CN113651667B - Cyclopropyl alkyl compound, preparation method and application thereof - Google Patents

Cyclopropyl alkyl compound, preparation method and application thereof Download PDF

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CN113651667B
CN113651667B CN202111041234.7A CN202111041234A CN113651667B CN 113651667 B CN113651667 B CN 113651667B CN 202111041234 A CN202111041234 A CN 202111041234A CN 113651667 B CN113651667 B CN 113651667B
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cyclopropane
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cyclopropane compound
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fuel
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邹吉军
张香文
潘伦
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/122—Compounds comprising a halogen and copper
    • 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
    • C07C2603/90—Ring systems containing bridged rings containing more than four rings
    • 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

Abstract

The invention discloses a pentacyclopropanyl compound which has the following structure：
Figure DDA0003248959050000011
Is named as: methyl pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9，11 ]Tridecane;
Figure DDA0003248959050000012
is named as: six-ring [7.3.1.1 3， 7 .0 2，8 .0 4，6 .0 10，12 ]Tetradecane;
Figure DDA0003248959050000013
is named as: pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9，11 ]Tridecane;
Figure DDA0003248959050000014
is named as: hexacyclic ring [7.3.1.1 3， 7 .0 2，8 .0 4，6 .0 10，12 ]Tetradecane;
Figure DDA0003248959050000015
is named as: 3-Methylspirocyclo [ cyclopropane-1,4' -pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9，11 ]Tridecane]. The invention also discloses a preparation method and application of the cyclopropane compound.

Description

Cyclopropyl alkyl compound, preparation method and application thereof
Technical Field
The invention belongs to the technical field of novel aerospace fuels, and particularly relates to a five-cyclopropane compound, a preparation method thereof and application of the five-cyclopropane compound in aerospace liquid fuels.
Background
With the rapid development of the aerospace industry, the demand on fuel energy density is also increased. The synthetic fuel has the advantages of high density and high volumetric heat value, and can increase the range and the effective load of the aircraft under the condition of not increasing the volume of the fuel tank. At present, the synthesized and applied fuels comprise RJ-4, JP-10 and the like, the density of the fuels can reach about 0.93g/mL, and the density is obviously improved compared with petroleum-based fuels such as No. 3 jet fuel. However, the hydrogen content of the fuel is low, which results in a low thermal mass value.
The cyclopropane structure stores higher tensile energy, and the fuel with the structure can compensate the reduction of the mass heat value caused by the reduction of the hydrogen content, so that the volume heat value of the fuel is further increased. The document (AIAA, 2013, 3968) reports a hydrocarbon fuel containing three cyclopropane ring structures and named "syntin", wherein the structure is
Figure BDA0003248959030000011
The fuel has 46.6MJ/kg of mass heat value, which is improved by 10.7 percent compared with JP-10 fuel; however, the density of the fuel is only 0.85g/mL, so the volume heating value is lower (39.61 MJ/L). The literature (Bull. Korean chem. Soc.,2007, 28, 322-324) discloses 5 cyclopropane-based fuels a-e (a: NB monocyclic propane, b: NBD bicyclic propane, c: DCPD bicyclic propane, d: DCPD cyclopentene bond monocyclic propane, e: DCPD norbornene bond monocyclic propane) synthesized from Norbornene (NB), dicyclopentadiene (DCPD) and Norbornadiene (NBD) as raw materials, wherein the mass calorific value of the fuel b is increased by 3.8% compared with that of a, and the mass calorific values of the fuels c, d and e are increased by 0.2%, 0.5% and 1.1% respectively compared with that of JP-10, and have a density of 0.99-1.02g/mL, a volume calorific value of 41.9-43.1MJ/L, and a volume calorific value 5.9-8.9% higher than that of JP-10. However, the volume heating value of the cyclopropane fuel is still not high enough and is less than 43.1MJ/L.
The invention provides several polycyclic cyclopropane-based fuels with higher density and volumetric heating values.
Disclosure of Invention
The invention discloses five high-energy density polycyclic cyclopropane compounds with higher density and volume heat value and a preparation method thereof. The technical scheme of the invention is as follows:
in a first aspect, the invention discloses five cyclopropane compounds, which have the following structures:
Figure BDA0003248959030000021
is named as: methyl pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9，11 ]Tridecane, english name: methylpentacyclo [6.3.1.1 3 ，6 .0 2，7 .0 9，11 ]tridecane；
Figure BDA0003248959030000022
Is named as: methyl hexacyclic ring [7.3.1.1 3，7 .0 2，8. 0 4，6 .0 10，12 ]Tetradecane, english name: methyl hexacyclo [7.3.1.1 3，7 .0 2，8 .0 4，6 .0 10，12 ]tetradecane；
Figure BDA0003248959030000023
Is named as: pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9，11 ]Tridecane, english name: pentacyclo [6.3.1.1 3，6 .0 2，7 .0 9，11 ]tridecane；
Figure BDA0003248959030000024
Is named as: six-ring [7.3.1.1 3，7 .0 2，8 .0 4，6 .0 10，12 ]Tetradecane, english name: hexacyclo [7.3.1.1 3，7 .0 2，8 .0 4，6 .0 10，12 ]tetradecane；
Figure BDA0003248959030000025
Is named as: 3-Methylspirocyclo [ cyclopropane-1,4' -pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9 ，11 ]Tridecane]The english name is: 3-methyl spiro [ cyclophane-1,4' -pentacyclo [6.3.1.1 3， 6 .0 2，7 .0 9，11 ]tridecane]。
Preferably, the density of the cyclopropane compound is not less than 1.03g/mL, and the volumetric heat value is not less than 43.3MJ/L.
The second aspect of the invention discloses a preparation method of the cyclopropane compound, which comprises the following steps:
(1) adding a solvent, polycyclic olefin, alkali liquor and a catalyst into a reactor in a nitrogen atmosphere;
(2) slowly adding diazomethane precursor to carry out cyclopropanation reaction;
(3) adding a quenching agent to quench the reaction after the reaction is finished to obtain an organic phase containing a cyclopropane product, and purifying to obtain the cyclopropane compound product.
Preferably, the polycyclic olefin in the step (1) is one or more of methyl cyclopentadiene norbornene, methyl cyclopentadiene norbornadiene, cyclopentadiene norbornene, cyclopentadiene norbornadiene or cyclopentadiene ethylidene norbornene.
Preferably, the catalyst in step (1) is a supported metal catalyst, the metal comprises Pd and Rh, wherein the amount of the catalyst is 1-10 wt% of the reactants of Pd or Rh in the catalyst. Or, the catalyst in the step (1) is CuCl or CuCl 2 The amount of the catalyst is 5-20 wt% of the reactants.
Preferably, the solvent in step (1) is one or more of 1,2-dichloroethane, dichloromethane, ethylene glycol dimethyl ether or methyl tert-butyl ether.
Preferably, the diazomethane precursor in the step (2) is one or more of N-methyl-N-nitrosourea, N-methyl-N-nitrosop-toluenesulfonamide or N-methyl-N-nitroso-N' -nitroguanidine; the molar ratio of diazomethane precursor to double bonds in the reactant polycycloolefin is (1-4) to 1.
Preferably, the cyclopropanation reaction temperature of step (2) is 10-70 ℃.
In a third aspect, the invention discloses the use of the cyclopropane compound for aerospace fuel.
The invention has the beneficial effects that:
1. the invention discloses a five-cyclopropanyl compound for the first time, which has the density of 1.03-1.09g/mL, the volume heat value of 43.3-46.4MJ/L and the volume heat value 9.9% -17.9% higher than that of JP-10.
2. The five-cyclopropanyl compound disclosed by the invention is simple in preparation method, and can be used as a high-energy fuel for space flight and aviation or as an additive of other fuels so as to improve the energy of the fuels.
Drawings
FIG. 1 is a mass spectrum of a cyclopropane compound obtained in example 1.
FIG. 2 is a mass spectrum of the cyclopropane compound obtained in example 6.
FIG. 3 is a mass spectrum of the cyclopropane compound obtained in example 10.
FIG. 4 is a mass spectrum of a cyclopropane compound obtained in example 11.
FIG. 5 is a mass spectrum of a cyclopropane compound obtained in example 13.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are conventional products which can be obtained by purchase, and are not indicated by manufacturers.
Example 1:
at 20 ℃ and N 2 Under an atmosphere, 45g of methylcyclopentadienyl norbornene, 100mL of 1,2-dichloroethane, 104g of a 50% by mass KOH solution and 9g of 5wt% Pd/SiO 2 Adding into a round-bottom flask with the volume of 1L; adding 80g of N-methyl-N-nitrosourea into a flask under mechanical stirring, and stirring for 2 hours after the addition is finished; after the reaction is finished, diluted acid is added to quench the reaction, an organic phase containing a cyclopropane product is collected, the gas chromatography is adopted to analyze the composition of the product, the yield of the cyclopropane product is 71.2 percent, and the product is collected, rectified and purified to obtain the methyl pentacyclic [6.3.1.1 ] 3，6 .0 2，7 .0 9，11 ]Tridecane. FIG. 1 is a mass spectrum of the obtained cyclopropane compound.
As can be seen from fig. 1, the resulting cyclopropane compound has the structure:
Figure BDA0003248959030000041
it is named as: methyl pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9，11 ]Tridecane; the density of the fuel is 1.030g/mL, the mass heat value is 42.08MJ/kg, the volume heat value is 43.34MJ/L, and the fuel is improved by 10% compared with JP-10 (the volume heat value is 39.4 MJ/L).
Examples 2 to 17:
the reaction procedure is the same as in example 1; except for the reaction conditions including the kind of catalyst, the amount of catalyst used, the kind of solvent, the reaction temperature and the reactants, etc., as shown in table 1 below. Wherein FIG. 2 is a mass spectrum of the cyclopropane compound obtained in example 6; FIG. 3 is a mass spectrum of a cyclopropane compound obtained in example 10; FIG. 4 is a mass spectrum of a cyclopropane compound obtained in example 11; FIG. 5 is a mass spectrum of a cyclopropane compound obtained in example 13.
According to the attached figures 2-5, the structures and names of the products of the methylcyclopentadiene norbornadiene, the cyclopentadiene norbornene, the cyclopentadiene norbornadiene and the cyclopentadiene ethylidene norbornene are respectively as follows:
Figure BDA0003248959030000042
is named as: methyl hexacyclic ring [7.3.1.1 3，7 .0 2，8 .0 4，6 .0 10，12 ]Tetradecane; corresponding to fig. 2;
Figure BDA0003248959030000043
is named as: pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9，11 ]Tridecane; corresponding to fig. 3;
Figure BDA0003248959030000044
is named as: six-ring [7.3.1.1 3，7 .0 2，8 .0 4，6 .0 10，12 ]Tetradecane; corresponding to fig. 4;
Figure BDA0003248959030000051
is named as: 3-Methylspirocyclo [ cyclopropane-1,4' -pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9 ，11 ]Tridecane](ii) a Corresponding to fig. 5.
Tests show that the density of the cyclopropane fuel is 1.052g/mL, 1.050g/mL, 1.087g/mL and 1.030g/mL respectively, and the mass and heat values are 42.85MJ/kg, 41.56MJ/kg, 42.73MJ/kg and 42.41 MJ/kg respectively; wherein, methyl hexacyclic [7.3.1.1 3，7 .0 2，8 .0 4，6 .0 10，12 ]Tetradecane, hexacyclic [7.3.1.1 3，7 .0 2，8 .0 4，6 .0 10，12 ]Tetradecane, and 3-methylspirocyclo [ cyclopropane-1,4' -pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9，11 ]The mass heat value of tridecane is higher than that of methyl pentacyclic ring [6.3.1.1 3，6 .0 2，7 .0 9，11 ]Tridecane and pentacyclic [6.3.1.1 3，6 .0 2，7 .0 9，11 ]The mass calorific value of tridecane. The volume calorific value of the cyclopropane compound fuel is 43.68-46.45MJ/L, which is 10.9-17.9% higher than that of the fuel JP-10.
Figure BDA0003248959030000061
From the above examples, it can be seen that the five cyclopropane compounds obtained are simple in preparation method and high in product yield. The fuel has higher density and volume heat value, and can obviously improve the energy of the fuel when being used as high-energy fuel for space flight and aviation or as additive of other fuels.
While specific embodiments of, and examples for, the invention are described herein for illustrative purposes, various changes in detail will be apparent to those skilled in the art without departing from the invention.

Claims (9)

1. A cyclopropane compound, characterized in that it has the following structure:
Figure DEST_PATH_IMAGE001
named as: 3-Methylspirocyclo [ cyclopropane-1,4' -pentacyclic [6.3.1.1 3, 6 .0 2, 7 .0 9, 11 ]Tridecane]。
2. The cyclopropane compound of claim 1, which has a density of 1.03g/mL and a mass heating value of 42.41 MJ/kg.
3. The process for producing a cyclopropane compound according to claim 1 or 2, which comprises the steps of:
(1) adding a solvent, polycyclic olefin, alkali liquor and a catalyst into a reactor under the nitrogen atmosphere;
(2) slowly adding diazomethane precursor to carry out cyclopropanation reaction;
(3) adding a quenching agent to quench the reaction after the reaction is finished, obtaining an organic phase containing a cyclopropane product, and purifying to obtain the cyclopropane compound.
4. The method according to claim 3, wherein the polycyclic olefin in the step (1) is cyclopentadienylethylidene norbornene.
5. The method of claim 3, wherein the catalyst of step (1) is a supported metal catalyst, the metal comprises Pd, and the amount of the catalyst is 5wt% of the reactants as Pd in the catalyst.
6. The method according to claim 3, wherein the solvent in step (1) is ethylene glycol dimethyl ether.
7. The production method according to claim 3, wherein the diazomethane precursor in the step (2) is N-methyl-N-nitroso-N' -nitroguanidine; the molar ratio of diazomethane precursor to double bonds in the reactant polycycloolefin is 4: 1.
8. The process according to claim 3, wherein the cyclopropanation reaction temperature in step (2) is 50 ℃.
9. Use of a cyclopropane compound according to claim 1 or 2 for aerospace fuel.
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