CN114195787A - A kind of 2-nitro-2-azadamantane-4,6,8-triol trinitrate and preparation method thereof - Google Patents
A kind of 2-nitro-2-azadamantane-4,6,8-triol trinitrate and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- FCUQIYNPBJJFIL-UHFFFAOYSA-N [O-][N+](N(C(CC1C(C2C3)O[N+]([O-])=O)C2O[N+]([O-])=O)C3C1O[N+]([O-])=O)=O Chemical compound [O-][N+](N(C(CC1C(C2C3)O[N+]([O-])=O)C2O[N+]([O-])=O)C3C1O[N+]([O-])=O)=O FCUQIYNPBJJFIL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 10
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 10
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000006396 nitration reaction Methods 0.000 claims abstract description 6
- -1 2-azaadamantane-4, 6, 8-triol Chemical compound 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 5
- 125000003047 N-acetyl group Chemical group 0.000 claims description 5
- YRRGPOPRKWXXFU-UHFFFAOYSA-N nona-3,7-dien-1-ol Chemical compound CC=CCCC=CCCO YRRGPOPRKWXXFU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000021736 acetylation Effects 0.000 abstract description 2
- 238000003379 elimination reaction Methods 0.000 abstract description 2
- 230000008030 elimination Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005474 detonation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- WENISBCJPGSITQ-UHFFFAOYSA-N 1-azatricyclo[3.3.1.13,7]decane Chemical compound C1C(C2)CC3CC1CN2C3 WENISBCJPGSITQ-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- ZLSDEVRDASOICE-UHFFFAOYSA-N 2-azaadamantane Chemical group C1C(N2)CC3CC1CC2C3 ZLSDEVRDASOICE-UHFFFAOYSA-N 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HONLSNLUVRQMEK-UHFFFAOYSA-N 1-nitroadamantane Chemical compound C1C(C2)CC3CC2CC1([N+](=O)[O-])C3 HONLSNLUVRQMEK-UHFFFAOYSA-N 0.000 description 1
- QKKRIUDGVWAMOQ-UHFFFAOYSA-N 2,4,4,8,8-pentanitro-2-azatricyclo[3.3.1.13,7]decane Chemical compound [N+](=O)([O-])N1C2C(C3CC(C(C1C3)([N+](=O)[O-])[N+](=O)[O-])C2)([N+](=O)[O-])[N+](=O)[O-] QKKRIUDGVWAMOQ-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- LEXUZPUJXTXGBE-UHFFFAOYSA-N 2-azatricyclo[3.3.1.13,7]decane-4,8-diol Chemical group OC1C2CC3CC1NC(C2)C3O LEXUZPUJXTXGBE-UHFFFAOYSA-N 0.000 description 1
- SGQNMEBCDRQVCK-UHFFFAOYSA-N 9-hydroxybicyclo[3.3.1]nonane-2,6-dione Chemical compound OC1C2C(CCC1C(CC2)=O)=O SGQNMEBCDRQVCK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- YLFIGGHWWPSIEG-UHFFFAOYSA-N aminoxyl Chemical compound [O]N YLFIGGHWWPSIEG-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BCJCJALHNXSXKE-UHFFFAOYSA-N azado Chemical group C1C(C2)CC3CC1N([O])C2C3 BCJCJALHNXSXKE-UHFFFAOYSA-N 0.000 description 1
- QWNPVTXLBMSEPN-UHFFFAOYSA-N bicyclo[3.3.1]nonane-2,6-dione Chemical compound C1C2C(=O)CCC1C(=O)CC2 QWNPVTXLBMSEPN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XJVXLZXIMBRIAJ-XEPYTYEKSA-N dapholdhamine b Chemical compound C1CC[C@@]2(O)[C@]3(CCC(O)=O)[C@@]4(C)CC[C@H](C(C)C)[C@H]3N3[C@H]1[C@H]2C[C@H]4C3 XJVXLZXIMBRIAJ-XEPYTYEKSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940052761 dopaminergic adamantane derivative Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/08—Bridged systems
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/32—Compositions containing a nitrated organic compound the compound being nitrated pentaerythritol
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate and a preparation method thereof. The method takes 9-hydroxy bicyclo [3.3.1] nonane-2, 6-diketone as a raw material, and finally synthesizes the 2-nitro-2-aza adamantane-4, 6, 8-triol trinitrate through the steps of hydrazonation, elimination, epoxidation, cyclization, acetylation, nitration and the like.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a new compound 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate and a synthesis method thereof.
Background
Adamantane has a three-dimensional cage-shaped carbon skeleton, a compact structure and good thermal stability, is an important organic compound, and can be widely applied to the fields of medicines, lubricants, functional polymers and the like. Wherein the nitro adamantane has the advantages of high energy, passivity and the like due to the unique molecular structure, and can be used for the compound containingThe material can be obtained, and research shows that the polynitro aza adamantane obtained by replacing carbon atoms on an adamantane ring by one or more nitrogen atoms has better detonation performance. For example, the results of the year 2018,
the adamantane is taken as a raw material to synthesize the adamantane-1, 3,5, 7-tetraol tetranitrate ester (
T M, chemplus chem,2018,83, 61). The calculation result shows that the detonation velocity is about 7282m.s < -1 > and the detonation pressure is about 22.9 GPa.
The azaadamantane derivative is widely applied to the fields of medicines, catalysis and energetic materials. Wherein the natural drug molecule Dapholdhamine B is 1-azaadamantane as a skeleton (Guo L D, J.Am.chem.Soc.,2019,141,11713); the 2-azaadamantane skeleton is another secondary amine type azaadamantane structure, and 2-azaadamantane-N-oxyl which is more researched can be used as a high-activity and high-selectivity catalytic oxidation reaction catalyst (Kawamata T, J.Am.chem.Soc.,2017,139,1814); the 2-azaadamantane-4, 8-diol backbone was used to synthesize a novel energetic compound, 2,4,4,8, 8-pentanitro-2-azaadamantane (Hou T, Eur.J.org.chem.,2017,6957). However, no report has been made on the method for constructing a 2-azaadamantane skeleton in a higher oxidation state.
Disclosure of Invention
The invention aims to provide 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate and a synthesis method thereof, the compound has higher oxidation degree and introduces four nitro groups, and has higher density and energy than other adamantane derivatives containing four nitro groups, and the synthesis method has the advantages of easily available raw materials, simple operation, higher yield and the like.
The technical solution for realizing the purpose of the invention is as follows:
2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate, which has the following structure:
the preparation method of the compound comprises the following steps:
(1) the bicyclo [3.3.1]]Epoxidation reaction of nonane-2, 6-diene-9-ol and m-chloroperoxybenzoic acid to prepare 3, 8-dioxatetracyclo [4.4.1.02,4.07,9]A step of extracting undecane-11-ol,
(2) the 3, 8-dioxatetracyclo [4.4.1.0 ]2,4.07,9]A step of preparing 2-azaadamantane-4, 6, 8-triol by cyclization reaction of undecane-11-ol and methanol solution of saturated ammonia gas,
(3) the 2-azaadamantane-4, 6, 8-triol is subjected to acetylation reaction under the action of acetic anhydride and alkali to prepare 2-acetyl adamantane-4, 6, 8-triol;
(4) a step of preparing 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate by sequentially carrying out alcohol hydroxyl nitration and N-acetyl nitrohydrolysis on 2-acetyl-2-azaadamantane-4, 6, 8-triol in a mixed acid system of fuming nitric acid and fuming sulfuric acid,
further, in the step (1), the epoxidation reaction is carried out in the presence of an organic solvent dichloromethane; the molar ratio of bicyclo [3.3.1] nonane-2, 6-diene-9-ol to m-chloroperoxybenzoic acid is 1: 2.4-3.0; the epoxidation reaction temperature is 25-40 ℃; the epoxidation reaction time is 24-36 h.
Further, in the step (2), the cyclization reaction temperature is 110-140 ℃; the cyclization reaction time is 24-48 h; 3, 8-dioxatetracyclo [4.4.1.0 ] -2,4.07,9]The molar ratio of the undecane-11-ol to the ammonia gas is 1: 40-50.
Further, in the step (3), acetylation is carried out in the presence of an organic solvent dichloromethane, and the molar ratio of 2-azaadamantane-4, 6, 8-triol to acetic anhydride is 1: 1.0-1.2; the base is triethylamine; the temperature of acetylation reaction is 0-30 ℃; the acetylation reaction time is 8-16 h.
Further, in the step (4), the volume ratio of fuming sulfuric acid to fuming nitric acid is 1: 1.5-2.5; the temperature of the alcohol hydroxyl nitration reaction is 0-25 ℃, and the reaction time is 0.5-1 h; the temperature of the N-acetyl nitrohydrolysis reaction is 60-80 ℃, and the reaction time is 4-8 h; the molar ratio of the 2-acetyl adamantane-4, 6, 8-triol to the fuming nitric acid is 1: 20-30.
Compared with the prior art, the invention has the following advantages: (1) the method has the advantages of easily obtained raw materials, simple synthesis steps, easy operation, high yield and easy scale-up preparation; (2) the invention introduces nitrogen heteroatom and nitroxyl radical on the basis of tetranitroadamantane, improves oxygen balance and enables the tetranitroadamantane to have higher density and energy.
Drawings
FIG. 1 shows a bicyclo [3.3.1] ring of the invention]Process for preparing nonane-2, 6-dien-9-ols1H NMR spectrum.
FIG. 2 shows a bicyclo [3.3.1] ring of the invention]Process for preparing nonane-2, 6-dien-9-ols13C NMR spectrum.
FIG. 3 shows a 3, 8-dioxatetracyclo [4.4.1.0 ] of the present invention2,4.07,9]Process for preparing undecane-11-ol1H NMR spectrum.
FIG. 4 shows a 3, 8-dioxatetracyclo [4.4.1.0 ] of the present invention2,4.07,9]Process for preparing undecane-11-ol13C NMR spectrum.
FIG. 5 is a drawing showing the preparation of 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate according to the present invention1H NMR spectrum.
FIG. 6 is a drawing showing 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate of the present invention13C NMR spectrum.
FIG. 7 is a FT-IR spectrum of 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate of the present invention.
FIG. 8 is a TG-DSC of 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and examples.
The general synthetic route of the 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate ester is as follows:
the synthesis method comprises the following specific steps:
(1) dissolving bicyclo [3.3.1] nonane-2, 6-dione and p-toluenesulfonyl hydrazide in an organic solvent methanol, stirring for 2-6 h at 65-75 ℃, and carrying out a hydrazonation reaction to synthesize 9-hydroxybicyclo [3.3.1] nonane-2, 6-diylidene bis (4-methylbenzenesulfonyl hydrazide);
(2) sequentially adding diisopropylamine and n-butyllithium into an organic solvent tetrahydrofuran at low temperature, then adding 9-hydroxybicyclo [3.3.1] nonane-2, 6-diylidene bis (4-methylbenzenesulfonyl hydrazide) into a reaction solvent in batches, stirring for 18-24 hours at the temperature of-68 to-78 ℃, and carrying out elimination reaction to synthesize bicyclo [3.3.1] nonane-2, 6-diene-9-ol;
(3) the bicyclo [3.3.1]]Dissolving nonane-2, 6-diene-9-alcohol and m-chloroperoxybenzoic acid in an organic solvent dichloromethane, stirring for 24-36 h at 25-40 ℃, and carrying out epoxidation reaction to synthesize 3, 8-dioxatetracyclo [4.4.1.0 ]2,4.07,9]Undecane-11-ol;
(4) the 3, 8-dioxatetracyclo [4.4.1.0 ]2,4.07,9]Adding undecane-11-ol into a methanol solution of saturated ammonia gas, stirring and reacting for 24-48 h at 110-140 ℃, and carrying out cyclization reaction to synthesize 2-azaadamantane-4, 6, 8-triol;
(5) dissolving 2-azaadamantane-4, 6, 8-triol in a solvent dichloromethane, adding acetic anhydride, adding triethylamine to neutralize acetic acid generated in the reaction process, stirring and reacting for 8-16 h at 0-30 ℃, and performing acetylation reaction to synthesize 2-acetyl-2-azaadamantane-4, 6, 8-triol;
(6) under the ice bath condition, fuming sulfuric acid and fuming nitric acid in a volume ratio of 1: 1.5-2.5 are mixed and stirred uniformly, then the fuming nitric acid and fuming sulfuric acid are added into 2-acetyl-2-azaadamantane-4, 6, 8-triol, and the mixture is stirred and reacted for 0.5-1 h at the temperature of 0-25 ℃ to generate nitration reaction of alcoholic hydroxyl; and then heating to 60-80 ℃, stirring and reacting for 4-8 h, and carrying out N-acetyl nitrohydrolysis reaction to synthesize 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate.
Example 1
Preparation of (mono) 9-hydroxybicyclo [3.3.1] nonane-2, 6-diylidenebis (4-methylbenzenesulfonyl hydrazide)
504mg (3.00mmol) of 9-hydroxybicyclo [3.3.1] nonane-2, 6-dione are added to 25mL of methanol, 1.34g (7.2mmol) of p-toluenesulfonylhydrazide is added thereto, and the mixture is heated to 68 ℃ and refluxed for 4 hours. The solvent was distilled off under reduced pressure, washed with cold absolute ethanol, and dried under vacuum to give 1.36g of a white solid. The yield thereof was found to be 90%.
Example 2
Preparation of (di) bicyclo [3.3.1] nonane-2, 6-dien-9-ol
At low temperature, adding 5.6mL (3.50mmol) of diisopropylamine and n-butyllithium into 15mL of tetrahydrofuran in sequence, adding 1.008g (2.00mmol) of raw materials in batches after the dropwise addition is finished, slowly raising the temperature to 25 ℃ after the raw materials are added, and continuing stirring and reacting for 12 hours. And dropwise adding 30mL of water under ice bath to quench the reaction, extracting with ethyl acetate, adjusting the pH to 4-5 with 10% diluted hydrochloric acid, washing with saturated saline solution, carrying out reduced pressure distillation to obtain 300mg of a golden yellow oily substance, and carrying out silica gel column chromatography to obtain 240mg of a white solid with the yield of 88%. Its characteristic map is shown in figure 1 andas shown in fig. 2.1H NMR(500MHz,CDCl3)δ:5.92-5.51(m,4H),3.95(d,J＝5.9Hz,1H),2.62-2.33(m,4H),2.07(dd,J＝17.8,4.7Hz,1H),1.94-1.80(m,2H)ppm.13C NMR(126MHz,CDCl3)δ:130.51,127.49,125.70,124.83,68.40,35.85,34.58,31.93,25.65ppm.。
Example 3
(III) 3, 8-dioxatetracyclo [4.4.1.02,4.07,9]Preparation of undecane-11-ol
272mg (2.00mmol) of bicyclo [3.3.1]Dissolving nonane-2, 6-dien-9-ol in 10mL of dichloromethane, adding 863mg (4.81mmol) of mCPBA, reacting at 25 ℃ for 24h, and dropwise adding 20mL of 10% NaHSO3The reaction was quenched with aqueous solution, extracted with dichloromethane, the combined organic phases were chromatographed on silica gel column to give 289mg of a white solid in 86% yield. The characterization maps are shown in fig. 3 and 4.1H NMR(500MHz,CDCl3)δ:3.81(s,1H),3.42(s,1H),3.32(t,J＝4.7Hz,1H),3.17(d,J＝8.4Hz,2H),3.11(t,J＝4.4Hz,1H),2.51-2.43(m,2H),2.37(d,J＝7.0Hz,1H),2.29(dd,J＝15.9,6.9Hz,1H),2.05-1.95(m,2H)ppm.13C NMR(126MHz,CDCl3)δ:66.21,59.05,58.11,50.93,49.32,31.53,30.94,26.92,22.79ppm.。
Example 4
Preparation of (tetra) 2-azaadamantane-4, 6, 8-triol
336mg (2.00mmol) of 3, 8-dioxatetracyclo [4.4.1.0 ]2,4.07,9]Adding 5mL of saturated ammonia gas methanol solution into undecane-11-ol, heating to 120 ℃ for reaction for 48h, cooling, filtering, washing with cold ethanol for 2-3 times, and distilling under reduced pressure to obtain 300mg of light yellow solid with the yield of 81%.
Example 5
Preparation of (penta) 2-acetyl-2-azaadamantane-4, 6, 8-triol
370mg (2.00mmol) of 2-azaadamantane-4, 6, 8-triol are dissolved in 7mL of dichloromethane, then 0.21mL (2.22mmol) of acetic anhydride and 0.56mL (4.05mmol) of triethylamine are added, the mixture is reacted for 8h at 25 ℃, 480mg of yellow oily matter is obtained by reduced pressure distillation, 364mg of white solid is obtained by silica gel column chromatography, and the yield is 80%.
Example 6
Preparation of (hexa) 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate
Under the ice bath condition, 2mL fuming nitric acid and 1.0mL fuming sulfuric acid are respectively added into a single-mouth bottle to be stirred and reacted for 20min, then the fuming nitric acid and the fuming sulfuric acid are added into 454mg (2.00mmol) of 2-acetyl-2-azaadamantane-4, 6, 8-triol, the mixture is stirred and reacted for 0.5h under the ice bath condition, then the temperature is increased to 65 ℃ to be reacted for 6h, the mixture is poured into ice water to be filtered, washed by cold ethanol and dried in vacuum, and 497mg of white solid is obtained, and the yield is 68%. The characterization maps are shown in FIGS. 5-7.1H NMR(500MHz,(CD3)2CO)δ:5.60-5.09(m,3H),5.05-4.89(m,1H),4.49(dd,J＝7.2,3.6Hz,1H),2.97(s,1H),2.86(d,J＝4.7Hz,1H),2.45-2.32(m,2H),2.15(d,J＝4.6Hz,2H)ppm.13C NMR(126MHz,(CD3)2CO)δ:80.93,80.51,79.37,79.02,78.46,48.07,47.87,42.29,42.09,32.44,32.39,31.87,31.82,24.65,23,20.51,20.47ppm.IR(thin film,υcm-1):2925,1624,1426,1267,1000,970,931,831.
The density of the compound is 1.79g.cm by theoretical calculation-3The detonation velocity was 8060m.s-1The detonation pressure was 28.73 GPa.
The thermal stability of the compound was studied by a thermogravimetric analyzer (TG) and a Differential Scanning Calorimeter (DSC), and its characterization map is shown in fig. 8. As can be seen from FIG. 8, there is a distinct endothermic peak at 175 ℃ indicating a melting point of 175 ℃ and a distinct exothermic peak at 196 ℃ indicating a sharp exotherm at 196 ℃. The total weight loss from the beginning to the end of the decomposition is 68 percent, and the results show that the 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate has better thermal stability.
Claims (7)
1. A 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate having the structure:
2. a preparation method of 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate is characterized by comprising the following steps:
(1) the bicyclo [3.3.1]]Epoxidation reaction of nonane-2, 6-diene-9-ol and m-chloroperoxybenzoic acid to prepare 3, 8-dioxatetracyclo [4.4.1.02,4.07,9]A step of extracting undecane-11-ol,
(2) the 3, 8-dioxatetracyclo [4.4.1.0 ]2,4.07,9]A step of preparing 2-azaadamantane-4, 6, 8-triol by cyclization reaction of undecane-11-ol and methanol solution of saturated ammonia gas,
(3) the 2-azaadamantane-4, 6, 8-triol is subjected to acetylation reaction under the action of acetic anhydride and alkali to prepare 2-acetyl adamantane-4, 6, 8-triol;
(4) a step of preparing 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate by sequentially carrying out alcohol hydroxyl nitration and N-acetyl nitrohydrolysis on 2-acetyl-2-azaadamantane-4, 6, 8-triol in a mixed acid system of fuming nitric acid and fuming sulfuric acid,
3. the process according to claim 2, wherein in step (1), the epoxidation reaction is carried out in the presence of an organic solvent, dichloromethane; the molar ratio of bicyclo [3.3.1] nonane-2, 6-diene-9-ol to m-chloroperoxybenzoic acid is 1: 2.4-3.0; the epoxidation reaction temperature is 25-40 ℃; the epoxidation reaction time is 24-36 h.
4. The method according to claim 2, wherein in the step (2), the cyclization reaction temperature is 110-140 ℃; the cyclization reaction time is 24-48 h; 3, 8-dioxatetracyclo [4.4.1.0 ] -2,4.07,9]The molar ratio of the undecane-11-ol to the ammonia gas is 1: 40-50.
5. The method according to claim 2, wherein in the step (3), the acetylation reaction is carried out in the presence of an organic solvent dichloromethane, and the molar ratio of 2-azaadamantane-4, 6, 8-triol to acetic anhydride is 1: 1.0-1.2; the base is triethylamine; the temperature of acetylation reaction is 0-30 ℃; the acetylation reaction time is 8-16 h.
6. The method according to claim 2, wherein in step (4), the volume ratio of fuming sulfuric acid to fuming nitric acid is 1: 1.5-2.5; the temperature of the alcohol hydroxyl nitration reaction is 0-25 ℃, and the reaction time is 0.5-1 h; the temperature of the N-acetyl nitrohydrolysis reaction is 60-80 ℃, and the reaction time is 4-8 h; the molar ratio of the 2-acetyl adamantane-4, 6, 8-triol to the fuming nitric acid is 1: 20-30.
7. Use of 2-nitro-2-azaadamantane-4, 6, 8-triol trinitrate according to claim 1 as an energetic material.
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