CN103864621A - Energetic material 4, 4, 8, 8-tetranitroadamantane-2, 6-dinitrate and preparation method thereof - Google Patents
Energetic material 4, 4, 8, 8-tetranitroadamantane-2, 6-dinitrate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an energetic material 4, 4, 8, 8-tetranitroadamantane-2, 6-dinitrate and a preparation method thereof. According to the preparation method, cyclooctadiene as the raw material undergoes the steps of hydroboration-oxidation, oxidation, formylation, cyclization, nitric acid esterification, oximation, germinal nitration and the like to be finally synthesized into 4, 4, 8, 8-tetranitroadamantane-2, 6-dinitrate. Polynitroadamantane and adamantine nitrate have the advantages of symmetrical structure, high density, excellent explosion property, low sensitivity and the like, and can be widely used in the fields of explosives, propellants, pyrotechnic compositions, fuels and the like.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of novel energetic material 4,4,8,8-tetranitro diamantane-2, the synthetic method of 6-dinitrate.
Background technology
Diamantane is a kind of structure uniqueness, the cage shape hydrocarbon of excellent property, easily there is a series of replacements, oxidizing reaction in its bridge carbon atom, generate the multiple adamantane derivative with important use, there is extensive use in fields such as pharmacy, fine chemistry industry, functional high molecule material, aerospace, be described as " fine chemical material of new generation ".Wherein nitro adamantane derivative, due to the high symmetry of molecular structure, has the advantage such as high energy, low sense, can be used for heat-resisting insensitiveness high energy material, therefore has broad application prospects, and synthesizes so far many nitros diamantane of multiple replacement.
1993, Dave synthesized 2,2,4,4,6,6-hexanitro-diamantane (HNA) (Paritosh, R. D. Tetrahedron. 1992,48,5839 take dimethyl malonate and paraformaldehyde as raw material; Paritosh, R. D.; Little, F. US 5202508,1983; Paritosh, R. D.; Little, F. US 5180853,1993).Calculation result shows, the explosion velocity of HNA is about 8700 ms
-1, detonation pressure is about 34.6 GPa, is a kind of high explosive of superior performance.But this synthetic method exists, and step is many, productive rate is low, cost is high, be difficult to the shortcomings such as amplification, therefore develops more low cost, more efficient nitro adamantane derivative and there is urgency and necessity.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of novel many nitros adamantane derivative, compared with the synthetic method of hexanitro-diamantane, the method raw material is easy to get, cost is low, it is little to pollute, simple to operate, productive rate is compared with advantages of higher.
The technical solution that realizes the object of the invention is:
A kind of 4,4,8,8-tetranitro diamantane-2,6-dinitrate, its structure is as follows:
The preparation method of above-claimed cpd, its syntheti c route is as follows:
The method comprises the steps:
(1) tetrahydrofuran solution of cyclooctadiene is slowly added in tetrahydrofuran (THF) borane complex, stirring at normal temperature starts to drip 3N aqueous sodium hydroxide solution after reaction for some time, after stirring for some time, adds 30wt% hydrogen peroxide, reacting by heating again, synthetic 1,5-ring ethohexadiol;
(2) under low temperature, oxalyl chloride is added to CH
2cl
2in, stir the lower DMSO of dropping, after reaction for some time, add step (1) described 1,5-encircle ethohexadiol, adds triethylamine after reacting for some time, and low-temp reaction obtains 1, and 5-encircles acetyl caproyl;
(3), by described step (2) 1,5-ring acetyl caproyl is dissolved in reaction solvent, adds solution and the ethyl formate of sodium methylate, reacting by heating, and synthetic 2,6-dioxo ring is pungent-1-formaldehyde;
(4) by described step (3) 2,6-dioxo ring is pungent-and 1-formaldehyde is dissolved in solvent, adds
l-proline(Pro), reacting by heating, synthetic 9-hydroxyl dicyclo [3.3.1] nonane-2,6-diketone;
(5) by step (4) described 9-hydroxyl dicyclo [3.3.1] nonane-2,6-diketone is dissolved in reaction solvent, adds solution and the ethyl formate of sodium methylate, reacting by heating, synthetic 9-hydroxyl-2,6-dioxo-bicyclo [3.3.1] nonane-3-formaldehyde;
(6), by the described 9-of step (5) hydroxyl-2,6-dioxo-bicyclo [3.3.1] nonane-3-formaldehyde is dissolved in solvent, adds
l-proline(Pro), reacting by heating, synthetic 4,8-dihydroxyl diamantane-2,6-diketone;
(7) under condition of ice bath, nitric acid is added in the mixing solutions of diacetyl oxide and acetic acid, under agitation condition, add step (6) described 4,8-dihydroxyl diamantane-2,6-diketone, stirring reaction, synthetic 4,8-dioxo diamantane-2,6-dinitrate;
(8) by described step (7) 4,8-dioxo diamantane-2,6-dinitrate, in solvent, adds oxammonium hydrochloride, sodium acetate, stirring reaction, synthetic 4,8-dihydroxyl imino-diamantane-2,6-dinitrate;
(9) by described step (8) 4,8-dihydroxyl imino-diamantane-2,6-dinitrate is dissolved in organic solvent, adds reaction promoter, under heating condition, slowly drip the organic solution of nitrogen pentoxide, synthetic 4,4,8,8-tetranitro diamantane-2,6-dinitrate.
Wherein, in step (3) 1, the mol ratio of 5-ring acetyl caproyl and sodium methylate is 1:1 ~ 3, is preferably 1:1 ~ 1.5; Dicyclo [3.3.1] nonane-2, the mol ratio of 6-diketone and ethyl formate is 1:1 ~ 4, is preferably 1:1.5 ~ 2.5; Reaction solvent is selected toluene, ethanol or methyl alcohol, particular methanol; Temperature of reaction is 20 ~ 60 ℃, is preferably 35 ~ 45 ℃.Reaction times is 6 ~ 20 h, is preferably 15 ~ 17 h.
In step (4) 2,6-dioxo ring is pungent-1-formaldehyde with
lthe mol ratio of-proline(Pro) is 1:0.2 ~ 0.5; Reaction solvent is selected DMF, CH
3cN or DMSO, preferably CH
3cN; Temperature of reaction is 40 ~ 80 ℃, is preferably 65 ~ 75 ℃; Reaction times is 5 ~ 10 h, is preferably 7 ~ 9 h.
9-hydroxyl dicyclo [3.3.1] nonane-2 in step (5), the mol ratio of 6-diketone and sodium methylate is 1:1 ~ 3, is preferably 1:1 ~ 1.5; Dicyclo [3.3.1] nonane-2, the mol ratio of 6-diketone and ethyl formate is 1:1 ~ 4, is preferably 1:1.5 ~ 2.5; Reaction solvent is selected toluene, ethanol or methyl alcohol, particular methanol; Temperature of reaction is 20 ~ 60 ℃, is preferably 35 ~ 45 ℃.Reaction times is 6 ~ 20 h, is preferably 15 ~ 17 h.
9-hydroxyl-2 in step (6), 6-dioxo-bicyclo [3.3.1] nonane-3-formaldehyde with
lthe mol ratio of-proline(Pro) is 1:0.2 ~ 0.5; Reaction solvent is selected DMF, CH
3cN or DMSO, preferably CH
3cN; Temperature of reaction is 40 ~ 80 ℃, is preferably 65 ~ 75 ℃; Reaction times is 5 ~ 10 h, is preferably 7 ~ 9 h.
In step (7) 4,8-dihydroxyl diamantane-2, the mol ratio of 6-diketone and acetic acid is 1:6 ~ 10; 4,8-dihydroxyl diamantane-2, the mol ratio of 6-diketone and diacetyl oxide is 1:2 ~ 8; 4,8-dihydroxyl diamantane-2, the mol ratio of 6-diketone and nitric acid is 1:2 ~ 8; Temperature of reaction is 0 ~ 25 ℃; Reaction times is 2 ~ 6 h.
In step (8), reaction solvent is selected methyl alcohol and ethanol, is preferably methyl alcohol; 4,8-dioxo diamantane-2, the mol ratio of 6-dinitrate and oxammonium hydrochloride is 1:2 ~ 6; 4,8-dioxo diamantane-2, the mol ratio of 6-dinitrate and sodium acetate is 1:2 ~ 6; Temperature of reaction is 40 ~ 70 ℃; Reaction times is 12 ~ 20 h.
In step (9) 4,8-dihydroxyl imino-diamantane-2, the mol ratio of 6-dinitrate and nitrogen pentoxide is 1:2.5 ~ 8; Reaction solvent is selected CH
2cl
2, CHCl
3, CH
2nO
2and ClCH
2cH
2cl, is preferably CH
2cl
2; Reaction promoter is molecular sieve or urea; Temperature of reaction is 35 ~ 55 ℃; Reaction times is 15 ~ 40 min.
Compared with prior art, its remarkable advantage is in the present invention: (1) 4,4,8,8-tetranitro diamantane-2,6-dinitrate and 2,2,4,4,6,6-hexanitro-diamantane is the same, belongs in six many nitros of replacement adamantane structures, but in its structure, two itrate groups are on contraposition position, sterically hindered lower, and structure is more symmetrical, in guaranteeing energy, has higher stability.(2) the present invention builds adamantane framework by the step of twice formylation, cyclization, has that post-reaction treatment is simple, productive rate advantages of higher.(3) reaction pollution is little, uses the green nitration agent N of equivalent together with denitrification step
2o
5carry out nitratedly, avoided traditional nitrated system to use the shortcoming of excessive nitrating agent, have that speed of response is fast, temperature of reaction is easy to control, product is easily separated, product purity is high, can effectively reduce the advantages such as spent acid.(4) construction process of adamantane framework in present method, can offer reference for the synthetic of other polysubstituted diamantane.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 the present invention 2,6-dioxo ring is pungent-1-formaldehyde
1h NMR spectrogram.
Fig. 2 the present invention 2,6-dioxo ring is pungent-1-formaldehyde
13c NMR spectrogram.
Fig. 3 the present invention 2,6-dioxo ring is pungent-the FT-IR spectrogram of 1-formaldehyde.
Fig. 4 9-hydroxyl of the present invention dicyclo [3.3.1] nonane-2,6-diketone
1h NMR spectrogram.
Fig. 5 9-hydroxyl of the present invention dicyclo [3.3.1] nonane-2,6-diketone
13c NMR spectrogram.
Fig. 6 9-hydroxyl of the present invention dicyclo [3.3.1] nonane-2, the FT-IR spectrogram of 6-diketone.
Fig. 7 9-of the present invention hydroxyl-2,6-dioxo-bicyclo [3.3.1] nonane-3-formaldehyde
1h NMR spectrogram.
Fig. 8 9-of the present invention hydroxyl-2, the FT-IR spectrogram of 6-dioxo-bicyclo [3.3.1] nonane-3-formaldehyde.
Fig. 9 the present invention 4,4,8,8-tetranitro diamantane-2,6-dinitrate
1h NMR spectrogram.
Figure 10 the present invention 4,4,8,8-tetranitro diamantane-2,6-dinitrate
13c NMR spectrogram.
Embodiment
The preparation of 1,5-ring ethohexadiol
N
2under protective condition, 20 mL 1M borine tetrahydrofuran complexes (20 mmol) are added in there-necked flask.By 2.45 mL 1,5-cyclooctadiene (20 mmol) adds in the dropping funnel that has 2.55 mL tetrahydrofuran (THF)s, and is slowly added drop-wise in there-necked flask under condition of ice bath.After being added dropwise to complete, normal-temperature reaction 1 h.With slowly dripping the 8 mL 3 M NaOH aqueous solution in backward system.After the NaOH aqueous solution drips completely, in system, drip 12 mL 30% superoxols, after dropping completely, react 4 h at 40 ℃.After finishing, reaction adds appropriate K
2cO
3to solution layering, be extracted with ethyl acetate organic phase anhydrous Na 3-6 time
2sO
4dry, underpressure distillation, except desolventizing, obtains the colourless viscous liquid of 2.6 g, productive rate 95%.
The preparation of 1,5-ring acetyl caproyl
Successively 55 mL methylene dichloride, 4.13 mL oxalyl chlorides (48.05 mmol) are added in there-necked flask, and be cooled to-68 ℃.N
2under protection, in system, slowly drip 6.62 mL DMSO(93.2 mmol), drip follow-up continuous stirring 15 min completely.By 3 g 1,5-ring ethohexadiol (20.8 mmol) is dissolved in 15 mL DMSO, and slowly drops in flask, and it is muddy that solution becomes, and drips after closing and continues at low temperatures reaction 70 min.Continue at low temperatures to drip 29.7 mL triethylamines (213 mmol), continue to stir 30 min, and allow reaction system in 1 h, slowly rise to normal temperature.After reaction finishes, the saturated aqueous solution washing of 150 mL ammonium chlorides and sodium bicarbonate for reaction system, with dichloromethane extraction, organic phase anhydrous sodium sulfate drying, underpressure distillation, except desolventizing, obtains the yellow dope of 2.9 g.Column chromatography purification obtains 2.52 g white solids, yield 86%.
2,6-dioxo ring is pungent-preparation of 1-formaldehyde
By 7.45 g(53 mmol) 1,5-ring acetyl caproyl adds in single port flask, and successively adds 20 mL methyl alcohol, 8.55 mL ethyl formates (106 mmol), stir solids is all dissolved.3.15 g sodium methylates (58.3 mmol) are dissolved in 20 mL methyl alcohol, and under condition of ice bath, slowly drop in reaction system, system is become faint yellow from achromaticity and clarification.After dripping completely, at 40 ℃ of reaction 16 h.Underpressure distillation is except desolventizing, and is adjusted to neutrality with 6 M hydrochloric acid, adds a small amount of water, use dichloromethane extraction (100 mL × 3), organic phase anhydrous Na
2sO
4, underpressure distillation removes desolventizing and obtains brown liquid, and column chromatography obtains 7.6 g white solids, yield 86%.
1H?NMR?(500?MHz,?CDCl
3)?δ:?15.05?(s,?1H),?8.35?(s,?1H),?2.57?–?2.51?(m,?2H),?2.50?–?2.44?(m,?2H),?2.43?–?2.32?(m,?5H),?1.78?(m,?2H);?
13C?NMR?(126?MHz,?CDCl
3)?δ:?212.27,?191.19,?182.52,?110.65,?48.16,?38.83,?34.35,?21.92,?21.35;?IR?(KBr)?ν:?2964,?1694,?1464.
Only change the amount of ethyl formate in embodiment 3 into 6.4 mL(79.5 mmol), temperature of reaction changes 60 ℃ into, and the reaction times changes 6 h into, and other operations are consistent with embodiment 3.6.9 g 2,6-dioxo ring is pungent-1-formaldehyde, yield 78%.
Only change reaction solvent in embodiment 3 into toluene, the amount of ethyl formate changes 17.1 mL(212 mmol into), CH
3the amount of ONa changes 8.6 g(159 mmol into), temperature of reaction changes 45 ℃ into, and the reaction times changes 17 h into, and other operations are consistent with embodiment 3.6.4 g 2,6-dioxo ring is pungent-1-formaldehyde, yield 72%.
Only change the amount of ethyl formate in embodiment 3 into 10.6 mL(132.5 mmol), CH
3the amount of ONa changes 4.3 g(79.5 mmol into), temperature of reaction changes 20 ℃ into, and the reaction times changes 17 h into, and other operations are consistent with embodiment 3.6.7 g 2,6-dioxo ring is pungent-1-formaldehyde, yield 76%.
Only change reaction solvent in embodiment 3 into ethanol, the amount of ethyl formate changes 4.3 mL(53 mmol into), CH
3the amount of ONa changes 5.33 g(98.5 mmol into), the reaction times changes 20 h into, and other operations are consistent with embodiment 3.7.1 g 2,6-dioxo ring is pungent-1-formaldehyde, yield 80%.
Only, by embodiment 3, the amount of ethyl formate changes 17.1 mL(212 mmol into), temperature of reaction changes 35 ℃ into, and the reaction times changes 15 h into, and other operations are consistent with embodiment 3.5.8 g 2,6-dioxo ring is pungent-1-formaldehyde, yield 66%.
9-hydroxyl dicyclo [3.3.1] nonane-2, the preparation of 6-diketone
Successively, by 4.18 g 2-formyl radical-1,5-encircles acetyl caproyl (22.4 mmol), 50 mL acetonitriles, 1.03 g
l-proline(Pro) adds in single port flask, under agitation condition, reacts 8 h at 70 ℃.Underpressure distillation is except desolventizing, and column chromatography obtains 2.07 g white solids, yield 80%.
1H?NMR?(500?MHz,?CDCl
3)?δ?4.32?(s,?1H),?3.59?(s,?1H),?2.83?(d,?
J?=?25.0?Hz,?2H),?2.57?(m,?1H),?2.52?–?2.39?(m,?2H),?2.31?(m,?2H),?2.01?–?1.87?(m,?2H),?1.87?–?1.78?(m,?1H);?
13C?NMR?(126?MHz,?CDCl
3)?δ?212.16,?211.06,?70.42,?50.23,?50.14,?36.07,?35.33,?21.23,?20.19;?IR?(KBr)?ν:?3442,?2941,?1683,?1455,?1228,?1068,?766.
Only by embodiment 9
lthe amount of-proline(Pro) changes 0.52 g(4.48 mmol into), temperature of reaction changes 75 ℃ into, and the reaction times changes 10 h into, and other operations are consistent with embodiment 9.Obtain 1.73 g 4-hydroxyl-2,6-diamantane diketone, yield 67%.
Only change reaction solvent in embodiment 9 into DMF,
lthe amount of-proline(Pro) changes 1.3 g(11.2 mmol into), change temperature of reaction into 40 ℃, the reaction times changes 10 h into, and other operations are consistent with embodiment 9.Obtain 2.02 g 4-hydroxyl-2,6-diamantane diketone, yield 78%.
Only change reaction solvent in embodiment 9 into DMSO, temperature of reaction changes 65 ℃ into, and the reaction times changes 7 h into, and other operations are consistent with embodiment 9.Obtain 1.91 g 4-hydroxyl-2,6-diamantane diketone, yield 74%.
Only change temperature of reaction in embodiment 9 into 80 ℃, the reaction times changes 5 h into, and other operations are consistent with embodiment 9.Obtain 1.86 g 4-hydroxyl-2,6-diamantane diketone, yield 72%.
Only by embodiment 9
lthe amount of-proline(Pro) changes 1.15 g(10 mmol into), temperature of reaction changes 65 ℃ into, and the reaction times changes 9 h into, and other operations are consistent with embodiment 9.Obtain 7.6 g 4-hydroxyl-2,6-diamantane diketone, yield 85%.
9-hydroxyl-2, the preparation of 6-dioxo-bicyclo [3.3.1] nonane-3-formaldehyde
By 3.5 g(20.8 mmol) 9-hydroxyl dicyclo [3.3.1] nonane-2,6-diketone adds in single port flask, and successively adds 20 mL methyl alcohol, 5.05 mL ethyl formates (62.43 mmol), stir solids is all dissolved.1.69 g sodium methylates (31.2 mmol) are dissolved in 20 mL methyl alcohol, and under condition of ice bath, slowly drop in reaction system, system is become faint yellow from achromaticity and clarification.After dripping completely, at 40 ℃ of reaction 16 h.Underpressure distillation is except desolventizing, and is adjusted to neutrality with 6 M hydrochloric acid, adds a small amount of water, use dichloromethane extraction (100 mL × 3), organic phase anhydrous Na
2sO
4, underpressure distillation removes desolventizing and obtains brown liquid, and column chromatography obtains 3.29 g white solids, yield 82%.
1H?NMR?(500?MHz,?DMSO)?δ?11.15?(s,?1H),?10.42?–?8.93?(m,?1H),?5.83?–?4.99?(m,?1H),?4.20?–?3.92?(m,?1H),?2.70?–?2.06?(m,?7H),?1.94?–?1.76?(m,?1H);?IR?(KBr)?ν:?3443,?766?(—O—H),?2941,?1455?(—C—H),?1684?(—C=O),?1228,?1068?(—C—O).
Only change the amount of ethyl formate in embodiment 15 into 2.5 mL(31.2 mmol), temperature of reaction changes 60 ℃ into, and the reaction times changes 6 h into, and other operations are consistent with embodiment 15.Obtain 3.13 g dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde, yield 78%.
Embodiment 17
Only change reaction solvent in embodiment 15 into toluene, the amount of ethyl formate changes 6.71 mL(83.2 mmol into), CH
3the amount of ONa changes 3.37 g(62.4 mmol into), temperature of reaction changes 45 ℃ into, and the reaction times changes 17 h into, and other operations are consistent with embodiment 15.Obtain 3.21 g dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde, yield 80%.
Embodiment 18
Only change the amount of ethyl formate in embodiment 15 into 4.18 mL(52 mmol), CH
3the amount of ONa changes 1.69 g(31.2 mmol into), temperature of reaction changes 45 ℃ into, and the reaction times changes 20 h into, and other operations are consistent with embodiment 15.Obtain 3.01 g dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde, yield 75%.
Embodiment 19
Only change the amount of ethyl formate in embodiment 15 into 1.69 mL(20.8mmol), CH
3the amount of ONa changes 1.13 g(20.8 mmol into), the reaction times changes 15 h into, and other operations are consistent with embodiment 15.Obtain 2.49 g dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde, yield 62%.
Only change reaction solvent in embodiment 15 into ethanol, temperature of reaction changes 35 ℃ into, and the reaction times changes 17 h into, and other operations are consistent with embodiment 15.Obtain 3.13 g dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde, yield 78%.
4,8-dihydroxyl diamantane-2, the preparation of 6-diketone
Embodiment 21
Successively by 2 g 9-hydroxyl-3-formyl radical dicyclo [3.3.1] nonane-2,6-diketone (10 mmol), 25 mL acetonitriles, 0.47 g
l-proline(Pro) adds in single port flask, under agitation condition, reacts 8 h at 70 ℃.Underpressure distillation is except desolventizing, and column chromatography obtains 1.6 g white solids, yield 80%.
Embodiment 22
Only by embodiment 21
lthe amount of-proline(Pro) changes 0.23 g(2 mmol into), temperature of reaction changes 80 ℃ into, and the reaction times changes 10 h into, and other operations are consistent with embodiment 21.Obtain 1.52 g 4,8-dihydroxyl diamantane-2,6-diketone, yield 76%.
Embodiment 23
Only change reaction solvent in embodiment 21 into DMF,
lthe amount of-proline(Pro) changes 0.58 g(5 mmol into), change temperature of reaction into 40 ℃, the reaction times changes 10 h into, and other operations are consistent with embodiment 21.Obtain 1.36 g 4,8-dihydroxyl diamantane-2,6-diketone, yield 68%.
Embodiment 24
Only change reaction solvent in embodiment 21 into DMSO, temperature of reaction changes 65 ℃ into, and the reaction times changes 7 h into, and other operations are consistent with embodiment 21.Obtain 1.56 g 4,8-dihydroxyl diamantane-2,6-diketone, yield 78%.
Only change temperature of reaction in embodiment 21 into 75 ℃, the reaction times changes 5 h into, and other operations are consistent with embodiment 21.Obtain 1.44 g 4,8-dihydroxyl diamantane-2,6-diketone, yield 72%.
Only by embodiment 21
lthe amount of-proline(Pro) changes 0.58 g(5 mmol into), temperature of reaction changes 65 ℃ into, and the reaction times changes 9 h into, and other operations are consistent with embodiment 21.Obtain 1.48 g 4,8-dihydroxyl diamantane-2,6-diketone, yield 74%.
4,8-dioxo diamantane-2, the preparation of 6-dinitrate
5 mL acetic acid (80 mmol) and 5 mL diacetyl oxides (50 mmol) are added in there-necked flask, slowly drip 3.4 g 98% nitric acid (50 mmol) at 0 ℃.After dripping, add 1.96 g 4 in batches, 8-dihydroxyl diamantane-2,6-diketone (10 mmol), and at 20 ℃ of reaction 4 h.After reaction finishes, reaction system is poured in mixture of ice and water, with dichloromethane extraction (100 mL × 3), the saturated NaHCO of organic phase
3solution washing 3 times, and use anhydrous Na
2sO
4dry, underpressure distillation removes desolventizing and obtains 2.72 g white solids, yield 95%.
Embodiment 28
Only change the amount of acetic acid in embodiment 27 into 3.76 mL(60 mmol); The amount of diacetyl oxide changes 2 mL(20 mmol into); Temperature of reaction changes 0 ℃ into, and other operations are consistent with embodiment 27.Obtain 2.12 g 4,8-dioxo diamantane-2,6-dinitrate, yield 74%.
Embodiment 29
Only change the amount of acetic acid in embodiment 27 into 6.24 mL(100 mmol); The amount of nitric acid changes 5.4 g(80 mmol into); Reaction times changes 2 h into, and other operations are consistent with embodiment 27.Obtain 2.58 g 4,8-dioxo diamantane-2,6-dinitrate, yield 90%.
Only change the amount of diacetyl oxide in embodiment 27 into 8.0 mL(80 mmol); The amount of nitric acid changes 1.36 g(20 mmol into); Reaction times changes 6 h into, and other operations are consistent with embodiment 27.Obtain 2.35 g 4,8-dioxo diamantane-2,6-dinitrate, yield 82%.
Embodiment 31
Only change the amount of acetic acid in embodiment 27 into 3.12 mL(50 mmol); The amount of nitric acid changes 2.04 g(80 mmol into), other operations are consistent with embodiment 27.Obtain 2.71 g 4,8-dioxo diamantane-2,6-dinitrate, yield 94%.
Embodiment 32
Only change the amount of acetic acid in embodiment 27 into 1.88 mL(30 mmol); The amount of diacetyl oxide changes 1 mL(10 mmol into); Temperature of reaction changes 25 ℃ into, and other operations are consistent with embodiment 27.Obtain 2.18 g 4,8-dioxo diamantane-2,6-dinitrate, yield 76%.
4,8-dihydroxyl imino-diamantane-2, the preparation of 6-dinitrate
Embodiment 33
By 3.15 g(11 mmol) 4,8-dioxo diamantane-2,6-dinitrate adds in 150 mL methyl alcohol, is stirred to completely and dissolves, and adds successively 3.04 g(44 mmol) and oxammonium hydrochloride, 3.59 g(44 mmol) anhydrous sodium acetate, room temperature reaction 16 h.After reaction finishes, underpressure distillation, obtains white solid, and solid dissolves with methylene dichloride, wash with saturated sodium bicarbonate aqueous solution, collect organic phase, organic phase anhydrous sodium sulfate drying, filters, underpressure distillation, thick methylene dichloride/normal hexane recrystallization for product, obtains 3.3 g white granular crystal, yield 95%.
Embodiment 34
Only change the amount of oxammonium hydrochloride in embodiment 33 into 1.52 g(22 mmol), the amount of anhydrous sodium acetate changes 1.8 g(22 mmol into), temperature of reaction changes 40 ℃ into, and the reaction times changes 20 h into, and other operations are consistent with embodiment 33.Obtain 1.52 g 4,8-dihydroxyl imino-diamantane-2,6-dinitrate, yield 76%.
Only change reaction solvent in embodiment 33 into ethanol, the amount of oxammonium hydrochloride changes 4.56 g(66 mmol into), change temperature of reaction into 40 ℃, the reaction times changes 12 h into, and other operations are consistent with embodiment 33.Obtain 1.36 g 4,8-dihydroxyl imino-diamantane-2,6-dinitrate, yield 68%.
Embodiment 36
Only change reaction solvent in embodiment 33 into ethanol, the amount of anhydrous sodium acetate changes 5.39 g(66 mmol into), temperature of reaction changes 70 ℃ into, and other operations are consistent with embodiment 33.Obtain 1.56 g 4,8-dihydroxyl imino-diamantane-2,6-dinitrate, yield 78%.
Embodiment 37
Only change temperature of reaction in embodiment 33 into 75 ℃, the reaction times changes 16 h into, and other operations are consistent with embodiment 33.Obtain 1.44 g 4,8-dihydroxyl imino-diamantane-2,6-dinitrate, yield 72%.
Embodiment 38
Only by embodiment 33
lthe amount of-proline(Pro) changes 0.58 g(5 mmol into), temperature of reaction changes 70 ℃ into, and the reaction times changes 12 h into, and other operations are consistent with embodiment 33.Obtain 1.48 g 4,8-dihydroxyl imino-diamantane-2,6-dinitrate, yield 74%.
4,4,8,8-tetranitro diamantane-2, the preparation of 6-dinitrate
Embodiment 39
By 6.58 g(20.81 mmol) 4,8-dihydroxyl imino-diamantane-2,6-dinitrate is dissolved in 200 mL methylene dichloride, in system, adds 7.48 g(124.86 mmol) urea and appropriate molecular sieve, be heated to 50 ℃.To methylene dichloride (20 mL) solution that slowly drips 13.5 g nitrogen pentoxides (124.86 mmol) in system, reaction 30 min.Reaction mixture is poured in the mixture of ice and water of 200 mL, stratification, takes off a layer organic phase, and organic phase anhydrous sodium sulfate drying filters, underpressure distillation obtains faint yellow solid, and silica gel column chromatography obtains 4.1 g 4,4,8,8-tetranitro diamantane-2,6-dinitrate, yield 45%.
1H?NMR?(500?MHz,?CDCl
3)?δ:?4.98?(s,?2H),?4.02?(s,?2H),?3.73?(s,?2H),?2.56?(s,?2H),?2.31?(s,?2H);?
13C?NMR?(126?MHz,?CDCl
3)?δ?117.04,?77.16,?33.76,?33.72,?25.89,?23.13.
Only change reaction solvent in embodiment 39 into chloroform, reaction promoter changes 9.98 g(166.48 mmol into) urea and appropriate molecular sieve, temperature of reaction changes 35 ℃ into, the amount of nitrogen pentoxide changes 18.04 g(166.48 mmol into), reaction times changes 40 min into, and other operations are consistent with embodiment 39.Obtain 2.9 g 4,4,8,8-tetranitro diamantane-2,6-dinitrate, yield 32%.
Embodiment 41
Only change embodiment 39 reaction promoters into 6.24 g(104.04 mmol) urea and appropriate molecular sieve, temperature of reaction changes 55 ℃ into.The amount of nitrogen pentoxide changes 11.24 g(104.04 mmol into), other operations are consistent with embodiment 39.Obtain 3. 28 g 4,4,8,8-tetranitro diamantane-2,6-dinitrate, yield 36%.
Embodiment 42
Only change reaction solvent in embodiment 39 into CH
3nO
2, reaction promoter changes appropriate molecular sieve into, and the reaction times changes 35 min into, and other operations are consistent with embodiment 39.Obtain 2.55 g 4,4,8,8-tetranitro diamantane-2,6-dinitrate, yield 28%.
Embodiment 43
Only change reaction solvent in embodiment 39 into ClCH
2cH
2cl, temperature of reaction changes 55 ℃ into, and other operations are consistent with embodiment 39.Obtain 3.83 g 4,4,8,8-tetranitro diamantane-2,6-dinitrate, yield 42%.
Embodiment 44
Only change reaction promoter in embodiment 39 into 6.24 g(104.04 mmol) urea, the amount of nitrogen pentoxide changes 9.40 g(104.4 mmol into), other operations are consistent with embodiment 39.Obtain 4.60 g 4,4,8,8-tetranitro diamantane-2,6-dinitrate, yield 40%.
Claims (9)
1. an energetic material 4,4,8,8-tetranitro diamantane-2,6-dinitrate, is characterized in that having following structure:
。
2. according to claim 14,4,8,8-tetranitro diamantane-2, the preparation method of 6-dinitrate, is characterized in that said method comprising the steps of:
(1) tetrahydrofuran solution of cyclooctadiene is slowly added in tetrahydrofuran (THF) borane complex, stirring at normal temperature starts to drip 3N aqueous sodium hydroxide solution after reaction for some time, after stirring for some time, adds 30wt% hydrogen peroxide, reacting by heating again, synthetic 1,5-ring ethohexadiol;
(2) under low temperature, oxalyl chloride is added to CH
2cl
2in, stir the lower DMSO of dropping, after reaction for some time, add step (1) described 1,5-encircle ethohexadiol, adds triethylamine after reacting for some time, and low-temp reaction obtains 1, and 5-encircles acetyl caproyl;
(3), by described step (2) 1,5-ring acetyl caproyl is dissolved in reaction solvent, adds solution and the ethyl formate of sodium methylate, reacting by heating, and synthetic 2,6-dioxo ring is pungent-1-formaldehyde;
(4) by described step (3) 2,6-dioxo ring is pungent-and 1-formaldehyde is dissolved in solvent, adds
l-proline(Pro), reacting by heating, synthetic 9-hydroxyl dicyclo [3.3.1] nonane-2,6-diketone;
(5) by step (4) described 9-hydroxyl dicyclo [3.3.1] nonane-2,6-diketone is dissolved in reaction solvent, adds solution and the ethyl formate of sodium methylate, reacting by heating, synthetic 9-hydroxyl-2,6-dioxo-bicyclo [3.3.1] nonane-3-formaldehyde;
(6), by the described 9-of step (5) hydroxyl-2,6-dioxo-bicyclo [3.3.1] nonane-3-formaldehyde is dissolved in solvent, adds
l-proline(Pro), reacting by heating, synthetic 4,8-dihydroxyl diamantane-2,6-diketone;
(7) under condition of ice bath, nitric acid is added in the mixing solutions of diacetyl oxide and acetic acid, under agitation condition, add step (6) described 4,8-dihydroxyl diamantane-2,6-diketone, stirring reaction, synthetic 4,8-dioxo diamantane-2,6-dinitrate;
(8) by described step (7) 4,8-dioxo diamantane-2,6-dinitrate, in solvent, adds oxammonium hydrochloride, sodium acetate, stirring reaction, synthetic 4,8-dihydroxyl imino-diamantane-2,6-dinitrate;
(9) by described step (8) 4,8-dihydroxyl imino-diamantane-2,6-dinitrate is dissolved in organic solvent, adds reaction promoter, under heating condition, slowly drip the organic solution of nitrogen pentoxide, synthetic 4,4,8,8-tetranitro diamantane-2,6-dinitrate.
3. according to claim 24,4,8,8-tetranitro diamantane-2, the preparation method of 6-dinitrate, is characterized in that: in step (3) 1, the mol ratio of 5-ring acetyl caproyl and sodium methylate is 1:1 ~ 3; Dicyclo [3.3.1] nonane-2, the mol ratio of 6-diketone and ethyl formate is 1:1 ~ 4; Reaction solvent is selected toluene, ethanol or methyl alcohol; Temperature of reaction is 20 ~ 60 ℃, and the reaction times is 6 ~ 20 h.
4. according to claim 24,4,8,8-tetranitro diamantane-2, the preparation method of 6-dinitrate, is characterized in that: in step (4) 2,6-dioxo ring is pungent-1-formaldehyde with
lthe mol ratio of-proline(Pro) is 1:0.2 ~ 0.5; Reaction solvent is selected DMF, CH
3cN or DMSO; Temperature of reaction is 40 ~ 80 ℃; Reaction times is 5 ~ 10 h.
5. according to claim 24,4,8,8-tetranitro diamantane-2, the preparation method of 6-dinitrate, is characterized in that: 9-hydroxyl dicyclo [3.3.1] nonane-2 in step (5), the mol ratio of 6-diketone and sodium methylate is 1:1 ~ 3; Dicyclo [3.3.1] nonane-2, the mol ratio of 6-diketone and ethyl formate is 1:1 ~ 4; Reaction solvent is selected toluene, ethanol or methyl alcohol; Temperature of reaction is 20 ~ 60 ℃; Reaction times is 6 ~ 20 h.
6. according to claim 24,4,8,8-tetranitro diamantane-2, the preparation method of 6-dinitrate, is characterized in that: 9-hydroxyl-2 in step (6), 6-dioxo-bicyclo [3.3.1] nonane-3-formaldehyde with
lthe mol ratio of-proline(Pro) is 1:0.2 ~ 0.5; Reaction solvent is selected DMF, CH
3cN or DMSO; Temperature of reaction is 40 ~ 80 ℃; Reaction times is 5 ~ 10 h.
7. according to claim 24,4,8,8-tetranitro diamantane-2, the preparation method of 6-dinitrate, is characterized in that: in step (7) 4,8-dihydroxyl diamantane-2, the mol ratio of 6-diketone and acetic acid is 1:6 ~ 10; 4,8-dihydroxyl diamantane-2, the mol ratio of 6-diketone and diacetyl oxide is 1:2 ~ 8; 4,8-dihydroxyl diamantane-2, the mol ratio of 6-diketone and nitric acid is 1:2 ~ 8; Temperature of reaction is 0 ~ 25 ℃; Reaction times is 2 ~ 6 h.
8. according to claim 24,4,8,8-tetranitro diamantane-2, the preparation method of 6-dinitrate, is characterized in that: in step (8), reaction solvent is selected methyl alcohol and ethanol; 4,8-dioxo diamantane-2, the mol ratio of 6-dinitrate and oxammonium hydrochloride is 1:2 ~ 6; 4,8-dioxo diamantane-2, the mol ratio of 6-dinitrate and sodium acetate is 1:2 ~ 6; Temperature of reaction is 40 ~ 70 ℃; Reaction times is 12 ~ 20 h.
9. according to claim 24,4,8,8-tetranitro diamantane-2, the preparation method of 6-dinitrate, is characterized in that: in step (9) 4,8-dihydroxyl imino-diamantane-2, the mol ratio of 6-dinitrate and nitrogen pentoxide is 1:2.5 ~ 8; Reaction solvent is selected CH
2cl
2, CHCl
3, CH
2nO
2and ClCH
2cH
2cl; Reaction promoter is molecular sieve or urea; Temperature of reaction is 35 ~ 55 ℃; Reaction times is 15 ~ 40 min.
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| CN109516986A (en) * | 2017-09-19 | 2019-03-26 | 南京理工大学 | Five nitros of 2,4,4,8,8- -2-aza-adamantane and its synthetic method |
| CN109516986B (en) * | 2017-09-19 | 2021-02-12 | 南京理工大学 | 2,4,4,8, 8-pentanitro-2-azaadamantane and synthetic method thereof |
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