CN104418697A - Method for synthesizing quadricyclane - Google Patents
Method for synthesizing quadricyclane Download PDFInfo
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- CN104418697A CN104418697A CN201310409541.5A CN201310409541A CN104418697A CN 104418697 A CN104418697 A CN 104418697A CN 201310409541 A CN201310409541 A CN 201310409541A CN 104418697 A CN104418697 A CN 104418697A
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- quadricyclane
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- norbornadiene
- photosensitizers
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Abstract
The invention relates to a method for synthesizing quadricyclane. The method particularly comprises the following steps: with petroleum ether/acetone as a mixed solvent, benzophenone as a photosensitizer and norbornadiene as a raw material, irradiating the components by using 365nm of ultraviolet light at room temperature for a certain period of time under a stirring condition; and carrying out reduced pressure distillation and purification on a reaction liquid, so as to obtain quadricyclane. The method is simple to operate and available in raw material; and the used solvent is low in toxicity, low in boiling point, relatively large in product difference and easy to remove, and large-scale production is easy to achieve.
Description
Technical field
The present invention relates to quadricyclane, refer to a kind of method of synthesizing quadricyclane especially.
Background technology
Liquid carbon hydrogen fuel is the important component part of liquid propellant, for various aerospace flight vehicle provides the key of motivational guarantee, fuel performance determines the airworthiness (Wang Zhen of aircraft, Wei Hao, He Fang, defend Hongyuan high-density synthin fuel progress. guided missile and carrying space technology, 2011,3 (313): 41-46.).The hydrocarbon fuel volume calorific value of current use, generally at about 35MJ/L, can not meet higher, faster, the farther demand of modernized war, must develop the liquid hydrocarbon fuel that volume calorific value is larger.Wherein, quadricyclane, as one typical high tensile caged liquid hydrocarbon, is considered to a kind of potential automotive fuel, also can improve the performance of fuel as additive.Its density is 0.98g/cm
3, boiling point 108 DEG C, freezing point-40 DEG C, volume calorific value is about 44.1MJ/L, higher than any liquid carbon hydrogen fuel used at present, is a kind of good high energy additive.In addition, the synthetic method of quadricyclane relatively simply, substantially nontoxic, good stability, can safety in transportation and storage, be also a kind of new and effective, non-toxic aq propelling agent, be expected to the hypertoxic hydrazine class I liquid I propelling agent that alternative current satellite uses.Quadricyclane is obtained through photic valence link isomerization reaction by norbornadiene.Conventional catalyzer has transition metal complex photosensitizers, and heterogeneous photosensitizers and triplet energies transmit photosensitizers.
As far back as 1985, just someone used the complex compound of copper to carry out catalysis norbornadiene isomerization reaction (D.J.Fife, W.M.Moore, K.W.Morse, J.Am.Chem.Soc.1985,107,7017-1083) as photosensitizers.Subsequently, Akioka uses transition metal carbonyl compound Rh
6(CO)
16for sensitizing agent, Virahol is under the condition of solvent, and the yield of reaction product reaches 62% (Akioka T, Inoue Y, YanagawaA, et al.J.Mol.Catal.A:Chem., 2003,202:31-39).But the synthesis of these metal complexs is comparatively complicated, expensive, limit its sizable application.The TiO that the people such as Zhu Bin use Zn, La to adjust
2and MCM-41 is as the heterogeneous photosensitizers of one, dimethylbenzene is as solvent, and reaction 12h, achieve the transformation efficiency up to 93%, and catalyzer is easy to be separated with reaction solution.But the dimethylbenzene more malicious easy carcinogenic solvent that is one and boiling point and quadricyclane close, not easily remove, bring certain difficulty (J.J.Zou, Y.Liu to later separation purifying, L.Pan, L.Wang, X.W.Zhang, Appl.Catal.B:Environmental, 2010,95,439).It is a quasi-tradition photosensitizers that triplet energies transmits photosensitizers (as aromatic ketone compounds), has sensitization efficiency high, and be easy to get the features such as convenience.The people such as Smith use methyl phenyl ketone (4.4wt%) as photosensitizers, and under nitrogen atmosphere, ether is as solvent, although obtain the quadricyclane of 70-80% yield, the reaction times reaches 48h(Smith C D.Quadricyclane, Organic Syntheses, 1988,6:962-964).The people such as Liu Fang use michaelis ketone as photosensitizers, and benzene is as solvent, and reaction 12h, achieves the transformation efficiency up to 93.9%, but benzene is the easy carcinogenic solvent of a kind of high poison and boiling point and product are more or less the same, and not easily removes, bring certain trouble (Liu Fang to later separation purifying, king arrives, Zhang Xiangwen, etc.The research of norbornadiene photoisomerization. chemical reaction engineering and technique, 2006,22 (6): 560-564).Therefore, so far, more the method for the synthesis quadricyclane of simple and effective remains extremely limited.
Summary of the invention
The object of the invention is to overcome the deficiency in background technology and defect, provide a kind of simple and effective to synthesize the method for quadricyclane.
After considering that reaction completes, the boiling point difference of solvent and product should be large as much as possible, and to be convenient to remove solvent, underpressure distillation obtains sterling.Therefore, the scheme of this technological invention is for mixed solvent with the sherwood oil/acetone of inexpensive, low toxicity, business-like aromatic ketone compounds is as photosensitizers, use 365nm UV-irradiation norbornadiene certain hour under room temperature condition, after reaction solution underpressure distillation being purified, can quadricyclane be obtained.
The mixed solvent that the solvent used is sherwood oil and acetone, preferred volume ratio is: sherwood oil/acetone=10/1.
The initial reaction concentration of norbornadiene is 0.6-4.2mol/L, is preferably 1.0mol/L.
Described photosensitizers is one or two or more kinds in methyl phenyl ketone, benzophenone, michaelis ketone or p-methoxy-acetophenone, and be preferably benzophenone, the consumption of photosensitizers is the 1wt%-8wt% of raw material norbornadiene, is preferably 6wt%.
Temperature of reaction is room temperature, and the reaction times is 1-30h, is preferably 15h.
During decompression, vacuum tightness is 0.098MPa.
The present invention passes through the screenings such as concentration, catalytic amount, reaction times, to obtaining the reaction conditions of more efficient easier synthesis quadricyclane.
The present invention is easy and simple to handle, and raw material is easy to get, and solvent for use low toxicity is harmless, and boiling point is low, and product difference is comparatively large, very easily removes, is easy to accomplish scale production.
Accompanying drawing explanation
Fig. 1 is quadricyclane provided by the present invention
1h nmr spectrum;
Fig. 2 is quadricyclane provided by the present invention
13c nmr spectrum.
Embodiment
Photosensitizers (kind and catalytic amount are in table 1) is weighed in 500mL reaction flask, add sherwood oil and acetone as mixed solvent (volume ratio is 10:1), adding norbornadiene (reaction density is in table 1), be filled with nitrogen excluding air, opening cooling circulating water (for cooling ultraviolet lamp tube, it is overheated to prevent, cause danger), open ultraviolet lamp and be adjusted to power demand 500w, in ultraviolet region, its dominant emission wavelength is 365nm, next is 313nm, 303nm.Under room temperature, after stirring reaction certain hour, sampling, gas chromatographic analysis detection reaction process.
Adopt the composition of HP6890 chromatographic product.Fid detector, chromatographic column is HP-5, capillary column (30m × 250 μm × 0.25 μm), temperature of vaporization chamber is 260 DEG C, and sensing chamber's temperature is 280 DEG C, and column temperature adopts temperature programming, starting temperature is 50 DEG C, and the residence time is 3min, with 8 DEG C/min ramp to 250 DEG C.The appearance time t=4.065min of norbornadiene, the appearance time t=5.829min of quadricyclane, the selectivity of reaction is 100%.
1h NMR and
13c NMR, by Bruker400MHz nmr determination, gets 32.5mg sample dissolution in 0.5mLCDCl
3in, analytical results is shown in accompanying drawing (Fig. 1 and Fig. 2).There are three kinds of hydrogen atoms in quadricyclane molecule, chemical shift is respectively:
1h NMR (400MHz, CDCl
3) δ 2.02 (s, 2H), 1.49 (d, J=4.3Hz, 4H), 1.35 (t, J=3.8Hz, 2H) ppm; This molecule is only containing three kinds of carbon atoms, and chemical shift is respectively:
13c NMR (101MHz, CDCl
3) δ 32.13,23.12,14.84ppm.More known with standard spectrogram further, after being separated, product is quadricyclane really.
The optimization of table 1 norbornadiene isomerization reaction condition and result
The productive rate that embodiment 1-18 in table 1 provides is the gas-chromatography productive rate of quadricyclane.Therefrom can find out, the norbornadiene of different concns is under the condition of photosensitizers at distinct fragrance ketone, and reaction certain hour all has quadricyclane to generate.But, optimized reaction conditions is: norbornadiene starting point concentration is 1.0mol/L, 6wt% benzophenone is photosensitizers, reaction 15h can obtain 93% transformation efficiency and 100% selectivity, quadricyclane can be obtained, colourless transparent liquid, yield about 73% through underpressure distillation (vacuum tightness is 0.098MPa), GC and NMR analyzes, its purity >95%.
Embodiment in above-mentioned embodiment is used for explaining and the present invention is described; instead of limit the invention; in the protection domain of spirit of the present invention and claim, to any amendment done by the present invention and change, all will fall within protection scope of the present invention.
The present invention is easy and simple to handle, and raw material is easy to get, and solvent for use low toxicity is harmless, and boiling point is low, and product difference is comparatively large, very easily removes, is easy to accomplish scale production.
Claims (6)
1. one kind is synthesized the method for quadricyclane, it is characterized in that: comprise with sherwood oil/acetone for mixed solvent, benzophenone is photosensitizers, under room temperature condition, use 365nm UV-irradiation norbornadiene to react, after reaction solution underpressure distillation being purified after reaction, can quadricyclane be obtained.
2. method according to claim 1, is characterized in that: the mixed solvent that the solvent used is sherwood oil and acetone, preferred volume ratio is: sherwood oil/acetone=10/1.
3. method according to claim 1 and 2, is characterized in that: the initial reaction concentration of norbornadiene is 0.6-4.2mol/L, is preferably 1.0mol/L.
4. the method according to claim 1,2 or 3, it is characterized in that: described photosensitizers is one or two or more kinds in methyl phenyl ketone, benzophenone, michaelis ketone or p-methoxy-acetophenone, be preferably benzophenone, the consumption of photosensitizers is the 1wt%-8wt% of raw material norbornadiene, is preferably 6wt%.
5. the method according to claim 1,2,3 or 4, is characterized in that: temperature of reaction is room temperature, and the reaction times is 1-30h, is preferably 15h.
6. method according to claim 1, is characterized in that: during decompression, vacuum tightness is 0.098MPa.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040031675A1 (en) * | 2000-06-07 | 2004-02-19 | Exciton, Inc. | Process of quadricyclane production |
| CN101417919A (en) * | 2008-12-04 | 2009-04-29 | 天津大学 | Method for preparing high energy liquid fuel by acid catalysis of norbornene dimerization |
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2013
- 2013-09-10 CN CN201310409541.5A patent/CN104418697A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040031675A1 (en) * | 2000-06-07 | 2004-02-19 | Exciton, Inc. | Process of quadricyclane production |
| CN101417919A (en) * | 2008-12-04 | 2009-04-29 | 天津大学 | Method for preparing high energy liquid fuel by acid catalysis of norbornene dimerization |
Non-Patent Citations (1)
| Title |
|---|
| 刘芳等: ""降冰片二烯光敏异构化反应的工艺研究"", 《化学反应工程与工艺》 * |
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