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Issue 9, 2012
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Salts of 1-(chloromethyl)-1,1-dimethylhydrazine and ionic liquids

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Abstract

The reaction of 1,1-dimethylhydrazine with excess dichloromethane led to the formation of the chloride salt of the 1-(chloromethyl)-1,1-dimethylhydrazinium cation ([(CH3)2N(CH2Cl)NH2]Cl, 1). The reaction of 1 with a suitable silver salt provided the nitrate ([(CH3)2N(CH2Cl)NH2][NO3], 2), perchlorate ([(CH3)2N(CH2Cl)NH2][ClO4], 3), azide ([(CH3)2N(CH2Cl)NH2][N3], 4), dicyanamide ([(CH3)2N(CH2Cl)NH2][N(CN)2], 5) and sulphate ([(CH3)2N(CH2Cl)NH2]2[SO4], 6) salts. Compound 6 reacted with barium 5,5′-azobistetrazolate pentahydrate (Ba[N4C–N[double bond, length as m-dash]N–CN4]·5H2O), barium dipicrate tetrahydrate (Ba[(NO2)3Ph–O]2·4H2O) and barium 5-amino-1H-tetrazolate tetrahydrate (Ba[H2N–CN4]2·4H2O) to form the corresponding metathesis products: [(CH3)2N(CH2Cl)NH2]2[N4C–N[double bond, length as m-dash]N–CN4] (7), [(CH3)2N(CH2Cl)NH2][(NO2)3Ph–O] (8) and [(CH3)2N(CH2Cl)NH2][H2N–CN4] (9). Compounds 1–9 were characterized by elemental analysis, mass spectrometry, NMR (1H and 13C) and vibrational spectroscopy (infrared and Raman). Additionally, we measured the 15N NMR spectrum of the nitrate salt 2 and identified the solid state structure of compounds 3, 6, 7 and 8 by low temperature X-ray crystallography (3: Triclinic P[1 with combining macron], a = 5.983(1) Å, b = 7.502(1) Å, c = 9.335(1) Å; α = 93.86(1)°, β = 101.21(1)°; γ = 91.13(1)°; V = 409.8(1) Å3, 6: Monoclinic C2/c, a = 11.674(2) Å, b = 17.503(3) Å, c = 6.616(1) Å; β = 90.27(1)°; V = 1351.8(4) Å3, 7: Triclinic P[1 with combining macron], a = 8.851(1) Å, b = 8.872(1) Å, c = 11.529(1) Å; α = 80.98(1)°, β = 83.47(1)°; γ = 71.37(1)°; V = 845.4(1) Å3 and 8: Monoclinic C2/c, a = 24.168(3) Å, b = 7.375(1) Å, c = 17.062(3) Å; β = 116.19(2)°; V = 1351.8(3) Å3). The solid state structure of barium dipicrate hexahydrate (Ba[(NO2)3Ph–O]2·6H2O) was also elucidated: Triclinic P[1 with combining macron], a = 6.641(1) Å, b = 11.588(1) Å, c = 15.033(1) Å; α = 84.64(1)°, β = 80.07(1)°; γ = 86.80(1)°; V = 1133.8(1) Å3. Furthermore, we studied the thermal properties of compounds 1–9 by differential scanning calorimetry (DSC). Salts 2–4, 8 and 9 fall within the category of ionic liquids. Lastly, the energetic salts were subjected to standard sensitivity tests and a software code was used to predict the detonation parameters and specific impulses of the compounds and their mixtures with an oxidizer.

Graphical abstract: Salts of 1-(chloromethyl)-1,1-dimethylhydrazine and ionic liquids

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Supplementary files

Article information


Submitted
28 Oct 2011
Accepted
01 Feb 2012
First published
06 Mar 2012

RSC Adv., 2012,2, 3691-3699
Article type
Paper

Salts of 1-(chloromethyl)-1,1-dimethylhydrazine and ionic liquids

C. Miró Sabaté, H. Delalu, V. Forquet and E. Jeanneau, RSC Adv., 2012, 2, 3691
DOI: 10.1039/C2RA00968D

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