CN102603560A - Tetra-azido alkane and preparation method thereof - Google Patents
Tetra-azido alkane and preparation method thereof Download PDFInfo
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- CN102603560A CN102603560A CN201210013927XA CN201210013927A CN102603560A CN 102603560 A CN102603560 A CN 102603560A CN 201210013927X A CN201210013927X A CN 201210013927XA CN 201210013927 A CN201210013927 A CN 201210013927A CN 102603560 A CN102603560 A CN 102603560A
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- azido
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- alkane
- heptanediol
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Abstract
The invention discloses a tetra-azido alkane and a preparation method thereof. A structural formula of the tetra-azido alkane is (N3CH2)2CH(CH2)3CH(CH2N3)2. The preparation method comprises the following steps of: under the protection of nitrogen, reacting diethyl malonate and 1,3-dibromopropane at a low temperature to obtain tetracthyl-1,1,5,5-pentanctetracarboxylate; under the protection of the nitrogen, carrying out ice bath at below 5 DEG C, and reacting the tetracthyl-1,1,5,5-pentanctetracarboxylate and a tetrahydroaluminate diethyl ether solution to obtain 2,6-dihydromethyl-1,7-heptandiol; carrying out the ice bath at below 5 DEG C, reacting paratoluensulfonyl chloride and a pyridine solution of the 2,6-dihydromethyl-1,7-heptandiol for 10h, and carrying out chloroform recrystallization to obtain 2,6-p-ditoluenosulfonate methyl-1,7-p-ditoluenosulfonate methyl heptaester; and adding an aqueous solution of sodium azide to a dimethylformamide solution of the 2,6-p-ditoluenosulfonate methyl-1,7-p-ditoluenosulfonate methyl heptaester to react for 15h at 80 DEG C to obtain a 2,6-biazido-1,7-di-azido heptane product.
Description
Technical field:
The present invention relates to a kind of high thermalization compound, particularly a kind of four azido-alkane and preparation method thereof.
Background technology:
In energetic materials such as propelling charge, propelling agent and high explosive, use sticker, softening agent, oxygenant and other additive that contains azido-; Can not only improve energy level (each azido-can provide the Enthalpies of Formation of 356kJ/mol); Can also give its many other excellent performances: improve the nitrogen content of system and do not influence its ratio of carbon-hydrogen, the free air delivery the during burning of increase system; Improve the combustionvelocity of propelling charge or propelling agent, and do not improve flame temperature; Reduce the target signature that various propulsion system produces, thereby improve the stealth of weapon.The synthetic triazo-compound generally is divided into nitrine polyethers, nitrine nitramine, nitrine nitro-compound, nitrine fluorine dinitro compound and nitrine alkane, nitrine ether and nitrine ester with it at present.Wherein, great majority in the nitrine hydride compounds and HMX, RDX are compatible, and good plasticising performance is arranged, and in the SP prescription, can replace inert plasticizer, have very wide practical value.At present; Synthetic four azido-alkane mainly contain the azido derivant of tetramethylolmethane, and this verivate can be energetic material more energy is provided owing to have four azido groups; But, make that its technology of preparing can not wide popularization and application because its combustionvelocity is slower.Given this, synthesize and have the fast four new azido-verivates of combustionvelocity and become the research focus, 2,6-diazido--1,7-two nitrine heptane are not seen relevant its report synthetic and performance at present as yet.This compound has good plasticising performance, and combustionvelocity is fast, synthesis technique simple and stable, characteristics such as productive rate height.
Summary of the invention:
The purpose of this invention is to provide a kind of energy content height and the fast plasticising performance of combustionvelocity and reach four high azido-alkane of synthesis technique simple and stable and productive rate and preparation method thereof well.Technical scheme of the present invention is that a kind of four azido-alkane is characterized in that: the structural formula of said four azido-alkane is:
(N3CH2)2CH(CH2)3CH(CH2N3)2。
A kind of method for preparing the described four azido-alkane of claim 1 is characterized in that following steps are arranged:
1) under the nitrogen protection, under nitrogen protection, 3.45g sodium piece is added in the 75mL absolute ethyl alcohol, at low temperatures (10 ℃-10 ℃) dissolving; Dissolving finishes, and in alcohol sodium solution, drips ethyl malonate solution 110mL, and gentle reflux drips 1 at last to reacting completely in mixed solution; 3-dibromopropane 5.1mL dropwises reaction solution was refluxed 12 hours, and ethanol is taken out in decompression, washs unreacted alkali with dilute sulphuric acid; ETHYLE ACETATE washing water merges initial organic phase and the extraction liquid of crossing with ethyl acetate extraction at last, uses the anhydrous sodium sulfate drying organic phase, the reclaim under reduced pressure ethyl malonate; Product after the recovery with oil pump under the 1.5mm mercury column, the decompression take out 1,1,5; 5-pentane end tetracarboxylic acid tetra-ethyl ester, boiling point 192-195 ℃, productive rate 60%;
2) the 6g Lithium Aluminium Hydride is dissolved in the 150ml anhydrous diethyl ether, nitrogen protection, ice bath-5 ℃ stirs slowly to drip down and is dissolved with 9.9g 1,1; 5, the 50ml anhydrous ether solution of 5-pentane end tetracarboxylic acid tetra-ethyl ester dropwises, and removes the ice bath device, reaction mixture is heated to little boiling refluxed 48 hours; Reaction finishes, and is cooled to 0 ℃ and in reaction mixture, adds the 10ml ethanolic soln that contains 5ml water again, uses 2mol/L sulfuric acid neutralization reaction liquid again, filters, and throw out is with boiling water extraction 5 times (100ml * 5); Filter, filtrating is steamed to half the, uses the 3g activated carbon decolorizing, filters the evaporate to dryness of will filtrating; Use the ebullient isopropanol extraction again 3 times (50ml * 3), the united extraction thing is concentrated into 25ml, and (5 ℃～5 ℃) are separated out crystal under the low temperature, use recrystallizing methanol again; Promptly get product 2,6-dihydroxymethyl-1,7-heptanediol, 95 ℃ of fusing points, productive rate 78%;
3) the 2.8g Tosyl chloride is dissolved in the 5ml pyridine, stirring and dissolving, ice bath is chilled to-5 ℃, slowly drips and is dissolved with 0.5g 2; 6-dihydroxymethyl-1, the 2ml pyridine solution of 7-heptanediol ,-5 ℃ were reacted 10 hours down, at room temperature reacted 24 hours again; Reaction solution becomes the pale pink suspension liquid by oyster white, fades to clarification at last, in the big water gaging of impouring, obtains yellow solid; The white solid that difference water and washing with alcohol are three times is used the toluene recrystallization again, promptly gets 2; 6-two methyl tosylate bases-1,7-two tosic acid heptanediol esters, productive rate 80%;
4) take by weighing 0.3g 2 respectively, 6-two methyl tosylate bases-1,7-two tosic acid heptanediol esters and 0.4g sodiumazide, sodiumazide excessive 12.5%.The aqueous solution of sodiumazide is added 2,6-two methyl tosylate bases-1, the N of 7-two tosic acid heptanediol esters; In the dinethylformamide solution, controlled temperature dilutes reaction product at 80 ℃ of reaction 12h with deionized water; Leave standstill, yellow small droplets is built up.Product liquid is extracted with anhydrous diethyl ether, washing, the product solution that obtains is used anhydrous sodium sulfate drying, and distillation is removed ether and is obtained 2,6-diazido--1,7-two nitrine heptane, productive rate 85%.The present invention and prior art relatively have the energy content height, combustionvelocity is fast and the speedup performance is good and synthesis technique simple and stable and the high remarkable advantage of productive rate.
Embodiment:
The compound method principle of the present invention's four azido-alkane is that available alkali metal azide has Lithium Azide, potassium azide and Sodium Azide, wherein preferred sodiumazide.The separation of product is carried out column chromatography for separation through silicagel column, thereby obtains the nitrine product.
Concrete synthetic route is following:
N=2 wherein, 3,4,5 or 6.
Compound method of the present invention has following steps:
11,1,5, the preparation and the sign of 5-pentane end tetracarboxylic acid tetra-ethyl ester
Under nitrogen protection, 3.45g sodium piece is added in the 75mL absolute ethyl alcohol, (10 ℃-10 ℃) dissolving at low temperatures, dissolving finishes; In alcohol sodium solution, drip ethyl malonate solution 110mL, gentle reflux drips 1 at last to reacting completely in mixed solution, 3-dibromopropane 5.1mL; Dropwise reaction solution was refluxed 12 hours, ethanol is taken out in decompression, washs unreacted alkali with dilute sulphuric acid, ETHYLE ACETATE washing water; At last initial organic phase and the extraction liquid of crossing with ethyl acetate extraction are merged, use the anhydrous sodium sulfate drying organic phase, reclaim under reduced pressure ethyl malonate, the product after the recovery with oil pump under the 1.5mm mercury column; The decompression take out 1,1,5; 5-pentane end tetracarboxylic acid tetra-ethyl ester, boiling point 192-195 ℃, productive rate 60%.
Product analytical data is following:
1HNMR(CDCl
3，500MHz)，δ：1.15(t，12H，-CH
3)，1.30(m，2H，-CH-)，1.85(q，-CH
2-)，3.22(t，2H，-CH-COO)，4.10(m，8H，-CH
2-COO)；
13CNMR (CDCl
3, 125MHz), δ: 168.98 (carbonyl carbon, COO), 61.09 (O-CH
2-), 51.50 (CH-), 28.08 (CH-CH
2-), 24.84 (CH
2-CH
2-CH
2-), 13.82 (CH
3);
DEPT (135 °), δ: 61.09 (oxyethyl group mesomethylene carbon), 51.50 (methine carbons), 28.08 (mesomethylene carbon), 24.84 (mesomethylene carbon), 13.82 (methyl carbon).
22,6-dihydroxymethyl-1, the preparation of 7-heptanediol and sign
The 6g Lithium Aluminium Hydride is dissolved in the 150ml anhydrous diethyl ether, nitrogen protection, ice bath-5 ℃ stirs slowly to drip down and is dissolved with 9.9g 1,1; 5, the 50ml anhydrous ether solution of 5-pentane end tetracarboxylic acid tetra-ethyl ester dropwises, and removes the ice bath device, reaction mixture is heated to little boiling refluxed 48 hours; Reaction finishes, and is cooled to 0 ℃ and in reaction mixture, adds the 10ml ethanolic soln that contains 5ml water again, uses 2mol/L sulfuric acid neutralization reaction liquid again, filters, and throw out is with boiling water extraction 5 times (100ml * 5); Filter, filtrating is steamed to half the, uses the 3g activated carbon decolorizing, filters the evaporate to dryness of will filtrating; Use the ebullient isopropanol extraction again 3 times (50ml * 3), the united extraction thing is concentrated into 25ml, and (5 ℃～5 ℃) are separated out crystal under the low temperature, use recrystallizing methanol again; Promptly get product 2,6-dihydroxymethyl-1,7-heptanediol, 95 ℃ of fusing points, productive rate 78%.
Product analytical data is following:
IR，v，cm
-1：3340～3180(w，-OH)，2928～2851(s，-CH
3，-CH
2)，1490～1465，1094～1024(CH
2-O)；
1H?NMR(CDCl
3，600MHz)，δ：3.59(d，8H，-CH
2OH)，1.68(m，2H，-CH-)，1.38(t，2H，-CH
2-CH
2-CH
2-)，1.32(q，4H，-CH-CH
2-)。
32,6-two methyl tosylate bases-1, the preparation and the sign of 7-two tosic acid heptanediol esters
The 2.8g Tosyl chloride is dissolved in the 5ml pyridine, stirring and dissolving, ice bath is chilled to-5 ℃, slowly drips and is dissolved with 0.5g 2; 6-dihydroxymethyl-1, the 2ml pyridine solution of 7-heptanediol ,-5 ℃ were reacted 10 hours down, at room temperature reacted 24 hours again; Reaction solution becomes the pale pink suspension liquid by oyster white, fades to clarification at last, in the big water gaging of impouring, obtains yellow solid; The white solid that difference water and washing with alcohol are three times is used the toluene recrystallization again, promptly gets 2; 6-two methyl tosylate bases-1,7-two tosic acid heptanediol esters, productive rate 80%.
Product analytical data is following:
1HNMR (CDCl
3, 600MHz), δ: 3.89～3.85 (dd, 8H, J=4.2,13.4Hz, O-CH
2-), 2.44 (s, 16H, 4 hydrogen on the phenyl ring), 1.17 (q, 4H, J=7.2Hz, CH-CH
2-), 1.86 (d, 2H, J=5.4Hz ,-CH-), 1.08 (d, 2H, J=5.4Hz ,-CH
2-CH
2-CH
2-);
MS，m/z：831.1(M+Na
+)，847.1(M+K
+)。The signal peak area ratio meets isotopic analysis.
42,6-diazido--1, the preparation and the sign of 7-two nitrine heptane
Take by weighing 0.3g 2 respectively, 6-two methyl tosylate bases-1,7-two tosic acid heptanediol esters and 0.4g sodiumazide, sodiumazide excessive 12.5%.The aqueous solution of sodiumazide is added 2,6-two methyl tosylate bases-1, the N of 7-two tosic acid heptanediol esters; In the dinethylformamide solution, controlled temperature dilutes reaction product at 80 ℃ of reaction 12h with deionized water; Leave standstill, yellow small droplets is built up.Product liquid is extracted with anhydrous diethyl ether, washing, the product solution that obtains is used anhydrous sodium sulfate drying, and distillation is removed ether and is obtained 2,6-diazido--1,7-two nitrine heptane, productive rate 85%.
Product analytical data is following:
1HNMR (CDCl
3, 600MHz), δ: 3.38～3.33 (m, 8H, J=4.8,14.6Hz, N
3-CH
2-, be respectively adjacent hydrocarbon coupling and with hydrocarbon coupling), 1.76 (t, 2H, J=5.4Hz ,-CH-), 1.344 (s, 6H ,-CH
2-CH
2-CH
2-);
13CNMR(CDCl
3，125MHz)，δ：52.5(N
3-CH
2-)，38.4(-CH-)，29.4(CH-CH
2-)，23.8(-CH
2-CH
2-)。
Claims (2)
1. azido-alkane, it is characterized in that: the structural formula of said four azido-alkane is: (N
3CH
2)
2CH (CH
2)
3CH (CH
2N
3)
2
2. one kind prepares the described four azido-alkane methods of claim 1, it is characterized in that following steps are arranged:
1) under the nitrogen protection, under nitrogen protection, 3.45g sodium piece is added in the 75mL absolute ethyl alcohol, at low temperatures (10 ℃-10 ℃) dissolving; Dissolving finishes, and in alcohol sodium solution, drips ethyl malonate solution 110mL, and gentle reflux drips 1 at last to reacting completely in mixed solution; 3-dibromopropane 5.1mL dropwises reaction solution was refluxed 12 hours, and ethanol is taken out in decompression, washs unreacted alkali with dilute sulphuric acid; ETHYLE ACETATE washing water merges initial organic phase and the extraction liquid of crossing with ethyl acetate extraction at last, uses the anhydrous sodium sulfate drying organic phase, the reclaim under reduced pressure ethyl malonate; Product after the recovery with oil pump under the 1.5mm mercury column, the decompression take out 1,1,5; 5-pentane end tetracarboxylic acid tetra-ethyl ester, boiling point 192-195 ℃, productive rate 60%;
2) the 6g Lithium Aluminium Hydride is dissolved in the 150ml anhydrous diethyl ether, nitrogen protection, ice bath-5 ℃ stirs slowly to drip down and is dissolved with 9.9g 1,1; 5, the 50ml anhydrous ether solution of 5-pentane end tetracarboxylic acid tetra-ethyl ester dropwises, and removes the ice bath device, reaction mixture is heated to little boiling refluxed 48 hours; Reaction finishes, and is cooled to 0 ℃ and in reaction mixture, adds the 10ml ethanolic soln that contains 5ml water again, uses 2mol/L sulfuric acid neutralization reaction liquid again, filters, and throw out is with boiling water extraction 5 times (100ml * 5); Filter, filtrating is steamed to half the, uses the 3g activated carbon decolorizing, filters the evaporate to dryness of will filtrating; Use the ebullient isopropanol extraction again 3 times (50ml * 3), the united extraction thing is concentrated into 25ml, and (5 ℃～5 ℃) are separated out crystal under the low temperature, use recrystallizing methanol again; Promptly get product 2,6-dihydroxymethyl-1,7-heptanediol, 95 ℃ of fusing points, productive rate 78%;
3) the 2.8g Tosyl chloride is dissolved in the 5ml pyridine, stirring and dissolving, ice bath is chilled to-5 ℃, slowly drips and is dissolved with 0.5g 2; 6-dihydroxymethyl-1, the 2ml pyridine solution of 7-heptanediol ,-5 ℃ were reacted 10 hours down, at room temperature reacted 24 hours again; Reaction solution becomes the pale pink suspension liquid by oyster white, fades to clarification at last, in the big water gaging of impouring, obtains yellow solid; The white solid that difference water and washing with alcohol are three times is used the toluene recrystallization again, promptly gets 2; 6-two methyl tosylate bases-1,7-two tosic acid heptanediol esters, productive rate 80%;
4) take by weighing 0.3g 2 respectively, 6-two methyl tosylate bases-1,7-two tosic acid heptanediol esters and 0.4g sodiumazide, sodiumazide excessive 12.5%.The aqueous solution of sodiumazide is added 2,6-two methyl tosylate bases-1, the N of 7-two tosic acid heptanediol esters; In the dinethylformamide solution, controlled temperature dilutes reaction product at 80 ℃ of reaction 12h with deionized water; Leave standstill, yellow small droplets is built up.Product liquid is extracted with anhydrous diethyl ether, washing, the product solution that obtains is used anhydrous sodium sulfate drying, and distillation is removed ether and is obtained 2,6-diazido--1,7-two nitrine heptane, productive rate 85%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012194A (en) * | 2012-11-16 | 2013-04-03 | 南京理工大学 | Nitrine ester compound and synthesis method thereof |
| CN105924368A (en) * | 2016-05-20 | 2016-09-07 | 泸州北方化学工业有限公司 | Synthesis method of azido energetic plasticizer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311163A (en) * | 2007-05-23 | 2008-11-26 | 北京化工大学 | Preparation method of diazido alkane |
-
2012
- 2012-01-16 CN CN201210013927XA patent/CN102603560A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311163A (en) * | 2007-05-23 | 2008-11-26 | 北京化工大学 | Preparation method of diazido alkane |
Non-Patent Citations (1)
| Title |
|---|
| 唐光诗 等: "2,6-二叠氮甲基-1,7-二叠氮庚烷的合成及表征", 《化学试剂》, vol. 31, no. 10, 31 October 2009 (2009-10-31), pages 843 - 845 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012194A (en) * | 2012-11-16 | 2013-04-03 | 南京理工大学 | Nitrine ester compound and synthesis method thereof |
| CN105924368A (en) * | 2016-05-20 | 2016-09-07 | 泸州北方化学工业有限公司 | Synthesis method of azido energetic plasticizer |
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Application publication date: 20120725 |