CN104892594B - The synthetic method of 4,5 pairs of (tetrazole radicals of 1H 5) furoxans - Google Patents

The synthetic method of 4,5 pairs of (tetrazole radicals of 1H 5) furoxans Download PDF

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CN104892594B
CN104892594B CN201510350570.8A CN201510350570A CN104892594B CN 104892594 B CN104892594 B CN 104892594B CN 201510350570 A CN201510350570 A CN 201510350570A CN 104892594 B CN104892594 B CN 104892594B
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furoxans
dicyano
tetrazole radicals
water
double
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CN104892594A (en
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翟连杰
樊学忠
汪伟
王伯周
霍欢
毕福强
付小龙
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Xian Modern Chemistry Research Institute
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    • 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

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Abstract

The invention discloses a kind of synthetic method of 4,5 pairs of (tetrazole radicals of 1H 5) furoxans, comprise the following steps：With 4,5 dicyano furoxans for raw material, its structural formula such as shown in (II), comprises the following steps：Under stirring, in 15 DEG C~25 DEG C of temperature, by zinc chloride and 4,5 dicyano furoxans are added to the water, sodium azide is added portionwise again, 75 DEG C~100 DEG C reaction 3h~8h are heated to after adding, then stopped reaction, it is down to after 25 DEG C, it is that 36% concentrated hydrochloric acid is acidified to pH=1~2 with mass fraction, then filtering, filter cake is through washing, drying, obtain 4,5 pairs of (tetrazole radicals of 1H 5) furoxans；Wherein the mol ratio of zinc chloride and 4,5 dicyano furoxans is 1:The mol ratio of 0.5~2.0,4,5 dicyano furoxans and sodium azide is 1:The mol ratio 1 of 2.0~4.0,4,5 dicyano furoxans and water:120~200.Present invention is mainly used for high explosive or gas-forming agent field.

Description

The synthetic method of double (1H-5- tetrazole radicals) furoxans of 4,5-
Technical field
The present invention relates to the synthetic method of double (1H-5- tetrazole radicals) furoxans of 4,5- of one kind, belong to energetic material field.
Background technology
High nitrogen stell is the study hotspot of current energetic material, not only with higher density, higher positive generation Enthalpy and relatively low sensitivity, while also having the features such as energy level is high, gas production is big, detonation product is cleaned.Such compound point Contain substantial amounts of C-N, C=N, N-N and N=N key in minor structure, a large amount of nitrogen are discharged during decomposition, produce higher-energy, head-on collision Hitting, rub etc. stimulates insensitive, therefore is pushed away available for the low sense explosive of high energy, gas-forming agent, burning ratemodifier, low signature Enter agent, flame formula inhibitor and pyrotechnic composition etc., the field as countries in the world energetic material researcher's common concern.4,5- is double (1H-5- tetrazole radicals) furoxan, is the rich nitrogen class energy-containing compound being made up of tetrazolium and furoxan construction unit, and its nitrogen contains Measure as 63.1%, decomposition temperature is 220 DEG C, and actual density is 1.62g/cm3, standard enthalpy of formation Δ ΗfFor 727.8kJ/mol, tool The features such as having high nitrogen content, big energy density and good heat endurance, its combination property is better than 4,5- bis- (tetrazolium -5- bases) furazan, It is a kind of rich nitrogen energetic material of function admirable.
, Haifeng Huang, Zhiming Zhou, Lixuan Liang et al. in 2012《Nitrogen-Rich Energetic monoanionic Salts of 3,4-Bis(1H-5-tetrazolyl)furoxan》Chemistry An Asian Journal, 2012,7,707-714 disclose the synthetic method of double (1H-5- tetrazole radicals) furoxans of 4,5- of one kind, Its synthetic route is as follows：
This method with 4,5- dicyanos furoxan be raw material, in solvent DMF, with NaN3With NH4Cl action-reactions generate double (1H-5- tetrazole radicals) furoxans of 4,5-, and reaction yield is 60.0%.But locate after this method Reason is cumbersome, it is necessary to ether is repeatedly extracted, and then also needs to wash away the DMF in ether extraction liquid with bittern；Together When, DMF does reaction dissolvent, is unfavorable for environmental protection and energy-saving and emission-reduction, and reaction yield is relatively low.
The content of the invention
The technical problems to be solved by the invention are to overcome the deficiencies in the prior art there is provided method is simple, energy-conservation The synthetic method of double (1H-5- tetrazole radicals) furoxans of the higher 4,5- of environmental protection, yield.
The synthetic route of double (1H-5- tetrazole radicals) furoxans of the 4,5- of the present invention is as follows：
The present invention synthetic route with 4,5- dicyanos furoxan be raw material, in ZnCl2With NaN under catalytic action3Reaction Obtain double (1H-5- tetrazole radicals) furoxans of 4,5-.
The synthetic method of double (1H-5- tetrazole radicals) furoxans of 4, the 5- of the present invention, 4,5- double (1H-5- tetrazole radicals) oxidations Furazan structural formula is such as shown in (I)：
With 4,5- dicyanos furoxan for raw material, its structural formula is such as shown in (II), and synthetic method of the present invention includes following Step：Under stirring, in 15 DEG C~25 DEG C of temperature, by zinc chloride and 4,5- dicyano furoxans are added to the water, then in batches plus Enter sodium azide, 75 DEG C~100 DEG C reaction 3h~8h are heated to after adding, then stopped reaction, is down to after 25 DEG C, uses matter Amount fraction is that 36% concentrated hydrochloric acid is acidified to pH=1~2, then filtering, and filter cake obtains double (the 1H-5- tetrazoliums of 4,5- through washing, drying Base) furoxan；The mol ratio of wherein zinc chloride and 4,5- dicyano furoxans is 1:0.5~2.0,4,5- dicyanos are aoxidized The mol ratio of furazan and sodium azide is 1:The mol ratio 1 of 2.0~4.0,4,5- dicyano furoxans and water:120~200.
The synthetic method of double (1H-5- tetrazole radicals) furoxans of currently preferred 4,5-, comprises the following steps：Stirring Under, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyano furoxans are added to In 30mL water, then 1.95g (30mmol) sodium azide is added portionwise, 90 DEG C of reaction 5h are heated to after adding, are then stopped React, be down to after 25 DEG C, be that 36% concentrated hydrochloric acid is acidified to pH=1~2 with mass fraction, then filtering, filter cake is through washing, doing It is dry, obtain double (1H-5- tetrazole radicals) furoxans of 4,5-.
Advantages of the present invention：
(1) double (1H-5- tetrazole radicals) the furoxan synthetic method reaction yields of 4,5- of the invention are higher, its reaction yield For 90.9%, and method in documents, reaction yield is 60.0%；(2) 4,5- of the invention double (1H-5- tetrazole radicals) oxidation The post processing of furazan synthetic method is simple, and reaction solution is directly filtered with regard to that can obtain double (1-H-5- tetrazole radicals) furoxans of 4,5-, and Method in documents, reaction solution need to repeatedly be extracted with ether, and solvent N, N- dimethyl methyl must could be removed through brine Acid amides；(3) double (1H-5- tetrazole radicals) the furoxan synthetic method energy-conserving and environment-protective of 4,5- of the invention, do reaction dissolvent, both with water Cost can be reduced and meet energy-saving and emission-reduction requirement again, and method in documents, reaction dissolvent is done with DMF.
Embodiment
The present invention is described in further details with reference to embodiment.
Embodiment 1
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.95g (30mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 2.0g of 4,5-, yield 90.1%, purity 99.2%；
Structural Identification：
Decomposition point：229 DEG C~230 DEG C；
Infrared spectrum：IR(KBr,cm-1)ν:3139,2990,2905,2752,2667,2514,1622,1581,1458, 1419,1387,1281,1234,1204,1182,1130,1094,1071,1026,1015,1004,960,935,824,782, 736,704,544；
Nuclear magnetic spectrum：1H NMR(DMSO-d6,500MHz),δ:8.28(s,2H,NH)；13CNMR(CDCl3,125MHz),δ: 149.01,146.18 (C-C=N), 146.05,106.76；
Elementary analysis：Structural formula C4H2N10O2
Theoretical value：C 21.63,H 0.91,N 63.06
Measured value：C 21.56,H 1.08,N 62.79；
Said structure appraising datum confirms that the material that this step is obtained is strictly 4,5- double (1H-5- tetrazole radicals) oxidation furan We；
Embodiment 2
Under stirring, in 15 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 20mL water, then 1.95g (30mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.98g of 4,5-, yield 89.2%, purity 98.9%, dec.:229 DEG C~230 DEG C；
Embodiment 3
Under stirring, in 25 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 40mL water, then 1.95g (30mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.95g of 4,5-, yield 87.8%, purity 98.7%, dec.:229 DEG C~230 DEG C；
Embodiment 4
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.30g (20mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.82g of 4,5-, yield 82.0%, purity 98.8%, dec.:229 DEG C~230 DEG C；
Embodiment 5
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.30g (20mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.82g of 4,5-, yield 82.0%, purity 98.8%, dec.:229 DEG C~230 DEG C；
Embodiment 6
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.62g (25mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.94g of 4,5-, yield 87.4%, purity 98.5%, dec.:229 DEG C~230 DEG C；
Embodiment 7
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.62g (35mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.99g of 4,5-, yield 89.6%, purity 99.1%, dec.:229 DEG C~230 DEG C；
Embodiment 8
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 2.60g (40mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.89g of 4,5-, yield 85.1%, purity 98.9%, dec.:229 DEG C~230 DEG C；
Embodiment 9
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.95g (30mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 3h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.66g of 4,5-, yield 74.8%, purity 97.5%, dec.:229 DEG C~230 DEG C；
Embodiment 10
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.95g (30mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 4h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.86g of 4,5-, yield 83.8%, purity 98.4%, dec.:229 DEG C~230 DEG C；
Embodiment 11
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.95g (30mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 7h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 2.00g of 4,5-, yield 90.1%, purity 99.4%, dec.:229 DEG C~230 DEG C；
Embodiment 12
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.95g (30mmol) sodium azide is added portionwise, and 90 DEG C of reactions are heated to after adding 8h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 2.01g of 4,5-, yield 90.5%, purity 99.0%, dec.:229 DEG C~230 DEG C；
Embodiment 13
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.95g (30mmol) sodium azide is added portionwise, and 75 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.69g of 4,5-, yield 76.1%, purity 98.4%, dec.:229 DEG C~230 DEG C；
Embodiment 14
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.95g (30mmol) sodium azide is added portionwise, and 85 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.87g of 4,5-, yield 84.2%, purity 97.9%, dec.:229 DEG C~230 DEG C；
Embodiment 15
Under stirring, in 20 DEG C of temperature, 1.36g (10mmol) zinc chloride and 1.36g (10mmol) 4,5- dicyanos are aoxidized Furazan is added in 30mL water, then 1.95g (30mmol) sodium azide is added portionwise, and 100 DEG C of reactions are heated to after adding 5h, then stopped reaction, is down to after 25 DEG C, is acidified to pH=1~2 with mass fraction for 36%, then filtering, filter cake is through water Wash, drying steps obtain double (1H-5- tetrazole radicals) the furoxan 1.99g of 4,5-, yield 89.6%, purity 98.9%, dec.:229 DEG C~230 DEG C.

Claims (2)

1. one kind 4, the synthetic method of double (1H-5- tetrazole radicals) furoxans of 5-, 4,5- double (1H-5- tetrazole radicals) furoxan knots Structure formula is such as shown in (I)：
With 4,5- dicyanos furoxan for raw material, its structural formula such as shown in (II), comprises the following steps：Under stirring, in temperature 15 DEG C~25 DEG C, by zinc chloride and 4,5- dicyano furoxans are added to the water, then sodium azide is added portionwise, and add after adding Heat is warming up to 75 DEG C~100 DEG C reaction 3h~8h, and then stopped reaction, is down to after 25 DEG C, is 36% concentrated hydrochloric acid with mass fraction PH=1~2 are acidified to, then filtering, filter cake obtains double (1H-5- tetrazole radicals) furoxans of 4,5- through washing, drying；Wherein chlorine The mol ratio for changing zinc and 4,5- dicyano furoxans is 1:0.5~2.0,4,5- dicyano furoxans and sodium azide rub You are than being 1:The mol ratio 1 of 2.0~4.0,4,5- dicyano furoxans and water:120~200.
2. the synthetic method of double (1-H-5- tetrazole radicals) furoxans of 4,5- according to claim 1, comprises the following steps： Under stirring, in 20 DEG C of temperature, by zinc chloride and 4,5- dicyano furoxans are added to the water, then 1.95g is added portionwise (30mmol) sodium azide, is heated to 90 DEG C of reaction 5h, then stopped reaction, is down to after 25 DEG C, with quality point after adding Number is acidified to pH=1~2 for 36% concentrated hydrochloric acid, then filtering, and filter cake obtains double (1H-5- tetrazole radicals) oxygen of 4,5- through washing, drying Change furazan；The mol ratio of wherein zinc chloride and 4,5- dicyano furoxans is 1:Isosorbide-5-Nitrae, 5- dicyanos furoxan and Azide The mol ratio of sodium is 1:The mol ratio 1 of 3,4,5- dicyano furoxans and water:167.
CN201510350570.8A 2015-06-23 2015-06-23 The synthetic method of 4,5 pairs of (tetrazole radicals of 1H 5) furoxans Expired - Fee Related CN104892594B (en)

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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN102952124A (en) * 2011-08-23 2013-03-06 北京理工大学 3,4-bis(1-hydro-5-tetrazolyl)furoxan ionic salt containing energy and preparation method thereof

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN102952124A (en) * 2011-08-23 2013-03-06 北京理工大学 3,4-bis(1-hydro-5-tetrazolyl)furoxan ionic salt containing energy and preparation method thereof

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Title
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"3 ，3’-二(四唑-5 -基)二呋咱基醚的合成与表征";李辉等;《含能材料》;20120225;第20卷(第1期);18-21 *
"4-Nitro-3-(5-tetrazole)furoxan and Its Salts: Synthesis, Characterization, and Energetic Properties";Lixuan Liang，et al.;《Chem. Eur. J.》;20130917;第19卷;14902–14910 *
"Nitrogen-Rich Energetic Dianionic Salts of 3,4-Bis(1H-5-tetrazolyl)furoxan with Excellent Thermal Stability";Haifeng Huang，et al.;《Z. Anorg. Allg. Chem.》;20111228;第638卷(第2期);392-400 *

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