CN103204758A - Tetracyclic decene dimer synthesis method - Google Patents
Tetracyclic decene dimer synthesis method Download PDFInfo
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- CN103204758A CN103204758A CN2012105475099A CN201210547509A CN103204758A CN 103204758 A CN103204758 A CN 103204758A CN 2012105475099 A CN2012105475099 A CN 2012105475099A CN 201210547509 A CN201210547509 A CN 201210547509A CN 103204758 A CN103204758 A CN 103204758A
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- dimerizing olefins
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Abstract
The invention provides a tetracyclic decene dimer synthesis method. A tetracyclic decylone is used as an initial raw material and undergoes a carbonyl reduction coupling reaction to synthesize a tension ring cage hydrocarbon tetracyclic decene dimer (C20H28). Compared with the prior art, the synthesis method has the advantages of simple synthetic technology, low cost, high synthetic yield and high product purity, and allows the target compound to be synthesized only through a one-step reaction, the yield to reach about 87% and the purity of the product to reach above 98%; and the tetracyclic decene dimer can be used as the fuel or fuel additive of solid rocket engines.
Description
Technical field
The present invention relates to a kind of tension link cage modle hydrocarbon polymer---the synthetic method of Fourth Ring ten alkane dimerizing olefins bodies (claiming diamantane dimerizing olefins body again), the productive rate height of the hydrocarbon polymer that this method synthesizes, purity height, and this reaction method is simple, cost is low.This compound can be used as high density carbon hydrogen fuel or the high energy additive in the rocket engine.
Background technology
Tension link cage modle hydrocarbon polymer has improved combustion heat value owing to have the ring strain energy in the compound molecule.When endothermic pyrolysis, in case some keys are broken, the just very fast fragmentation of whole molecule gives off energy, and alleviates the generation of carbon distribution phenomenon, has tangible performance advantage.And high-density tension link cage modle hydrocarbon polymer is a kind of high Energy Density Materials (HEDM) of specific type, and their molecule is whole or major part is elementary composition by carbon, two kinds of hydrogen, has positive generation heat and higher density value (ρ 〉=1g/cm
3).
Recent two decades comes, and the U.S. as the HEDM target, has synthesized a series of tension link compounds with high-density tension link cage modle hydrocarbon polymer, wherein the most important thing is polynuclear hydrocarbon and cage type hydrocarbon.Particularly the latter because condensing of many rings becomes the high deformation structure, has bigger tension force energy and density.Wherein Fourth Ring ten alkane derivatives are a class important in the high-density propellant.
Along with Fourth Ring ten alkane derivatives average carbon atom numbers increase, fuel proportion, flash-point, minimum pumping temperature and net heat of combustion value all increase.This hydrocarbon fuel does not obtain by synthetic, but the minor by-products in the Mobil company production of hydrocarbons, though for its large-scale application bigger restriction is arranged, because it has bigger density and high combustion value, has been subjected to various countries' research organizations pay much equally.Fourth Ring ten alkane dimerizing olefins bodies are two hydrocarbon polymers that cage modle Fourth Ring ten alkyl structures link together by two keys, and its density is 1.14g/cm
3, the quality calorific value is 42.14MJ/kg, easy distillation unlike ten alkane of Fourth Ring.And its synthetic raw material wide material sources, have great advantage at cost, in military affairs and space industry, all have broad application prospects.
Tolstikov and Lerman etc. in the time of 20 ℃, with the ring sulfoxide compound of Fourth Ring ten alkane simultaneously at different solvent C H
3Reaction is 16 hours among I and the MeI, after the processing, has all made Fourth Ring ten alkane dimerizing olefins bodies in two kinds of solvents respectively.In ethyl acetate, reacted 15 hours and Abu-Yousef and Harpp etc. will encircle sulfoxide, also obtain product Fourth Ring ten alkane dimerizing olefins bodies.
Gerson and Lopez add n-BuSnCl and LiAID in diethyl ether after, add the bromide of Fourth Ring ten alkane, reacted 30 hours, make Fourth Ring ten alkane dimerizing olefins bodies.
Hogenkamp and Greene etc. make Fourth Ring ten alkane dimerizing olefins bodies after the trinitride of Fourth Ring ten alkane reacts in dodecane in the time of 137 ℃.This researchist changes reaction conditions afterwards, at CH
2Cl
2Middle 2,6-di-tert-butyl pyridine and the (p-Br-C of adding
6H
4) 4N
(1+)Sb
6 (1-)After, the azo compound that adds Fourth Ring ten alkane reacted 0.0125 hour, obtained Fourth Ring ten alkane dimerizing olefins bodies.
Fourth Ring ten alkane ketone are a kind of medicine intermediates commonly used, and coupling can obtain Fourth Ring ten alkane dimerizing olefins bodies after two molecule Fourth Rings, ten alkane ketone were sloughed carbonyl.The maximum a kind of synthetic method of research is to adopt low valent titanium reagent catalysis of carbonyl generation reductive coupling reaction to generate corresponding alkene at present.After finding that ketone and aldehyde generate alkene through low valent titanium reagent deoxidation coupling, and the researchist find that the reaction between the mono-carbonylation adduct molecule generates the dimerizing olefins body, and intramolecular dicarbonyl compound generates cycloolefin through exploring in more detail.
The synthetic method of the Fourth Ring ten alkane dimerizing olefins bodies of above bibliographical information, the subject matter of existence is:
1, the synthetic difficulty of starting material, and price is higher, because ten alkane ketone are introduced heteroatoms at the Fourth Ring, space steric effect makes that the heteroatomic reaction difficulty of introducing is bigger.Therefore, the price of Fourth Ring ten alkane ketone derivatives is far above Fourth Ring ten alkane ketone.
2, used chemical reagent toxicity is bigger, and is bigger to operator's injury, as trinitride, the CH of Fourth Ring ten alkane
2Cl
2Solvent etc.
3, the synthetic cost of Fourth Ring ten alkane dimerizing olefins bodies is higher, and used reagent and the cost of solvent are all higher, as n-BuSnCl, (p-Br-C
6H
4) 4N
(1+)Sb
6 (1-)Deng.
Summary of the invention
The object of the present invention is to provide the synthetic method of the Fourth Ring ten alkane dimerizing olefins bodies that a kind of synthesis technique is simple, low-cost, synthetic yield is high and product purity is high.
Solution of the present invention is (except explanation was arranged, the ratio that adopts among the present invention was the mole proportioning):
Be starting raw material with Fourth Ring ten alkane ketone, adopting combined reducing agent in solvent is TiCl4-LiAlH
4, under the effect of catalyzer, carry out the carbonyl reduction linked reaction, synthesize target compound tension link cage modle hydrocarbon polymer---Fourth Ring ten alkane dimerizing olefins body (C
20H
28), the building-up reactions formula is as follows:
Described carbonyl reduction linked reaction is: anhydrous tetrahydro furan adds in the reactor, and under argon shield, 0 ℃ drips combined reducing agent TiCl
4-LiAlH
4Stir 30 minutes post-heating under the room temperature to 60-70 ℃ of backflow 30 minutes, be cooled to 0 ℃ ± 2 ℃ again, add pyridine earlier, drip the tetrahydrofuran solution of dissolving Fourth Ring ten alkane ketone then, remove refrigerating unit, be heated to 60-70 ℃ of backflow (tetrahydrofuran (THF) begins to reflux) 24 ± 2 hours hours in this temperature range, be cooled to room temperature; Drip 10% solution of potassium carbonate, after filtration, anhydrous diethyl ether is washed and wash after, dry Fourth Ring ten alkane dimerizing olefins bodies.Fourth Ring ten alkane ketone: TiCl wherein
4: LiAlH
4Feed ratio (mol ratio) be: 1:0.9-1.3:2.1-2.5; Catalyst levels is 0.91-0.95 times of Fourth Ring ten alkane ketone molar weights, and the consumption of solvent is 10-12 times of Fourth Ring ten alkane ketone quality.
Fourth Ring ten alkane ketone: TiCl among the present invention
4: LiAlH
4Feed ratio (mol ratio) be: 1:1.1:2.3.
The present invention compared with prior art, synthesis technique is simple, low-cost, synthetic yield is high and the product purity height, also has the following advantages:
(1) with TiCl
4-LiAlH
4For combined reducing agent is not seen bibliographical information for the synthesis of Fourth Ring ten alkane dimerizing olefins bodies;
(2) synthesising reacting time is 24 hours, than 46 hours of similar document report having shortened 22 hours;
(3) productive rate of Fourth Ring ten alkane dimerizing olefins bodies is 87.68%, has improved 25% than the productive rate that uses original synthesis technique to prepare Fourth Ring ten alkane dimerizing olefins bodies.
Embodiment
Embodiment 1
In the there-necked flask of 500ml, add 100 ml anhydrous tetrahydro furans, argon shield, holding temperature dripped 11.38 g(0.060 mol at 0 ℃ with horizontal pressure funnel in 30 minutes) titanium tetrachloride, stir fast; Add LiAlH then in batches altogether
45.31 g g(0.140 mol) after dropwising, removes refrigerating unit, at room temperature stirs after 30 minutes reheat and refluxes 30 minutes to 60-70 ℃.After reflux finishing, be cooled to 0 ℃ again, drip 4.80 g(0.0607 mol) pyridine; Then drip 10.00 g(0.0667 mol) tetrahydrofuran solution 120 ml of Fourth Ring ten alkane ketone, remove refrigerating unit, be heated to 60-70 ℃, back flow reaction 24 hours (argon shield).After reaction finishes, cool to room temperature drips new 10% solution of potassium carbonate, 300 ml that prepare, and filters, filter cake anhydrous diethyl ether washed twice, merging filtrate washs the organic phase anhydrous sodium sulfate drying with distilled water (3 * 50 ml) then, vacuum rotary steam is removed ether, obtain white solid Fourth Ring ten alkane dimerizing olefins bodies, 6.88 g, productive rate 86.79%, purity 98.40%.
Embodiment 2
In the there-necked flask of 500ml, add 100 ml anhydrous tetrahydro furans, argon shield, holding temperature dripped 13.77 g(0.0726 mol at 0 ℃ with horizontal pressure funnel in 30 minutes) titanium tetrachloride, stir fast; Add LiAlH then in batches altogether
45.81 g(0.153 mol), after dropwising, remove refrigerating unit, at room temperature stir after 30 minutes reheat and refluxed 30 minutes to 60-70 ℃.After reflux finishing, cool to 0 ℃ again, drip 4.89 g(0.0618 mol) pyridine; Then drip 10.00 g(0.0667 mol) tetrahydrofuran solution 120 ml of Fourth Ring ten alkane ketone, remove refrigerating unit, be heated to 60-70 ℃, reflux 24 hours (argon shield).After reaction finishes, cool to room temperature drips new 10% solution of potassium carbonate, 300 ml that prepare, and filters, filter cake anhydrous diethyl ether washed twice, merging filtrate washs the organic phase anhydrous sodium sulfate drying with distilled water (3 * 50 ml) then, vacuum rotary steam is removed ether, obtain white solid Fourth Ring ten alkane dimerizing olefins bodies, 7.83 g, productive rate 87.68%, purity 98.15%.
Embodiment 3
In the there-necked flask of 500ml, add 100 ml anhydrous tetrahydro furans, argon shield, holding temperature dripped 16.45 g(0.0867 mol at 0 ℃ with horizontal pressure funnel in 30 minutes) titanium tetrachloride, stir fast; Add LiAlH4 6.34 g(0.167 mol then in batches altogether), after dropwising, remove refrigerating unit, at room temperature stir after 30 minutes reheat and refluxed 30 minutes to 60-70 ℃.After reflux finishing, cool to 0 ℃ again, Dropwise 5 .01 g(0.0634 mol) pyridine; Then drip 10.00 g(0.0667 mol) tetrahydrofuran solution 120 ml of Fourth Ring ten alkane ketone, remove refrigerating unit, be heated to 60-70 ℃, reflux 24 hours (argon shield).After reaction finishes, cool to room temperature drips new 10% solution of potassium carbonate, 300 ml that prepare, and filters, filter cake anhydrous diethyl ether washed twice, merging filtrate washs the organic phase anhydrous sodium sulfate drying with distilled water (3 * 50 ml) then, vacuum rotary steam is removed ether, obtain white solid Fourth Ring ten alkane dimerizing olefins bodies, 7.87 g, productive rate 88.15%, purity 98.73%.
Claims (4)
1. the synthetic method of Fourth Ring ten alkane dimerizing olefins bodies is to be starting raw material with Fourth Ring ten alkane ketone, and adopting combined reducing agent in solvent is TiCl4-LiAlH
4, under the effect of catalyzer pyridine, carry out the carbonyl reduction linked reaction, synthesize target compound.
2. according to the synthetic method of the described Fourth Ring of claim 10 alkane dimerizing olefins bodies, it is characterized in that: described carbonyl reduction linked reaction is: anhydrous tetrahydro furan adds in the reactor, and under argon shield, 0 ℃ drips combined reducing agent TiCl
4-LiAlH
4, stir 30 minutes post-heating under the room temperature to 60-70 ℃ of backflow 30 minutes, be cooled to 0 ℃ ± 2 ℃ again, add pyridine earlier, drip the tetrahydrofuran solution of dissolving Fourth Ring ten alkane ketone then, remove refrigerating unit, be heated to 60-70 ℃ and refluxed 24 ± 2 hours hours, be cooled to room temperature; Fourth Ring ten alkane ketone: TiCl wherein
4: LiAlH
4Molar ratio be: 1:0.9-1.3:2.1-2.5; Catalyst levels is 0.91-0.95 times of Fourth Ring ten alkane ketone molar weights, and the consumption of solvent is 10-12 times of Fourth Ring ten alkane ketone quality.
3. according to the synthetic method of the described Fourth Ring of claim 20 alkane dimerizing olefins bodies, it is characterized in that also comprising: drip 10% solution of potassium carbonate, after filtration, anhydrous diethyl ether is washed and wash after, dry Fourth Ring ten alkane dimerizing olefins bodies.
4. according to the synthetic method of the described Fourth Ring of claim 20 alkane dimerizing olefins bodies, it is characterized in that: Fourth Ring ten alkane ketone: TiCl
4: LiAlH
4Molar ratio be: 1:1.1:2.3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449818A (en) * | 2013-09-22 | 2015-03-25 | 湖北航天化学技术研究所 | Cyclopentadiene high-density liquid hydrocarbon fuel and synthetic method thereof |
| CN105273780A (en) * | 2014-07-22 | 2016-01-27 | 湖北航天化学技术研究所 | Diesel oil additive |
| CN105779037A (en) * | 2014-12-26 | 2016-07-20 | 湖北航天化学技术研究所 | Gasoline additive |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449818A (en) * | 2013-09-22 | 2015-03-25 | 湖北航天化学技术研究所 | Cyclopentadiene high-density liquid hydrocarbon fuel and synthetic method thereof |
| CN104449818B (en) * | 2013-09-22 | 2016-08-03 | 湖北航天化学技术研究所 | Cyclopentadiene high density liquid hydrocarbon fuel and synthetic method thereof |
| CN105273780A (en) * | 2014-07-22 | 2016-01-27 | 湖北航天化学技术研究所 | Diesel oil additive |
| CN105779037A (en) * | 2014-12-26 | 2016-07-20 | 湖北航天化学技术研究所 | Gasoline additive |
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| CN103204758B (en) | 2014-11-26 |
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