CN108250227A - Nitrogen heterocyclic ring double carbine subunit boranes ionic liquid and preparation method thereof - Google Patents
Nitrogen heterocyclic ring double carbine subunit boranes ionic liquid and preparation method thereof Download PDFInfo
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- CN108250227A CN108250227A CN201810227294.XA CN201810227294A CN108250227A CN 108250227 A CN108250227 A CN 108250227A CN 201810227294 A CN201810227294 A CN 201810227294A CN 108250227 A CN108250227 A CN 108250227A
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- triazoles
- subunit
- ionic liquid
- boranes
- alkyl
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 43
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 37
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 5
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 11
- 229910002027 silica gel Inorganic materials 0.000 claims description 11
- 229960001866 silicon dioxide Drugs 0.000 claims description 11
- 150000000178 1,2,4-triazoles Chemical class 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005649 metathesis reaction Methods 0.000 claims description 9
- -1 triazole halide Chemical class 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000446 fuel Substances 0.000 abstract description 6
- 239000003380 propellant Substances 0.000 abstract description 6
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000002269 spontaneous effect Effects 0.000 description 6
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 238000006197 hydroboration reaction Methods 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- SEAZNTDWFMFOKA-UHFFFAOYSA-N 4-ethyl-1,2,4-triazole Chemical class CCN1C=NN=C1 SEAZNTDWFMFOKA-UHFFFAOYSA-N 0.000 description 2
- UDUGWXQKDABZNV-UHFFFAOYSA-N 4-propyl-1,2,4-triazole Chemical class CCCN1C=NN=C1 UDUGWXQKDABZNV-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 2
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ZOMKCDYJHAQMCU-UHFFFAOYSA-N 4-butyl-1,2,4-triazole Chemical class CCCCN1C=NN=C1 ZOMKCDYJHAQMCU-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DFFDSQBEGQFJJU-UHFFFAOYSA-N butyl hydrogen carbonate Chemical class CCCCOC(O)=O DFFDSQBEGQFJJU-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000005682 diethyl carbonates Chemical class 0.000 description 1
- 150000005686 dimethyl carbonates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000033772 system development Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a kind of nitrogen heterocyclic ring double carbine subunit boranes ionic liquids and preparation method thereof.The structure of the nitrogen heterocyclic ring double carbine subunit boranes ionic liquid is shown in formula I.The method of compound, has main steps that shown in formula I：By 1,2,4 triazole and carbonats compound by alkylated reaction, then with halogenated hydrocarbons occur quaternary ammonium reaction, finally reacted with sodium borohydride, obtain target product.Ionic liquid provided by the present invention may be used as self-ignition type green propellant fuel, have the advantages such as ignition delay time is short, and water stability is good, and density specific impulse value is big.In Formulas I, R1Any one in alkyl；R2Any one in hydrocarbyl substituent.
Description
Technical field
The present invention relates to a kind of spontaneous combustion ionic liquid and preparation method thereof, specifically, being related to a kind of nitrogen heterocyclic ring double carbine
Subunit boranes ionic liquid and preparation method thereof.
Background technology
In recent years, with the continuous expansion of space technology and national defence, performance of propellant index has become influence and has promoted
The key factor of System Development.Hydrazine liquid propellant fuel endangers to environmental and human health impacts because its toxicity is big, volatility is high
Evil is big, to thermostimulation, shock impingement etc. it is external because it is more sensitive the shortcomings of, actual application value is restricted.
Ionic liquid (ILs), by spies such as its liquid journey is wide, steam forces down, designability is strong, physical and chemical performance stabilizations
Property, it is received significant attention in fields such as chemical, material, the energy.The beginning of this century, Edwards AFB of the U.S. are right first
The design of " containing can change " of anions and canons and " can burning ", proposes novel spontaneous combustion ion in theory in ionic liquid structure
The concept of liquid, this is finds optimum energetic material and provides for the engineer application of a certain specific crowd, environment, instrument
It may.Compared with traditional Hydrazine fuel, spontaneous combustion ionic liquid has environmental protection, safety, convenient for storage transport and practical operation etc.
Advantage.
Ideal propellant fuel requires it with extremely short ignition delay time, good water, thermal stability, high density
Specific impulse, it is environmental-friendly the features such as.However, the spontaneous combustion ionic liquid reported at present cannot still meet above-mentioned requirements simultaneously, such as：-N
(CN)2With-N (NO3) (CN) although class ionic liquid has good water stability, its ignition delay time is long；-BH4
With-Al (BH4)4For class ionic liquid although with shorter ignition delay time, its water stability is poor, is unfavorable for protecting for a long time
It deposits；-BH2(CN)2Although class ionic liquid has good water stability and shorter ignition delay time simultaneously, it is synthesized
Raw material is hypertoxic and expensive.Therefore, be directed to above-mentioned spontaneous combustion ionic liquid there are the problem of, design is novel containing can ionic liquid
Following area research heat will be become by taking into account the characteristics of short ignition delay time, water and thermal stability are good, density ratio is leapt high simultaneously
Point.
Invention content
It is double it is an object of the present invention to provide a kind of novel nitrogen azacyclo- in order to improve the deficiencies in the prior art
Cabbeen subunit boranes ionic liquid.Further object of the present invention is to provide above-mentioned nitrogen heterocyclic ring double carbine subunit boranes ionic liquid
The preparation method of body.
The technical scheme is that：A kind of nitrogen heterocyclic ring double carbine subunit boranes ionic liquid, structure such as Formulas I institute
Show：
Wherein R1Any one in alkyl；R2Any one in hydrocarbyl substituent.
It is preferred that the substituent R on No. 4 positions of 1,2,4- triazoles1Selected from methyl, ethyl, propyl or normal-butyl.It is preferred that 1,2,
Substituent R on No. 1,2 positions of 4- triazoles2Selected from alkyl or alkenyl or alkynyl.
The present invention also provides the preparation method of above-mentioned nitrogen heterocyclic ring double carbine subunit boranes ionic liquid, specific steps
For：
(1) carbonats compound is added to the mixture of 1,2,4- triazoles (compound shown in formula II) and carbonate
In, gained suspension is under nitrogen protection in back flow reaction；Volatile matter in reaction extraction raffinate, solvent washing, filtering is removed in vacuum
Solid impurity, filtrate revolving, obtains colourless liquid 4- alkyl -1,2,4- triazoles (compound shown in formula III)；
(2) the 4- alkyl -1,2 for obtaining step (1), 4- triazoles stir under nitrogen protection with halogenated hydrocarbons, and reflux is anti-
Quaternary ammonium reaction should occur, product is washed through solvent, rotated, and obtains weak yellow liquid 1,2- dialkyl -4- alkyl -1,2,4- tri-
Nitrogen azoles halide (compound shown in formula IV)；
(3) the 1,2- dialkyl -4- alkyl -1,2,4- triazoles halide that step (2) obtains is dissolved in sodium borohydride
It in toluene, stirs under nitrogen protection, metathesis reaction occurs for back flow reaction, and crude product is filtered, revolving, silica gel post separation carry
It is pure, obtain target product nitrogen heterocyclic ring double carbine subunit boranes ionic liquid (compound shown in Formulas I).
In formula III, R1Any one in alkyl；In formula IV, X is halogen, R2It is arbitrary in hydrocarbyl substituent
It is a kind of.
The temperature of back flow reaction is 120~200 DEG C in preferred steps (1), and reflux time is 16~20h.
Carbonats compound is dimethyl carbonate, diethyl carbonate, dipropyl carbonate or carbonic acid two in preferred steps (1)
One kind in N-butyl；Carbonate is one kind in potassium carbonate, sodium carbonate, magnesium carbonate or calcium carbonate；1,2,4- triazoles and carbon
The molar ratio of acid esters compound is 1:5~1:10；The molar ratio of carbonate and 1,2,4- triazoles is 1:2~1:4；It washs molten
Agent is chloroform, one kind in n-hexane, carbon tetrachloride.
Whipping temp is 60~90 DEG C in preferred steps (2), and reflux time is 24~48h；Stirring temperature in step (3)
It is 100~160 DEG C to spend, reflux time for 20~for 24 hours.
The molar ratio of 4- alkyl -1,2,4- triazoles and halogenated hydrocarbons is 1 in preferred steps (2):2~1:3, cleaning solvent is
One kind in n-hexane, carbon tetrachloride, ether.Halogenated hydrocarbons in preferred steps (2) is chloroethanes, vinyl chloride, n-propyl chloride
Or propargyl chloride.
The molar ratio of 1,2- dialkyl -4- alkyl -1,2,4- triazoles halide and sodium borohydride is in preferred steps (3)
1:2~1:4.
The volume ratio of ethyl acetate and n-hexane is 1 in silicagel column eluent in preferred steps (3):1~1:12.
Advantageous effect：
Ionic liquid provided by the present invention may be used as self-ignition type green propellant fuel, when having firing delay
Between short, the advantages such as water stability is good, and density specific impulse value is big.
Specific embodiment
It is for a more detailed description to the present invention with embodiment below.These embodiments are only to the best embodiment party of the present invention
The description of formula, does not have any restrictions to protection scope of the present invention.
Embodiment 1
The preparation of two subunit borine ionic liquids of 1,2- diethyl -4- methyl -3,5-
Formulas Ia：
250mmol dimethyl carbonates are added to 50mmol 1,2,4- triazoles and 12.5mmol sodium carbonate by step 1.
In mixture, gained suspension is under nitrogen protection in 120 DEG C of stirrings, condensing reflux 16h.It is removed in vacuum in reaction extraction raffinate and volatilizees
Object, with chloroform debris, filtering solid contaminants, filtrate revolving obtains colourless liquid 4- methyl-1s, 2,4- triazoles
3.74g。
Step 2. stirs 40mmol 4- methyl-1s, 2,4- triazoles with 80mmol chloroethanes in 60 DEG C under nitrogen protection
It mixes, quaternary ammonium reaction occurs for 24 hours for condensing reflux, and reaction product is washed with n-hexane, rotated, and obtains weak yellow liquid 1,2- diethyls
Base -4- methyl-1s, 2,4- triazole chlorides 7.80g.
For step 3. by 35mmol 1,2- diethyl -4- methyl-1s, 2,4- triazoles chloride and 70mmol sodium borohydrides are molten
In 80ml toluene, under nitrogen protection in 100 DEG C of stirrings, condensing reflux 20h completes metathesis reaction, filtration of crude product, rotation
Silicagel column purification is crossed after steaming, eluent uses ethyl acetate and n-hexane volume ratio as 1:1 mixed liquor obtains white solid production
Object (Formulas IaShown compound) 3.51g.
Embodiment 2
The preparation of two subunit borine ionic liquids of 1,2- divinyl -4- methyl -3,5-
Formulas Ib：
Step 1. step is identical with step 1 preparation process in embodiment one.
Step 2. is by 40mmol 4- methyl-1s, and 2,4- triazoles are with 100mmol vinyl chlorides under nitrogen protection in 70 DEG C
Stirring, condensing reflux 36h complete quaternary ammonium reaction, and reaction product is washed with carbon tetrachloride, rotated, and obtains weak yellow liquid 1,2-
Divinyl -4- methyl-1s, 2,4- triazole chlorides 7.65g.
Step 3. is by 35mmol 1,2- divinyl -4- methyl-1s, 2,4- triazoles chloride and 100mmol hydroborations
Sodium is dissolved in 80ml toluene, and under nitrogen protection in 140 DEG C of stirrings, condensing reflux 20h completes metathesis reaction, crude product mistake
Silicagel column purification is crossed after filter, revolving, eluent uses ethyl acetate and n-hexane volume ratio as 1:4 mixed liquor obtains colourless
Product liquid (Formulas IbShown compound) 3.48g.
Embodiment 3
The preparation of two subunit borine ionic liquids of 1,2- divinyl -4- ethyls -3,5-
Formulas Ic：
400mmol diethyl carbonates are added to the mixed of 50mmol 1,2,4- triazoles and 20mmol potassium carbonate by step 1.
It closes in object, gained suspension is under nitrogen protection in 170 DEG C of stirrings, condensing reflux 18h.It is removed in vacuum in reaction extraction raffinate and volatilizees
Object, with n-hexane debris, filtering solid contaminants, filtrate revolving obtains colourless liquid 4- ethyls -1,2,4- triazoles
4.37g。
Step 2. is by 40mmol 4- ethyl -1,2,4- triazoles and 100mmol vinyl chlorides under nitrogen protection in 70 DEG C
Stirring, condensing reflux 36h complete quaternary ammonium reaction, and reaction product is washed with carbon tetrachloride, rotated, and obtains weak yellow liquid 1,2-
Divinyl -4- ethyl -1,2,4- triazole chlorides 8.17g.
Step 3. is by 35mmol 1,2- divinyl -4- ethyls -1,2,4- triazoles chlorides and 100mmol hydroborations
Sodium is dissolved in 80ml toluene, and under nitrogen protection in 140 DEG C of stirrings, condensing reflux 20h completes metathesis reaction, crude product mistake
Silicagel column purification is crossed after filter, revolving, eluent uses ethyl acetate and n-hexane volume ratio as 1:6 mixed liquor obtains colourless
Product liquid (Formulas IcShown compound) 3.84g.
Embodiment 4
The preparation of two subunit borine ionic liquids of 1,2- dipropyl -4- ethyls -3,5-
Formulas Id：
Step 1. step is identical with step 1 preparation process in embodiment 3.
Step 2. is by 40mmol 4- ethyl -1,2,4- triazoles and 120mmol n-propyl chlorides under nitrogen protection in 90
DEG C stirring, condensing reflux 48h complete quaternary ammonium reaction, and reaction product washed with ether, rotated, and obtains weak yellow liquid 1,2- bis-
Propyl -4- ethyl -1,2,4- triazole chlorides 9.25g.
Step 3. is by 35mmol 1,2- dipropyl -4- ethyls -1,2,4- triazoles chlorides and 140mmol sodium borohydrides
It is dissolved in 80ml toluene, is stirred under nitrogen protection in 150 DEG C, condensing reflux 22h completion metathesis reactions, filtration of crude product,
Revolving, crosses silicagel column purification, and eluent uses ethyl acetate and n-hexane volume ratio as 1:10 mixed liquor, obtains colourless liquid
Product (Formulas IdShown compound) 4.24g.
Embodiment 5
The preparation of two subunit borine ionic liquids of 1,2- diethyl -4- propyl -3,5-
Formulas Ie：
450mmol dipropyl carbonates are added to the mixed of 50mmol 1,2,4- triazoles and 25mmol calcium carbonate by step 1.
It closes in object, gained suspension is under nitrogen protection in 190 DEG C of stirrings, condensing reflux 19h.It is removed in vacuum in reaction extraction raffinate and volatilizees
Object, with carbon tetrachloride debris, filtering solid contaminants, filtrate revolving obtains colourless liquid 4- propyl -1,2,4- triazoles
4.77g。
Step 2. stirs 40mmol 4- propyl -1,2,4- triazoles with 100mmol chloroethanes in 75 DEG C under nitrogen protection
It mixes, condensing reflux 48h completes quaternary ammonium reaction, and reaction product is washed with n-hexane, rotated, and obtains weak yellow liquid 1,2- diethyls
Base -4- propyl -1,2,4- triazole chlorides 8.78g.
Step 3. is by 35mmol 1,2- diethyl -4- propyl -1,2,4- triazoles chlorides and 120mmol sodium borohydrides
It is dissolved in 80ml toluene, under nitrogen protection in 160 DEG C of stirrings, condensing reflux completes metathesis reaction for 24 hours, filtration of crude product,
Revolving, crosses silicagel column purification, and eluent uses ethyl acetate and n-hexane volume ratio as 1:12 mixed liquor, obtains colourless liquid
Product (Formulas IeShown compound) 3.96g.
Embodiment 6
The preparation of two subunit borine ionic liquids of 1,2- diethyl -4- normal-butyls -3,5-
Formulas If：
500mmol n-butyl carbonates are added to 50mmol 1,2,4- triazoles and 25mmol magnesium carbonate by step 1.
In mixture, gained suspension is under nitrogen protection in 200 DEG C of stirrings, condensing reflux 20h.It is removed in vacuum in reaction extraction raffinate and volatilizees
Object, with carbon tetrachloride debris, filtering solid contaminants, filtrate revolving obtains colourless liquid 4- normal-butyls -1,2, tri- nitrogen of 4-
Azoles 5.25g.
Step 2. is by 40mmol 4- normal-butyl -1,2,4- triazoles and 100mmol chloroethanes under nitrogen protection in 90 DEG C
Stirring, condensing reflux 48h complete quaternary ammonium reaction, and reaction product is washed with n-hexane, rotated, and obtains weak yellow liquid 1,2- bis-
Ethyl -4- normal-butyl -1,2,4- triazole chlorides 9.25g.
Step 3. is by 35mmol 1,2- diethyl -4- normal-butyls -1,2,4- triazoles chlorides and 140mmol hydroborations
Sodium is dissolved in 80ml toluene, and under nitrogen protection in 160 DEG C of stirrings, condensing reflux completes metathesis reaction, crude product mistake for 24 hours
Filter, revolving, cross silicagel column purification, and eluent uses ethyl acetate and n-hexane volume ratio as 1:12 mixed liquor, obtains white
Solid product (Formulas IfShown compound) 4.17g.
Embodiment 7
The preparation of two subunit borine ionic liquids of 1,2- dipropargyl -4- methyl -3,5-
Formulas Ig：
Step 1. step is identical with step 1 preparation process in embodiment one.
Step 2. is by 40mmol 4- methyl-1s, and 2,4- triazoles are with 120mmol propargyl chlorides under nitrogen protection in 90 DEG C
Stirring, condensing reflux 48h complete quaternary ammonium reaction, and reaction product is washed with carbon tetrachloride, rotated, and obtains weak yellow liquid 1,2-
Dipropargyl -4- methyl-1s, 2,4- triazole chlorides 8.35g.
Step 3. is by 35mmol 1,2- dipropargyl -4- methyl-1s, 2,4- triazoles chloride and 140mmol hydroborations
Sodium is dissolved in 80ml toluene, and under nitrogen protection in 160 DEG C of stirrings, condensing reflux completes metathesis reaction, crude product mistake for 24 hours
Filter, revolving, cross silicagel column purification, and eluent uses ethyl acetate and n-hexane volume ratio as 1:10 mixed liquor obtains colourless
Product liquid (Formulas IgShown compound) 3.80g.
Embodiment 8
Test the physical and chemical performance of nitrogen heterocyclic ring double carbine subunit boranes ionic liquid provided by the invention, and with it is existing
The physical and chemical performance of propellant fuel uns-dimethylhydrazine be compared, the results are shown in Table 1.
Table 1
Note：1. above-mentioned novel spontaneous combustion ionic liquid (Formulas Ia~IgShown compound) the physical-chemical parameters such as without particular/special requirement,
The data obtained measures at 25 DEG C；
Uns-dimethylhydrazine 2. (UDMH) data come from bibliography：Chem.Eur.J.2015,21,13297-13301.
As shown in Table 1：Novel self-ignition type nitrogen heterocyclic ring double carbine subunit boranes ionic liquid (such as Formulas I provided by the inventionb
Shown compound) compared with using extensive uns-dimethylhydrazine (UDMH) at present, there is more stable physicochemical characteristics, higher
Loading density, the higher enthalpy of formation and vacuum specific impulse, while to water and air have preferable stability.
Claims (10)
1. a kind of nitrogen heterocyclic ring double carbine subunit boranes ionic liquid, structure is shown in formula I：
Wherein R1Any one in alkyl；R2Any one in hydrocarbyl substituent.
2. nitrogen heterocyclic ring double carbine subunit boranes ionic liquid as described in claim 1, it is characterised in that R1Selected from methyl, second
Base, propyl or normal-butyl.
3. nitrogen heterocyclic ring double carbine subunit boranes ionic liquid as described in claim 1, it is characterised in that R2Selected from alkyl or
Alkenyl or alkynyl.
4. a kind of method for preparing nitrogen heterocyclic ring double carbine subunit boranes ionic liquid as described in claim 1, specific to walk
Suddenly it is：
(1) carbonats compound is added in the mixture of 1,2,4- triazoles and carbonate, gained suspension is in nitrogen
In back flow reaction under gas shielded；Volatile matter in reaction extraction raffinate is removed in vacuum, solvent washs, filtering solid contaminants, and filtrate revolving obtains
To colourless liquid 4- alkyl -1,2,4- triazoles；
(2) the 4- alkyl -1,2 for obtaining step (1), 4- triazoles stir under nitrogen protection with halogenated hydrocarbons, back flow reaction hair
Raw quaternary ammonium reaction, product are washed through solvent, are rotated, and obtain weak yellow liquid 1,2- dialkyl -4- alkyl -1,2,4- triazoles
Halide；
(3) the 1,2- dialkyl -4- alkyl -1,2,4- triazoles halide that step (2) obtains is dissolved in toluene with sodium borohydride
In, it stirring under nitrogen protection, metathesis reaction occurs for back flow reaction, and crude product is filtered, revolving, silicagel column separating-purifying,
Obtain target product nitrogen heterocyclic ring double carbine subunit boranes ionic liquid.
5. method as claimed in claim 4, it is characterised in that the temperature of back flow reaction is 120~200 DEG C in step (1), is returned
The stream reaction time is 16~20h.
6. method as claimed in claim 4, it is characterised in that carbonats compound is dimethyl carbonate, carbon in step (1)
One kind in diethyl phthalate, dipropyl carbonate or n-butyl carbonate；Carbonate is potassium carbonate, sodium carbonate, magnesium carbonate or carbonic acid
One kind in calcium；The molar ratio of 1,2,4- triazoles and carbonats compound is 1:5~1:10；Carbonate and tri- nitrogen of 1,2,4-
The molar ratio of azoles is 1:2~1:4；Cleaning solvent is chloroform, one kind in n-hexane, carbon tetrachloride.
7. method as claimed in claim 4, it is characterised in that whipping temp is 60~90 DEG C in step (2), during back flow reaction
Between be 24~48h；Whipping temp is 100~160 DEG C in step (3), reflux time for 20~for 24 hours.
8. preparation method as claimed in claim 4, it is characterised in that：In step (2) 4- alkyl -1,2,4- triazoles with it is halogenated
The molar ratio of hydrocarbon is 1:2~1:3, cleaning solvent is n-hexane, one kind in carbon tetrachloride, ether.
9. preparation method as claimed in claim 4, it is characterised in that：1,2- dialkyl -4- alkyl -1,2,4- in step (3)
The molar ratio of triazole halide and sodium borohydride is 1:2~1:4.
10. method as claimed in claim 4, it is characterised in that in step (3) in silicagel column eluent ethyl acetate with just oneself
The volume ratio of alkane is 1:1~1:12.
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