CN105418534B - Azo furazan compound and preparation method thereof - Google Patents
Azo furazan compound and preparation method thereof Download PDFInfo
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- CN105418534B CN105418534B CN201510772085.XA CN201510772085A CN105418534B CN 105418534 B CN105418534 B CN 105418534B CN 201510772085 A CN201510772085 A CN 201510772085A CN 105418534 B CN105418534 B CN 105418534B
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- 0 Cc1n[o]c(*)n1 Chemical compound Cc1n[o]c(*)n1 0.000 description 1
- FZAXBPZVVJOFKX-UHFFFAOYSA-N Cc1n[o]cn1 Chemical compound Cc1n[o]cn1 FZAXBPZVVJOFKX-UHFFFAOYSA-N 0.000 description 1
- DNFUTAVRGAVUKE-UHFFFAOYSA-N N/C(/c1n[o]nc1N)=N\O Chemical compound N/C(/c1n[o]nc1N)=N\O DNFUTAVRGAVUKE-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/08—1,2,5-Oxadiazoles; Hydrogenated 1,2,5-oxadiazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
Abstract
The invention discloses the invention discloses a kind of azo furazan compound with and preparation method thereof, comprise the concrete steps that：Amino isonitroso furazan intermediate is obtained by raw material and oxidant reaction of malononitrile；Again by amino isonitroso furazan intermediate and different cyclization reagent (triethyl orthoformates, bromination nitrile, acetic anhydride, TFAA etc.) reaction, the furazan intermediate of amino substitution is obtained, then separates out precipitated azo furazan compound with potassium permanganate and 10% 20% hydrochloric acid reaction.Preparation method of the present invention is simple, disposably the azo furazan compounds of different substituents can be made by high flux compared with prior art, and safe operation, cost are cheap.
Description
Technical field
Embodiments of the present invention are related to the preparation of organic synthesis field energetic material, more specifically, the implementation of the present invention
Mode is related to azo furazan compound and preparation method thereof.
Background technology
In high-nitrogen energetic materials, most study, most typically azole energy-containing compound.Especially with furazan ring (1,
2,5- oxadiazoles) and triazole ring be basic structural unit energetic derivative, by it is introduced contain can side base, such as nitro, three
Azoles ring, tetrazole ring, azido etc., a series of furazan class richness nitrogen high energy energy-containing compounds can be obtained.Furazan has Solarium lycopersicoide
Big pi-conjugated system, improves compound stability and energy density；Oxygen atom on furazan ring not directly with carbon or hydrogen atom phase
Even, it is effective oxygen, is combined releasable certain heat with carbon when thermally decomposing, it is easier to realize oxygen balance；Furazan chemical combination
Thing is high by the connected not only nitrogen content of azo bond, and has higher positive standard enthalpy of formation.Generally speaking, azo furazan compound
Energetic material has the characteristics that ring strain is small, stability is good, the positive enthalpy of formation is high, it has also become the research heat in current explosive wastewater field
Point.But the synthetic method of azo furazan compound reports seldom (J.Org.Chem.1996,61,1510-1511 at present；
Russian Chemical Bulletin,International Edition,54,8,1915-1922,2005；Journal
of Energetic Materials,28:229–249,2010；Propellants Explos.Pyrotech.2011,36,
233–239；J.Phys.Chem.C, 2015,119,12887-12895), can only obtain single azo furazan compound.At present
For low cost, the preparation method of high flux synthesis azo furazan compound and its derivative is rarely reported both at home and abroad.The present invention
Purpose be to provide one kind and prepare simply, the azo furazan compound and its derivative of different substituents can be prepared with high flux
Method.Safe operation compared with prior art, it is adapted to the azo furazan compound for preparing different functional groups substitution, and cost is low
It is honest and clean.
The content of the invention
Instant invention overcomes the deficiencies in the prior art, there is provided azo furazan compound and its high flux preparation method, can be with
The azo furazan compound containing a variety of substituent functional groups is prepared, it is expected that series can be obtained occasionally by simple method
Nitrogen furazan compound.
To solve above-mentioned technical problem, one embodiment of the present invention uses following technical scheme：
A kind of azo furazan compound, it is characterised in that there is following structural formula：
Wherein, the structure of R substituent be-CN,
The preparation method of above-mentioned azo furazan compound comprises the following steps：
(1) compound AFA preparation
It is compound AFA to prepare 4- amino furazan -3- amidoxims with malononitrile, natrium nitrosum and hydrochloric acid；
(2) preparation of the amino furazan chemical compounds I of the substituent containing target
Compound AFA participates in substitution reaction, obtains the amino furazan compound I with following structure：The structure of wherein R substituent be-CN,
(3) preparation of azo furazan compound
At 10 DEG C -30 DEG C, compound I is dissolved in the hydrochloric acid that appropriate concentration is 10%-20%, added under stirring condition
Potassium permanganate solution, the mol ratio of the compound I and potassium permanganate are 1:1-2, concentration is used after reacting 30min-60min
Reaction system is quenched to colourless in 5%-10% hydrogen peroxide, and it is azo furazan compound to separate out solid.
In the preparation method of above-mentioned azo furazan compound, when the structure of R substituent is-CN, the compound I is 4-
Amino 3 cyano furazan, its preparation method are：AFA is dissolved in appropriate acetic acid at 20 DEG C -25 DEG C, adds brown lead oxide,
The mol ratio of AFA and brown lead oxide is 8：7-8, at room temperature stirring reaction 1h-5h, then filtered, extraction, neutralize, be dry
To solid, then solid is added in dichloromethane and stirs 30min-60min, dichloromethane is removed after filtering and obtains object.
In the preparation method of above-mentioned azo furazan compound, when the structure of R substituent isWhen, the compound I
For 3- amino -4- (1,2,3,4- tetrazolium -5- bases) furazan, its preparation method is：By the 4- Amino 3 cyanos furazan and hydration
Hydrazine is according to mol ratio 1:8-10 obtains white solid in -35 DEG C of reaction 5h-10h of 10 DEG C of temperature, then by white solid and nitrous acid
Sodium is in 10 DEG C -35 DEG C of temperature according to mol ratio 1:2-5 reacts 10h-20h in the hydrochloric acid that enough concentration is 10%-20%, obtains
Object；When the structure of R substituent isWhen, the compound I be 3- amino -4- (1- amino -1,2,3,4- tetra-
Azoles -5- bases) furazan, its preparation method is：3- amino-the 4- (1,2,3,4- tetrazolium -5- bases) furazan is dissolved in enough dioxies
In six rings, 2,4,6- trimethylbenzene sulfonamides, 3- amino -4- (1,2,3,4- tetrazolium -5- bases) furazan and 2,4,6- front threes are added
The mol ratio of base benzsulfamide is 1:8,15h-24h is reacted at room temperature, and decompression removes solvent, extraction, obtains object after drying.
In the preparation method of above-mentioned azo furazan compound, when the structure of R substituent isWhen, the chemical combination
Thing I is 3- amino -4- (5- amino-1,2,4-triazole -3- bases) furazan, and its preparation method is：By the white solid and bromination
Nitrile is according to mol ratio 1:1-2 reacts 18h-24h in the potassium bicarbonate solution that enough concentration is 10%-50%, obtains object.
In the preparation method of above-mentioned azo furazan compound, when the structure of R substituent isWhen, the chemical combination
Thing I is 3- amino -4- (5- methyl isophthalic acids, 2,4- triazole -3- bases) furazan, and its preparation method is：According to mol ratio 1:10-20 is by institute
State white solid to add in acetic anhydride, in 90 DEG C of -130 DEG C of back flow reaction 15-24h of temperature, decompression removes solvent, adds acetic acid second
Ester extracts, then is neutralized with saturated sodium bicarbonate solution, removes solvent and obtains object；When the structure of R substituent isWhen, the compound I is 3- amino -4- (5- Trifluoromethyl-1s, 2,4- triazole -3- bases) furazan, its preparation side
Method is：According to mol ratio 1:10-20 adds the white solid in TFAA, in 90 DEG C of -130 DEG C of back flow reactions of temperature
15h-24h, decompression remove solvent, add ethyl acetate extraction, then are neutralized with saturated sodium bicarbonate solution, remove solvent and obtain mesh
Mark thing.
In the preparation method of above-mentioned azo furazan compound, when the structure of R substituent isWhen, the compound I is
3- amino -4- (1,2,4- oxadiazole -3- bases) furazan, its preparation method are：According to mol ratio 1:10-20 takes AFA and borontrifluoride
Boron mass content is 46.5% boron trifluoride ether solution, and AFA is dissolved in into appropriate triethyl orthoformate, adds boron trifluoride
Diethyl ether solution, 1h is stirred at room temperature, in 90 DEG C of -110 DEG C of back flow reaction 15h-24h of temperature, decompression removes solvent, obtains target
Thing.
In the preparation method of above-mentioned azo furazan compound, when the structure of R substituent isWhen, the amino
Furazan compound I is 3- amino -4- (5- amino -1,2,4- oxadiazole -3- bases) furazan, and its preparation method is：AFA is suspended in
In ethanol in proper amount, KHCO is added3The aqueous solution, AFA and KHCO3Mol ratio be 7:8, cyanogen bromide is added portionwise under stirring condition,
Cyanogen bromide is 1 with AFA mol ratios:1, reaction 24h is stirred at room temperature, filtering to precipitate, and washed, dried, obtain target
Thing.
In the preparation method of above-mentioned azo furazan compound, when the structure of R substituent isWhen, the amino
Furazan compound I is 3- amino -4- (5- methyl isophthalic acids, 2,4- oxadiazole -3- bases) furazan, and its preparation method is：20℃-25℃
Under, proportionally 8mmol:AFA is dissolved in acetic anhydride by 10-30ml, in 90 DEG C of -130 DEG C of back flow reaction 15h-24h of temperature,
Decompression removes solvent, adds ethyl acetate extraction, then is neutralized with saturated sodium bicarbonate solution, removes solvent and obtains object.
In the preparation method of above-mentioned azo furazan compound, when the structure of R substituent isWhen, the amino
Furazan compound I is 3- amino -4- (5- Trifluoromethyl-1s, 2,4- oxadiazole -3- bases) furazan, and its preparation method is：20℃-25
At DEG C, proportionally 8mmol:AFA is dissolved in TFAA by 10ml-30ml, in 90 DEG C of -130 DEG C of back flow reactions of temperature
15h-24h, decompression remove solvent, add ethyl acetate extraction, then are neutralized with saturated sodium bicarbonate solution, remove solvent and obtain mesh
Mark thing.
Compared with prior art, one of beneficial effects of the present invention are：The present invention prepares series occasionally using high throughput method
Nitrogen furazan compound, has the characteristics that to prepare that simple, safe, cost is cheap.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic spectrogram (H-NMR) of gained solid in the specific embodiment of the invention 1.
Fig. 2 is the carbon nuclear magnetic spectrogram (C-NMR) of gained solid in the specific embodiment of the invention 1.
Fig. 3 is the mass spectrogram of gained solid in the specific embodiment of the invention 1.
Fig. 4 is double [5- amino -1,2,4- oxazole -3- bases] -4,4- azos of gained 3,3- in the specific embodiment of the invention 12
The hydrogen nuclear magnetic spectrogram (H-NMR) of furazan.
Fig. 5 is double [5- amino -1,2,4- oxazole -3- bases] -4,4- azos of gained 3,3- in the specific embodiment of the invention 12
The carbon nuclear magnetic spectrogram (C-NMR) of furazan.
Fig. 6 is double [5- amino -1,2,4- oxazole -3- bases] -4,4- azos of gained 3,3- in the specific embodiment of the invention 12
The mass spectrogram of furazan.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Embodiment 1
The preparation of 4- amino furazan -3- amidoxims (AFA)
70mL water is preheating to 45 DEG C, malononitrile (3.20g, 50mmol) is added, stirs 5min at such a temperature.Ice bath is cold
But to 0 DEG C -5 DEG C, natrium nitrosum (3.80g, 55mmol) is added.6mol/L hydrochloric acid (0.55mL), temperature are added at such a temperature
10 DEG C, after 15min are gradually risen up to, removes ice bath, continues stirring reaction 1.5h.Then reaction system is cooled to 10 DEG C of left sides
The right side, it is disposable to add 50% aqueous hydroxylamine solution (9.90g, 150mmol).Reaction temperature gradually rises up to 25 DEG C, and in the temperature
Under continue react 1h.Further back flow reaction 2h, naturally cools to room temperature.Under ice bath cooling, control system temperature is less than 5 DEG C,
PH 7.0 is adjusted with 6mol/L hydrochloric acid (8.0mL).Filtering, gained precipitation are washed with water, and vacuum drying (50 DEG C) obtains solid i.e. 4-
Amino furazan -3- amidoxims (AFA), analysis collection of illustrative plates such as Fig. 1~3.
Fusing point：189-190℃.
Mass spectrum：143.8.
1H-NMR:10.49(s,1H)；6.29(s,2H)；6.21(s,2H).
13C-NMR:154.43；143.96；140.01.
Embodiment 2-11 is the preparation embodiment of chemical compounds I.
Embodiment 2
The preparation of 4- Amino 3 cyano furazans
1.14g (8mmol) AFA is dissolved in 5ml acetic acid under the conditions of 20 DEG C, adds 1.78g (7.4mmol) dioxy
Change lead.5h is stirred at room temperature, after filtering, is extracted with ethyl acetate, then is neutralized with saturated sodium carbonate solution, anhydrous sodium sulfate is done
Dry, evaporated under reduced pressure ethyl acetate, solid, which is added in dichloromethane, stirs 30-60min, and dichloromethane is removed after filtering and obtains 4-
Amino 3 cyano furazan.
Fusing point:85-87℃.
Mass spectrum:110(M+).
1H-NMR:7.11(s,1H)。
13C-NMR:157.45；126.47；108.69.
Or 8mmolAFA is dissolved in 5ml acetic acid at 25 DEG C, add 8mmol brown lead oxide and reaction is stirred at room temperature
1h, after filtering, it is extracted with ethyl acetate, then is neutralized with saturated sodium carbonate solution, anhydrous sodium sulfate drying, evaporated under reduced pressure acetic acid second
Ester, solid, which is added in dichloromethane, stirs 30min, and dichloromethane is removed after filtering and obtains 4- Amino 3 cyano furazans.
Embodiment 3
The preparation of 3- amino -4- (1,2,3,4- tetrazolium -5- bases) furazan
Using method same as Example 2,4- Amino 3 cyano furazans are obtained, according still further to mol ratio 1:8 in temperature 15
DEG C with hydration hydrazine reaction 10h obtain white solid (4- amino -1,2,5- oxazole -3- acylhydrazones), by white solid and natrium nitrosum
In 35 DEG C of temperature according to mol ratio 1:2 react 10h in the hydrochloric acid that enough concentration is 20% obtains 3- amino -4- (1,2,3,4-
Tetrazolium -5- bases) furazan.
Mass spectrum:151.8(M-).
Or method same as Example 2 is used, 4- Amino 3 cyano furazans are obtained, according still further to mol ratio 1:10
30 DEG C of temperature obtains white solid with hydration hydrazine reaction 5h, by white solid and natrium nitrosum in 15 DEG C of temperature according to mol ratio 1:
5 react 15h in the hydrochloric acid that enough concentration is 15% obtains 3- amino -4- (1,2,3,4- tetrazolium -5- bases) furazan.
Embodiment 4
The preparation of 3- amino -4- (1- amino -1,2,3,4- tetrazolium -5- bases) furazan
Using method same as Example 3,3- amino -4- (1,2,3,4- tetrazolium -5- bases) furazan is obtained, then by solid
3- amino -4- (1,2,3,4- tetrazolium -5- bases) furazan 15.3g (10mmol) is dissolved in 50ml dioxane, stirred Cheng Zhongjia
Enter 2,4,6- trimethylbenzene sulfonamide MSH 17.2g (80mmol), react 20h at room temperature, decompression removes solvent, uses dichloromethane
Alkane extracts, and anhydrous magnesium sulfate removes organic solvent after drying, and obtains 3- amino -4- (1- amino -1,2,3,4- tetrazolium -5- bases) furan
We.
Embodiment 5
The preparation of 3- amino -4- (5- amino -1,2,4- triazole -3- bases) furazan
White solid is obtained using method same as Example 3, according to mol ratio is 1 by white solid and bromination nitrile:2
24h is reacted in the potassium bicarbonate solution that mass concentration is 10%, obtains 3- amino -4- (5- amino-1,2,4-triazole -3- bases)
Furazan.
Or white solid is obtained using method same as Example 3, by white solid and bromination nitrile according to mol ratio
For 1:1 mass concentration be 40% potassium bicarbonate solution in react 18h, obtain 3- amino -4- (5- amino-1,2,4-triazoles -
3- yls) furazan.
Embodiment 6
The preparation of 3- amino -4- (5- methyl isophthalic acids, 2,4- triazole -3- bases) furazan
White solid is obtained using method same as Example 3, according to mol ratio 1:10 add the white solid
Into acetic anhydride, in 100 DEG C of back flow reaction 24h of temperature, decompression removes solvent, adds ethyl acetate extraction, then use unsaturated carbonate
Hydrogen sodium solution is neutralized, and 3- amino -4- (5- methyl isophthalic acids, 2,4- triazole -3- bases) furazan is obtained after removing organic solvent.
Or white solid is obtained using method same as Example 3, according to mol ratio 1:18 by the white solid
It is added in acetic anhydride, in 120 DEG C of back flow reaction 15h of temperature, decompression removes solvent, adds ethyl acetate extraction, then use saturation
Sodium bicarbonate solution is neutralized, and 3- amino -4- (5- methyl isophthalic acids, 2,4- triazole -3- bases) furazan is obtained after removing organic solvent.
Embodiment 7
The preparation of 3- amino -4- (5- Trifluoromethyl-1s, 2,4- triazole -3- bases) furazan
White solid is obtained using method same as Example 3, according to mol ratio 1:10 add the white solid
Into TFAA, in 100 DEG C of back flow reaction 24h of temperature, decompression removes solvent, adds ethyl acetate extraction, then use saturation
Sodium bicarbonate solution is neutralized, and 3- amino -4- (5- Trifluoromethyl-1s, 2,4- triazole -3- bases) furazan is obtained after removing organic solvent.
White solid is obtained using method same as Example 3, according to mol ratio 1:18 add the white solid
Into TFAA, in 120 DEG C of back flow reaction 15h of temperature, decompression removes solvent, adds ethyl acetate extraction, then use saturation
Sodium bicarbonate solution is neutralized, and 3- amino -4- (5- Trifluoromethyl-1s, 2,4- triazole -3- bases) furazan is obtained after removing organic solvent.
Embodiment 8
The preparation of 3- amino -4- (1,2,4- oxadiazole -3- bases) furazan
1.14g (8mmol) AFA is dissolved in 2ml triethyl orthoformates under the conditions of 25 DEG C, it is borontrifluoride to add 1ml
Borate ether solution (mass content of boron trifluoride is 46.5%).1h is stirred at room temperature, in 90 DEG C of back flow reaction 24h of temperature,
Decompression removes solvent and obtains 3- amino -4- (1,2,4- oxadiazole -3- bases) furazan.1H-NMR:9.18(s,1H)；5.42(s,
2H)。
13C-NMR:155.12；145.11；130.51；117.93.
Or 8mmol AFA is dissolved in 5ml triethyl orthoformates at 20 DEG C, it is molten to add 2ml BFEEs
Liquid (mass content of boron trifluoride is 46.5%).1h is stirred at room temperature, in 110 DEG C of back flow reaction 15h of temperature, decompression removes
Solvent obtains 3- amino -4- (1,2,4- oxadiazole -3- bases) furazan.
Embodiment 9
The preparation of 3- amino -4- (5- amino -1,2,4- oxadiazole -3- bases) furazan (AAOF)
5g (35mmol) AFA is suspended in 25mL ethanol, adds 4g (40mmol) KHCO3The 30mL aqueous solution.Then,
Cyanogen bromide (3.71g, 35mmol) is added portionwise under agitation.After charging, reaction is stirred at room temperature in reactant mixture
24h, filtering, gained precipitation are washed with water, dry, obtain 3- amino -4- (5- amino -1,2,4- oxadiazole -3- bases) furazan
(AAOF)4.78g。
Fusing point:>250℃.
Mass spectrum:167.01(M-).
Embodiment 10
The preparation of 3- amino -4- (5- methyl isophthalic acids, 2,4- oxadiazole -3- bases) furazan
1.14g (8mmol) AFA is dissolved in 20ml acetic anhydrides at 20 DEG C, in 120 DEG C of back flow reaction 15h of temperature,
Decompression removes solvent, adds ethyl acetate extraction, then is neutralized with saturated sodium bicarbonate solution, and 3- ammonia is obtained after removing organic solvent
Base -4- (5- methyl isophthalic acids, 2,4- oxadiazole -3- bases) furazan.
Or 1.14g (8mmol) AFA is dissolved in 10ml acetic anhydrides under the conditions of 25 DEG C, in 90 DEG C of backflows of temperature
24h is reacted, decompression removes solvent, adds ethyl acetate extraction, then is neutralized with saturated sodium bicarbonate solution, after removing organic solvent
Obtain 3- amino -4- (5- methyl isophthalic acids, 2,4- oxadiazole -3- bases) furazan.
Embodiment 11
The preparation of 3- amino -4- (5- Trifluoromethyl-1s, 2,4- oxadiazole -3- bases) furazan
8mmol AFA is dissolved in 10ml TFAAs under the conditions of 25 DEG C, in 90 DEG C of back flow reaction 24h of temperature,
Decompression removes solvent, adds ethyl acetate extraction, then is neutralized with saturated sodium bicarbonate solution, and 3- ammonia is obtained after removing organic solvent
Base -4- (5- Trifluoromethyl-1s, 2,4- oxadiazole -3- bases) furazan.
1H-NMR:5.47 (d, J=8Hz, 2H).
13C-NMR:167.71；159.49；156.01；137.60；117.91.
Or 8mmol AFA is dissolved in 30ml TFAAs under the conditions of 20 DEG C, it is anti-in 130 DEG C of backflows of temperature
15h is answered, decompression removes solvent, adds ethyl acetate extraction, then is neutralized with saturated sodium bicarbonate solution, after removal organic solvent
To 3- amino -4- (5- Trifluoromethyl-1s, 2,4- oxadiazole -3- bases) furazan.
Embodiment 12-21 is the preparation embodiment of target compound azo furazan.
Embodiment 12
The preparation of double [5- amino -1,2,4- oxazole -3- the bases] -4,4- azo furazans of 3,3-
3- amino -4- (5- amino -1,2,4- oxadiazole -3- bases) furazan (AAOF) (4.00g, 23.8mmol) is added
In the mixed liquor of 80ml acetonitriles and 50ml hydrochloric acid (concentration 20%)；3.76g (23.8mmol) potassium permanganate is used to as far as possible few water
Dissolving, is added dropwise in reaction system.Gained reactant mixture continues to stir 45min or so, is diluted with 300ml water, adds appropriate
The hydrogen peroxide of mass concentration 5% is until solution becomes colourless.The precipitation separated out is filtered, is scattered in 50ml acetonitriles, is heated to back
Stream, is filtered, gained solid naturally dry while hot, obtains 2.30g products 3, double [5- amino -1,2, the 4- oxazole -3- bases] -4,4- of 3-
Azo furazan, yield 63%, analysis collection of illustrative plates such as Fig. 4~6.
Fusing point:184.85℃.
Mass spectrum:330.92(M-).
1H-NMR:8.38(s,4H)。
13C-NMR:171.07；160.11；155.88；140.27.
Embodiment 13
The preparation of 3,3- dicyano -4,4- azo furazans
Using with the identical method of embodiment 12,20mmol4- Amino 3 cyanos furazan is added into 80ml acetonitriles and 50ml
In the mixed liquor of hydrochloric acid (concentration 10%).By with the potassium permanganate of 4- Amino 3 cyano furazan equimolar amounts with as far as possible few water
Dissolving, is added dropwise in reaction system.Gained reactant mixture continues to stir 50min or so, adds the double of appropriate mass concentration 5%
Oxygen water is until solution becomes colourless.The precipitation that filtering separates out is product 3,3- dicyano -4,4- azo furazans.
Fusing point:157.47℃.
Mass spectrum:215.7(M+).
13C-NMR:162.61；124.66；105.33.
Embodiment 14
The preparation of 3,3- bis- (1,2,4- oxazole -3- bases) -4,4- azo furazans
Using with the identical method of embodiment 12,3- amino -4- (1,2,4- oxadiazole -3- bases) furazan is added to concentration
In the mixed liquor of 15% hydrochloric acid.The potassium permanganate of equimolar amounts is dissolved with as far as possible few water, is added dropwise in reaction system, obtains
To product 3,3- bis- (1,2,4- oxazole -3- bases) -4,4- azo furazans.
Fusing point:235.39℃.
1H-NMR:9.69(s,2H)。
13C-NMR:169.80；164.11；159.25；142.34.
Embodiment 15
The preparation of 3,3- bis- (1,2,3,4- tetrazolium -5- bases) -4,4- azo furazans
Using with the identical method of embodiment 12,3- amino -4- (1,2,3,4- tetrazolium -5- bases) furazan is added to concentration
In the mixed liquor of 20% hydrochloric acid.The potassium permanganate of equimolar amounts is dissolved with as far as possible few water, is added dropwise in reaction system, obtains
To product 3,3- bis- (1,2,3,4- tetrazolium -5- bases) -4,4- azo furazans.
Fusing point:168.92℃.
13C-NMR:162.16；159.98；139.80.
Embodiment 16
The preparation of double [5- methyl isophthalic acids, 2,4- oxazole -3- the bases] -4,4- azo furazans of 3,3-
Using with the identical method of embodiment 12,3- amino -4- (5- methyl isophthalic acids, 2,4- oxadiazole -3- bases) furazan is added
Enter into the mixed liquor of the hydrochloric acid of concentration 10%.The potassium permanganate of equimolar amounts is dissolved with as far as possible few water, is added dropwise to reaction
In system, product 3, double [5- methyl isophthalic acids, 2,4- oxazole -3- bases] -4, the 4- azo furazans of 3- are obtained.
Fusing point:235.39℃.
1H-NMR:2.78(s,6H)。
13C-NMR:179.48；162.39；159.98；157.35；140.56.
Embodiment 17
The preparation of double [5- Trifluoromethyl-1s, 2,4- oxazole -3- the bases] -4,4- azo furazans of 3,3-
Using with the identical method of embodiment 12, by 3- amino -4- (5- Trifluoromethyl-1s, 2,4- oxadiazole -3- bases) furan
We is added in the mixed liquor of the hydrochloric acid of concentration 15%.The potassium permanganate of equimolar amounts is dissolved with as far as possible few water, is added dropwise to
In reaction system, product 3, double [5- Trifluoromethyl-1s, 2,4- oxazole -3- bases] -4, the 4- azo furazans of 3- are obtained.Fusing point:
135.73℃。
Embodiment 18
The preparation of double [5- amino -1,2,4- triazole -3- the bases] -4,4- azo furazans of 3,3-
Using with the identical method of embodiment 12, by 3- amino -4- (5- amino-1,2,4-triazole -3- bases) furazan add
Into the mixed liquor of the hydrochloric acid of concentration 12%.The potassium permanganate of equimolar amounts is dissolved with as far as possible few water, is added dropwise to reactant
In system, product 3, double [5- amino-1,2,4-triazole -3- bases] -4, the 4- azo furazans of 3- are obtained.
Fusing point:181.91℃.
1H-NMR:8.53(s,2H)；5.96(s,4H).
Embodiment 19
The preparation of double [5- methyl isophthalic acids, 2,4- triazole -3- the bases] -4,4- azo furazans of 3,3-
Using with the identical method of embodiment 12, by 3- amino -4- (5- methyl isophthalic acids, 2,4- triazole -3- bases) furazan add
Into the mixed liquor of the hydrochloric acid of concentration 20%.The potassium permanganate of equimolar amounts is dissolved with as far as possible few water, is added dropwise to reactant
In system, product 3, double [5- methyl isophthalic acids, 2,4- triazole -3- bases] -4, the 4- azo furazans of 3- are obtained.
Embodiment 20
The preparation of double [5- Trifluoromethyl-1s, 2,4- triazole -3- the bases] -4,4- azo furazans of 3,3-
Using with the identical method of embodiment 12, by 3- amino -4- (5- Trifluoromethyl-1s, 2,4- triazole -3- bases) furazan
It is added in the mixed liquor of the hydrochloric acid of concentration 18%.The potassium permanganate of equimolar amounts is dissolved with as far as possible few water, is added dropwise to anti-
Answer in system, obtain product 3, double [5- Trifluoromethyl-1s, 2,4- triazole -3- bases] -4, the 4- azo furazans of 3-.
Embodiment 21
The preparation of double [1- amino -1,2,3,4- tetrazolium -5- the bases] -4,4- azo furazans of 3,3-
Using with the identical method of embodiment 15, obtain product 3 first, 3- bis- (1,2,3,4- tetrazolium -5- bases) -4,4- is even
Nitrogen furazan, then solid 3,3- bis- (1,2,3,4- tetrazolium -5- bases) -4,4- azo furazans are dissolved in dioxane, it is stirred into
2,4,6- trimethylbenzene sulfonamide MSH of middle addition, mol ratio 1:6-12,15h-24h is reacted at room temperature, be removed under reduced pressure molten
Agent, extracted with dichloromethane, anhydrous magnesium sulfate removes organic solvent after drying, obtain 3,3- it is double [1- amino -1,2,3,4- tetra-
Azoles -5- bases] -4,4- azo furazans.
Although reference be made herein to invention has been described for multiple explanatory embodiments of the invention, however, it is to be understood that
Those skilled in the art can be designed that a lot of other modifications and embodiment, and these modifications and embodiment will fall in this Shen
Please be within disclosed spirit and spirit.More specifically, can be to theme combination layout in the range of disclosure
Building block and/or layout carry out a variety of variations and modifications.Except the variations and modifications carried out to building block and/or layout
Outside, to those skilled in the art, other purposes also will be apparent.
Claims (1)
1. the preparation method of azo furazan compound, the azo furazan compound has following structural formula：
Wherein, the structure of R substituent is
It is characterized in that comprise the following steps：
(1) compound AFA preparation
It is compound AFA to prepare 4- amino furazan -3- amidoxims with malononitrile, natrium nitrosum and hydrochloric acid；
(2) preparation of the amino furazan chemical compounds I of the substituent containing target
Compound AFA participates in substitution reaction, obtains the amino furazan compound I with following structure：
The structure of wherein R substituent is
(3) preparation of azo furazan compound
At 10 DEG C -30 DEG C, compound I is dissolved in the hydrochloric acid that appropriate concentration is 10%-20%, Gao Meng is added under stirring condition
Sour aqueous solutions of potassium, the mol ratio of the compound I and potassium permanganate are 1:1-2, concentration 5%- is used after reacting 30min-60min
Reaction system is quenched to colourless in 10% hydrogen peroxide, and it is azo furazan compound to separate out solid；
When the structure of R substituent isWhen, the compound I is 3- amino -4- (5- methyl isophthalic acids, 2,4- triazole -3-
Base) furazan, its preparation method is：According to mol ratio 1:10-20 adds the white solid in acetic anhydride, 90 DEG C of temperature-
130 DEG C of back flow reaction 15-24h, decompression remove solvent, add ethyl acetate extraction, then are neutralized with saturated sodium bicarbonate solution, go
Except solvent obtains object；When the structure of R substituent isWhen, the compound I is 3- amino -4- (5- fluoroforms
Base -1,2,4- triazole -3- bases) furazan, its preparation method is：According to mol ratio 1:The white solid is added trifluoro by 10-20
In acetic anhydride, in 90 DEG C of -130 DEG C of back flow reaction 15h-24h of temperature, decompression removes solvent, adds ethyl acetate extraction, then with satisfying
Neutralized with sodium bicarbonate solution, remove solvent and obtain object.
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