CN115850279A - Theophylline derived autoignition ionic salt and preparation method thereof - Google Patents
Theophylline derived autoignition ionic salt and preparation method thereof Download PDFInfo
- Publication number
- CN115850279A CN115850279A CN202211560076.0A CN202211560076A CN115850279A CN 115850279 A CN115850279 A CN 115850279A CN 202211560076 A CN202211560076 A CN 202211560076A CN 115850279 A CN115850279 A CN 115850279A
- Authority
- CN
- China
- Prior art keywords
- theophylline
- salt
- derived
- autoignition
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 title claims abstract description 331
- 150000003839 salts Chemical class 0.000 title claims abstract description 200
- 229960000278 theophylline Drugs 0.000 title claims abstract description 199
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 ion salt Chemical class 0.000 claims abstract description 119
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 150000001450 anions Chemical class 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 13
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 150000008282 halocarbons Chemical class 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000003380 propellant Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 47
- 230000002269 spontaneous effect Effects 0.000 abstract description 44
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 18
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 5
- ZNPKAOCQMDJBIK-UHFFFAOYSA-N nitrocyanamide Chemical compound [O-][N+](=O)NC#N ZNPKAOCQMDJBIK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 description 20
- 238000006073 displacement reaction Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- 150000004714 phosphonium salts Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000002608 ionic liquid Substances 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- RPOQNHMXOPWCEK-UHFFFAOYSA-N 7-ethyl-1,3-dimethylpurine-2,6-dione Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2CC RPOQNHMXOPWCEK-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N 1,3,9-trimethylpurine-2,6-dione Chemical compound CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 3
- ZGIBYCLLIMGXEZ-UHFFFAOYSA-N 1,3-dimethyl-7-prop-2-enylpurine-2,6-dione Chemical compound O=C1N(C)C(=O)N(C)C2=C1N(CC=C)C=N2 ZGIBYCLLIMGXEZ-UHFFFAOYSA-N 0.000 description 3
- CPRWWXKLQNLTSZ-UHFFFAOYSA-N 7-butyl-1,3-dimethylpurine-2,6-dione Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2CCCC CPRWWXKLQNLTSZ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229960001948 caffeine Drugs 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 125000005394 methallyl group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JSFMCJBSPUHNHS-UHFFFAOYSA-N silver;cyanoiminomethylideneazanide Chemical compound [Ag+].N#C[N-]C#N JSFMCJBSPUHNHS-UHFFFAOYSA-N 0.000 description 3
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MQMALSJXHPJEAX-UHFFFAOYSA-N cyanoiminomethylideneazanide 1-methyl-1,2,4-triazol-4-ium-4-amine Chemical compound N#C[N-]C#N.C[N+]1=CN(N)C=N1 MQMALSJXHPJEAX-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- IUXHPSPHPKXTPA-UHFFFAOYSA-N 1-bromobut-1-ene Chemical compound CCC=CBr IUXHPSPHPKXTPA-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical group CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a theophylline derived spontaneous combustion ionic salt and a preparation method thereof, and the theophylline belongs to fused ring aromatic hydrocarbon, and specifically comprises an imidazole five-membered ring and a hydropyrimidine six-membered ring, wherein a quaternary ammonium nitrogen atom is positioned on the imidazole five-membered ring, so that the theophylline derived spontaneous combustion ionic salt has better thermal stability. In addition, because the theophylline contains four nitrogen atoms, the content of nitrogen is higher, the energy density is higher, and the density specific impulse is higher. The anion is selected from dicyanamide, nitrocyanamide, dicyano dihydroborate and the like with excellent ignition performance, and the ignition performance of the theophylline derived spontaneous combustion ion salt is further improved while the high stability of the theophylline derived spontaneous combustion ion salt is maintained.
Description
Technical Field
The invention relates to the field of spontaneous combustion ionic salts, in particular to a theophylline derived spontaneous combustion ionic salt and a preparation method thereof.
Background
At present, hydrazine and derivatives thereof (such as homodi, unsym-dimethylhydrazine and the like) are commonly used two-component self-combustion rocket propellant fuel. The hydrazine compound as liquid fuel has the advantages of high specific impulse, short ignition delay time and the like, but the hydrazine compound also has the characteristics of high volatility, high toxicity and strong carcinogenicity. In order to meet the current continuously-improved environmental protection requirements, the development of green, low-toxicity and low-pollution novel fuels for replacing hydrazine compounds is highly emphasized by the scientific community, and becomes one of the research fronts in the field of rocket propellants.
The spontaneous combustion ionic salt (containing ionic liquid) rocket propellant is a research hotspot in recent years due to good combustion characteristic and other performances, the ionic salt is composed of anions and cations and has the characteristic of designable structure, but most of the traditional ionic salts have the problems of low decomposition temperature and poor thermal stability, and in addition, the existing ionic salt has lower energy density and limitation in the aspect of filling amount. Therefore, the stability and energy density of the pyrophoric ion salt in the prior art have yet to be improved.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a theophylline derived autoignition ionic salt and a preparation method thereof, aiming at solving the problem that the stability and energy density of the autoignition ionic salt in the prior art need to be improved.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a theophylline derived autoignition ionic salt, wherein the structural general formula of the theophylline derived autoignition ionic salt is as follows:
wherein R is selected from one of alkyl groups of 1 to 8 carbon atoms, Y - Selected from (CN) 2 N - 、(NO 2 )(CN)N - 、H 2 (CN) 2 B - One or more of (a).
The theophylline is derived from a phosphonium salt, wherein R is selected from one of methyl, ethyl, allyl, butyl and alkene butyl.
The theophylline derivative autoignition ionic salt is characterized in that the decomposition temperature of the theophylline derivative autoignition ionic salt is more than 200 ℃, and the density specific impulse of the theophylline derivative autoignition ionic salt is more than 330 s.g.cm -3 。
A process for the preparation of theophylline derived autoignition ion salts as described in any one of the preceding claims, comprising the steps of:
under the condition of inert atmosphere and preheating and stirring, dissolving theophylline and strong base by adopting a first solvent, adding halogenated hydrocarbon, and reacting to obtain an alkyl theophylline solution; wherein, the alkyl in the halogenated hydrocarbon is selected from one of alkyl with 1 to 8 carbon atoms, the halogen is selected from one of Cl, br and I, and the preheating and stirring temperature is 50 to 120 ℃;
and filtering the alkyl theophylline solution, filtering insoluble inorganic substances, concentrating and separating out filtrate, filtering again, collecting filtrate, and drying to obtain the alkyl theophylline.
Adding a mixed solution of DMF and methyl iodide into the alkyl theophylline, reacting for 2-3 days, adding a second solvent, and filtering and drying to obtain alkyl methyl theophylline iodide salt;
dissolving the alkyl methyl theophylline iodide salt and cyanide by using distilled water, heating for reaction, and filtering and drying to obtain theophylline derived autoignition ionic salt; wherein the anion of the cyanide is selected from (CN) 2 N - 、(NO 2 )(CN)N - 、H 2 (CN)B - The cation in the cyanide is silver, the heating reaction temperature is 25-80 ℃, and the heating reaction time is 3-10 h.
The preparation method of the theophylline derivative spontaneous combustion ionic salt comprises the following steps of preparing theophylline, preparing a mixture of theophylline and alkali, wherein the molar ratio of the theophylline to the alkali is 1:1-1.2, the molar ratio of the theophylline to the halohydrocarbon is 1:3-10, and the molar ratio of DMF to methyl iodide is 1:2-10.
The preparation method of the theophylline derivative autoignition ionic salt comprises the step of preparing theophylline derivative autoignition ionic salt, wherein the molar ratio of the theophylline to the halogenated hydrocarbon is 1:5-8.
The preparation method of the theophylline derivative autoignition ionic salt comprises the following steps of adopting at least one of nitrogen, argon and helium as inert atmosphere;
the strong base comprises: one or more of sodium hydroxide, potassium hydroxide, cesium carbonate, potassium carbonate, barium hydroxide, and calcium hydroxide.
The preparation method of the theophylline derivative autoignition ionic salt comprises the following steps: one or more of N, N-dimethylformamide, chloroform, ethyl acetate, acetone, dichloromethane, N-methylpyrrolidone, tetrahydrofuran, dioxane, dimethyl sulfoxide, methyl ethyl ketone and acetonitrile;
the second solvent includes: one or more of ethyl acetate and diethyl ether.
The preparation method of the theophylline derived autoignition ionic salt comprises the following steps of heating to react at the temperature of 35-60 ℃; the heating reaction time is 5-6 h.
Use of a theophylline-derived autoignition salt as described in any one of the preceding claims in an aerospace propellant.
Has the advantages that: because theophylline belongs to fused ring aromatic hydrocarbon, the fused ring aromatic hydrocarbon has an imidazole five-membered ring and a hydropyrimidine six-membered ring, and a quaternary ammonium nitrogen atom is positioned on the imidazole five-membered ring, the fused ring aromatic hydrocarbon has better thermal stability. In addition, because the theophylline contains four nitrogen atoms, the theophylline has higher nitrogen content, higher energy density and higher density specific impulse. The anion is selected from dicyanamide, nitrocyanamide, dicyano dihydroborate and the like with excellent ignition performance, so that the high stability of the theophylline derived spontaneous combustion ionic salt is maintained, and the ignition performance of the theophylline derived spontaneous combustion ionic salt is further improved.
Drawings
FIG. 1 is a diagram of an isobologram representing the calculated enthalpy of formation in the present invention.
Figure 2a is a photograph of an ionic salt of the present invention before ignition.
Figure 2b is a photograph of an ionic salt of the present invention after ignition.
FIG. 3 is a structural diagram of the crystal molecules of the self-ignition ionic salt of methallyl theophylline dicyanamide salt of the present invention.
FIG. 4 is a crystal molecular structural diagram of a self-ignition ionic salt of methylbutyl theophylline dicyanamide salt according to the present invention.
FIG. 5 is a nuclear magnetic hydrogen spectrum of 7,9-dimethyltheophylline dicyanamide salt self-ignition ion salt in the present invention.
FIG. 6 is a nuclear magnetic carbon spectrum of 7,9-dimethyltheophylline dicyanamide salt self-ignition ion salt in accordance with the present invention.
FIG. 7 is a nuclear magnetic hydrogen spectrum of a self-ignition ionic salt of methyl ethyl theophylline dicyanamide salt in the present invention.
FIG. 8 is a nuclear magnetic carbon spectrum of the self-ignition ionic salt of the methyl ethyl theophylline dicyanamide salt of the present invention.
FIG. 9 is a nuclear magnetic hydrogen spectrum of a self-ignition ionic salt of methallyl theophylline dicyanamide salt in accordance with the present invention.
FIG. 10 is a nuclear magnetic carbon spectrum of a self-ignition ionic salt of methallyl theophylline dicyanamide salt of the present invention.
FIG. 11 is the nuclear magnetic hydrogen spectrum of the self-ignition ionic salt of methylbutyl theophylline dicyanamide salt in the present invention.
FIG. 12 is a nuclear magnetic carbon spectrum of the self-ignition ionic salt of methylbutyl theophylline dicyanamide salt according to the invention.
FIG. 13 is a nuclear magnetic hydrogen spectrum of a self-ignition ionic salt of methylen butyl theophylline dicyanamide salt in accordance with the present invention.
FIG. 14 is a nuclear magnetic carbon spectrum of a self-ignition ionic salt of methylen butyl theophylline dicyanamide salt according to the present invention.
Fig. 15 is a first general structural formula of theophylline derived from a phosphonium salt according to the present invention.
Fig. 16 is a second general structural formula of theophylline derived from a phosphonium salt according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring also to fig. 1-16, some embodiments of theophylline derived autoignition salts are provided.
Referring to fig. 15 and 16, theophylline derived from a phosphonium salt according to the present invention has the general structural formula:
wherein R is selected from one of alkyl groups of 1 to 8 carbon atoms, Y - Selected from (CN) 2 N - 、(NO 2 )(CN)N - 、H 2 (CN) 2 B - One or more of (a).
Specifically, in the self-ignition ionic salt of the present application, the cation is a 7-alkyl-9-methylphylline quaternary ammonium ion or a 7-methyl-9-alkylphylline quaternary ammonium ion, and the anion is a cyanamide ion or cyanoborohydride ion, and the cyanamide ion may be (CN) 2 N - 、(NO 2 )(CN)N - The cyanoborohydride ion may be H 2 (CN) 2 B - . The theophylline belongs to fused ring aromatic hydrocarbon, and specifically comprises an imidazole five-membered ring and a hydropyrimidine six-membered ring, and the quaternary ammonium nitrogen atom is positioned on the imidazole five-membered ring, so that the theophylline has better thermal stability. In addition, because the theophylline contains four nitrogen atoms, the content of nitrogen is higher, the energy density is higher, and the density specific impulse is higher. The anion is selected from dicyanamide, nitrocyanamide, dicyano dihydroborate and the like with excellent ignition performance, so that the high stability of the theophylline derived spontaneous combustion ionic salt is maintained, and the ignition performance of the theophylline derived spontaneous combustion ionic salt is further improved.
Depending on the anion, theophylline derived from a phosphonium salt can be expressed as:
in a preferred implementation of the embodiments of the present invention, R is selected from one of methyl, ethyl, allyl, butyl, and alkenyl butyl.
In particular, the alkyl group R is selected from one of methyl, ethyl, allyl, butyl, and alkene butyl. And (3) replacing hydrogen protons on the nitrogen atom at the 7-position (or the 9-position) of theophylline with alkyl groups according to needs.
In a preferred implementation of an embodiment of the invention, the theophylline-derived autoignition ion salt has a decomposition temperature greater than 200 ℃ and a density specific impulse greater than 330 s-g-cm -3 。
Specifically, the decomposition temperature of the traditional ionic salt (ionic liquid) is lower than 180 ℃, the decomposition temperature of the theophylline derivative derived from the ionic salt is higher than 200 ℃, and the theophylline derivative has higher thermal stability. And the specific impact of the density is more than 330 s.g.cm -3 . Because the decomposition temperature of the theophylline derived autoignition ionic salt is higher, the theophylline derived autoignition ionic salt has high heat-resistant stability, is more stable in use and has higher safety. And because the density specific impulse is higher, more energy can be provided for the propelling process of spacecrafts such as rockets and the like.
In the prior art, the 1-methyl-4-amino-4H-1,2,4-triazolium dicyanamide salt ionic liquid is ionic liquid of monocyclic cation, four nitrogen atoms are contained in the monocyclic cation, and the thermal decomposition temperature is 143 ℃. The theophylline derived autoignition ionic salt is an ionic liquid of condensed ring cations, four nitrogen atoms are contained in the condensed ring cations, and the thermal decomposition temperature is higher than 200 ℃. Compared with the prior art, the binary condensed ring structure in the condensed ring cation is beneficial to improving the thermal decomposition temperature of the ionic liquid and ensuring that the thermal stability of the ionic liquid is higher.
The structural formula of the 1-methyl-4-amino-4H-1,2,4-triazolium dicyanamide salt ionic liquid can be represented as follows:
in a preferred embodiment of the inventionIn this way, the theophylline derived autoignition ionic salt has a density greater than or equal to 1.30 g-cm -3 。
In particular, theophylline derived from a phosphonium salt has a relatively high density, greater than or equal to 1.30g cm -3 . Higher densities have higher loadings.
In summary, the theophylline derived autoignition ionic salts of the present invention have the following effects:
the theophylline derivative spontaneous combustion ionic salt has the advantages that firstly, the theophylline has a binary condensed ring structure, the stability of a compound can be improved, the theophylline can be used as a framework to synthesize a series of spontaneous combustion ionic salts with high heat resistance and excellent comprehensive performance, the decomposition temperature of the theophylline derivative spontaneous combustion ionic salt obtained by the application is higher than 200 ℃, and the theophylline derivative spontaneous combustion ionic salt has good thermal stability;
secondly, the theophylline derivative ion salt has higher density, and higher filling amount if the density is higher, and the density of the theophylline derivative ion salt obtained by the application is more than or equal to 1.30 g-cm -3 Higher loadings can be achieved in applications, while higher densities also represent higher specific impact densities, which can provide more energy for the propulsion process.
And thirdly, the theophylline with the binary fused ring structure can be extracted from tea leaves, the theophylline is taken as a cation precursor, the obtained ionic salt has the advantages of reproducibility, low toxicity and the like, and the combustion product is green and environment-friendly and has little harm to the environment.
Based on the theophylline derived autoignition ionic salt described in any of the above embodiments, the present invention further provides a preferred embodiment of a method for preparing the theophylline derived autoignition ionic salt:
the preparation method of the theophylline derived autoignition ionic salt provided by the embodiment of the invention comprises the following steps:
step S100, dissolving theophylline and strong base by adopting a first solvent under the conditions of inert atmosphere, preheating and stirring, adding halohydrocarbon, and reacting to obtain an alkyl theophylline solution; wherein, the alkyl in the halogenated hydrocarbon is selected from one of alkyl with 1 to 8 carbon atoms, the halogen is selected from one of Cl, br and I, and the preheating and stirring temperature is 50 to 120 ℃.
Specifically, the molar ratio of the theophylline to the strong base is 1:1-1.2, and the molar ratio of the theophylline to the halogenated hydrocarbon is 1:3-10. Preferably, the molar ratio of the theophylline to the halogenated hydrocarbon is 1:5 to 8.
The inert atmosphere adopts at least one of nitrogen, argon and helium.
The strong base comprises: one or more of sodium hydroxide, potassium hydroxide, cesium carbonate, potassium carbonate, barium hydroxide and calcium hydroxide. The strong base is added to grab hydrogen protons on nitrogen atoms in theophylline, so that hydrocarbon group carbon positive ions can more easily attack nitrogen negative ions. The sodium hydroxide, the potassium hydroxide, the cesium carbonate, the potassium carbonate, the barium hydroxide, the calcium hydroxide and the like can well promote the reaction, and the sodium carbonate, the sodium bicarbonate and other strong and weak acid salts have no effect, so the reaction can be promoted by adding strong base in S100, and the halohydrocarbon replaces the hydrogen on the nitrogen atom at the 7-position of theophylline.
The first solvent includes: one or more of N, N-dimethylformamide, chloroform, ethyl acetate, acetone, dichloromethane, N-methylpyrrolidone, tetrahydrofuran, dioxane, dimethyl sulfoxide, methyl ethyl ketone and acetonitrile.
And S200, filtering the alkyl theophylline solution, filtering insoluble inorganic matters, concentrating and separating out filtrate, filtering again, collecting filtrate, and drying to obtain the alkyl theophylline.
Specifically, the alkyltheophylline solution is filtered to remove insoluble matter, then concentrated to precipitate and dried to obtain the alkyltheophylline.
And step S300, adding a mixed solution of DMF (dimethyl formamide) and methyl iodide into the alkyl theophylline, reacting for 2-3 days, adding a second solvent, and filtering and drying to obtain the alkyl methyl theophylline iodate.
Specifically, the molar ratio of DMF to methyl iodide is 1:2-10, and the second solvent comprises: one or more of ethyl acetate and diethyl ether. Methyl iodide is added to further quaternization. The alkyl methyl theophylline iodate is insoluble in the second solvent, and the second solvent is added after the reaction is carried out for 2 to 3 days, so that the alkyl methyl theophylline iodate can be separated out.
Step S400, dissolving the alkyl methyl group by using distilled waterTheophylline iodonium salt and cyanide are heated to react, and theophylline derived spontaneous combustion ionic salt is obtained after filtration and drying; wherein the anion of the cyanide is selected from (CN) 2 N - 、(NO 2 )(CN)N - 、H 2 (CN) 2 B - The cation in the cyanide is silver, the heating reaction temperature is 25-80 ℃, and the heating reaction time is 3-10 h.
Preferably, the temperature of the heating reaction is 35-60 ℃; the heating reaction time is 5-6 h.
Specifically, inorganic salt precipitates such as iodide and the like are removed through a reduced-pressure suction filtration device to obtain a solution containing theophylline derived autoignition ionic salt, and then a vacuum rotary evaporator is used for removing the solvent to obtain the theophylline derived autoignition ionic salt with high purity.
The theophylline derivative spontaneous combustion ionic salt with excellent ignition performance, such as containing dicyandiamide negative roots, is prepared by taking theophylline as a cation precursor to prepare theophylline quaternary ammonium salt through an anion exchange reaction. And the preparation method is simple, the experimental conditions are safe and easy to obtain, and no complex post-treatment step is needed. The specific reaction process is as follows:
it should be noted that theophylline exists as a tautomer and the final product is a mixture of the two products.
Example 1
S1, weighing 3.60g (0.02 mol) of theophylline and 0.88g (0.022 mol) of sodium hydroxide, adding into a three-neck flask, adding acetonitrile, and introducing N 2 The gas was allowed to completely displace the air in the reactor with nitrogen. Placing in a constant temperature oil bath kettle preheated to 70 ℃, stirring for 50min to completely dissolve theophylline, dropwise adding 17.04g (0.12 mol) of methyl iodide into the system, continuing to react, and monitoring the reaction end point through a silica gel plate to obtain methyl theophylline solution (7-methyl theophylline and 9-methyl theophylline exist in the solution).
S2, filtering the system, filtering insoluble inorganic matters, concentrating and separating out the filtrate, filtering again, collecting the filtrate, and drying to obtain methyl theophylline (7-methyl theophylline and 9-methyl theophylline).
S3, dropwise adding a mixed solution of 17.04g (0.12 mol) of methyl iodide and 2.92g (0.04 mol) of DMF into the methyl theophylline (7-methyl theophylline and 9-methyl theophylline), continuing to react for 2 days, adding ethyl acetate to precipitate after the reaction is finished, filtering, and drying the solid to obtain 5.44g of 7,9-dimethyl theophylline iodide salt, wherein the yield is 80.95%.
S4, weighing 3.36g (0.01 mol) 7,9-dimethyl theophylline iodonium salt and 2.09g (0.012 mol) silver dicyanamide, adding a proper amount of distilled water, placing in an oil bath kettle heated to 40 ℃, and continuing to react for 4 hours.
S5, after the reaction is finished, filtering, collecting filtrate, and drying to obtain 2.58g of 7,9-dimethyltheophylline dicyanamide salt spontaneous combustion ion salt, wherein the yield is 93.82%.
As shown in fig. 5 and 6, the nuclear magnetic hydrogen spectra of 7,9-dimethyltheophylline dicyanamide salt prepared in this example, as a self-ignition ionic salt, are δ 4.22ppm (s, 3H), 4.16ppm (s, 3H), 3.84ppm (s, 3H), 3.38ppm (s, 3H); the nuclear magnetic carbon spectrums are delta 153.34ppm,150.23ppm,139.68ppm,139.30ppm,119.06ppm,107.79ppm,36.81ppm,35.64ppm,31.31ppm and 28.43ppm; the Fourier infrared spectrum is 3480cm -1 ，3060cm -1 ，2220cm -1 ，2128cm -1 ，1660cm -1 ，1544cm -1 ，1300cm -1 ，1056cm -1 ，880cm -1 ，774cm -1 (ii) a Calculated values for elemental analysis (%): c48.00, H4.76, N35.62; the experimental values are (%): c47.85, H4.89, N35.69. The specific structure of the spontaneous combustion ion salt of 7,9-dimethyltheophylline dicyanamide salt is as follows:
the physicochemical properties of the pyrophoric salt of 7,9-dimethyltheophylline dicyanamide salt prepared in this example were determined. Its phase transition temperature (T) g /T m ) At 180 ℃ and a thermal decomposition temperature (T) d ) At 220 ℃ 7,9-dimethyltheophylline dicyanamide salt is illustratedThe spontaneous combustion ionic salt has a wide liquid range and excellent thermal stability. The density of the powder is 1.38g cm -3 With conventional dimethylhydrazine fuel (0.79 g cm) -3 ) In comparison, the filling amount is higher.
Example 2
S1, weighing 3.60g (0.02 mol) of theophylline and 0.88g (0.022 mol) of sodium hydroxide, adding into a three-neck flask, adding tetrahydrofuran, and introducing argon gas to completely replace the air in the reactor with argon gas. Placing in a constant temperature oil bath kettle preheated to 50 ℃, stirring for 80min to completely dissolve theophylline, dropwise adding 11.39g (0.12 mol) of bromoethane into the system, continuing to react, and monitoring the reaction end point through a silica gel plate to obtain an ethyl theophylline solution (7-ethyl theophylline and 9-ethyl theophylline exist in the solution).
S2, filtering the system, filtering insoluble inorganic matters, concentrating and separating out the filtrate, filtering again, collecting the filtrate, and drying to obtain the ethyl theophylline (7-ethyl theophylline and 9-ethyl theophylline).
S3, dropwise adding a mixed solution of 17.04g (0.12 mol) of methyl iodide and 2.92g (0.04 mol) of DMF into the ethyl theophylline (7-ethyl theophylline and 9-ethyl theophylline), continuing to react for 3 days, adding diethyl ether to precipitate after the reaction is finished, filtering, and drying the solid to obtain 4.49g of methyl ethyl theophylline iodide salt (namely 7-ethyl-9-methyl theophylline iodide salt and 7-methyl-9-ethyl theophylline iodide salt), wherein the yield is 64.14%.
S4, weighing 3.50g (0.01 mol) of methyl ethyl theophylline iodonium salt and 2.09g (0.012 mol) of silver dicyanamide, adding a proper amount of distilled water, placing in an oil bath kettle heated to 35 ℃, and continuing to react for 10 hours.
S5, after the reaction is finished, filtering, collecting filtrate, and drying to obtain 2.68g of spontaneous combustion ionic salts of the methyl ethyl theophylline dicyanamide salt (namely the spontaneous combustion ionic salts of the 7-ethyl-9-methyl theophylline dicyanamide salt and the spontaneous combustion ionic salts of the 7-methyl-9-ethyl theophylline dicyanamide salt), wherein the yield is 92.73%.
As shown in fig. 7 and 8, the nmr spectrum of the methyl ethyl theophylline dicyanamide salt prepared in this example with the pyrophoric ion salt was δ 4.56ppm (q, J =7.1hz, 2h), 4.20ppm (s, 3H), 3.82ppm (s, 3H), 3.37ppm (s, 3H), 1.54ppm (t, J =7.2hz, 3h); nuclear magnetic carbon spectrum thereofDelta 154.25ppm,151.47ppm,139.88ppm,119.55ppm,108.22ppm,45.28ppm,36.99ppm,31.64ppm,28.63ppm,14.34ppm; the Fourier infrared spectrum is 3476cm -1 ，3072cm -1 ，2220cm -1 ，2120cm -1 ，1668cm -1 ，1540cm -1 ，1306cm -1 ，1008cm -1 ，882cm -1 ，760cm -1 (ii) a Calculated values for elemental analysis (%): c49.82, H5.23, N33.89; the experimental values are (%): c49.90, H5.01, N33.85. The specific structure of the spontaneous combustion ionic salt of the methyl ethyl theophylline dicyanamide salt is as follows:
the physicochemical properties of the spontaneous combustion ion salts of the methyl ethyl theophylline dicyanamide salt prepared in this example were measured. Thermal decomposition temperature (T) of methyl ethyl theophylline dicyanamide salt spontaneous combustion ion salt d ) At 204 deg.C, and a density of 1.37g cm -3 . A higher density of fuel indicates that more fuel is filled in a given space. At the same time, a higher density also represents a higher specific impulse of density, so that more energy can be provided for the propulsion process.
Example 3
S1, weighing 3.60g (0.02 mol) of theophylline and 0.88g (0.022 mol) of sodium hydroxide, adding into a three-neck flask, adding acetonitrile, and introducing N 2 And (3) gas, so that the air in the reactor is completely replaced by nitrogen. Placing in a constant temperature oil bath kettle preheated to 120 ℃, stirring for 30min to completely dissolve theophylline, dropwise adding 14.52g (0.12 mol) of bromopropylene into the system, continuing the reaction, and monitoring the reaction end point through a silica gel plate to obtain an allyl theophylline solution (7-allyl theophylline and 9-allyl theophylline exist in the solution).
S2, filtering the system, filtering insoluble inorganic matters, concentrating and separating out the filtrate, filtering again, collecting the filtrate, and drying to obtain the allyl theophylline (7-allyl theophylline and 9-allyl theophylline).
S3, adding a mixed solution of 17.04g (0.12 mol) of methyl iodide and 2.92g (0.04 mol) of DMF (dimethyl formamide) dropwise into allyl theophylline (7-allyl theophylline and 9-allyl theophylline), continuing to react for 2 days, adding ethyl acetate to precipitate after the reaction is finished, filtering, and drying the solid to obtain 4.36g of methallyl theophylline iodide salt (namely 7-allyl-9-methyl theophylline iodide salt and 7-methyl-9-allyl theophylline iodide salt), wherein the yield is 60.22%.
S4, weighing 3.62g (0.01 mol) of methallyl theophylline iodide salt and 2.09g (0.012 mol) of silver dicyanamide, adding a proper amount of distilled water, placing in an oil bath kettle heated at 60 ℃, and continuing to react for 3 hours.
S5, after the reaction is finished, filtering, collecting filtrate, and drying to obtain 2.76g of spontaneous combustion ionic salts of methallyl theophylline dicyanamide salt (namely the spontaneous combustion ionic salts of 7-allyl-9-methyl theophylline dicyanamide salt and 7-methyl-9-allyl theophylline dicyanamide salt), wherein the yield is 91.69%.
As shown in fig. 9 and 10, the nmr spectrum of the methallyl theophylline dicyanamide salt prepared in this example was δ 6.05ppm (ddt, J =16.3, 10.5,5.9hz, 1h), 5.37ppm (dd, J =39.5, 13.7hz, 2h), 5.11ppm (d, J =5.9hz, 2h), 4.17ppm (s, 3H), 3.79ppm (s, 3H), 3.33ppm (s, 3H); the nuclear magnetic carbon spectra thereof are delta 154.19ppm,151.40ppm,139.89ppm,129.51ppm,121.43ppm,119.50ppm,108.15ppm, 51.111ppm, 37.13ppm,31.64ppm and 28.63ppm; the Fourier infrared spectrum is 3424cm -1 ，3020cm -1 ，2228cm -1 ，2132cm -1 ，1672cm -1 ，1540cm -1 ，1308cm -1 ，1000cm -1 ，876cm -1 ，760cm -1 (ii) a Calculated values for elemental analysis (%): c52.82, H5.02, N32.54; the experimental values are (%): c52.71, H5.22, N32.49. The specific structure of the spontaneous combustion ion salt of methallyl theophylline dicyanamide salt is as follows:
the crystal molecular structure diagram of the spontaneous combustion ion salt of methallyl theophylline dicyanamide salt prepared in this example is shown in fig. 3, and the molecular formula is C 13 H 15 N 7 O 2 The crystal structure is monoclinic, P2 1/c Space group, cell parameter of
α =90 °, β =119.095 (16) °, γ =90 °, Z =4, and the unit cell volume is £ r>
TABLE 1 Crystal data Table for the spontaneously combusting ionic salts of methallyl theophylline dicyanamide salt
The atomic coordinates (x 10) of the self-igniting ionic salt of methallyl theophylline dicyanamide salt prepared in this example 4 ) And equivalent isotropic atomic displacement parameter
The analytical data are shown in Table 2, wherein U (eq) is defined as orthogonal U ij One third of the trace amount of tensor.
TABLE 2 atomic coordinates and equivalent Isotropic atomic Shift parameters of methallyltheophylline dicyanamide salt from a phosphonium salt
Anisotropic atom displacement parameters of self-igniting ionic salt of methallyl theophylline dicyanamide salt prepared in this example
The analytical data are shown in table 3, where the anisotropic atomic displacement factor powers are in the form: -2 π 2 [h 2 a* 2 U 11 +2hka*b*U 12 +…]。
TABLE 3 Anisotropic atom Displacement parameters of Methylallyphylline dicyanamide salt from Ionic salts
The chemical bond length of the self-ignition ionic salt of methallyl theophylline dicyanamide salt prepared in this example
Analytical data are shown in table 4.
TABLE 4 bond lengths of various chemical bonds of methallyltheophylline dicyanamide salt pyrophoric ionic salt
The analytical data of each bond angle (°) of the pyrophoric ionic salt of methallyl theophylline dicyanamide salt prepared in this example are shown in table 5.
TABLE 5 bond angles of various chemical bonds of methallyl theophylline dicyanamide salt autoignition ion salts
The analysis data of the twist angle (°) of each chemical bond of the spontaneous combustion ionic salt of methallyl theophylline dicyanamide salt prepared in this example are shown in table 6.
TABLE 6 twist angle of each bond of methallyltheophylline dicyanamide salt pyrophoric ion salt
The hydrogen atom coordinates of the self-ignition ionic salt of methallyl theophylline dicyanamide salt prepared in this example
And isotropic atom displacement parameters>
Analytical data are shown in Table 7.
TABLE 7 hydrogen atom coordinates and isotropic atom displacement parameters of methallyl theophylline dicyanamide salt self-ignition ionic salt
The physicochemical properties of the pyrophoric ion salt of methallyl theophylline dicyanamide salt prepared in this example were measured. Phase transition temperature (T) of methallyl theophylline dicyanamide salt from ionic salts g /T m ) At 90 ℃ and a thermal decomposition temperature (T) d ) At 212 deg.C, and a density of 1.35 g.cm -3 。
Example 4
S1, weighing 3.60g (0.02 mol) of theophylline and 0.88g (0.022 mol) of sodium hydroxide, adding into a three-neck flask, adding acetonitrile, and introducing N 2 The gas was allowed to completely displace the air in the reactor with nitrogen. Placing in a constant temperature oil bath kettle preheated to 70 ℃, stirring for 50min to completely dissolve theophylline, then dropwise adding 16.44g (0.12 mol) of bromobutane into the system, continuing the reaction, and monitoring the reaction end point through a silica gel plate to obtain butyl theophylline solution (7-butyl theophylline and 9-butyl theophylline exist in the solution).
S2, filtering the system, filtering insoluble inorganic matters, concentrating and separating out the filtrate, filtering again, collecting the filtrate, and drying to obtain butyl theophylline (7-butyl theophylline and 9-butyl theophylline).
S3, adding a mixed solution of 17.04g (0.12 mol) of methyl iodide and 2.92g (0.04 mol) of DMF (dimethyl formamide) into butyl theophylline (7-butyl theophylline and 9-butyl theophylline) dropwise, continuing to react for 2 days, adding ethyl acetate to precipitate after the reaction is finished, filtering, and drying the solid to obtain 5.33g of methyl butyl theophylline iodonium salt (namely 7-butyl-9-methyl theophylline iodonium salt and 7-methyl-9-butyl theophylline iodonium salt), wherein the yield is 70.50%.
S4, weighing 3.79g (0.01 mol) of methyl butyl theophylline iodide and 2.09g (0.012 mol) of silver dicyandiamide, adding a proper amount of distilled water, placing in an oil bath kettle heated to 40 ℃, and continuing to react for 4 hours.
S5, after the reaction is finished, filtering, collecting filtrate, and drying to obtain 2.92g of spontaneous combustion ion salts of the methyl butyl theophylline dicyanamide salt (namely the spontaneous combustion ion salts of the 7-butyl-9-methyl theophylline dicyanamide salt and the spontaneous combustion ion salts of the 7-methyl-9-butyl theophylline dicyanamide salt), wherein the yield is 92.11%.
As shown in fig. 11 and 12, the nmr spectrum of the self-ignition ionic salt of methylbutyl theophylline dicyanamide salt prepared in this example was δ 4.53ppm (t, J =7.2hz, 2h), 4.20ppm (s, 3H), 3.83ppm (s, 3H), 3.38ppm (s, 3H), 1.95-1.84ppm (m, 2H), 1.42-1.30ppm (m, 2H), 0.94ppm (t, J =7.4hz, 3h); the nuclear magnetic carbon spectra are delta 154.30ppm,151.48ppm,139.93ppm,119.70ppm,108.24ppm,49.44ppm,37.01ppm,31.64ppm,31.18ppm,28.64ppm,18.68ppm and 12.64ppm; the Fourier infrared spectrum is 3488cm -1 ，3044cm -1 ，2228cm -1 ，2144cm -1 ，1680cm -1 ，1544cm -1 ，1308cm -1 ，1004cm -1 ，896cm -1 ，760cm -1 (ii) a Calculated values for elemental analysis (%): c52.99, H6.03, N30.90; the experimental values are (%): c53.01, H5.92, N30.97. The specific structure of the spontaneous combustion ionic salt of the methyl butyl theophylline dicyanamide salt is as follows:
the crystal molecular structure diagram of the self-ignition ionic salt of methylbutyl theophylline dicyanamide salt is shown in figure 4,molecular formula of C 14 H 19 N 7 O 2 Characterized in that the crystal structure is monoclinic, P2 1/n Space group, cell parameter of
α =90 °, β =95.289 (9) °, γ =90 °, Z =4, and a cell volume of ÷ based on ÷ or +>
TABLE 8 Crystal data sheet for methylbutyl theophylline dicyanamide salt spontaneous combustion ionic salt
The atomic coordinates (x 10) of the self-igniting ionic salt of methylbutyl theophylline dicyanamide salt prepared in this example 4 ) And equivalent isotropic atomic displacement parameter
The analytical data are shown in Table 9, in which U (eq) is defined as orthogonal U ij One third of the trace amount of tensor.
TABLE 9 atomic coordinates and equivalent Isotropic atomic Displacement parameters of methylbutyl theophylline dicyanamide salt pyrophoric ionic salt
Anisotropic atom displacement parameters of self-ignition ionic salt of methylbutyl theophylline dicyanamide salt prepared in this example
The analytical data are shown in table 10, where the anisotropic atomic displacement factor powers are in the form: -2 pi 2 [h 2 a* 2 U 11 +2hka*b*U 12 +…]。
TABLE 10 Anisotropic atom Displacement parameters of methylbutyl theophylline dicyanamide salt pyrophoric ionic salt
The bond length of each chemical bond of the self-ignition ionic salt of methylbutyl theophylline dicyanamide salt prepared in this example
The analytical data are shown in Table 11.
TABLE 11 bond lengths of various chemical bonds of methylbutyl theophylline dicyanamide salt autoignition ionic salt
The analytical data of each bond angle (°) of the self-ignition ionic salt of methylbutyl theophylline dicyanamide salt prepared in this example are shown in table 12.
TABLE 12 bond angles of each chemical bond of methylbutyl theophylline dicyanamide salt pyrophoric ionic salt
The analysis data of the twist angle (°) of each chemical bond of the self-ignition ionic salt of methylbutyl theophylline dicyanamide salt prepared in this example are shown in table 13.
TABLE 13 twist angle of each bond of methylbutyl theophylline dicyanamide salt from the phosphonium salt
The hydrogen atom coordinates of the self-ignition ionic salt of methylbutyl theophylline dicyanamide salt prepared in this example
And isotropic atom shift parameter>
The analytical data are shown in Table 14.
TABLE 14 hydrogen atom coordinates and isotropic atom displacement parameters of methylbutyl theophylline dicyanamide salt self-ignition ionic salt
The physicochemical properties of the self-ignition ionic salt of methylbutyl theophylline dicyanamide salt prepared in this example were determined. The phase transition temperature (T) of the self-ignition ionic salt of the methylbutyl theophylline dicyanamide salt can be obtained g /T m ) At 112 ℃ and a thermal decomposition temperature (T) d ) At 221 deg.C, the density was 1.30 g.cm -3 。
Example 5
S1, weighing 3.60g (0.02 mol) of theophylline and 0.88g (0.022 mol) of sodium hydroxide, adding into a three-neck flask, adding acetonitrile, and introducing N 2 The gas was allowed to completely displace the air in the reactor with nitrogen. Placing in a constant temperature oil bath kettle preheated to 70 deg.C, stirring for 50min to completely dissolve theophylline, adding dropwise 16.20g (0.12 mol) bromobutene into the system, continuing reaction, and monitoring the reaction end point with silica gel plate to obtain alkene butyl theophylline solution (containing 7-alkene butyl theophylline and 9-alkene butyl theophylline in the solution)-enbutyl theophylline).
S2, filtering the system, filtering insoluble inorganic matters, concentrating and separating out the filtrate, filtering again, collecting the filtrate, and drying to obtain the alkene butyl theophylline (7-alkene butyl theophylline and 9-alkene butyl theophylline).
S3, dripping a mixed solution of 17.04g (0.12 mol) of methyl iodide and 2.92g (0.04 mol) of DMF into the alkenyl butyl theophylline (7-alkenyl butyl theophylline and 9-alkenyl butyl theophylline), continuing to react for 2 days, adding ethyl acetate to separate out after the reaction is finished, filtering, and drying the solid to obtain 4.62g of methyl alkenyl butyl theophylline iodized salt (namely 7-alkenyl butyl-9-methyl theophylline iodized salt and 7-methyl-9-alkenyl butyl theophylline iodized salt), wherein the yield is 61.44%.
S4, weighing 3.77g (0.01 mol) of methyl alkene butyl theophylline iodide salt and 2.09g (0.012 mol) of silver dicyandiamide, adding a proper amount of distilled water, placing in an oil bath kettle heated to 40 ℃, and continuing to react for 4 hours.
S5, after the reaction is finished, filtering, collecting filtrate, and drying to obtain 2.89g of the methyl alkene butyl theophylline dicyanamide salt spontaneous combustion ionic salt (namely 7-alkene butyl-9-methyl theophylline dicyanamide salt spontaneous combustion ionic salt and 7-methyl-9-alkene butyl theophylline dicyanamide salt spontaneous combustion ionic salt), wherein the yield is 91.75%.
As shown in fig. 13 and 14, the nmr spectrum of the pyrophoric salt of methallyl butyl theophylline dicyanamide salt prepared in this example was δ 5.83ppm (ddt, J =17.3, 10.2,7.1hz, 1h), 5.16-5.00ppm (m, 2H), 4.63ppm (t, J =6.6hz, 2h), 4.21ppm (s, 3H), 3.83ppm (s, 3H), 3.38ppm (s, 3H), 2.67ppm (q, J =6.7hz, 2h); the nuclear magnetic carbon spectra thereof are delta 154.18ppm,151.35ppm,139.91ppm,132.65ppm,119.30ppm,118.13ppm,107.98ppm,48.81ppm,37.13ppm,33.49ppm,31.66ppm and 28.70ppm; the Fourier infrared spectrum is 3400cm -1 ，2948cm -1 ，2140cm -1 ，1600cm -1 ，1448cm -1 ，1336cm -1 ，1060cm -1 ，932cm -1 ，732cm -1 (ii) a Calculated values for elemental analysis (%): c53.33, H5.43, N31.09; the experimental values are (%): c53.03, H5.63 and N31.18. The specific structure of the spontaneous combustion ionic salt of the methyl alkene butyl theophylline dicyanamide salt is as follows:
the physicochemical properties of the pyrophoric ion salt of methylen butyl theophylline dicyanamide salt prepared in this example were measured. Phase transition temperature (T) of spontaneous combustion ionic salt of methyl alkene butyl theophylline dicyanamide salt g /T m ) Is composed of<-70 ℃ and a thermal decomposition temperature (T) d ) At 215 ℃ and a density of 1.33g cm -3 。
Test example 1
The enthalpy of formation and density specific impulse of the ionic salt were calculated by Gaussian 09 software and EXPLO (Version 6.02) software. Wherein the enthalpy of formation of the ionic salt is calculated by the iso-bond reaction and the Born-Haber energy cycle method, as shown in FIG. 1. And calculating the specific impulse of the ionic salt by using EXPLO (Version 6.02) software according to the molecular composition of the autoignition ionic salt, the calculated formation enthalpy and the experimentally measured density. The calculation results are shown in table 15 below:
TABLE 15 Theine derived from the formation enthalpy and Density specific Impulse of the phosphonium salt
The measurement results show that the density specific impulse of the 5 ionic salts obtained by the method is far higher than that of unsymmetrical dimethylhydrazine (215.7 s.g.cm) which is a traditional propellant -3 ) And the excellent application potential is shown.
Test example 2
The ignition performance of the theophylline derived autoignition ionic salt synthesized by the application is researched by adopting an ignition observation platform provided with a microscopic high-speed camera, an online high-temperature infrared thermometer and a flame detector. The oxidant used in the test was 100% nitric acid. The test procedure was as follows: a drop of 100% nitric acid was added by a dropper to a beaker containing about 3mL of an ionic salt and the contact was observed for combustion and spontaneous ignition.
1. Testing equipment: the self-ignition testing device comprises a microscopic high-speed camera, an online high-temperature infrared thermometer and a flame detector.
2. The testing steps are as follows: the ionic salts obtained in examples 1 to 5 were reacted with 100% nitric acid and the ignitability was recorded by an auto-ignition test apparatus.
TABLE 16 statistical table of ignition delay time of ionic salt
The results in table 16 show that all 5 ionic salts synthesized in this application can spontaneously ignite with 100% nitric acid, and the ignition pattern is shown in fig. 2a and 2 b.
Based on the theophylline derived autoignition ionic salt described in any of the above embodiments, the present invention further provides an embodiment of an application of the theophylline derived autoignition ionic salt to an aerospace propellant:
specifically, the theophylline derived autoignition ionic salt is used for preparing the space propellant, and has the following effects: firstly, the heat stability is good, and the safety is higher; second, higher loading is available; and thirdly, more energy is provided for the propelling process.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A theophylline derived autoignition ionic salt is characterized in that the structural general formula of the theophylline derived autoignition ionic salt is as follows:
wherein R is selected from one of alkyl groups of 1 to 8 carbon atoms, Y - Selected from (CN) 2 N - 、(NO 2 )(CN)N - 、H 2 (CN) 2 B - One or more of (a).
2. Theophylline derived autoignition salt according to claim 1, wherein R is selected from one of methyl, ethyl, allyl, butyl, and alkene butyl.
3. The theophylline-derived autoignition ion salt of claim 2, wherein the theophylline-derived autoignition ion salt has a decomposition temperature greater than 200 ℃ and a density specific impulse greater than 330 s-g-cm -3 。
4. A process for the preparation of theophylline derived autoignition ion salts as claimed in any of claims 1 to 3 comprising the steps of:
under the condition of inert atmosphere and preheating and stirring, dissolving theophylline and strong base by adopting a first solvent, adding halogenated hydrocarbon, and reacting to obtain an alkyl theophylline solution; wherein, the alkyl in the halohydrocarbon is selected from one of the alkyl with 1 to 8 carbon atoms, the halogen is selected from one of Cl, br and I, and the preheating and stirring temperature is between 50 and 120 ℃;
filtering the alkyl theophylline solution, filtering insoluble inorganic substances, concentrating and separating out filtrate, filtering again, collecting filtrate, and drying to obtain alkyl theophylline;
adding a mixed solution of DMF and methyl iodide into the alkyl theophylline, reacting for 2-3 days, adding a second solvent, and filtering and drying to obtain alkyl methyl theophylline iodide salt;
dissolving the alkyl methyl theophylline iodide salt and cyanide by using distilled water, heating for reaction, and filtering and drying to obtain theophylline derived autoignition ionic salt; wherein the anion of the cyanide is selected from (CN) 2 N - 、(NO 2 )(CN)N - 、H 2 (CN)B - The cation in the cyanide is silver, the heating reaction temperature is 25-80 ℃, and the heating reaction time is 3-10 h.
5. The method for preparing the theophylline derived autoignition ion salt according to claim 4, wherein the molar ratio of the theophylline to the strong base is 1:1-1.2, the molar ratio of the theophylline to the halogenated hydrocarbon is 1:3-10, and the molar ratio of DMF to methyl iodide is 1:2-10.
6. The method for preparing the theophylline derivative autoignition ionic salt according to claim 5, wherein the molar ratio of the theophylline to the halogenated hydrocarbon is 1:5-8.
7. The method for preparing theophylline derived autoignition salt according to claim 4, wherein the inert atmosphere is at least one of nitrogen, argon, helium;
the strong base comprises: one or more of sodium hydroxide, potassium hydroxide, cesium carbonate, potassium carbonate, barium hydroxide and calcium hydroxide.
8. The method for preparing theophylline derived autoignition salt according to claim 4, wherein the first solvent comprises: one or more of N, N-dimethylformamide, chloroform, ethyl acetate, acetone, dichloromethane, N-methylpyrrolidone, tetrahydrofuran, dioxane, dimethyl sulfoxide, methyl ethyl ketone and acetonitrile;
the second solvent includes: one or more of ethyl acetate and diethyl ether.
9. The method for preparing theophylline derived autoignition ion salt according to claim 4, wherein the temperature of the heating reaction is 35-60 ℃; the heating reaction time is 5-6 h.
10. Use of theophylline-derived autoignition salts as claimed in any one of claims 1 to 3 in an aerospace propellant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211560076.0A CN115850279A (en) | 2022-12-05 | 2022-12-05 | Theophylline derived autoignition ionic salt and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211560076.0A CN115850279A (en) | 2022-12-05 | 2022-12-05 | Theophylline derived autoignition ionic salt and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115850279A true CN115850279A (en) | 2023-03-28 |
Family
ID=85670523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211560076.0A Pending CN115850279A (en) | 2022-12-05 | 2022-12-05 | Theophylline derived autoignition ionic salt and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115850279A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB933153A (en) * | 1958-11-21 | 1963-08-08 | Sandoz Ltd | Improvements in or relating to theophylline derivatives |
| CN107141312A (en) * | 2017-06-28 | 2017-09-08 | 北京理工大学 | A kind of tetrazolium cyano group borate ion liquid and preparation method thereof |
| CN112521338A (en) * | 2021-01-11 | 2021-03-19 | 郑州大学 | Spontaneous combustion ionic liquid containing tension ring structure and application |
| CN113149933A (en) * | 2020-01-22 | 2021-07-23 | 中山大学 | Compounds, methods for their preparation and their use as energetic materials |
-
2022
- 2022-12-05 CN CN202211560076.0A patent/CN115850279A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB933153A (en) * | 1958-11-21 | 1963-08-08 | Sandoz Ltd | Improvements in or relating to theophylline derivatives |
| CN107141312A (en) * | 2017-06-28 | 2017-09-08 | 北京理工大学 | A kind of tetrazolium cyano group borate ion liquid and preparation method thereof |
| CN113149933A (en) * | 2020-01-22 | 2021-07-23 | 中山大学 | Compounds, methods for their preparation and their use as energetic materials |
| CN112521338A (en) * | 2021-01-11 | 2021-03-19 | 郑州大学 | Spontaneous combustion ionic liquid containing tension ring structure and application |
Non-Patent Citations (4)
| Title |
|---|
| STEFAN ILIC 等: "Thermodynamic Hydricities of Biomimetic Organic Hydride Donors", 《J. AM. CHEM. SOC.》, vol. 140, 16 March 2018 (2018-03-16), pages 4569 * |
| 张计传 等: "富氮稠环含能化合物：平衡能量与稳定性的新一代含能材料", 《含能材料》, vol. 26, no. 11, 28 September 2018 (2018-09-28), pages 983 - 990 * |
| 王林剑 等: "嘧啶类含能化合物的分子设计与性能预测", 《化工新型材料》, vol. 49, no. 9, 30 September 2021 (2021-09-30), pages 179 - 187 * |
| 薛云娜 等: "新型多氮杂环阳离子十氢十硼酸盐的合成、表征及热性能", 《含能材料》, no. 03, 25 March 2016 (2016-03-25), pages 274 - 278 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101643481B (en) | Synthesis technique for obtaining difluoro oxalate lithium borate and di-oxalate lithium borate | |
| JP2014531415A (en) | Bisquaternary ammonium salt ionic liquid having two centers, process for its preparation and use | |
| JP2001220393A (en) | Alkylspiroboric acid salt to be used for electrochemical cell | |
| CN107141312A (en) | A kind of tetrazolium cyano group borate ion liquid and preparation method thereof | |
| CN112707418A (en) | Preparation method of lithium hexafluorophosphate | |
| CN101397305B (en) | Method for preparing bisoxalatoborate | |
| CN113264961A (en) | Novel phosphorus-nitrogen-containing DOPO flame retardant and preparation method and application thereof | |
| CN113793933B (en) | Lithium sulfide for solid electrolyte and preparation method and application thereof | |
| CN115850279A (en) | Theophylline derived autoignition ionic salt and preparation method thereof | |
| WO2024002386A1 (en) | Preparation method for lithium difluorophosphate and product obtained therefrom | |
| CN111137870B (en) | Lithium difluorophosphate, preparation method thereof and lithium ion battery electrolyte | |
| CN115304629B (en) | Preparation method of difluoro oxalic acid sodium borate | |
| CN115322174B (en) | Iodine-enriched energetic compound and preparation method and application thereof | |
| CN114275757B (en) | Preparation method of lithium difluorophosphate | |
| CN114085189B (en) | Preparation method and application of metal biimidazole salt ionic liquid catalyst | |
| US9196424B2 (en) | Double-center bipyridyl cationic ion liquid, preparation method therefor and use thereof | |
| US10249403B2 (en) | P(CN)3 reactions with lithium dicynamide producing metalated carbon phosphonitride extended solids | |
| CN112939751B (en) | Fluoren aromatic hydrocarbon macrocycle, preparation method thereof and application thereof in construction of functional conjugated band-shaped compound | |
| Ul Amin et al. | Synthesis of Ferrocene‐based Esters as Burning Rate Catalysts and their Anti‐migration Study | |
| CN102952058B (en) | Maleimide ionic liquid, and preparation method and application thereof | |
| CN110204473B (en) | Double-center cationic liquid for lithium battery and preparation method thereof | |
| CN115894493B (en) | Alkaloid derived ionic liquid based on dicyandiamide anions and preparation method thereof | |
| CN108329360B (en) | Ferrocene picrate ionic compound and preparation method thereof | |
| CN114790217B (en) | Boron-containing self-ignition ionic liquid and preparation method thereof | |
| CN112939708A (en) | Imidazole and pyrazole combustion rate catalyst containing ferrocenyl methyl-1, 2, 3-triazolyl group and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |