CN105254636A - 3,6,7-triamino-1,2,4-triazolocycle ionic type nitroazole compound and preparation method thereof - Google Patents
3,6,7-triamino-1,2,4-triazolocycle ionic type nitroazole compound and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 nitroazole compound Chemical class 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- FTBBGQKRYUTLMP-UHFFFAOYSA-N 2-nitro-1h-pyrrole Chemical compound [O-][N+](=O)C1=CC=CN1 FTBBGQKRYUTLMP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 14
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000005474 detonation Methods 0.000 abstract description 13
- 238000004364 calculation method Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- QJTIRVUEVSKJTK-UHFFFAOYSA-N 5-nitro-1,2-dihydro-1,2,4-triazol-3-one Chemical compound [O-][N+](=O)C1=NC(=O)NN1 QJTIRVUEVSKJTK-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 231100000167 toxic agent Toxicity 0.000 abstract 1
- 239000003440 toxic substance Substances 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 36
- 230000005311 nuclear magnetism Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- VYDWQPKRHOGLPA-UHFFFAOYSA-N 5-nitroimidazole Chemical compound [O-][N+](=O)C1=CN=CN1 VYDWQPKRHOGLPA-UHFFFAOYSA-N 0.000 description 12
- 208000032826 Ring chromosome 3 syndrome Diseases 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000004880 explosion Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 150000003852 triazoles Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 208000002991 Ring chromosome 4 syndrome Diseases 0.000 description 1
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/91—Nitro radicals
- C07D233/92—Nitro radicals attached in position 4 or 5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/14—Nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a 3,6,7-triamino-1,2,4-triazolocycle ionic type nitroazole compound and a preparation method thereof. The preparation method of the 3,6,7-triamino-1,2,4-triazolocycle ionic type nitroazole compound comprises the following steps: dispersing a 3,6,7-triamino-1,2,4-triazolocycle compound and a nitroazole type-1H compound in right amount of deionized water, heating, reacting, then standing, filtering out a solid after temperature is reduced to normal temperature, washing the solid, and drying, so that the 3,6,7-triamino-1,2,4-triazolocycle ionic type nitroazole compound is obtained, wherein the nitroazole type-1H compound is one of 2,4-dinitroimidazole-1H, 4,5-dinitroimidazole-1H, 3,5-dinitroparazole-1H, 3-amino-5-nitro-1,2,4-triazole-1H, 3-nitro-1,2,4-triazole-5-one and 5,5'-dinitro-3,3'-bi-triazole-1H,1'H. The preparation method of the 3,6,7-triamino-1,2,4-triazolocycle ionic type nitroazole compound is simple, no toxic substance or byproduct is produced, conditions are mild, yield is high, and detonation velocity, through quantum chemistry calculation, of the obtained product is 8500-9200m/s.
Description
Technical field
Embodiments of the present invention relate to organic chemistry filed, and more specifically, embodiments of the present invention relate to 3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds and preparation method thereof.
Background technology
Ionic energetic material is that a class nitrogen content is high and the energy-containing compound that Heat of Formation is high, enjoys the concern in Shattering rate field in recent years.Its degradation production mostly is the nitrogen tetroxide that density is large, steam forces down, and therefore compares traditional single chmical compound explosive more friendly to environment.Due to features such as its detonation property is excellent, mechanical sensitivity is low, Heat of Formation is high, good heat stabilities, therefore can be used as high energy component for fields such as military affairs, aerospace, civil blasts.Rich nitrogen azole compounds is the carrier of the good ionic energetic material of a class, usually containing C=N, N=N or C=C conjugated double bond and the group such as primary amine, secondary amine in its molecular structure, therefore being not only conducive to when forming ionic energetic material forming positively charged ion, also can forming negatively charged ion.Positively charged ion 3,6,7-triamino-1,2,4-triazolo cyclic cpds used in the present invention adopts the people such as K.T.Potts at J.Org.Chem.1968, and the method described in 33,143-150 obtains, and route is as follows:
Further between organic molecule by the one-tenth key mode synthesizing new organic ion type energetic material of ionic linkage, be one of the effective way of current structure, Design & preparation high-energy-density energetic material.Nitro azole-1H compound representatively high nitrogen stell, its density, nitrogen content and Heat of Formation are higher, and mechanical sensitivity and electric spark sensitivity comparatively insensitiveness, but molecule presents acidity, and easy moisture absorption, can be used as negatively charged ion.There is no at present and utilize above-mentioned positively charged ion 3,6,7-triamino-1,2,4-triazolo cyclic cpds and nitro azole-1H compound to carry out composite synthesis, to obtain the relevant report of the compound more stable, detonation property is higher, mechanical sensitivity is lower.
Summary of the invention
Instant invention overcomes the deficiencies in the prior art, provide 3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds and preparation method thereof, to expect the ionic nitro azole compounds can stablized, detonation property is high by simple composite synthetic method, sensitivity is low.
For solving above-mentioned technical problem, one embodiment of the present invention by the following technical solutions:
3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds, their structural formula is as follows:
wherein
or
The operation steps of the preparation method of 3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds is as follows:
By 3,6,7-triamino-1,2,4-triazolo cyclic cpds and nitro azole-1H compound are scattered in appropriate deionized water, reacting by heating, then leave standstill, when temperature is down to normal temperature, leach solid, by described solid washing, drying, namely obtain described 3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds.
Described nitro azole-1H compound is 2,4-Nitroimidazole-1H, 4,5-Nitroimidazole-1H, 3,5-binitropyrazole-1H, 3-amino-5-nitro-1,2,4-triazole-1H, 3-nitro-1,2,4-triazole-5-ketone or 5,5 '-dinitrobenzene-3,3 '-Lian triazole-1H, the one in 1 ' H.
The mol ratio of described 3,6,7-triamino-1,2,4-triazolo cyclic cpdss and nitro azole-1H compound is 1 ~ 2:1.
The Heating temperature of described reacting by heating is 80 ~ 100 DEG C.
The reaction times of described reacting by heating is 0.5 ~ 1h.
The mol ratio of described deionized water and nitro azole-1H compound is 500 ~ 2200:1.
By 3,6,7-triamino-1,2,4-triazolo cyclic cpds and nitro azole-1H compound carry out composite synthesis, not only can increase intramolecular hydrogen bond and thermostability, reactive hydrogen can also be eliminated, improve nitrogen content, promote the detonation property of compound simultaneously, reduce mechanical sensitivity.
Compared with prior art, the present invention has the following advantages:
1, obtain 3,6,7-new triamino-1,2,4-triazolo ring ionic nitro azole compounds and there is not yet bibliographical information.
2,3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds in the present invention are through quantum chemistry calculation, and its explosion velocity is between 8500 ~ 9200m/s.
3,3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds preparation methods of the present invention are comparatively easy, and non-toxic by-products, mild condition, productive rate is high.
Accompanying drawing explanation
Fig. 1 is that the synthetic route of the present invention 3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds realizes.
Fig. 2 is the present invention 3,6,7-triamino-1,2,4-triazolo ring-2,4-Nitroimidazole
13c nuclear-magnetism carbon is composed.
Fig. 3 is the present invention 3,6,7-triamino-1,2,4-triazolo ring-4,5-Nitroimidazole
13c nuclear-magnetism carbon is composed.
Fig. 4 is the crystalline structure of the present invention 3,6,7-triamino-1,2,4-triazolo ring-4,5-Nitroimidazole monohydrate.
Fig. 5 is the present invention 3,6,7-triamino-1,2,4-triazolo ring-3,5-binitropyrazole
13c nuclear-magnetism carbon is composed.
Fig. 6 is the present invention 3,6,7-triamino-1,2,4-triazolo ring-3-amino-5-nitro-triazole
13c nuclear-magnetism carbon is composed.
Fig. 7 is the crystalline structure of the present invention 3,6,7-triamino-1,2,4-triazolo ring-3-nitro-1,2,4-triazole-5-ketone.
Fig. 8 is the present invention 3,6,7-triamino-1,2,4-triazolo ring-3-nitro-1,2,4-triazole-5-ketone
13c nuclear-magnetism carbon is composed.
Fig. 9 is the present invention 3,6,7-triamino-1,2,4-triazolo ring-5,5 '-dinitrobenzene-3,3 '-Lian triazole
13c nuclear-magnetism carbon is composed.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Fig. 1 is the present invention 3,6,7-triamino-1, the synthetic route of 2,4-triazolo ring ionic nitro azole compounds, by 3,6,7-triamino-1,2,4-triazolo cyclic cpds and nitro azole-1H compound are scattered in appropriate deionized water according to certain mol proportion, after reacting by heating for some time, leave standstill and leach solid when temperature is down to normal temperature, washing, drying, obtain 3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds.
Embodiment 1
The structure of 3,6,7-triamino-1,2,4-triazolo ring-2,4-Nitroimidazole is as follows:
Its preparation method is as follows:
By 158mg (1mmol) 2,4-Nitroimidazole-1H joins in 10mL (0.5mol) aqueous solution, adds 3,6 under stirring, 7-triamino-1,2,4-triazolo cyclic cpds 154mg (1mmol), is heated to 80 DEG C, solution shoals yellow transparent solution, continue to stir, leave standstill after reaction 1h, be down to after room temperature until temperature and separate out yellow crystals, leach washing, target compound 3,6,7-triamino-1 is obtained after drying, 2,4-triazolo ring-2,4-Nitroimidazole 280mg, yield 89.7%.
3,6,7-triamino triazolo ring-2,4-Nitroimidazole
1h nuclear-magnetism (DMSO, δ, ppm): 8.18 (2H), 7.30 (1H), 7.24 (2H), 5.78 (2H);
13c nuclear-magnetism is (DMSO, δ, ppm) as shown in Figure 2: 160.61, and 156.83,147.91,141.61,98.83; Infrared (KBr, cm
-1): 3420 (s), 3357 (m), 3255 (s), 1679 (s), 1650 (s), 1517 (m), 1474 (m), 1440 (w), 1357 (w), 1299 (s), 1079 (w), 1004 (w), 841 (w), 659 (w), 616 (w); Ultimate analysis: theoretical value is N (50.90%), C (21.82%), H (3.05%); Measured value is N (49.31%), C (21.01%), H (2.89%).
Embodiment 2
Condition is with embodiment 1, and temperature of reaction is changed into 90 DEG C, the reaction times changes 0.5h into, obtains target compound 3,6,7-triamino triazolo ring-2,4-Nitroimidazole 295mg, yield 94.5%.
Embodiment 3
The structure of 3,6,7-triamino-1,2,4-triazolo ring-4,5-Nitroimidazole is as follows:
Its preparation method is as follows:
By 158mg (1mmol) 4,5-Nitroimidazole-1H joins in 10mL (0.5mol) aqueous solution, 3 are added under stirring, 6,7-triamino-1,2,4-triazolo cyclic cpds 154mg (1mmol), be heated to 85 DEG C, solution shoals yellow transparent solution, continues to stir, leave standstill after reaction 0.5h, be down to after room temperature until temperature and separate out yellow crystals, leach washing, after drying, obtain target compound 3,6,7-triamino triazolo ring-4,5-Nitroimidazole 290mg, yield 92.9%.
3 are obtained after recrystallization, 6,7-triamino triazolo ring-4, the monocrystalline of 5-Nitroimidazole monohydrate, as shown in Figure 3, its spacer is P-1 to its crystalline structure, unit cell parameters is α=79.688 (5) °, β=74.117 (6) °, γ=80.828 (5) °, the crystalline density under 293K is 1.678g/cm
3: its
1h nuclear-magnetism (DMSO, δ, ppm): 8.20 (2H), 7.24 (2H), 6.96 (1H), 5.78 (2H),
13c nuclear-magnetism is (DMSO, δ, ppm) as shown in Figure 4: 160.61, and 147.91,141.60,140.69,139.81; Infrared (KBr, cm
-1): 3613 (m), 3449 (s), 3371 (s), 3302 (s), 2963 (m), 2641 (m), 1689 (s), 1562 (s), 1521 (m), 1495 (m), 1473 (s), 1445 (s), 1350 (s), 1303 (m), 1241 (s), 1167 (m), 1097 (m), 973 (w), 902 (w), 846 (m), 808 (m), 754 (w), 718 (w), 678 (w), 619 (w), 596 (w), 495 (w), 427 (w); Ultimate analysis: theoretical value is N (50.90%), C (21.82%), H (3.05%); Measured value is N (50.77%), C (21.57%), H (2.74%).
Embodiment 4
Temperature of reaction, with embodiment 3, is changed into 90 DEG C by condition, the reaction times will change 0.5h into, obtains target compound 3,6,7-triamino triazolo ring-4,5-Nitroimidazole 289mg, yield 91.9%.
Embodiment 5
The structure of 3,6,7-triamino-1,2,4-triazolo ring-3,5-binitropyrazole is as follows:
By 158mg (1mmol) 3,5-binitropyrazole-1H joins in 18mL (1mol) aqueous solution, adds 154mg (1mmol) 3,6 under stirring, 7-triamino-1,2,4-triazolo cyclic cpds, is heated to 90 DEG C, solution shoals yellow transparent solution, continue to stir, leave standstill after reaction 1h, be down to after room temperature until temperature and separate out yellow crystals, leach washing, target compound 3,6,7-triamino-1 is obtained after drying, 2,4-triazolo ring-3,5-binitropyrazole 276mg, yield 88.5%.
3,6,7-triamino triazolo ring-3,5-binitropyrazole
1h nuclear-magnetism (DMSO, δ, ppm): 8.18 (2H), 7.30 (1H), 7.24 (2H), 5.78 (2H),
13c nuclear-magnetism is (DMSO, δ, ppm) as shown in Figure 5: 160.61, and 156.83,147.91,141.61,98.83, infrared (KBr, cm
-1): 3357 (s), 3487 (m), 3398 (s), 3339 (s), 3157 (s), 2625 (m), 1704 (s), 1674 (s), 1632 (s), 1582 (s), 1538 (s), 1486 (s), 1446 (m), 1362 (s), 1328 (m), 1283 (w), 1184 (m), 1153 (w), 1099 (w), 1026 (w), 1001 (w), 971 (w), 895 (m), 833 (m), 748 (m), 723 (w), 705 (w), 634 (w), 551 (w), 451 (w), ultimate analysis: theoretical value is N (50.90%), C (21.82%), H (3.05%), measured value is N (49.31%), C (21.01%), H (2.89%).
Embodiment 6
Temperature of reaction, with embodiment 5, is changed into 100 DEG C by condition, the reaction times will change 0.5h into, obtains target compound 3,6,7-triamino triazolo ring-3,5-binitropyrazole 281mg, yield 90.1%.
Embodiment 7
The structure of 3,6,7-triamino-1,2,4-triazolo ring-3-amino-5-nitro-triazole is as follows
Its preparation method is:
By 129mg (1mmol) 3-amino-5-nitro-1,2,4-triazole-1H joins in 15mL (0.8mol) aqueous solution, adds 154mg (1mmol) 3 under stirring, 6,7-triamino-1,2,4-triazolo cyclic cpds, be heated to 90 DEG C, solution shoals orange clear solution, continues to stir, and leaves standstill after reaction 1h, be down to after room temperature until temperature and separate out orange crystal, leach washing, obtain target compound 3 after drying, 6,7-triamino-1,2,4-triazolo ring-3-amino-5-nitro-triazole 270mg, yield 95.4%.
3,6,7-triamino triazolo ring-3-amino-5-nitro-1,2,4-triazole
1h nuclear-magnetism (DMSO, δ, ppm): 6.82 (2H), 6.47 (2H), 5.71 (2H), 5.63 (2H);
13c nuclear-magnetism is as shown in Figure 6: (DMSO, δ, ppm) 161.34,159.10,158.01,149.35,143.79; Infrared (KBr, cm
-1): 3615 (m), 3439 (s), 3336 (s), 3199 (s), 2939 (w), 2880 (w), 2691 (m), 1678 (s), 1620 (s), 1565 (s), 1510 (s), 1378 (m), 1305 (s), 1256 (w), 1150 (w), 1052 (w), 1025 (w), 962 (w), 904 (w), 842 (w), 754 (w), 721 (w), 701 (w), 607 (w), 473 (w); Ultimate analysis: theoretical value is N (64.29%), C (21.20%), H (3.20%); Measured value is N (49.31%), C (21.01%), H (2.89%).
Embodiment 8
Temperature of reaction, with embodiment 7, is changed into 100 DEG C by condition, the reaction times will change 0.5h into, obtains target compound 3,6,7-triamino triazolo ring-3-amino-5-nitro-1,2,4-triazole 267mg, yield 94.2%.
Embodiment 9
The structure of 3,6,7-triamino-1,2,4-triazolo ring-3-nitro-1,2,4-triazole-5-ketone is as follows:
Its preparation method is:
130mg (1mmol) 3-nitro-1,2,4-triazole-5-ketone is joined in 10mL (0.5mol) aqueous solution, 154mg (1mmol) 3 is added under stirring, 6,7-triamino-1,2,4-triazolo cyclic cpds, be heated to 80 DEG C, solution shoals glassy yellow clear solution, leaves standstill after continuing to stir 1h, be down to after room temperature until temperature and separate out pale yellow crystals, leach washing, obtain target compound 3 after drying, 6,7-triamino-1,2,4-triazolo ring-3-nitro-1,2,4-triazole-5-ketone 260mg, yield 90.9%.
3 are obtained after recrystallization, 6, the monocrystalline of 7-triamino triazolo ring-3-nitro-1,2,4-triazole-5-ketone, its crystalline structure as shown in Figure 7, its spacer is P-1, and unit cell parameters is α=79.214 (4) °, β=79.689 (5) °, γ=77.498 (5) °, crystalline density is 1.699g/cm
3: its
1h nuclear-magnetism: (DMSO, δ, ppm) 7.39 (3H), 7.06 (2H), 6.92 (2H), 5.74 (1H), 5.71 (1H),
13c nuclear-magnetism is as shown in Figure 8: (DMSO, δ, ppm) 160.01,148.46,142.65,142.61; Infrared (KBr, cm
-1): 3330 (s), 3228 (m), 3118 (s), 2852 (m), 2781 (m), 1688 (s), 1664 (s), 1633 (s), 1601 (s), 1518 (s), 1447 (m), 1384 (s), 1313 (s), 1281 (m), 1167 (w), 1118 (w), 1059 (m), 1022 (w), 979 (w), 947 (m), 844 (w), 828 (w), 782 (s), 748 (s), 749 (m), 722 (m), 708 (w), 615 (w), 597 (w); Ultimate analysis: theoretical value is N (59.14%), C (21.13%), H (2.84%); Measured value is N (59.08%), C (20.85%), H (2.48%).
Embodiment 10
Temperature of reaction, with embodiment 9, is changed into 90 DEG C by condition, the reaction times will change 0.5h into, obtains target compound 3,6,7-triamino triazolo ring-3-nitro-1,2,4-triazole-5-ketone 272mg, yield 95.1%.
Embodiment 11
The structure of 3,6,7-triamino-1,2,4-triazolo ring-5,5 '-dinitrobenzene-3,3 '-Lian triazole is as follows:
Its preparation method is as follows:
By 226mg (1mmol) 5,5 '-dinitrobenzene-3,3 '-Lian triazole-1H, 1H ' is scattered in 40mL (2.2mol) aqueous solution, adds 308mg (2mmol) 3,6 under stirring, 7-triamino-1,2,4-triazolo cyclic cpds, is heated to 90 DEG C, solution shoals yellow transparent solution, leave standstill after continuing to stir 1h, be down to after room temperature until temperature and separate out yellow crystals, leach washing, target compound 3 is obtained after drying, 6,7-triamino-1,2,4-triazolo ring-5,5 '-dinitrobenzene-3,3 '-Lian triazole 500mg, yield 93.6%.
3,6,7-triamino triazolo ring-5,5 '-dinitrobenzene-3,3 '-Lian triazole
1h nuclear-magnetism (DMSO, δ, ppm): 8.18 (2H), 7.30 (1H), 7.24 (2H), 5.78 (2H),
13c nuclear-magnetism is (DMSO, δ, ppm) as shown in Figure 9: 160.61, and 156.83,147.91,141.61,98.83, infrared (KBr, cm
-1): 3357 (s), 3487 (m), 3398 (s), 3339 (s), 3157 (s), 2625 (m), 1704 (s), 1674 (s), 1632 (s), 1582 (s), 1538 (s), 1486 (s), 1446 (m), 1362 (s), 1328 (m), 1283 (w), 1184 (m), 1153 (w), 1099 (w), 1026 (w), 1001 (w), 971 (w), 895 (m), 833 (m), 748 (m), 723 (w), 705 (w), 634 (w), 551 (w), 451 (w), ultimate analysis: theoretical value is N (50.90%), C (21.82%), H (3.05%), measured value is N (49.31%), C (21.01%), H (2.89%).
Embodiment 12
Temperature of reaction, with embodiment 11, is changed into 100 DEG C by condition, the reaction times will change 0.5h into, obtains target compound 3,6,7-triamino triazolo ring-5,5 '-dinitrobenzene-3,3 '-Lian triazole 525mg, yield 98.3%.
Based on the detonation property of compound in Kamlet-Jacobs detonation parameter calculation formula predictions above-described embodiment 1 ~ 12, as follows respectively:
The explosion velocity of 3,6,7-triamino-1,2,4-triazolo ring-2,4-Nitroimidazole is 8500m/s, and detonation pressure is 30GPa;
The explosion velocity of 3,6,7-triamino-1,2,4-triazolo ring-4,5-Nitroimidazole is 8500m/s, and detonation pressure is 31GPa;
The explosion velocity of 3,6,7-triamino-1,2,4-triazolo ring-3,5-Nitroimidazole is 8700m/s, and detonation pressure is 32GPa;
The explosion velocity of 3,6,7-triamino-1,2,4-triazolo ring-3-amino-5-nitro-triazole is 8900m/s, and detonation pressure is 34GPa;
The explosion velocity of 3,6,7-triamino triazolo imidazoles-3-nitro-1,2,4-triazole-5-ketone is 8700m/s, and detonation pressure is 32GPa;
The explosion velocity of 3,6,7-triamino-1,2,4-triazolo ring-5,5 '-dinitrobenzene-3,3 '-Lian triazole is 9200m/s, and detonation pressure is 36GPa.
Although with reference to multiple explanatory embodiment of the present invention, invention has been described here, but, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiment, these amendments and embodiment will drop within spirit disclosed in the present application and spirit.More particularly, in scope disclosed in the present application, multiple modification and improvement can be carried out to the building block of subject combination layout and/or layout.Except the modification of carrying out building block and/or layout is with except improvement, to those skilled in the art, other purposes also will be obvious.
Claims (7)
1.3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds, is characterized in that their structural formula is as follows:
wherein
The preparation method of 2.3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds, is characterized in that its operation steps is as follows:
By 3,6,7-triamino-1,2,4-triazolo cyclic cpds and nitro azole-1H compound are scattered in appropriate deionized water, reacting by heating, then leave standstill, when temperature is down to normal temperature, leach solid, by described solid washing, drying, namely obtain described 3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds.
3. 3,6,7-triaminos-1 according to claim 2, the preparation method of 2,4-triazolo ring ionic nitro azole compounds, is characterized in that described nitro azole-1H compound is 2,4-Nitroimidazole-1H, 4,5-Nitroimidazole-1H, 3,5-binitropyrazole-1H, 3-amino-5-nitro-1,2,4-triazole-1H, 3-nitro-1,2,4-triazole-5-ketone or 5,5 '-dinitrobenzene-3,3 '-Lian triazole-1H, the one in 1 ' H.
4. 3,6,7-triaminos-1,2 according to claim 2, the preparation method of 4-triazolo ring ionic nitro azole compounds, is characterized in that described 3,6, the mol ratio of 7-triamino-1,2,4-triazolo cyclic cpds and nitro azole-1H compound is 1 ~ 2:1.
5. the preparation method of 3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds according to claim 2, is characterized in that the Heating temperature of described reacting by heating is 80 ~ 100 DEG C.
6. the preparation method of 3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds according to claim 2, is characterized in that the reaction times of described reacting by heating is 0.5 ~ 1h.
7. the preparation method of 3,6,7-triamino-1,2,4-triazolo ring ionic nitro azole compounds according to claim 2, is characterized in that the mol ratio of described deionized water and nitro azole-1H compound is 500 ~ 2200:1.
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| CN110256442A (en) * | 2019-07-15 | 2019-09-20 | 西安近代化学研究所 | The synthetic method of 3,6,7- triamido triazol triazole |
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