum hydride is 1: (9~15):(0.1~0.3):(9~15):(18~27).

5. The preparation method according to claim 4, characterized in that, The organic solvent mentioned in step 1 is selected from any one of dichloromethane, tetrahydrofuran, chloroform and 1,2-dichloroethane.

6. The preparation method according to claim 3, characterized in that, The ultra-dry solvent mentioned in step 4 is selected from any one or more of ultra-dry tetrahydrofuran, ultra-dry diethylene glycol dimethyl ether, ultra-dry diethyl ether, and ultra-dry methyl tert-butyl ether.

7. The preparation method according to claim 3, characterized in that, The strong base includes potassium hydroxide and sodium hydroxide, etc.; the crown ether includes 18-crown ether-6 and 15-crown ether-5.

8. The use of the hydrocarbon containing a three-membered ring as described in claim 1 or claim 2 as a fuel or fuel additive.

9. The application as described in claim 8, characterized in that, The fuels in the fuel additive include gasoline, diesel, aviation kerosene, and high-energy fuel HD-01.

10. The application as described in claim 8, characterized in that, When used as a fuel additive, the amount of the hydrocarbon containing three-membered rings added is 0.1% to 40% of the fuel mass.

Images