CN101891698A

CN101891698A - 3,4-di(3',5'-dinitryl-4'-methyl phenyl) furoxan compound

Info

Publication number: CN101891698A
Application number: CN 201010232735
Authority: CN
Inventors: 薛云娜; 吕剑; 杨建明; 余秦伟; 李亚妮; 刘波; 李春迎
Original assignee: Xian Modern Chemistry Research Institute
Current assignee: Xian Modern Chemistry Research Institute
Priority date: 2010-07-21
Filing date: 2010-07-21
Publication date: 2010-11-24
Anticipated expiration: 2030-07-21
Also published as: CN101891698B

Abstract

The invention discloses a 3,4-di(3',5'-dinitryl-4'-methyl phenyl) furoxan compound, the structural formula of which is shown in the specification. The compound is mainly applied to energetic materials.

Description

3,4-two (3 ', 5 '-dinitrobenzene-4 '-aminomethyl phenyl) furoxan compound

Technical field

The present invention relates to a kind of 3,4-two (3 ', 5 '-dinitrobenzene-4 '-aminomethyl phenyl) furoxan compound.

Background technology

The furoxan compounds is the important energy-containing compound of a class, and intramolecular furoxan ring can provide higher energy density relatively as explosive group.Replace a nitro can make compound density improve 0.06～0.08g/cm with a furoxan base ³, explosion velocity improves about about 300m/s; The furoxan derivative increases detonation pressure as containing the oxygen balance that the energy additive can improve system; In addition, the furoxan ring also can be given its derivative ring strain and high standard Enthalpies of Formation.Aromatic ring introduced to give its better thermostability in the furoxan structure.The aryl oxidized furazan compounds that many nitros replace combines nitro aryl and furoxan base, both can improve energy density, can strengthen thermostability again.For example " 3,4-two (3 ', 5 '-dinitrobenzene-1 '-yl) furoxan is synthetic " synthetic chemistry, 2009,17 (2): 208-210 discloses a kind of 3,4-two (3 ', 5 '-dinitrobenzene-1 '-yl) furoxan, its structural formula is as follows:

The thermolysis peak temperature of this compound is 274 ℃, and the thermolysis peak area is 1972J/g, but exists thermostability lower, the deficiency that the thermolysis heat release is less.

Summary of the invention

Technical problem to be solved by this invention is to overcome the deficiencies in the prior art and defective, provides a kind of thermostability higher and decomposition heat bigger by 3,4-two (3 ', 5 '-dinitrobenzene-4 '-aminomethyl phenyl) furoxan compound.

Of the present invention 3,4-two (3 ', 5 '-dinitrobenzene-4 '-aminomethyl phenyl) furoxan compound structural formula is as follows:

Of the present invention 3, the synthetic route of 4-two (3 ', 5 '-dinitrobenzene-4 '-aminomethyl phenyl) furoxan compound is as follows:

This synthetic method may further comprise the steps:

1) adds p-tolyl aldehyde, ethanol in the reaction flask, add the oxammonium hydrochloride aqueous solution again, use Na ₂CO ₃The aqueous solution transfers to neutrality with reaction solution, and 20 ℃～30 ℃ reaction 1～2h filter, and get the p-tolyl aldehyde oxime.P-tolyl aldehyde and oxammonium hydrochloride mol ratio are 1: 1～1: 1.2.

2) add p-tolyl aldehyde oxime, chlorosuccinimide (NCS) and the trichloromethane that step 1) obtains in the reaction flask, the mol ratio that adds right-tolyl aldehyde oxime and NCS is 1: 1～1: 1.2; Under agitation, 25～30 ℃ of reaction 2h use Na at 0～2 ℃ again ₂CO ₃Solution transfers to neutrality with system.Keep 0～5 ℃ of reaction 2～3h, steam to remove chloroform, filter crude product, get 3 with ethyl alcohol recrystallization, 4-two (4 '-aminomethyl phenyl) furoxan.

3) stir down, with 3,4-two (4 '-aminomethyl phenyl) furoxan is dissolved in the vitriol oil, drip industrial nitric acid, behind the normal-temperature reaction 1h, 80 ℃～100 ℃ reaction 3h, filtration, cold wash, dry 3,4-two (3 ', 5 '-dinitrobenzene-4 '-aminomethyl phenyl) furoxan.

Advantage of the present invention:

1) heat decomposition temperature of The compounds of this invention improves, and peak temperature is 285 ℃.The thermolysis peak temperature of compound is 274 ℃ in the documents.

2) the thermolysis thermal discharge of The compounds of this invention increases, and is 2348J/g.The thermolysis thermal discharge of compound is 1972J/g in the documents.

Embodiment

Embodiment 13,4-two (4 '-methyl-3 ', 5 '-dinitrophenyl) furoxan synthetic

Take into account in the reaction flask of reflux and add p-tolyl aldehyde 12g (0.1mol), ethanol 60mL successively having mechanical stirring, temperature, add the aqueous solution that contains the 10.4g oxammonium hydrochloride again, sodium carbonate solution transfers to neutrality with reaction solution, at 20 ℃～30 ℃ reactions of temperature, 1～2h, after reaction finishes, after filtration, the washing, the oven dry aftertreatment, 10.8g p-tolyl aldehyde oxime.Yield 80%.

In the 250mL there-necked flask, add p-tolyl aldehyde oxime 2.1g (0.015mol), chloroform 20mL, make the tolyl aldehyde oxime be dissolved in chloroform under the magnetic agitation, 20 ℃ of temperature, add 2.0g (0.016mol) chlorosuccinimide, at 25 ℃～30 ℃ reactions of temperature 2h, TLC point plate is followed the tracks of, after question response is complete, make temperature of reaction system reduce to 0 ℃, the system pH value is transferred to neutrality with dilute sodium carbonate solution with ice-water bath, continue to keep 0-5 ℃ of reaction 2h, TLC point plate is followed the tracks of, and after reacting completely, steams chloroform, separate out a large amount of white solids, filter, washing, dry white solid 2.6g, get white solid 1.3g with ethyl alcohol recrystallization, yield 65%.

In the 100mL there-necked flask, add the 20mL vitriol oil, stir and add 2.7g 3 down, 4-two (4 '-aminomethyl phenyl) furoxan makes its dissolving, and controlled temperature is lower than 0 ℃, slowly the 7mL nitrosonitric acid is splashed in the reaction soln.Warming-in-water to 80 ℃ reaction 3h slowly pours reaction solution in the 100g trash ice and to stir, and separates out yellow solid, after filtration, washing, oven dry aftertreatment, the 2.3g crude product, get the 1.7g light yellow solid through ethyl alcohol recrystallization.Purity is 99.2% (HPLC), yield 37.8%.

Structure is identified:

Ultimate analysis:

Molecular formula: C ₁₆H ₁₀N ₆O ₁₀

Theoretical value: C 43.06, H 2.260, and N 18.83;

Measured value: C 43.25, H 2.229, and N 18.91.

Infrared (KBr, cm ^-1): 3085,1608,1596,1535,1351,1101,905.

¹HNMR (deuterated acetone, δ/ppm): δ 2.59 (s, 3H), δ 2.61 (s, 3H), 8.470 (s, 4H).

Above-mentioned analytical data confirms that the material that obtains by this synthetic method is 3 really, 4-two (4 '-methyl-3 ', 5 '-dinitrophenyl) furoxan.

Thermal performance test

Carrying out thermal characteristics with DSC and TGA measures.

Compound 3,4-two (4 '-methyl-3 ', 5 '-dinitrophenyl) the Thermal Decomposition Characteristics amount of furoxan compound, the fusing peak temperature is 232.7 ℃, decomposing peak temperature is 285.8 ℃, and decomposition peak's area is 2348J/g, and initial weightless temperature is 265.5 ℃, the fastest weightless temperature is 280.0 ℃, and the constant weight temperature is 525.6 ℃.

Claims

1. one kind 3,4-two (3 ', 5 '-dinitrobenzene-4 '-aminomethyl phenyl) furoxan compound, its structural formula is as follows: