CN113336620B - Preparation method of bicyclobutane and application of bicyclobutane as aerospace high-energy fuel - Google Patents
Preparation method of bicyclobutane and application of bicyclobutane as aerospace high-energy fuel Download PDFInfo
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- 150000003519 bicyclobutyls Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000446 fuel Substances 0.000 title abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000005859 coupling reaction Methods 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 6
- 238000003747 Grignard reaction Methods 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 150000001930 cyclobutanes Chemical class 0.000 claims description 26
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 19
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- KXVUSQIDCZRUKF-UHFFFAOYSA-N bromocyclobutane Chemical compound BrC1CCC1 KXVUSQIDCZRUKF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Substances BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims 4
- MICMHFIQSAMEJG-UHFFFAOYSA-N 1-bromopyrrolidine-2,5-dione Chemical compound BrN1C(=O)CCC1=O.BrN1C(=O)CCC1=O MICMHFIQSAMEJG-UHFFFAOYSA-N 0.000 claims 1
- TXWRERCHRDBNLG-UHFFFAOYSA-N cubane Chemical compound C12C3C4C1C1C4C3C12 TXWRERCHRDBNLG-UHFFFAOYSA-N 0.000 abstract description 5
- GTKAAVZEFUFXDD-UHFFFAOYSA-N syntin Chemical compound C1CC1C1(C)CC1C1CC1 GTKAAVZEFUFXDD-UHFFFAOYSA-N 0.000 abstract description 5
- PGPFRBIKUWKSTJ-UHFFFAOYSA-N cyclopropylcyclopropane Chemical compound C1CC1C1CC1 PGPFRBIKUWKSTJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000007818 Grignard reagent Substances 0.000 abstract description 2
- 150000004795 grignard reagents Chemical class 0.000 abstract description 2
- 230000000877 morphologic effect Effects 0.000 abstract description 2
- 125000001995 cyclobutyl group Chemical class [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- -1 tetracycloheptane Chemical compound 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 3
- 239000003380 propellant Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- DENCHDMOLAALHN-UHFFFAOYSA-N cyclobutylcyclobutane Chemical compound C1CCC1C1CCC1 DENCHDMOLAALHN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
- C07C1/326—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being a magnesium atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- 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
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of aerospace fuels, and provides a preparation method of bicyclobutane and application of bicyclobutane as an aerospace high-energy fuel, which overcome the problems of high production cost, poor heat stability of tetracycloheptane, normal-temperature morphological limitation of cubane and the like in the existing syntin and bicyclopropane preparation method, and the preparation method comprises the steps of taking halogenated cyclobutane as a raw material, firstly obtaining a corresponding Grignard reagent through Grignard reaction in a room-temperature environment, and then obtaining bicyclobutane through carbon-carbon coupling reaction in the room-temperature environment or a slightly high-temperature environment by adding a catalyst and an additive; the invention has the advantages of easily obtained reaction raw materials, low cost, mild reaction conditions, no byproduct in the reaction process, high yield up to more than 70% and high purity up to more than 99%.
Description
Technical Field
The invention belongs to the technical field of aerospace fuels, and particularly relates to a preparation method of bicyclobutane and application of bicyclobutane as an aerospace high-energy fuel.
Background
Propellant is an energy source for aerospace vehicles, which are always moving towards ever increasing speeds or loads, and correspondingly, the energy level of the propellant is also increasing. In particular, for carrier rockets, the requirements on the take-off weight are strict, the improvement of the specific impulse of the propellant is important, the specific impulse depends on various factors such as fuel energy, an oxidant matched with the fuel energy, the composition of combustion products and the like, but the improvement of the fuel energy is the most direct method capable of improving the specific impulse.
The high-energy liquid hydrocarbon fuel (high-energy fuel for short) artificially synthesized by a chemical method is basically the same as liquid hydrocarbon fuel (such as aviation kerosene, aerospace kerosene and the like) refined by petroleum, and compared with the aerospace kerosene, the energy of the high-energy fuel is greatly improved, so that the high-energy liquid hydrocarbon fuel has higher heat value.
It can be seen from the molecular structure of hydrocarbons that to obtain higher energy, it is necessary to artificially synthesize hydrocarbons having a small ring structure.
Recent studies have shown that high energy fuel molecules have the following characteristics: the tension ring structure consisting of 3-4 carbons to increase energy (tension energy), higher specific impulse and lower low temperature viscosity is a promising liquid fuel. High-energy fuels are greatly researched in various countries in the world, and the specific flushing ratio of syntin, bicyclopropane ([ n ] ivyane), tetracycloheptane, cubane and the like which are developed at present is improved by several seconds to tens of seconds respectively compared with that of space kerosene. But the syntin and the bicyclo propane are expensive in production cost and are not beneficial to industrial production; the tetracycloheptane has poor thermal stability and cannot be used as a coolant for rocket engines; the normal temperature form of the cubane is solid, which limits the use environment, and the hydrocarbon compounds have various problems in practical application.
Disclosure of Invention
The invention provides a preparation method of an aerospace liquid hydrocarbon bicyclo butane with high heat value, high energy and high thermal stability, which aims to solve the problems of high production cost, poor thermal stability of tetracycloheptane, normal-temperature morphological limitation of cubane and the like in the existing syntin and bicyclo propane preparation method.
Bicyclobutane, also known as cyclobutylcyclobutane, is a compound containing two four-membered rings, formula C 8 H 11 Density of 0.828g/cm 3 The calorific value is 44.308MJ/kg, the theoretical specific impulse is 370s, and the theoretical specific impulse is 7s higher than that of rocket kerosene. Therefore, by comparative analysis, it is considered that the bicyclobutane can also be used as a high-energy fuel. However, it has been found that, through extensive searching, no synthesis method of bicyclobutane has been reported in the literature. Dupont (Synthetic Communications,20 (7), 1011-1021, 1990), in the literature, produced bicyclobutane, but the bicyclobutane was produced as a by-product in a yield of only 39%, which is not advantageous for industrial production.
The technical scheme of the invention is as follows:
the preparation method of the bicyclo-butane is characterized by comprising the following steps of:
step 1, generating a format reagent of the 1-halogenated cyclobutane by carrying out Grignard reaction on the 1-halogenated cyclobutane and Mg powder in a solvent;
step 2, adding a catalyst and an additive into the reaction liquid in the step 1, and carrying out carbon-carbon self-coupling reaction under the protection of inert gas or nitrogen, and carrying out post-treatment to obtain the bicyclobutane;
wherein the catalyst is copper salt, ferric salt and/or cobalt salt, and the molar ratio of the catalyst to the 1-halogenated cyclobutane is 0.01-0.50;
wherein the additive is an oxidant, and the mol ratio of the additive to the 1-halogenated cyclobutane is 0.50-5.00.
Further, the copper salt is CuCl 2 Or Cu (NO) 3 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the The ferric salt is Fe 3 O 4 、Fe 2 O 3 Or FeCl 3 The method comprises the steps of carrying out a first treatment on the surface of the Cobalt salt is Co (NO) 3 ) 2 。
Further, the oxidizing agent is t-butanol peroxide, NBS, or the like.
Further, in step 2, the following post-treatment is performed: firstly, cooling the reaction liquid to room temperature; and secondly, filtering the cooled reaction liquid, collecting filtrate, washing filter residues for a plurality of times by adopting diethyl ether, merging the washing liquid into the filtrate, adding anhydrous magnesium sulfate for drying, and carrying out distillation separation to obtain a bicyclobutane product, wherein the post-treatment process is simple and convenient, and the industrial production can be realized.
Further, the reaction temperature in the step 1 is room temperature; in the step 2, the reaction temperature is between room temperature and 100 ℃, and the reaction condition is mild.
Further, the solvent in the step 1 is anhydrous diethyl ether, tetrahydrofuran, methylene dichloride or toluene and the like, and the use amount of the solvent is that the molar concentration of the 1-halogenated cyclobutane reaches 0.25mol/L-5mol/L. The 1-halocyclobutane in step 1 is 1-bromocyclobutane.
In order to further improve the yield, the solvent in the step 1 is toluene, and the catalyst in the step 2 is CuCl 2 ，CuCl 2 With 1-halocyclobutanesThe molar ratio is 0.1-0.5, the oxidant is NBS, the molar ratio of NBS to 1-halogenated cyclobutane is 0.5-5, the reaction temperature is 100 ℃, and the reaction time is 15h.
Further, the solvent in the step 1 is anhydrous diethyl ether, and the catalyst in the step 2 is CuCl 2 ，CuCl 2 The molar ratio of the catalyst to the 1-halogenated cyclobutane is 0.1, the oxidant is tert-butyl peroxide, the molar ratio of the tert-butyl peroxide to the 1-halogenated cyclobutane is 1, the reaction temperature is 25 ℃, and the reaction time is 15 hours. High yields can be obtained while the reaction is completed at room temperature.
Further, the solvent in the step 1 is anhydrous diethyl ether, and the catalyst in the step 2 is CuCl 2 ，CuCl 2 The molar ratio of the catalyst to the 1-halogenated cyclobutane is 0.1, the oxidant is NBS, the molar ratio of NBS to the 1-halogenated cyclobutane is 1, the reaction temperature is 25 ℃, and the reaction time is 15 hours. High yields can be obtained while the reaction is completed at room temperature.
The use of bicyclobutane as a high temperature fuel.
The beneficial effects of the invention are as follows:
1. the invention takes halogenated cyclobutane as a raw material, firstly, a corresponding Grignard reagent is obtained through Grignard reaction in a room temperature environment, and then, a catalyst and an additive are added to obtain the bicyclobutane through carbon-carbon coupling reaction in the room temperature environment or a slightly higher temperature environment; the invention has the advantages of easily obtained reaction raw materials, low cost, mild reaction conditions, no byproduct in the reaction process, high yield up to more than 70% and high purity up to more than 99%.
2. In the invention, the reaction substrate is oxidized by adding the oxidant in the carbon-carbon coupling reaction process, so that the reaction substrate is converted into the free radical intermediate, the corresponding coupling reaction is realized, and the coupling reaction yield is improved.
3. Compared with syntin and cyclopropane, the bicyclobutane has the advantages of low cost and high thermal stability compared with tetracycloheptane, and is liquid at normal temperature compared with cubane, thereby being more suitable for being used as high-energy fuel for aerospace.
Drawings
FIG. 1 is a nuclear magnetic carbon spectrum of the bicyclobutane prepared in example 1.
FIG. 2 is a chromatogram of the bicyclobutane prepared in example 1.
Detailed Description
The invention is further described below with reference to the accompanying drawings and specific embodiments.
Example 1
Taking 1.2mol of magnesium chips which are dried in vacuum at 100 ℃, adding the magnesium chips and 1mol of monobromocyclobutane into 3L of anhydrous diethyl ether under the protection of nitrogen, adding a small amount of elemental iodine to initiate reaction, and reacting for 40min at room temperature to prepare the cyclobutyl magnesium bromide format reagent in situ. Then 0.10mol of anhydrous copper chloride and 1.00mol of tert-butyl peroxide are added for carbon-carbon self-coupling reaction, and the reaction is carried out for 15 hours at 25 ℃, and mechanical stirring is adopted in the process. Cooling to room temperature after the reaction is finished, filtering, taking filtrate, washing filter residues with diethyl ether for three times, mixing washing liquid with the mixed filtrate, adding anhydrous magnesium sulfate for drying, and distilling and separating to obtain a bicyclobutane product, wherein the product yield is 77.0%. The structure identification is carried out by adopting a carbon spectrum (see figure 1), the purity is detected by adopting figure 2, and the purity reaches more than 99 percent.
Examples 2 to 20
Examples 2-20 the reaction steps were the same as in example 1, except that some of the reaction conditions were different, and the different reaction conditions include solvents and amounts, self-coupling reaction time, self-coupling reaction temperature, self-coupling reaction catalyst and amounts added, self-coupling reaction additives and amounts added, and the like, as shown in Table 1.
Table 1 examples 2 to 20
As can be seen from the above examples, when the solvent is anhydrous diethyl ether, the catalyst is CuCl 2 ，CuCl 2 The molar ratio of the catalyst to the 1-halogenated cyclobutane is 0.1, the oxidant is tert-butyl peroxide, the molar ratio of the tert-butyl peroxide to the 1-halogenated cyclobutane is 1, the reaction temperature is 25 ℃, the reaction time is 15 hours, and the yield of the bicyclobutane can reach 77.0%. When the solvent is anhydrous diethyl ether, the catalyst is CuCl 2 ，CuCl 2 With 1-halocyclobutanesThe molar ratio is 0.1, the oxidant is NBS, the molar ratio of NBS to 1-halogenated cyclobutane is 1, the self-coupling reaction temperature is 25 ℃, and the yield of the bicyclobutane can reach 68.30% when the reaction time is 15 hours. When toluene is selected as the solvent, cuCl is selected as the catalyst 2 ，CuCl 2 The molar ratio of the catalyst to the 1-halogenated cyclobutane is 0.1, 0.3, 0.5 and 0.1, the oxidant is NBS, the molar ratio of NBS to the 1-halogenated cyclobutane is 1, 0.5, 3 and 5 respectively, and when the self-coupling reaction temperature is 100 ℃ and the reaction time is 15 hours, the yield of the bicyclobutane can reach 92.80%, 93.00%, 93.30% and 95.00% respectively.
Claims (7)
1. The preparation method of the bicyclo-butane is characterized by comprising the following steps:
step 1, generating a format reagent of the 1-halogenated cyclobutane by carrying out Grignard reaction on the 1-halogenated cyclobutane and Mg powder in a solvent;
step 2, adding a catalyst and an additive into the reaction liquid in the step 1, and carrying out carbon-carbon self-coupling reaction under the protection of inert gas or nitrogen, and after the reaction is completed, carrying out post-treatment to obtain the bicyclobutane;
wherein the catalyst is CuCl 2 、Cu(NO 3 ) 2 、Fe 2 O 3 、FeCl 3 Or Co (NO) 3 ) 2 The molar ratio of the catalyst to the 1-halogenated cyclobutane is 0.01-0.50;
wherein the additive is an oxidant, and the oxidant is tert-butyl peroxide or N-bromosuccinimide NBS; the molar ratio of the additive to the 1-halocyclobutane is 0.50-5.00.
2. The method for preparing the bicyclobutane according to claim 1, wherein: the following post-treatment is carried out in the step 2: firstly, cooling the reaction liquid to room temperature; and secondly, filtering the cooled reaction liquid, collecting filtrate, washing filter residues for a plurality of times by adopting diethyl ether, merging the washing liquid into the filtrate, adding anhydrous magnesium sulfate for drying, and distilling and separating to obtain a bicyclobutane product.
3. The method for preparing the bicyclobutane according to claim 2, wherein: the reaction temperature in the step 1 is room temperature; the reaction temperature in step 2 is from room temperature to 100 ℃.
4. A process for preparing a bicyclobutane as claimed in claim 3, wherein: the solvent in the step 1 is anhydrous diethyl ether, tetrahydrofuran, methylene dichloride or toluene, and the using amount of the solvent is that the molar concentration of the 1-halogenated cyclobutane reaches 0.25mol/L-5mol/L; the 1-halocyclobutane in step 1 is 1-bromocyclobutane.
5. The method for producing bicyclobutane according to claim 4, wherein: the solvent in the step 1 is toluene, and the catalyst in the step 2 is CuCl 2 ，CuCl 2 The molar ratio of the catalyst to the 1-halogenated cyclobutane is 0.1-0.5, the oxidant is NBS, the molar ratio of NBS to the 1-halogenated cyclobutane is 0.5-5, the reaction temperature is 100 ℃, and the reaction time is 15 hours.
6. The method for producing bicyclobutane according to claim 4, wherein: the solvent in the step 1 is anhydrous diethyl ether, and the catalyst in the step 2 is CuCl 2 ，CuCl 2 The molar ratio of the catalyst to the 1-halogenated cyclobutane is 0.1, the oxidant is tert-butyl peroxide, the molar ratio of the tert-butyl peroxide to the 1-halogenated cyclobutane is 1, the reaction temperature is 25 ℃, and the reaction time is 15 hours.
7. The method for producing bicyclobutane according to claim 4, wherein: the solvent in the step 1 is anhydrous diethyl ether, and the catalyst in the step 2 is CuCl 2 ，CuCl 2 The molar ratio of the catalyst to the 1-halogenated cyclobutane is 0.1, the oxidant is NBS, the molar ratio of NBS to the 1-halogenated cyclobutane is 1, the reaction temperature is 25 ℃, and the reaction time is 15 hours.
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| RU2175312C1 (en) * | 2000-06-27 | 2001-10-27 | Открытое акционерное общество "Всероссийский научно-исследовательский институт органического синтеза" | Method of production of dicyclobutyl |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2175312C1 (en) * | 2000-06-27 | 2001-10-27 | Открытое акционерное общество "Всероссийский научно-исследовательский институт органического синтеза" | Method of production of dicyclobutyl |
Non-Patent Citations (1)
| Title |
|---|
| A convenient large-scale synthesis of cyclobutyl halides;Dupont, Andrea C. et al.;《Synthetic Communications》;第20卷(第7期);第1011-1021页 * |
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