CN103435490A - Synthesis method for 2,2,4,4,6,6-hexanitro-adamantane - Google Patents
Synthesis method for 2,2,4,4,6,6-hexanitro-adamantane Download PDFInfo
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Abstract
The invention discloses a synthesis method for 2,2,4,4,6,6-hexanitro-adamantane. According to the method, diethyl malonate is used as a raw material, and the steps of cyclization, ozonization and the like with complex aftertreatment and low yield in the traditional route are avoided by a new route; and in the new route, N2O5 is used as a nitration agent in a nitration step, and the advantages of fast reaction speed, easily-controlled reaction temperature, easily-separated products, high product purity, capacity of effectively reducing waste acid, and the like are achieved. The method is lower in cost, less in reaction pollution and higher in yield compared with the traditional route, the reaction yield is increased to 14% from 0.5% of the original route, and possibility is provided for industrialized production for 2,2,4,4,6,6-hexanitroadamantane.
Description
Technical field
The present invention relates to a kind of synthetic method of adamantane derivative, be specifically related to a kind of 2,2,4,4,6, the synthetic method of 6-hexanitro-diamantane.
Background technology
Diamantane and derivative thereof are the important compounds of a class in organic cage compound, can be widely used in the fields such as medicine, energetic material, functional polymer.Wherein many nitros diamantane, due to the high symmetry of its molecular structure, has the advantages such as high energy, low sense, can be used in the fields such as explosive, propelling agent, pyrotechnics composition and fuel, therefore its theory and experimental study are subject to people's great attention.The energy of many nitros diamantane and detonation property improve along with the increase of its contained nitro number.Calculation result shows that the explosion velocity of 2,2,4,4,6,6-hexanitro-diamantane is about 8700 ms
-1, detonation pressure is about 34.6 GPa, is a kind of high explosive of superior performance.
1993, it was starting raw material that Dave be take dimethyl malonate and paraformaldehyde, through cyclization, decarboxylation, ketone carbonyl-protection, ozonize, oximate, together with the step such as nitrated, successfully synthesize 2,2,4,4,6,6-hexanitro-diamantane (HNA), overall yield is less than 0.5%(Paritosh, R. D. Tetrahedron. 1992,48,5839; Paritosh, R. D.; Little, F. US 5202508,1983; Paritosh, R. D.; Little, F. US 5180853,1993).Intermediate 4-methylene radical diamantane-2 wherein, the 6-diketone is by dicyclo [3.3.1] nonane-2,6-diketone and dense H
2sO
4/ Ac
2the effect of O system generates, and productive rate only has 38%.And two steps all adopt nitric acid to make nitrating agent together with nitration reaction, productive rate is respectively 37% and 21%.This reaction scheme step is long, spent acid is many, pollution is heavy, productive rate is low.Therefore develop efficiently, the novel synthesis of hexanitro-diamantane has urgency and necessity cheaply.
Summary of the invention
In order to overcome the shortcomings of existing route, the invention provides a kind of 2,2,4,4,6, the synthetic method of 6-hexanitro-diamantane, the method raw material is easy to get, cost is low, it is little to pollute, simple to operate, productive rate is higher.
The objective of the invention is to be achieved through the following technical solutions:
A kind of 2,2,4,4,6, the synthetic method of 6-hexanitro-diamantane, method comprises the steps:
(1) diethyl malonate and paraformaldehyde are dissolved in reaction solvent, under whipped state, add catalyzer, reacting by heating, underpressure distillation obtains weak yellow liquid; Weak yellow liquid is added in the methanol solution of sodium methylate, heating, carry out ring-closure reaction, cooling, filters to obtain white solid; White solid is soluble in water, regulate pH to 4 ~ 5, synthetic Meerwein ' s ester;
(2) above-mentioned Meerwein ' s ester is dissolved in acetic acid, reflux, stirring, add HCl, back flow reaction, synthetic [3.3.1] nonane-2,6-diketone;
(3) by above-mentioned dicyclo [3.3.1] nonane-2, the 6-diketone is dissolved in reaction solvent, adds the solution of sodium methylate, ethyl formate, and reacting by heating obtains dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde;
(4) by above-mentioned dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde is dissolved in solvent, adds L-PROLINE, reacting by heating, synthetic 4-hydroxyl-2,6-diamantane diketone;
(5) by above-mentioned 4-hydroxyl-2,6-diamantane diketone is dissolved in toluene, adds tosic acid and ethylene glycol, reflux, dewaters, synthetic 2,2,6,6-diethylene dioxy base-4-adamantanol;
(6) after potassium hydrogen persulfate is ground to form to solid, add in ethyl acetate vigorous stirring, add again above-mentioned 2,2,6, the ethyl acetate solution of 6-diethylene dioxy base-4-adamantanol, adjacent sulphur benzene sulfonic acid sodium salt, anhydrous sodium sulphate, reacting by heating, synthetic 2,2,6,6-diethylene dioxy base-4-diamantane ketone;
(7) by above-mentioned 2,2,6,6-diethylene dioxy base-4-diamantane ketone is dissolved in ethanol, adds oxammonium hydrochloride, sodium acetate, stirring reaction, synthetic 2,2,6,6-diethylene dioxy base-4-diamantane ketoxime;
(8) by above-mentioned 2,2,6,6-diethylene dioxy base-4-diamantane ketoxime is dissolved in organic solvent, adds reaction promoter, slowly drips the organic solution of nitrogen pentoxide under heating condition, synthetic 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane;
(9) by above-mentioned 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane is dissolved in methylene dichloride, adds the vitriol oil, stirring reaction, synthetic 4,4-dinitrobenzene-2,6-diamantane diketone;
(10) by above-mentioned 4,4-dinitrobenzene-2,6-diamantane diketone is dissolved in methyl alcohol, adds oxammonium hydrochloride, sodium acetate, heating, stirring reaction, synthetic 4,4-dinitrobenzene-2,6-diamantane two ketoximes;
(11) by above-mentioned 4,4-dinitrobenzene-2,6-diamantane two ketoximes are dissolved in organic solvent, add reaction promoter, slowly drip the organic solution of nitrogen pentoxide under heating condition, synthetic 2,2,4,4,6,6-hexanitro-diamantane.
Wherein, in step (1), the mol ratio of diethyl malonate and paraformaldehyde is 1:0.7 ~ 1; Described reaction solvent is selected toluene or benzene, is preferably toluene; Described catalysts is selected diethylamine, piperidines, and piperazine,
n-methylpiperazine, be preferably
n-methylpiperazine; Reaction is first reacted 7 ~ 9 h at 80 ~ 110 ℃, then at 110 ~ 130 ℃ of reaction 9 ~ 11 h; The mol ratio of diethyl malonate and sodium methylate is 1:0.5 ~ 1; The temperature of reaction of ring-closure reaction is 40 ~ 70 ℃; The reaction times of ring-closure reaction is 8 ~ 16 h.
In step (2), the mol ratio of Meerwein ' s ester and hydrochloric acid is 1:3.65; Temperature of reaction is 120 ℃; Reaction times is 12 h.
Dicyclo [3.3.1] nonane-2 in step (3), 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, and ethanol or methyl alcohol, be preferably methyl alcohol; Temperature of reaction is 20 ~ 60 ℃, is preferably 35 ~ 45 ℃; Reaction times is 6 ~ 20 h, is preferably 15 ~ 17 h.
Dicyclo [3.3.1] nonane-2 in step (4), the mol ratio of 6-diketone-3-formaldehyde and L-PROLINE is 1:0.2 ~ 0.5, reaction solvent is selected DMF, CH
3cN, DMSO, be preferably CH
3cN; Temperature of reaction is 20 ~ 80 ℃, is preferably 65 ~ 75 ℃; Reaction times is 5 ~ 10 h, is preferably 7 ~ 9 h.
4-hydroxyl-2 in step (5), the mol ratio of 6-diamantane diketone and tosic acid is 1:0.05 ~ 0.3; 4-hydroxyl-2, the mol ratio of 6-diamantane diketone and ethylene glycol is 1:2 ~ 4; Temperature of reaction is 100 ~ 140 ℃; Reaction times is 1 ~ 4 h.
In step (6) 2,2,6, the mol ratio of 6-diethylene dioxy base-4-adamantanol and potassium hydrogen persulfate is 1:0.6 ~ 1; The mol ratio of 2,2,6,6-diethylene dioxy base-4-adamantanol and adjacent iodobenzene sodium sulfonate is 1:0.01 ~ 0.1; Temperature of reaction is 50 ~ 80 ℃; Reaction times is 4 ~ 8 h.
In step (7) 2,2,6, the mol ratio of 6-diethylene dioxy base-4-diamantane ketone and oxammonium hydrochloride is 1:2; The mol ratio of 2,2,6,6-diethylene dioxy base-4-diamantane ketone and sodium acetate is 1:2; Reaction times is 10 h.
In step (8) 2,2,6, the mol ratio of 6-diethylene dioxy base-4-diamantane ketoxime and nitrogen pentoxide is 1:1.25 ~ 4; Reaction solvent is selected CH
2cl
2, CHCl
3, CH
2nO
2, ClCH
2cH
2cl, be preferably CH
2cl
2; Reaction promoter is selected molecular sieve or urea; Temperature of reaction is 35 ~ 55 ℃; Reaction times is 15 ~ 40 min.
In step (9) 2,2,6,6-diethylene dioxy base-4, the mol ratio of 4-dinitrobenzene diamantane and the vitriol oil is 1:60; Reaction times is 2 h.
In step (10) 4,4-dinitrobenzene-2, the mol ratio of 6-diamantane diketone and oxammonium hydrochloride is 1:6; 4,4-dinitrobenzene-2, the mol ratio of 6-diamantane diketone and sodium acetate is 1:6; Temperature of reaction is 65 ℃; Reaction times is 12 h.
In step (11) 4,4-dinitrobenzene-2, the mol ratio of 6-diamantane two ketoximes and nitrogen pentoxide is 1:2.5 ~ 8; Reaction solvent is selected CH
2cl
2, CHCl
3, CH
2nO
2, ClCH
2cH
2cl, be preferably CH
2cl
2; Reaction promoter is selected molecular sieve or urea; Temperature of reaction is 35 ~ 55 ℃; Reaction times is 15 ~ 40 min.
Prepared 2,2,4,4,6 according to the present invention, 6-hexanitro-diamantane overall yield is 14%.Method yield of the present invention is high, and raw material is easy to get, and is a kind of preparation method that good suitability for industrialized production is worth that has.Its remarkable advantage is as follows:
(1) the present invention be take diethyl malonate as raw material, lower than the dimethyl malonate cost in traditional route, productive rate is higher.(2) the reaction pollution is little, and denitrification step is used the green nitration agent N of equivalent
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.(3) post-reaction treatment is simple, uses variation route to replace aftertreatment complexity in original route, the cyclization that productive rate is lower, ozonize step.(4) present method has been synthesized three kinds of new intermediates: dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde, 4-hydroxyl-2,6-diamantane diketone, 2,2,6,6-diethylene dioxy base-4-adamantanol.(5) reaction yield is higher, by former route productive rate, less than 0.5%, brings up to 14%, for its suitability for industrialized production provides possibility.(6) present method can be other adamantane framework structure and the synthetic of many nitros diamantane are offered reference.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
The accompanying drawing explanation
Fig. 1 the present invention 2,2,4,4,6, the synthetic route of 6-hexanitro-diamantane.
Fig. 2 dicyclo of the present invention [3.3.1] nonane-2,6-diketone-3-formaldehyde
1h NMR spectrogram.
Fig. 3 dicyclo of the present invention [3.3.1] nonane-2,6-diketone-3-formaldehyde
13c NMR spectrogram.
Fig. 4 4-hydroxyl-2 of the present invention, 6-diamantane diketone
1h NMR spectrogram.
Fig. 5 4-hydroxyl-2 of the present invention, 6-diamantane diketone
13c NMR spectrogram.
Fig. 6 the present invention 2,2,6,6-diethylene dioxy base-4-adamantanol
1h NMR spectrogram.
Fig. 7 the present invention 2,2,6,6-diethylene dioxy base-4-adamantanol
13c NMR spectrogram.
Fig. 8 the present invention 2,2,4,4,6,6-hexanitro-diamantane
1h NMR spectrogram.
Fig. 9 the present invention 2,2,4,4,6,6-hexanitro-diamantane
13c NMR spectrogram.
Embodiment
' preparation of s ester
embodiment 1
By 228 mL(1.50 mol) diethyl malonate, 37.5 g(1.25 mol) paraformaldehyde, 200 mL toluene add in 500 mL round-bottomed flasks successively, add 4.2 mL(0.038 mol under stirring)
n-methylpiperazine, first at 100 ℃ of reaction 8 h, then at 120 ℃ of reaction 10 h.Underpressure distillation, except desolventizing, obtains light yellow oily liquid, is cooled to room temperature, stand-by.By 57.4 g(1.06 mol) sodium methylate adds in 400 mL anhydrous methanols, is stirred to fully and dissolves, to be cooled to room temperature, adds wherein the light yellow oily liquid of above-mentioned gained.65 ℃ of 12 h that reflux, separate out light yellow solid, after being cooled to room temperature, and suction filtration, the mixed solvent washing of ether and methyl alcohol for filter cake, obtain white solid.White solid is dissolved in 500 mL water, with 6 mol/L salt acid for adjusting pH to 4～5, separates out a large amount of white solids, suction filtration, collect filter cake, and drying, obtain 101 g Meerwein ' s esters, yield 70%.
embodiment 2
Only change the amount of paraformaldehyde in embodiment 1 into 31.5 g(1.05 mol), reaction changes into first reacts 9 h at 80 ℃, the amount of sodium methylate changes 81.2 g(1.50 mol into), other operations are consistent with embodiment 1.Obtain 80.8 g Meerwein ' s esters, yield 56%.
embodiment 3
Only change selected catalyzer in embodiment 1 into 3.75 mL(0.038 mol) piperidines, reaction changes into first reacts 7 h at 110 ℃, then, at 110 ℃ of reaction 11 h, the temperature of reaction of ring-closure reaction changes 40 ℃ into, the reaction times of ring-closure reaction changes 16 h into, and other operations are consistent with embodiment 1.Obtain 89.5 g Meerwein ' s esters, yield 62%.
embodiment 4
Only change the amount of paraformaldehyde in embodiment 1 into 45 g(1.50 mol), selected catalyzer changes 3.27 g(0.038 mol into) piperazine, reaction solvent changes benzene into, and reaction changes into first reacts 8 h at 80 ℃, then at 110 ℃ of reaction 9 h.The amount of sodium methylate changes 40.6 g(0.75 mol into), the temperature of reaction of ring-closure reaction changes 70 ℃ into, and the reaction times of ring-closure reaction changes 8 h into, and other operations are consistent with embodiment 1.Obtain 77.9 g Meerwein ' s esters, yield 54%.
embodiment 5
Only change selected catalyzer in embodiment 1 into 3.9 mL(0.038 mol) diethylamine, reaction changes into first reacts 9 h at 80 ℃, then, at 120 ℃ of reaction 9 h, other operations are consistent with embodiment 1.Obtain 62 g Meerwein ' s esters, yield 43%.
embodiment 6
Only change selected catalyzer in embodiment 1 into 3.9 mL(0.038 mol) diethylamine, reaction changes into first reacts 7 h at 80 ℃, then, at 130 ℃ of reaction 9 h, other operations are consistent with embodiment 1.Obtain 78 g Meerwein ' s esters, yield 54%.
dicyclo [3.3.1] nonane-2, the preparation of 6-diketone
embodiment 7
By 101 g(0.26 mol) Meerwein ' s ester is dissolved in 240 mL Glacial acetic acid, is heated to 120 ℃, slowly drips 165 mL 6 mol/L(0.95 mol) hydrochloric acid, react 12 h.Underpressure distillation obtains light yellow solid, and solid dissolves with 100 mL methylene dichloride, with the saturated sodium bicarbonate aqueous solution washing, collects organic phase, the organic phase anhydrous sodium sulfate drying, filter underpressure distillation, obtain 31.2 g dicyclo [3.3.1] nonanes-2,6-diketone, yield 78%.
dicyclo [3.3.1] nonane-2, the preparation of 6-diketone-3-formaldehyde
embodiment 8
By 10 g(65.7 mmol) dicyclo [3.3.1] nonane-2, the 6-diketone is dissolved in 35 mL methyl alcohol, by 10.6 mL(131.4 mmol) ethyl formate adds in reaction flask, stirs, and in reaction system, slowly drips the CH of new system
3oNa(4.26 g, 78.8 mmol) methyl alcohol (10 mL) solution, after dripping be upgraded to temperature of reaction 40 ℃ of reaction 16 h.After reaction finishes, underpressure distillation, except desolventizing, obtains the tawny sticky solid.Solid dissolves with a small amount of methylene dichloride, and regulates pH to neutral with 6 mol/L HCl, and separatory, get organic phase, the organic phase anhydrous sodium sulfate drying, filter, and underpressure distillation obtains brown solid, silica gel column chromatography, obtain 11.2 g dicyclo [3.3.1] nonanes-2,6-diketone-3-formaldehyde, yield 95%.
1H-NMR?(CDCl
3，500?MHz):?δ?=?15.81?(s，1H)，2.86?(s，1H)，2.73-2.67?(dd，
J?=?16，6.9?Hz，2H)，2.44-2.25?(m，4H)，2.15?(s，3H)，2.09-1.99?(m，3H)。
13C-NMR?(CDCl
3，125?MHz):?δ?=?212.72，199.79，181.70，105.07，44.14，36.55，34.87，29.75，29.62，27.72，25.38。IR?(KBr)?
ν:?2940，2850，1710，1650，1590，1310，1240，862。
embodiment 9
Only change the amount of ethyl formate in embodiment 8 into 5.3 mL(65.7 mmol), temperature of reaction changes 60 ℃ into, and the reaction times changes 6 h into, and other operations are consistent with embodiment 8.Obtain 9.58 g dicyclo [3.3.1] nonanes-2,6-diketone-3-formaldehyde, yield 91%.
embodiment 10
Only change reaction solvent in embodiment 8 into toluene, the amount of ethyl formate changes 21.2 mL(262.8 mmol into), CH
3the amount of ONa changes 10.65 g(197 mmol into), temperature of reaction changes 45 ℃ into, and the reaction times changes 17 h into, and other operations are consistent with embodiment 8.Obtain 9.67 g dicyclo [3.3.1] nonanes-2,6-diketone-3-formaldehyde, yield 82%.
embodiment 11
Only change the amount of ethyl formate in embodiment 8 into 13.2 mL(164.3 mmol), CH
3the amount of ONa changes 3.55 g(65.7 mmol into), temperature of reaction changes 35 ℃ into, and the reaction times changes 15 h into, and other operations are consistent with embodiment 8.Obtain 10.3 g dicyclo [3.3.1] nonanes-2,6-diketone-3-formaldehyde, yield 87%.
embodiment 12
Only change the amount of ethyl formate in embodiment 8 into 8.0 mL(98.6 mmol), 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 8.Obtain 8.96 g dicyclo [3.3.1] nonanes-2,6-diketone-3-formaldehyde, yield 76%.
embodiment 13
Only change reaction solvent in embodiment 8 into ethanol, the amount of ethyl formate changes 21.2 mL(262.8 mmol into), temperature of reaction changes 45 ℃ into, and the reaction times changes 17 h into, and other operations are consistent with embodiment 8.Obtain 9.67 g dicyclo [3.3.1] nonanes-2,6-diketone-3-formaldehyde, yield 82%.
4-hydroxyl-2, the preparation of 6-diamantane diketone
embodiment 14
By 9 g(50 mmol) dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde is dissolved in the 75mL acetonitrile, in system, adds 2.3 g(20 mmol) L-PROLINE.Temperature of reaction is upgraded to 70 ℃ of reaction 8 h.After reaction finishes, underpressure distillation, except desolventizing, obtains brown solid, and with methylene dichloride, by dissolution of solid, with the saturated sodium bicarbonate solution washing, the organic phase anhydrous sodium sulfate drying, filter, and underpressure distillation, obtain yellow solid.Silica gel column chromatography, obtain 8.6 g 4-hydroxyls-2,6-diamantane diketone, yield 96%.
1H-NMR?(CDCl
3，500?MHz):?δ?=?3.49?(s，1H)，2.74-2.70?(m，1H)，2.60-2.55?(m，4H)，2.26-2.14?(m，2H)，2.13-1.96?(m，3H)，1.33?(s，3H)。
13C-NMR?(CDCl
3，125?MHz):?δ?=?213.92，212.53，78.07，57.15，44.02，43.91，40.21，34.45，33.60，26.50。IR?(KBr)?
ν:?3380，2940，2860，1700，1460，1290，1230，1080，924。
embodiment 15
Only change the amount of L-PROLINE in embodiment 14 into 1.15 g(10 mmol), temperature of reaction changes 80 ℃ into, and the reaction times changes 10 h into, and other operations are consistent with embodiment 14.Obtain 7.7 g 4-hydroxyls-2,6-diamantane diketone, yield 86%.
embodiment 16
Only change reaction solvent in embodiment 14 into DMF, the amount of L-PROLINE changes 2.88 g(25 mmol into), change temperature of reaction into 20 ℃, the reaction times changes 10 h into, and other operations are consistent with embodiment 14.Obtain 6.99 g 4-hydroxyls-2,6-diamantane diketone, yield 78%.
embodiment 17
Only change reaction solvent in embodiment 14 into DMSO, temperature of reaction changes 65 ℃ into, and the reaction times changes 7 h into, and other operations are consistent with embodiment 14.Obtain 8.15 g 4-hydroxyls-2,6-diamantane diketone, yield 91%.
embodiment 18
Only change temperature of reaction in embodiment 14 into 75 ℃, the reaction times changes 5 h into, and other operations are consistent with embodiment 14.Obtain 8.2 g 4-hydroxyls-2,6-diamantane diketone, yield 92%.
embodiment 19
Only change the amount of L-PROLINE in embodiment 14 into 1.15 g(10 mmol), temperature of reaction changes 65 ℃ into, and the reaction times changes 9 h into, and other operations are consistent with embodiment 14.Obtain 7.6 g 4-hydroxyls-2,6-diamantane diketone, yield 85%.
The preparation of 2,2,6,6-diethylene dioxy base-4-adamantanol
By 5.4g(30mmol) 4-hydroxyl-2,6-diamantane diketone, 0.57g(3mmol) tosic acid, 5.2mL(90mmol) ethylene glycol, 150mL toluene adds in the round-bottomed flask of 250mL successively, 130 ℃ of back flow reaction 2h.Underpressure distillation obtains faint yellow solid, solid dissolves with the 100mL methylene dichloride, and with saturated common salt water washing three times, organic phase anhydrous sodium sulfate drying, filter, underpressure distillation, thick methylene dichloride for product/normal hexane recrystallization, obtain 7.6g2,2,6,6-diethylene dioxy base-4-adamantanol, yield 95%.
1H-NMR(CDCl
3，500MHz):δ=4.24-4.21(d，J=10.4Hz，1H)，4.10-4.09(d，J=1.9Hz，1H)，4.08-3.89(m，8H)，2.16-2.12(dd，J=13.5，2.8Hz，1H)，1.98-1.82(m，7H)，1.81-1.70(m，2H)。
13C-NMR(CDCl
3，125MHz):δ=110.85，110.41，72.89，64.50，64.37，64.15，63.83，42.74，39.91，35.04，34.23，31.46，28.80，25.84。IR(KBr)ν:3490，2940，2890，1460，1420，1370，1250，1110，928。
embodiment 21
Only change the amount of tosic acid in embodiment 20 into 0.29 g(1.5 mmol), the quantitative change of ethylene glycol is 6.9 mL(120 mmol), the reaction times changes 4 h into, and other operations are consistent with embodiment 20.Obtain 7.3 g 2,2,6,6-diethylene dioxy base-4-adamantanol, yield 92%.
embodiment 22
Only change the amount of ethylene glycol in embodiment 20 into 7.8 mL(60 mmol), the reaction times changes 4 h into, and other operations are consistent with embodiment 20.Obtain 7.1 g 2,2,6,6-diethylene dioxy base-4-adamantanol, yield 89%.
embodiment 23
Only change temperature of reaction in embodiment 20 into 140 ℃, the reaction times changes 1 h into, and other operations are consistent with embodiment 20.Obtain 7.5 g 2,2,6,6-diethylene dioxy base-4-adamantanol, yield 94%.
embodiment 24
Only change the amount of ethylene glycol in embodiment 20 into 6.9 mL(120 mmol), temperature of reaction changes 140 ℃ into, and other operations are consistent with embodiment 20.Obtain 7.4 g 2,2,6,6-diethylene dioxy base-4-adamantanol, yield 93%.
embodiment 25
Only change the amount of tosic acid in embodiment 20 into 1.71 g(9 mmol), other operations are consistent with embodiment 20.Obtain 5.8 g 2,2,6,6-diethylene dioxy base-4-adamantanol, yield 73%.
The preparation of 2,2,6,6-diethylene dioxy base-4-diamantane ketone
Embodiment 26
By 11.45g(18.6mmol) potassium hydrogen persulfate that is ground into powder adds in the 120mL ethyl acetate, normal temperature vigorous stirring 2h.Again by 0.14g(0.45mmol) adjacent iodobenzene sodium sulfonate, the 23g anhydrous sodium sulphate, 6.1g(22.7mmol) 2,2,6,6-diethylene dioxy base-4-adamantanol adds in reaction flask successively, 70 ℃ of reaction 6h.After reaction finishes, filtered while hot, filter cake with the ethyl acetate washing for several times, is collected organic phase, and washes with water for several times, the organic phase anhydrous sodium sulfate drying, filter, and underpressure distillation, except desolventizing, obtains 6.05g2,2,6,6-diethylene dioxy base-4-diamantane ketone, yield 100%.
embodiment 27
Only change the amount of potassium hydrogen persulfate in embodiment 26 into 8.37 g(13.6 mmol), temperature of reaction changes 80 ℃ into, and the reaction times changes 8 h into, and other operations are consistent with embodiment 21.Obtain 4.84 g 2,2,6,6-diethylene dioxy base-4-diamantane ketone, yield 80 %.
embodiment 28
Only change the amount of potassium hydrogen persulfate in embodiment 26 into 13.97 g(22.7 mmol), the amount of adjacent iodobenzene sodium sulfonate changes 0.84 g(2.7 mmol into), temperature of reaction changes 50 ℃ into, and other operations are consistent with embodiment 21.Obtain 5.57 g 2,2,6,6-diethylene dioxy base-4-diamantane ketone, yield 92 %.
embodiment 29
Only change the amount of adjacent iodobenzene sodium sulfonate in embodiment 26 into 0.35 g(1.14 mmol), temperature of reaction changes 80 ℃ into, and the reaction times changes 4 h into, and other operations are consistent with embodiment 21.Obtain 5.57 g 2,2,6,6-diethylene dioxy base-4-diamantane ketone, yield 92 %.
Only change the amount of potassium hydrogen persulfate in embodiment 26 into 8.38 g(13.6 mmol), other operations are consistent with embodiment 21.Obtain 4.72 g 2,2,6,6-diethylene dioxy base-4-diamantane ketone, yield 78 %.
embodiment 31
Only change the amount of adjacent iodobenzene sodium sulfonate in embodiment 26 into 0.07 g(0.23 mmol), other operations are consistent with embodiment 21.Obtain 5.26 g 2,2,6,6-diethylene dioxy base-4-diamantane ketone, yield 87 %.
the preparation of 2,2,6,6-diethylene dioxy base-4-diamantane ketoxime
embodiment 32
By 5.83 g(21.9 mmol) 2,2,6,6-diethylene dioxy base-4-diamantane ketone adds in 150 mL ethanol, is stirred to fully and dissolves, and adds successively 3.04 g(43.8 mmol) oxammonium hydrochloride, 3.59 g(43.8 mmol) anhydrous sodium acetate, room temperature reaction 10 h.After reaction finishes, underpressure distillation, obtain white solid, and solid dissolves with methylene dichloride, with saturated sodium bicarbonate aqueous solution, wash, collect organic phase, the organic phase anhydrous sodium sulfate drying, filter, underpressure distillation, thick methylene dichloride for product/normal hexane recrystallization, obtain 5.85 g white granular crystal, yield 95%.
2,2,6,6-diethylene dioxy base-4, the preparation of 4-dinitrobenzene diamantane
embodiment 33
By 5.85 g(20.81 mmol) 2,2,6,6-diethylene dioxy base-4-diamantane ketoxime is dissolved in 175 mL methylene dichloride, in system, adds 3.74 g(62.43mmol) urea and appropriate molecular sieve, be heated to 50 ℃.Slowly drip methylene dichloride (20 mL) solution of 6.75 g nitrogen pentoxides (62.43 mmol) in system, react 30 min.Reaction mixture is poured in the mixture of ice and water of 200 mL, stratification, take off a layer organic phase, the organic phase anhydrous sodium sulfate drying, filter, and underpressure distillation obtains faint yellow solid, silica gel column chromatography, obtain 4.63 g 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane, 1.12 g 2,2,6,6-diethylene dioxy base-4-diamantane ketone.2,2,6,6-diethylene dioxy base-4-diamantane ketone is continued to oximate, together with nitrated, obtain 0.78 g 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane.Obtain altogether 5.41 g white solids for twice, yield 76%.m.p.235.4～236.5?℃。
embodiment 34
Only change reaction solvent in embodiment 33 into chloroform, reaction promoter changes 4.99 g(83.24 mmol into) urea and appropriate molecular sieve, temperature of reaction changes 35 ℃ into, the amount of nitrogen pentoxide changes 9.02 g(83.24 mmol into), reaction times changes 40 min into, and other operations are consistent with embodiment 28.Obtain 3.7 g 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane, yield 52%.
embodiment 35
Only change embodiment 33 reaction promoters into 1.56 g(26.01mmol) urea and appropriate molecular sieve, temperature of reaction changes 55 ℃ into.The amount of nitrogen pentoxide changes 2.81 g(26.01 mmol into), other operations are consistent with embodiment 28.Obtain 3.42 g 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane, yield 48%.
embodiment 36
Only change reaction solvent in embodiment 33 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 28.Obtain 2.71 g 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane, yield 38%.
embodiment 37
Only change reaction solvent in embodiment 33 into ClCH
2cH
2cl, temperature of reaction changes 55 ℃ into, and other operations are consistent with embodiment 28.Obtain 4.84 g 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane, yield 68%.
embodiment 38
Only change reaction promoter in embodiment 33 into 3.12 g(52.02 mmol) urea, the amount of nitrogen pentoxide changes 5.62 g(62.43 mmol into), other operations are consistent with embodiment 28.Obtain 3.49 g 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane, yield 49%.
4,4-dinitrobenzene-2, the preparation of 6-diamantane diketone and oxammonium hydrochloride
embodiment 39
By 5.41 g(15.81 mmol) 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane is dissolved in 200 mL methylene dichloride, adds 51.2 mL(960 mmol) and the vitriol oil, room temperature reaction 2 h.Reaction mixture is poured in 200 mL mixture of ice and water, and stratification, take off a layer organic phase, the organic phase anhydrous sodium sulfate drying, and underpressure distillation, thick acetone for product/normal hexane recrystallization, obtain 3.82 g white granular crystal, yield 95%.
4,4-dinitrobenzene-2, the preparation of 6-diamantane two ketoximes
embodiment 40
By 3.82 g(15.02mmol) 4,4-dinitrobenzene-2,6-diamantane diketone is dissolved in 150 mL methyl alcohol, adds successively 6.26 g(90.12 mmol) and oxammonium hydrochloride, 7.39 g(90.12 mmol) sodium acetate, 65 ℃ of back flow reaction 12 h.Underpressure distillation obtains white solid, and solid dissolves with methylene dichloride, and washs with saturated sodium bicarbonate aqueous solution, the organic phase anhydrous sodium sulfate drying, filter underpressure distillation, thick methylene dichloride for product/normal hexane recrystallization, obtain 3.93 g white granular crystal, yield 92%.
the preparation of 2,2,4,4,6,6-hexanitro-diamantane
embodiment 41
By 3.93 g(13.83 mmol) 4,4-dinitrobenzene-2,6-diamantane two ketoximes are dissolved in 125 mL methylene dichloride, in system, add 4.98 g(82.98 mmol) urea and appropriate molecular sieve, be heated to 50 ℃.To slowly dripping 8.97 g(82.98 mmol in system) methylene dichloride (25 mL) solution of nitrogen pentoxide, react 30 min.Reaction mixture is poured in the mixture of ice and water of 150 mL, stratification, take off a layer organic phase, the organic phase anhydrous sodium sulfate drying, filter, underpressure distillation obtains faint yellow solid, and silica gel column chromatography obtains 1.96 g 2,2,4,4,6,6-hexanitro-diamantane, 1.82 g 2,2,4,4-tetranitro-6-diamantane ketone, 0.53 g4,4-dinitrobenzene-2,6-diamantane diketone.Ketone is continued to oximate, together with nitrated, obtain 0.68 g 2,2,4,4,6,6-hexanitro-diamantane.Obtain altogether 2.64 g white solids for twice, yield 47%.mp:?198.9～200.4?℃。
1H?NMR?(CDCl
3，500?MHz)?
δ:?4.82～4.77?(m，2H)，3.40～3.10?(m，4H)，2.76～2.68?(m，2H)，2.07～2.03?(m，2H)。
13C?NMR?(CDCl
3，125?MHz)
δ:?119.72，119.42，37.47，32.67，30.26，29.77。IR?(KBr)?
ν:?3010，1580，474，1358，935，839?cm
-1。Anal.?calcd?for?C
10H
10N
6O
12:?C?29.57，H?2.48，N?20.69；found:?C?29.43，H?2.56，N?20.48。
embodiment 42
Only change reaction solvent in embodiment 41 into ClCH
2cH
2cl, reaction promoter changes 2.08 g(34.58 mmol into) urea and appropriate molecular sieve, temperature of reaction changes 55 ℃ into, and the amount of nitrogen pentoxide changes 3.74 g(34.58 mmol into), the reaction times changes 40 min into, and other operations are consistent with embodiment 36.Obtain 1.80 g 2,2,4,4,6,6-hexanitro-diamantane, yield 32%.
embodiment 43
Only change reaction solvent in embodiment 41 into chloroform, reaction promoter changes 6.64 g(110.6 mmol into) urea and appropriate molecular sieve, temperature of reaction changes 35 ℃ into, the amount of nitrogen pentoxide changes 11.96 g(110.6 mmol into), reaction times changes 15 min into, and other operations are consistent with embodiment 36.Obtain 1.97 g 2,2,4,4,6,6-hexanitro-diamantane, yield 35%.
embodiment 44
Only change reaction solvent in embodiment 41 into CH
3nO
2, the reaction times changes 40 min into, and other operations are consistent with embodiment 36.Obtain 1.80 g 2,2,4,4,6,6-hexanitro-diamantane, yield 32%.
embodiment 45
Only change reaction promoter in embodiment 41 into 2.07 g(34.58 mmol) urea and appropriate molecular sieve, temperature of reaction changes 35 ℃ into, the amount of nitrogen pentoxide changes 3.74 g(34.58 mmol into), the reaction times changes 40 min into, and other operations are consistent with embodiment 36.Obtain 1.57 g 2,2,4,4,6,6-hexanitro-diamantane, yield 28%.
embodiment 46
Only change reaction promoter in embodiment 41 into 6.64 g(110.64 mmol) urea and appropriate molecular sieve, temperature of reaction changes 55 ℃ into, the amount of nitrogen pentoxide changes 11.96 g(82.98 mmol into), the reaction times changes 15 min into, and other operations are consistent with embodiment 36.Obtain 1.74 g 2,2,4,4,6,6-hexanitro-diamantane, yield 31%.
Claims (8)
1. one kind 2,2,4,4,6, the synthetic method of 6-hexanitro-diamantane, is characterized in that comprising the steps:
(1) diethyl malonate and paraformaldehyde are dissolved in reaction solvent, under whipped state, add catalyzer, reacting by heating, underpressure distillation obtains weak yellow liquid; Weak yellow liquid is added in the methanol solution of sodium methylate, heating, carry out ring-closure reaction, cooling, filters to obtain white solid; White solid is soluble in water, regulate pH to 4 ~ 5, synthetic Meerwein ' s ester;
(2) above-mentioned Meerwein ' s ester is dissolved in acetic acid, reflux, stirring, add HCl, back flow reaction, synthetic [3.3.1] nonane-2,6-diketone;
(3) by above-mentioned dicyclo [3.3.1] nonane-2, the 6-diketone is dissolved in reaction solvent, adds solution and the ethyl formate of sodium methylate, and reacting by heating obtains dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde;
(4) by above-mentioned dicyclo [3.3.1] nonane-2,6-diketone-3-formaldehyde is dissolved in solvent, adds L-PROLINE, reacting by heating, synthetic 4-hydroxyl-2,6-diamantane diketone;
(5) by above-mentioned 4-hydroxyl-2,6-diamantane diketone is dissolved in toluene, adds tosic acid and ethylene glycol, reflux, dewaters, synthetic 2,2,6,6-diethylene dioxy base-4-adamantanol;
(6) after potassium hydrogen persulfate is ground to form to solid, add in ethyl acetate vigorous stirring, add again above-mentioned 2,2,6, the ethyl acetate solution of 6-diethylene dioxy base-4-adamantanol, adjacent iodobenzene sodium sulfonate, anhydrous sodium sulphate, reacting by heating, synthetic 2,2,6,6-diethylene dioxy base-4-diamantane ketone;
(7) by above-mentioned 2,2,6,6-diethylene dioxy base-4-diamantane ketone is dissolved in ethanol, adds oxammonium hydrochloride, sodium acetate, stirring reaction, synthetic 2,2,6,6-diethylene dioxy base-4-diamantane ketoxime;
(8) by above-mentioned 2,2,6,6-diethylene dioxy base-4-diamantane ketoxime is dissolved in organic solvent, adds reaction promoter, slowly drips the organic solution of nitrogen pentoxide under heating condition, synthetic 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane;
(9) by above-mentioned 2,2,6,6-diethylene dioxy base-4,4-dinitrobenzene diamantane is dissolved in methylene dichloride, adds the vitriol oil, stirring reaction, synthetic 4,4-dinitrobenzene-2,6-diamantane diketone;
(10) by above-mentioned 4,4-dinitrobenzene-2,6-diamantane diketone is dissolved in methyl alcohol, adds oxammonium hydrochloride, sodium acetate, heating, stirring reaction, synthetic 4,4-dinitrobenzene-2,6-diamantane two ketoximes;
(11) by above-mentioned 4,4-dinitrobenzene-2,6-diamantane two ketoximes are dissolved in organic solvent, add reaction promoter, slowly drip the organic solution of nitrogen pentoxide under heating condition, synthetic 2,2,4,4,6,6-hexanitro-diamantane.
2. according to claim 12,2,4,4,6, the synthetic method of 6-hexanitro-diamantane, is characterized in that in step (1), the mol ratio of diethyl malonate and paraformaldehyde is 1:0.7 ~ 1; The mol ratio of diethyl malonate and sodium methylate is 1:0.5 ~ 1; Described solvent is selected toluene or benzene, is preferably toluene; Described catalyzer select diethylamine, piperidines, piperazine,
n-methylpiperazine, be preferably
n-methylpiperazine; Temperature of reaction is first 80 ~ 110 ℃, then is 110 ~ 130 ℃; Reaction times is first 7 ~ 9 h, then is 9 ~ 11 h; The temperature of reaction of ring-closure reaction is 40 ~ 70 ℃; The reaction times of ring-closure reaction is 8 ~ 16 h.
3. according to claim 12,2,4,4,6, the synthetic method of 6-hexanitro-diamantane, is characterized in that dicyclo [3.3.1] nonane-2 in step (3), and 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.
4. according to claim 12,2,4,4,6, the synthetic method of 6-hexanitro-diamantane, is characterized in that dicyclo [3.3.1] nonane-2 in step (4), and the mol ratio of 6-diketone-3-formaldehyde and L-PROLINE is 1:0.2 ~ 0.5; Reaction solvent is selected DMF, CH
3cN or DMSO, preferably CH
3cN; Temperature of reaction is 20 ~ 80 ℃, is preferably 65 ~ 75 ℃; Reaction times is 5 ~ 10 h, is preferably 7 ~ 9 h.
5. according to claim 12,2,4,4,6, the synthetic method of 6-hexanitro-diamantane, is characterized in that 4-hydroxyl-2 in step (5), and the mol ratio of 6-diamantane diketone and tosic acid is 1:0.05 ~ 0.3; 4-hydroxyl-2, the mol ratio of 6-diamantane diketone and ethylene glycol is 1:2 ~ 4; Temperature of reaction is 100 ~ 140 ℃; Reaction times is 1 ~ 4 h.
6. according to claim 12,2,4,4,6, the synthetic method of 6-hexanitro-diamantane, is characterized in that in step (6) 2,2,6, and the mol ratio of 6-diethylene dioxy base-4-adamantanol and potassium hydrogen persulfate is 1:0.6 ~ 1;
The mol ratio of 2,2,6,6-diethylene dioxy base-4-adamantanol and adjacent iodobenzene sodium sulfonate is 1:0.01 ~ 0.1; Temperature of reaction is 50 ~ 80 ℃; Reaction times is 4 ~ 8 h.
7. according to claim 12,2,4,4,6, the synthetic method of 6-hexanitro-diamantane, is characterized in that in step (8) 2,2,6, and the mol ratio of 6-diethylene dioxy base-4-diamantane ketoxime and nitrogen pentoxide is 1:1.25 ~ 4; Reaction solvent is selected CH
2cl
2, CHCl
3, CH
2nO
2and ClCH
2cH
2cl, be preferably CH
2cl
2; Reaction promoter is molecular sieve or urea; Temperature of reaction is 35 ~ 55 ℃; Reaction times is 15 ~ 40 min.
8. according to claim 12,2,4,4,6, the synthetic method of 6-hexanitro-diamantane, is characterized in that in step (11) 4,4-dinitrobenzene-2, and the mol ratio of 6-diamantane two ketoximes and nitrogen pentoxide is 1:2.5 ~ 8; Reaction solvent is selected CH
2cl
2, CHCl
3, CH
2nO
2and ClCH
2cH
2cl, be preferably CH
2cl
2; Reaction promoter is molecular sieve or urea; Temperature of reaction is 35 ~ 55 ℃; Reaction times is 15 ~ 40 min.
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| CN106478604A (en) * | 2015-08-28 | 2017-03-08 | 南京理工大学 | 2,4,9- trinitro- -2,4,9- three azepine -7- adamantanol nitrate and its synthetic method |
| 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 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864621A (en) * | 2014-02-21 | 2014-06-18 | 南京理工大学 | Energetic material 4, 4, 8, 8-tetranitroadamantane-2, 6-dinitrate and preparation method thereof |
| CN103864621B (en) * | 2014-02-21 | 2016-03-02 | 南京理工大学 | Energetic material 4,4,8,8-tetranitro adamantane-2,6-dinitrate and preparation method thereof |
| CN106478604A (en) * | 2015-08-28 | 2017-03-08 | 南京理工大学 | 2,4,9- trinitro- -2,4,9- three azepine -7- adamantanol nitrate and its synthetic method |
| CN106478604B (en) * | 2015-08-28 | 2018-11-13 | 南京理工大学 | Three azepine -7- adamantanols nitrates of 2,4,9- trinitro-s -2,4,9- and its synthetic method |
| 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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