CN107118170A - A kind of preparation method of azoxy tetrazolium - Google Patents
A kind of preparation method of azoxy tetrazolium Download PDFInfo
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- CN107118170A CN107118170A CN201710556316.2A CN201710556316A CN107118170A CN 107118170 A CN107118170 A CN 107118170A CN 201710556316 A CN201710556316 A CN 201710556316A CN 107118170 A CN107118170 A CN 107118170A
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- tetrazolium
- bis
- azoxy
- triazenes
- azoxies
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
- C07D257/06—Five-membered rings with nitrogen atoms directly attached to the ring carbon atom
Abstract
The present invention relates to a kind of preparation method of azoxy tetrazolium, belong to organic synthesis and energetic material field.Methods described is with 1,3 two (substitution tetrazole radical) triazenes are raw material, substitution 5, the 5' azoxy tetrazoliums of 2,2' bis- are prepared using fuming nitric aicd and acid anhydrides, simply, efficiently, preparation 2 can be significantly improved, 2' bis- replaces the yield of 5,5' azoxy tetrazoliums, yield can reach 53~82%, or from 5 Aminotetrazoles of substitution be that to calculate yield be 44%~71% to raw material.
Description
Technical field
The present invention relates to a kind of preparation method of azoxy tetrazolium, specifically, it is related to one kind 2,2'- bis- and replaces -5,
The preparation method of 5'- azoxy tetrazoliums, belongs to organic synthesis and energetic material field.
Background technology
Azoxy structure, which is applied to energy-containing compound, can not only keep the good heat endurance of azo-compound and machinery
Sensitivity, also by introducing oxygen atom raising density and improving oxygen balance (Zhang J, Shreeve J
M.Nitroaminofurazans with Azo and Azoxy Linkages:A Comparative Study of
Structural,Electronic,Physicochemical,and Energetic Properties[J],Journal of
Physical Chemistry C,2015,119,12887–12895.).Wherein, azoxy tetrazolium have higher energy and
Good heat endurance, is rare azoxy energy-containing compound (Fischer N, et in addition to azoxy furazan
al.5,5'-Azoxytetrazolates–a new nitrogen-rich dianion and its comparison to
5,5'-azotetrazolate[J].Dalton Transactions,2012,41,11201–11211.).And it is even to limit oxidation
The biggest obstacle that N structure is applied in energy-containing compound is the scarcity of its synthetic method.
The method of existing several synthesis azoxy structures, including amino group (Coburn M D.Oxidation of
heterocyclic nitrogen ylides to nitro heterocycles.Comparison of a
sulfilimine and a phosphine imine[J].Journal of Heterocyclic Chemistry,1986,
23,421-423.), nitro reduction (Cravotto G, et al.An Easy Access to Aromatic Azo
Compounds under Ultrasound/Microwave Irradiation[J].Synlett,2006,2605–2608.)
Or azido nitrogen rejection oxidation (Shaforosta K V, et al.4-Azidoquinoline N-Oxide:Synthesis
And Photolysis [J] .Russian Journal of Organic Chemistry, 2008,44,728-730.) etc., most
The intermediate of nitrous based structures will be passed through eventually, further coupling obtains azoxy compound.Because amino-compound is phase
To the raw material for being easiest to obtain, so amino group method is also the current synthesis topmost method of azoxy compound, but by
Formation always with nitro compound and azo-compound is reacted in amino group, and most reaction azoxy compounds are only
For accessory substance, therefore most of reaction yields are all very low.Passing through using substitution -5- Aminotetrazoles as raw material for current document report is straight
Connect oxidizing process prepare 2,2'- bis- replace -5,5'- azoxy tetrazoliums maximum output be 35% (Churakov A M, et
al.The oxidation of heterocyclic amines to nitro compounds using dinitrogen
pentoxide[J].Mendeleev Communications,1995,5,102–103.)。
The content of the invention
The defect existed for prior art, it is an object of the invention to provide a kind of preparation side of azoxy tetrazolium
Method, methods described is simple, efficient, can significantly improve preparation 2,2'- bis- replaces the yield of -5,5'- azoxy tetrazoliums.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of azoxy tetrazolium, methods described step is：
Method one
By hair that (substitution tetrazole radical) triazenes of 1,3- bis- and mass fraction are 80%~100% at -15 DEG C~10 DEG C
Cigarette nitric acid is according to 1:10~30 mol ratio carries out being mixed to get reaction solution, by reaction solution in 0 DEG C~25 DEG C stirring reactions
6h~48h；Then in -15 DEG C~10 DEG C addition acid anhydrides, the mol ratio of fuming nitric aicd and acid anhydrides is 1:1~3；At 0 DEG C~25 DEG C
Continue to react after 1h~12h, reaction solution is poured into frozen water, extract, dry, vacuum distillation, then using silica gel column chromatography partition method
Separated, again vacuum distillation, obtain the azoxy tetrazolium, be that 2,2'- bis- replaces -5,5'- azoxy tetrazoliums；Or
Method two
By 1,3- bis- (substitution tetrazole radical) triazenes, the smoke that mass fraction is 80%~100% at -15 DEG C~10 DEG C
Nitric acid and acid anhydrides are according to 1:10~30:10~90 mol ratio, and fuming nitric aicd is not more than 1 with anhydride molar ratio:1 is mixed
Conjunction obtains reaction solution；By reaction solution after 0 DEG C~25 DEG C stirring reaction 4h~24h, reaction solution is poured into frozen water, extracted,
Dry, vacuum distillation, then separated using silica gel column chromatography partition method, vacuum distillation again obtains the azoxy four
Azoles, is that 2,2'- bis- replaces -5,5'- azoxy tetrazoliums.
The 2,2'- bis- replaces -5,5'- azoxies tetrazolium for 2,2'- dimethyl -5,5'- azoxies tetrazolium, 2,
2'- diethyl -5,5'- azoxies tetrazolium, 2,2'- diisopropyl -5,5'- azoxies tetrazolium, 2,2'- di-t-butyl -5,
5'- azoxies tetrazolium, 2,2'- dicyan methyl -5,5'- azoxies tetrazolium, 2,2'- dibromoethyl -5,5'- azoxies four
Azoles, 2,2'- dimethoxy acyl methyl -5,5'- azoxies tetrazolium, 2,2'- diacetyl methyl -5,5'- azoxies tetrazolium, 2,
Carboxymethyl -5,5'- azoxies the tetrazoliums of 2'- bis- or 2,2'- dinitric acid ester group ethyl -5,5'- azoxy tetrazoliums.
1,3- bis- (substitution tetrazole radical) triazenes is 1,3- bis- (2- methyl tetrazolium -5- bases) triazenes, (2- of 1,3- bis-
Ethyl tetrazolium -5- bases) triazenes, 1,3- bis- (2- isopropyl tetrazolium -5- bases) triazenes, (the 2- tert-butyl group tetrazoliums -5- of 1,3- bis-
Base) triazenes, 1,3- bis- (2- cyanogen methyl tetrazolium -5- bases) triazenes, 1,3- bis- (2- bromoethyl tetrazolium -5- bases) triazenes, 1,
3- bis- (2- methoxy acyl methyl tetrazolium -5- bases)-triazenes, 1,3- bis- (2- acetonyl tetrazolium -5- bases) triazenes, 1,3- bis-
(2- carboxymethyl tetrazolium -5- bases) triazenes or 1,3- bis- (2- ethoxy tetrazolium -5- bases) triazenes.
It is preferred that the acid anhydrides be acetic anhydride, propionic andydride, n butanoic anhydride, isobutyric anhydride, valeric anhydride, isovaleric anhydride, caproic anhydride,
One or more of succinic anhydride, glutaric anhydride, benzoyl oxide and TFAA.
Beneficial effect
The invention provides a kind of preparation method of azoxy tetrazolium, methods described is with 1,3- bis- (substitution tetrazole radical) three
Nitrence is raw material, and preparing 2,2'- bis- using fuming nitric aicd and acid anhydrides replaces -5,5'- azoxy tetrazoliums, simple, efficient,
Preparation 2 can be significantly improved, 2'- bis- replaces the yield of -5,5'- azoxy tetrazoliums, yield can reach 53~82%, or from taking
Generation -5- Aminotetrazoles are that raw material calculating yield is 44%~71%.
Brief description of the drawings
Fig. 1 is the mono-crystalline structures figure of the 2,2'- dimethyl -5,5'- azoxy tetrazoliums prepared in embodiment 1.
Fig. 2 is the means of differential scanning calorimetry (DSC) of the 2,2'- dimethyl -5,5'- azoxy tetrazoliums prepared in embodiment 1
Figure.
Fig. 3 is the infrared spectrum of the 2,2'- dimethyl -5,5'- azoxy tetrazoliums prepared in embodiment 1.
Fig. 4 is the nucleus magnetic hydrogen spectrum figure of the 2,2'- dimethyl -5,5'- azoxy tetrazoliums prepared in embodiment 1.
Fig. 5 is the nuclear-magnetism carbon spectrogram of the 2,2'- dimethyl -5,5'- azoxy tetrazoliums prepared in embodiment 1.
Fig. 6 is the DSC figures of the 2,2'- dicyan methyl -5,5'- azoxy tetrazoliums prepared in embodiment 2.
Fig. 7 is the infrared spectrum of the 2,2'- dicyan methyl -5,5'- azoxy tetrazoliums prepared in embodiment 2.
Fig. 8 is the nucleus magnetic hydrogen spectrum figure of the 2,2'- dicyan methyl -5,5'- azoxy tetrazoliums prepared in embodiment 2.
Fig. 9 is the nuclear-magnetism carbon spectrogram of the 2,2'- dicyan methyl -5,5'- azoxy tetrazoliums prepared in embodiment 2.
Figure 10 is the high resolution mass spectrum figure of the 2,2'- dicyan methyl -5,5'- azoxy tetrazoliums prepared in embodiment 2.
Figure 11 is the nucleus magnetic hydrogen spectrum of the 2,2'- dinitric acid ester group ethyl -5,5'- azoxy tetrazoliums prepared in embodiment 3
Figure.
Figure 12 is the nuclear-magnetism carbon spectrum of the 2,2'- dinitric acid ester group ethyl -5,5'- azoxy tetrazoliums prepared in embodiment 3
Figure.
Embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description.
In following examples：
In silica gel column chromatography partition method, used silica gel is the column chromatography silica gel of the mesh of commercially available 200 mesh~300, and mobile phase is stone
The mixed solution of oily ether and ethyl acetate；
Rotary Evaporators：Model N1001, producer EYELA；
Micro-meldometer：XT4A (thermometer is not corrected), Beijing Fu Kai Instrument Ltd. of producer；
Differential scanning calorimeter：Model DSC-1, producer METTLER TOLEDO, heating rate during test for 5 DEG C/
min；
Infrared spectrometer：Model ALPHA FT-IR-Spektrometer, producer Bruker；
Nuclear magnetic resonance chemical analyser：Model Avance III 400M, producer Buruker；
Elemental analyser：Model Vario EL, producer Elementar；
Fourier ion involution Transform Mass Spectrometry：Model Apex IV, producer Bruker；
X-ray single crystal diffractometer：Model Saturn 724CCD, producer Rigaku.
Molal quantity × the 2,2'- bis- of theoretical yield=1,3- bis- (substitution tetrazole radical) triazenes replaces -5,5'- azoxies
The molal weight of tetrazolium；Yield=actual production/theoretical yield.
It is that raw material calculates yield=yield × substitution -5- Aminotetrazoles synthesis (substitutions of 1,3- bis- from substitution -5- Aminotetrazoles
Tetrazole radical) (document yield is with reference to Wang Q, et al.Pentazadiene for the document yield of triazenes:a high-nitrogen
linkage in energetic materials[J].Chemical Communications,2017,53,2327–
2330.)。
Embodiment 1
The synthesis of 2,2'- dimethyl -5,5'- azoxy tetrazoliums
At 0 DEG C, by 0.5mmol 1,3- bis- (2- methyl tetrazolium -5- bases) triazenes adds 0.5mL mass fractions and is
Reaction solution is mixed to get in 92% fuming nitric aicd (10.9mmol), by reaction solution in 0 DEG C of stirring reaction 12h；Then 0
1.5mL acetic anhydrides (15.9mmol) are added dropwise to reaction solution at DEG C, continues to react 12h at 0 DEG C, reaction solution is poured into 15mL afterwards
In frozen water, it is extracted with ethyl acetate twice, the organic phase after separation merges, is extracted once with water successively afterwards, saturated aqueous common salt
Once, then the organic phase of separation is dried with anhydrous sodium sulfate for extraction, then dried organic phase is steamed using rotation
Hair instrument carries out vacuum distillation at 0.01MPa, 30 DEG C and removes solvent, is finally separated with silica gel column chromatography, mobile phase is petroleum ether
It is 1 with ethyl acetate volume ratio:1 mixed solution, reuses Rotary Evaporators at 0.01MPa, 30 DEG C by having after separation
Machine mutually carries out vacuum distillation and removes solvent, you can obtain end-product.
End-product prepared by the present embodiment is carried out to characterize and test as follows：
Prepared end-product quality is 56mg, and it is 53% to be computed that yield can be obtained, or is from 2- methyl -5- Aminotetrazoles
It is 44% that raw material, which calculates yield,.
Prepared end-product is characterized using X-ray single crystal diffractometer, its mono-crystalline structures figure is obtained, such as Fig. 1 institutes
Show.
Prepared end-product is tested using differential scanning calorimeter, it is 162 that its fusing point can be learnt from Fig. 2
DEG C, initial decomposition temperature is 208 DEG C.
Prepared end-product is characterized with infrared spectrometer, in Fig. 3 infared spectrum, 1513.22cm-1With
1491.04cm-1For the characteristic peak of azoxy structure, 1448.60cm-1And 1287.54cm-1For the characteristic peak of tetrazole ring.
Fig. 4 and Fig. 5 is characterized by nuclear magnetic resonance chemical analyser and obtained, Fig. 4 proton nmr spectra (400MHz, DMSO-
d6) in have one group 1 at 4.55ppm and 4.50ppm:1 unimodal, the methyl substitution in corresponding end-product on two tetrazole rings respectively
Base；Fig. 5 carbon-13 nmr spectra (100MHz, DMSO-d6) in two carbon in 165.5ppm tetrazole rings corresponding with 162.9ppm,
Two carbon of the methyl substituents on 41.1ppm tetrazole rings corresponding with 40.3ppm.
Prepared end-product is tested using elemental analyser, the mass fraction that test result is C is
The mass fraction that 23.17%, H mass fraction are 2.75%, N is 66.47% and 2,2'- dimethyl -5,5'- azoxy four
The theoretical value (C 22.86%, H 2.88%, N 66.65%) of each element is closely in azoles.
Prepared end-product is characterized using Fourier ion involution Transform Mass Spectrometry, [M+Na] measured+Molecule
Measure [M+Na] for 233.0613 and 2,2'- dimethyl -5,5'- azoxy tetrazoliums+The almost phase of theoretical molecular 233.0618
Deng.
From above-mentioned characterization result, the end-product prepared by the present embodiment is 2,2'- dimethyl -5,5'- azoxies
Tetrazolium.
Calculated by Gaussian 09 (Revision is B.01) software, prepared 2,2'- dimethyl -5 can be predicted,
The enthalpy of formation of 5'- azoxy tetrazoliums is 519.8kJmol-1, density is 1.57gcm-3, can be pre- with software EXPLO5
The prediction explosion velocity for estimating 2,2'- dimethyl -5,5'- azoxy tetrazoliums is 7465ms-1, detonation pressure is 19.0GPa, and quick-fried heat is
3945J·g-1。
Embodiment 2
The synthesis of 2,2'- dicyan methyl -5,5'- azoxy tetrazoliums
At -15 DEG C, by 0.5mmol 1,3- bis- (2- cyanogen methyl tetrazolium -5- bases) triazenes adds 0.25mL mass fractions
To be mixed to get reaction solution in 100% fuming nitric aicd (5.9mmol), by reaction solution in 25 DEG C of stirring reaction 6h；Then
0.8mL propionic andydrides (6.2mmol) are added dropwise to reaction solution at 10 DEG C, continues to react 1h at 25 DEG C, afterwards pours into reaction solution
In 15mL frozen water, it is extracted with ethyl acetate twice, the organic phase after separation merges, is extracted once with water successively afterwards, saturation food
Salt solution is extracted once, and then the organic phase of separation is dried with anhydrous sodium sulfate, then dried organic phase is used into rotation
Turn evaporimeter and vacuum distillation removing solvent is carried out at 0.01MPa, 30 DEG C, finally separated with silica gel column chromatography, mobile phase is stone
Oily ether is 1 with ethyl acetate volume ratio:1 mixed solution, reuses Rotary Evaporators at 0.01MPa, 30 DEG C by after separation
Organic phase carry out vacuum distillation remove solvent, you can obtain end-product.
End-product prepared by the present embodiment is carried out to characterize and test as follows：
Prepared end-product quality is 98mg, and it is 76% to be computed obtaining yield, or from 2- cyanogen methyl -5- Aminotetrazoles
It is 65% to calculate yield for raw material.
Prepared end-product is tested using differential scanning calorimeter, can learn that its starting is decomposed from Fig. 6
Temperature is 182 DEG C.
Prepared end-product is characterized with infrared spectrometer, in Fig. 7 infared spectrum, 1518.04cm-1With
1491.04cm-1For the characteristic peak of azoxy structure, 1413.88cm-1And 1347.34cm-1For the characteristic peak of tetrazole ring.
Fig. 8 and Fig. 9 is characterized by nuclear magnetic resonance chemical analyser and obtained, Fig. 8 proton nmr spectra (400MHz, DMSO-
d6) in have one group 1 at 6.46ppm and 6.40ppm:1 it is unimodal, the methylene in end-product on two tetrazole rings is corresponded to respectively and is taken
Dai Ji；Fig. 9 carbon-13 nmr spectra (100MHz, DMSO-d6) in two in 165.7ppm tetrazole rings corresponding with 163.2ppm
Two carbon of the cyano substituent on carbon, 113.2ppm tetrazole rings corresponding with 112.8ppm, 42.3ppm corresponding with 41.5ppm four
Two carbon of the methylene substituent on azoles ring.
Prepared end-product is characterized using Fourier ion involution Transform Mass Spectrometry, as a result as shown in Figure 10, surveyed
[the M-H]-molecular weight obtained is 259.0557 [M-H]-theoretical moleculars with 2,2'- dicyan methyl -5,5'- azoxy tetrazoliums
259.0558 it is almost equal.
From above-mentioned characterization result, the end-product prepared by the present embodiment aoxidizes even for 2,2'- dicyan methyl -5,5'-
Nitrogen tetrazolium.
Calculated by Gaussian 09 (Revision is B.01) software, can predict prepared 2,2'- dicyan methyl-
The enthalpy of formation of 5,5'- azoxy tetrazoliums is 869.0kJmol-1, density is 1.58gcm-3, can be with software EXPLO5
The prediction explosion velocity for estimating 2,2'- dicyan methyl -5,5'- azoxy tetrazoliums is 7262ms-1, detonation pressure is 18.7GPa, and quick-fried heat is
4379J·g-1。
Embodiment 3
The synthesis of 2,2'- dinitric acid ester group ethyl -5,5'- azoxy tetrazoliums
At 10 DEG C, by 0.5mmol 1,3- bis- (2- ethoxy tetrazolium -5- bases) triazenes adds 0.75mL mass fractions
To be mixed to get reaction solution in 80% fuming nitric aicd (13.9mmol), by reaction solution in 25 DEG C of stirring reaction 48h；Then
5.5mL TFAAs (39.0mmol) are added dropwise to reaction solution at -15 DEG C, continue to react 6h at 0 DEG C, afterwards by reaction solution
Pour into 15mL frozen water, be extracted with ethyl acetate twice, the organic phase after separation merges, extracted once with water successively afterwards, satisfied
With saline solution extraction once, then the organic phase of separation is dried with anhydrous sodium sulfate, then dried organic phase is made
Vacuum distillation is carried out at 0.01MPa, 30 DEG C with Rotary Evaporators and removes solvent, is finally separated with silica gel column chromatography, mobile phase
It is that petroleum ether and ethyl acetate volume ratio are 2:1 mixed solution, reusing Rotary Evaporators will divide at 0.01MPa, 30 DEG C
Organic phase from after carries out vacuum distillation and removes solvent, you can obtain end-product.
End-product prepared by the present embodiment is carried out to characterize and test as follows：
Prepared end-product quality is 148mg, and it is 82% to be computed obtaining yield, or from 2- ethoxy -5- amino four
Azoles is that raw material calculating yield is 57%.
Prepared end-product is tested using differential scanning calorimeter, understands that its fusing point is 114 DEG C by result, rises
Beginning decomposition temperature is 175 DEG C.
Prepared end-product is characterized with infrared spectrometer, 1635.71cm-1For the characteristic peak of itrate group,
1521.90cm-1And 1507.43cm-1For the characteristic peak of azoxy structure, 1457.28cm-1And 1283.68cm-1For tetrazole ring
Characteristic peak.
Figure 11 and Figure 12 is characterized by nuclear magnetic resonance chemical analyser and obtained, Figure 11 proton nmr spectra (400MHz,
DMSO-d6) in have one group 1 at 5.34ppm and 5.29ppm:1 it is unimodal, correspond to respectively close in ethyl substituent in end-product
The methylene of tetrazole ring, should be triplet, but due to split point not substantially thus with it is similar it is unimodal occur, and the list at 5.12ppm
Peak is that the methylene of close itrate group in two ethyl substituents overlaps generation；Figure 12 carbon-13 nmr spectra (100MHz,
DMSO-d6) in two carbon in 165.7ppm tetrazole rings corresponding with 163.2ppm, and 70.2ppm, 69.9ppm, 52.0ppm and
Four carbon of 51.2ppm correspondence both sides ethyl substituents.
Prepared end-product is characterized using Fourier ion involution Transform Mass Spectrometry, [M+H] measured+Molecular weight
For 361.0712 [M+H] with 2,2'- dinitric acid ester group ethyl -5,5'- azoxy tetrazoliums+Theoretical molecular more than 361.0712
It is equal.
From above-mentioned characterization result, the end-product prepared by the present embodiment is 2,2'- dinitric acid ester group ethyls -5,5'-
Azoxy tetrazolium.
Calculated by Gaussian 09 (Revision is B.01) software, prepared 2,2'- dinitrates can be predicted
The enthalpy of formation of base ethyl -5,5'- azoxy tetrazoliums is 345.4kJmol-1, density is 1.68gcm-3, with software
The prediction explosion velocity that EXPLO5 can estimate 2,2'- dinitric acid ester group ethyl -5,5'- azoxy tetrazoliums is 8066ms-1, detonation pressure
For 25.8GPa, quick-fried heat is 4944Jg-1。
Embodiment 4
The synthesis of 2,2'- dibromoethyl -5,5'- azoxy tetrazoliums
At -15 DEG C, by 0.5mmol 1,3- bis- (2- bromoethyl tetrazolium -5- bases) triazenes adds 1.201g succinic anhydrides
(12.0mmol) and 0.5mL mass fractions react molten in the solution of 95% fuming nitric aicd (11.3mmol) be mixed to get
Liquid；By reaction solution in 0 DEG C of stirring reaction 24h, reaction solution is poured into 15mL frozen water afterwards, is extracted with ethyl acetate twice,
Organic phase after separation merges, and is extracted once with water successively afterwards, and saturated aqueous common salt is extracted once, then with anhydrous sodium sulfate pair
The organic phase of separation is dried, then dried organic phase is depressurized using Rotary Evaporators at 0.01MPa, 30 DEG C
Solvent is distilled off, is finally separated with silica gel column chromatography, mobile phase is petroleum ether and ethyl acetate volume ratio is 2:1 mixing is molten
Liquid, reuses Rotary Evaporators and the organic phase after separation is carried out into vacuum distillation removing solvent at 0.01MPa, 30 DEG C, you can
Obtain end-product.
End-product prepared by the present embodiment is carried out to characterize and test as follows：
Prepared end-product quality is 158mg, and it is 80% to be computed obtaining yield, or from 2- bromoethyl -5- amino four
Azoles is that raw material calculating yield is 71%.
Prepared end-product is tested using micro-meldometer, its fusing point is obtained for 124 DEG C~125 DEG C.
Prepared end-product is characterized with infrared spectrometer, 1513.22cm-1And 1491.04cm-1It is even for oxidation
The characteristic peak of N structure, 1437.99cm-1And 1302.97cm-1For the characteristic peak of tetrazole ring.
Proton nmr spectra (400MHz, DMSO-d6) in have one group 1 at 5.35ppm and 5.29ppm:1 triplet, point
Methylene that Dui Ying be in end-product in ethyl substituent close to tetrazole ring, and one group 1 at 4.11ppm and 4.09ppm:1
Triplet is the methylene of close bromine atoms in ethyl substituent；Carbon-13 nmr spectra (100MHz, DMSO-d6) in 165.6ppm
Two carbon in tetrazole ring corresponding with 163.1ppm, and 55.9ppm, 55.0ppm, 29.8ppm both sides ethyl corresponding with 29.3ppm
Four carbon of substituent.
Prepared end-product is characterized using Fourier ion involution Transform Mass Spectrometry, [M+H] measured+Molecular weight
For 394.9320 [M+H] with 2,2'- dibromoethyl -5,5'- azoxy tetrazoliums+The almost phase of theoretical molecular 394.9322
Deng.
From above-mentioned characterization result, the material prepared by the present embodiment is 2,2'- dibromoethyl -5,5'- azoxies
Tetrazolium.
Embodiment 5
The synthesis of 2,2'- dimethoxy acyl methyl -5,5'- azoxy tetrazoliums
At 10 DEG C, by 0.5mmol 1,3- bis- (2- methoxy acyl methyl tetrazolium -5- bases) triazenes adds 8mL isovaleric anhydrides
(41.0mmol) and 0.75mL mass fractions are mixed to get reaction for progress in the solution of 86% fuming nitric aicd (15.0mmol)
Solution；By reaction solution in 25 DEG C of stirring reaction 4h, reaction solution is poured into 15mL frozen water afterwards, two are extracted with ethyl acetate
Secondary, the organic phase after separation merges, and is extracted once with water successively afterwards, and saturated aqueous common salt is extracted once, then uses anhydrous slufuric acid
The organic phase of separation is dried sodium, then dried organic phase is carried out using Rotary Evaporators at 0.01MPa, 30 DEG C
Vacuum distillation removes solvent, is finally separated with silica gel column chromatography, and mobile phase is petroleum ether and ethyl acetate volume ratio is 2:1 it is mixed
Solution is closed, Rotary Evaporators is reused and the organic phase after separation is subjected to vacuum distillation removing solvent at 0.01MPa, 30 DEG C,
It can obtain end-product.
End-product prepared by the present embodiment is carried out to characterize and test as follows：
Prepared end-product quality is 124mg, and it is 76% to be computed obtaining yield, or from 2- methoxy acyl methyl -5- ammonia
Base tetrazolium is that raw material calculating yield is 63%.
Prepared end-product is tested using micro-meldometer, its fusing point is obtained for 133 DEG C~134 DEG C.
Prepared end-product is characterized with infrared spectrometer, 1746.62cm-1For the characteristic peak of ester group,
1514.19cm-1And 1495.86cm-1For the characteristic peak of azoxy structure, 1441.85cm-1And 1244.14cm-1For tetrazole ring
Characteristic peak.
Proton nmr spectra (400MHz, DMSO-d6) at 6.12ppm and 6.04ppm and 3.79ppm and 3.77ppm
There is two group 1:1 triplet, corresponds to end-product methylene and methyl substituents respectively；Carbon-13 nmr spectra (100MHz,
DMSO-d6) in two carbon in 166.3ppm tetrazole rings corresponding with 163.7ppm, 166.8ppm methoxy acyls corresponding with 166.3ppm
The carbonyl carbon of methyl, and the methylene and first of 55.3ppm, 54.5ppm, 53.7ppm both sides methoxy acyl methyl corresponding with 53.6ppm
Four carbon of base.
Prepared end-product is characterized using Fourier ion involution Transform Mass Spectrometry, [M+H] measured+Molecular weight
For 327.0904 [M+H] with 2,2'- dimethoxy acyl methyl -5,5'- azoxy tetrazoliums+Theoretical molecular 327.0908 is almost
It is equal.
From above-mentioned characterization result, the end-product prepared by the present embodiment is 2,2'- dimethoxy acyl methyl -5,5'- oxygen
Change azotetrazole.
In summary, presently preferred embodiments of the present invention is these are only, is not intended to limit the scope of the present invention.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the present invention's
Within protection domain.
Claims (2)
1. a kind of preparation method of azoxy tetrazolium, it is characterised in that：Methods described step is：
Method one
By smoke nitre that (substitution tetrazole radical) triazenes of 1,3- bis- and mass fraction are 80%~100% at -15 DEG C~10 DEG C
Acid is according to 1:10~30 mol ratio carries out being mixed to get reaction solution, by reaction solution 0 DEG C~25 DEG C stirring reaction 6h~
48h；Then in -15 DEG C~10 DEG C addition acid anhydrides, the mol ratio of fuming nitric aicd and acid anhydrides is 1:1~3；In 0 DEG C~25 DEG C continuation
React after 1h~12h, reaction solution is poured into frozen water, extract, dry, vacuum distillation, then carried out using silica gel column chromatography partition method
Separation, vacuum distillation again obtains the azoxy tetrazolium, is that 2,2'- bis- replaces -5,5'- azoxy tetrazoliums；Or
Method two
By 1,3- bis- (substitution tetrazole radical) triazenes, the fuming nitric aicd that mass fraction is 80%~100% at -15 DEG C~10 DEG C
And acid anhydrides is according to 1:10~30:10~90 mol ratio, and fuming nitric aicd is not more than 1 with anhydride molar ratio:1 mix
To reaction solution；By reaction solution after 0 DEG C~25 DEG C stirring reaction 4h~24h, reaction solution is poured into frozen water, extracted, is dried,
Vacuum distillation, then separated using silica gel column chromatography partition method, vacuum distillation again obtains the azoxy tetrazolium, is
2,2'- bis- replaces -5,5'- azoxy tetrazoliums；
2,2'- bis- replace -5,5'- azoxies tetrazolium for 2,2'- dimethyl -5,5'- azoxies tetrazolium, 2,2'- diethyl -
5,5'- azoxies tetrazolium, 2,2'- diisopropyl -5,5'- azoxies tetrazolium, 2,2'- di-t-butyl -5,5'- azoxies
Tetrazolium, 2,2'- dicyan methyl -5,5'- azoxies tetrazolium, 2,2'- dibromoethyl -5,5'- azoxies tetrazolium, 2,2'- bis-
Methoxy acyl methyl -5,5'- azoxies tetrazolium, 2,2'- diacetyl methyl -5,5'- azoxies tetrazolium, the carboxymethyls of 2,2'- bis- -
5,5'- azoxies tetrazolium or 2,2'- dinitric acid ester group ethyl -5,5'- azoxy tetrazoliums；
1,3- bis- (substitution tetrazole radical) triazenes is 1,3- bis- (2- methyl tetrazolium -5- bases) triazenes, (the 2- ethyls four of 1,3- bis-
Azoles -5- bases) triazenes, 1,3- bis- (2- isopropyl tetrazolium -5- bases) triazenes, 1,3- bis- (2- tert-butyl group tetrazolium -5- bases) three nitrogen
Alkene, 1,3- bis- (2- cyanogen methyl tetrazolium -5- bases) triazenes, 1,3- bis- (2- bromoethyl tetrazolium -5- bases) triazenes, (2- of 1,3- bis-
Methoxy acyl methyl tetrazolium -5- bases)-triazenes, 1,3- bis- (2- acetonyl tetrazolium -5- bases) triazenes, (the 2- carboxymethyls of 1,3- bis-
Tetrazolium -5- bases) triazenes or 1,3- bis- (2- ethoxy tetrazolium -5- bases) triazenes.
2. a kind of preparation method of azoxy tetrazolium according to claim 1, it is characterised in that：Acid anhydrides be acetic anhydride,
Propionic andydride, n butanoic anhydride, isobutyric anhydride, valeric anhydride, isovaleric anhydride, caproic anhydride, succinic anhydride, glutaric anhydride, benzoyl oxide and
One or more of TFAA.
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| ALEKSANDR M.CHURAKOV等: "The Oxidation of Heterocyclic Amines to Nitro Compounds using Dinitrogen Pentoxide", 《MENDELEEV COMMUNICATIONS》 * |
| QI WANG等: "Pentazadiene: a high-nitrogen linkage in energetic materials", 《CHEM. COMMUN.》 * |
| QI WANG等: "Synthesis and characterization of functionalized 1,3-bis(2-alkyltetrazol-5-yl)triazenes", 《CHINESE CHEMICAL LETTERS》 * |
| QI WANG等: "Synthesis of 5,50-azoxybistetrazole via nitration and de-oxygen rearrangement of triazene", 《NEWJ.CHEM.》 * |
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