Differential thermal analysis of nitramines, amine salts, and guanidine derivatives

Carignan, Yvon P.; Satriana, Daniel R.

doi:10.1021/jo01288a008

Cited by 23 publications

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“…The high-resolution XH NMR spectrum of 12 in (CDs^CO reveals four methylene singlets, corresponding to a nearly statistical distribution of the symmetrical and asymmetrical forms 12a and 12b (1:3 ratio). The results are in agreement with the X3C spectrum and an earlier report of proton spectra by Urbanski and co-workers, although their reported signals of the two forms were not completely resolved.XOc The dinitroso compound 13 exhibits XH and X3C NMR spectra HOCH.NHCHOH 17 14 ^hoch",nhch2nh2 hoc:hn'hch2nhch,nh2 Mechanism of Hexamine Formation. Mechanisms of hexamine formation from formaldehyde and ammonia have been discussed by others in several reports.…”

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confidence: 99%

“…Methylenimine (15) is assumed to be the reactive aminomethylation intermediate, although its concentration is negligible relative to aminals 14 and 16. Reaction intermediates of Scheme I are of acyclic and cyclic types. Acyclics include monomers (14,15,16), dimers (17,18), and trimers (19,20,21). As discussed above, there exists kinetic and NMR evidence for hemiaminal monomer 14.…”

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confidence: 99%

“…6 The instability and solubility of these are greatest when R is a small group (CH3, C2H5). Dissociation to aldimines, RCH=NH, or retrogression to reactants occurs very readily; thus, the parent homologue (14) would be expected to be extremely reactive and labile. Acetaldimine (CH3CH=NH), derived from CH3CH(OH)NH2 but not isolated, trimerizes very rapidly compared to its higher homologues;6 owing to its low steady-state concentration, methylenimine (15) would be expected to be undetectable spectroscopically but to trimerize very rapidly to hexahydrotriazine 2. Acyclic dimers 17 and 18 and trimer 19 could be represented by broad NCH20 peaks seen near 4.5 (Figure 1).…”

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Structure and chemistry of the aldehyde ammonias. 3. Formaldehyde-ammonia reaction. 1,3,5-Hexahydrotriazine

Nielsen¹,

Moore²,

Ogan³

et al. 1979

J. Org. Chem.

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The formaldehyde-ammonia reaction has been examined in DzO solvent with the aid of 'H and 13C NMR spectroscopy. Reaction intermediates, including 1,3,5-hexahydrotriazine (2) and 1,3,5,7-tetraazabicyclo[3.3.l]nonane (6), are observed, and the mechanisms of their formation and conversion into hexamine are discussed. Solutions previously reported to contain 2 alone have been shown to be complex mixtures.The formaldehyde-ammonia reaction under appropriate conditions leads quantitatively to hexamine (1, eq lL3 Despite HN-O n n HN-NH 1 its importance, it has received limited detailed study; understanding of this complex reaction sequence is tentative.In the present work 'H and 13C NMR spectroscopy have been employed to follow the reaction and identify some intermediates.The most extensive recent study of the formaldehydeammonia reaction is that of Richmond, Myers, and Wright.4 From chemical evidence they concluded that 1,3,5-hexahydrotriazine (2) is a reaction intermediate. This result is in I I H H 2 3, R = alkyl 3a, R = CH, agreement with the early reports of Duden and Scharff,j who first correctly assigned structure 1 to hexamine. The present study provides NMR evidence for formation of 2. Our previous studies on reaction of rz-alkanals with ammonia showed that the ultimate reaction products are usually 2,4,6-trialkyl-1,3,5-hexahydrotriazines (3).'s6 The kinetics of the formaldehyde-ammonia reaction have been examined by several workers.7 Results and Discussion 1H and I3C NMR Spectra of Formaldehyde-AmmoniaSolutions. In the present work lH and 13C NMR spectra of various D20 solutions of ammonium-d4 hydroxide and formaldehyde a t 25 "C were determined a t intervals. The 'H spectra clearly reveal the rapid formation of hexamine and the presence of reaction intermediates (Figure 1). The methylene signals are grouped in two principal regions. Rather broad signals near 6 4.5 are attributed to NCHPO-type methylenes; compare these signals with those of 1,3-perhydrotriazine (4) in which the C-2 methylenes appear at 6 4.558a (Table I). Sharper, more defined signals appear near 6 3.5-4.0 and represent NCHPN-type methylenes (with the exception of hexamine itself which appears as a singlet at 6 4.75).9 Altering the formaldehyde-ammonia molar ratio from 1:4 to 3:2 provides the same products in each experiment, and their relative distribution at a given time is changed but slightly. 4 5 1,3,5-Hexahydrotriazine (2) exhibits a sharp singlet at 63.95. This value may be compared with the C-2 methylene signal of 1,3-hexahydrodiazine (5, 6 3.73)8b and the ring methine signal of 2,4,6-trimethyl-1,3,5-hexahydrotriazine [3a, 6 3.80 (q)] in D20 solvent (Table I). Hexahydrotriazine forms rapidly and ultimately is the principal species present other than hexamine. Initially, its concentration is much greater than that of hexamine, a fact supported by low temperature (-10 O C ) I3C NMR spectra observations; e.g., the peak height ratio of 2/1 equals 3 after 1 h.Signals attributed to 1,3,5,7-tetraazabicyclo[3.3.l]nonane (6) persist in the lH NM...

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Structure and chemistry of the aldehyde ammonias. 3. Formaldehyde-ammonia reaction. 1,3,5-Hexahydrotriazine

Nielsen¹,

Moore²,

Ogan³

et al. 1979

J. Org. Chem.

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“…In contrast, DTA traces of the guanidine derivativesamino-, diamino-and triaminoguanidinium nitrates -showed overlapping exothermic changes with several peak maxima in the range 497-587 K (Carignan & Satriana, 1967 7163 2Symmetry codes: (iii) Àx þ 2; y À 1 2 ; z þ 1 2 ; (iv) x; Ày þ 1 2 ; Àz þ 1 2 ; (v) x À 1 2 ; y; Àz þ 1.…”

Section: Thermal Stability and Oxygen Balance Of (I)mentioning

confidence: 97%

Formaldehyde–aminoguanidine condensation and aminoguanidine self-condensation products: syntheses, crystal structures and characterization

et al. 2018

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Guanidine is the functional group on the side chain of arginine, one of the fundamental building blocks of life. In recent years, a number of compounds based on the aminoguanidine (AG) moiety have been described as presenting high anticancer activities. The product of condensation between two molecules of AG and one molecule of formaldehyde was isolated in the protonated form as the dinitrate salt (systematic name: 2,8-diamino-1,3,4,6,7,9-hexaazanona-1,8-diene-1,9-diium dinitrate), CHN·2NO, (I). The cation lacks crystallographically imposed symmetry and comprises two terminal planar guanidinium groups, which share an N-C-N unit. Each cation in (I) builds 14 N-H...O hydrogen bonds and is separated from adjacent cations by seven nitrate anions. The AG self-condensation reaction in the presence of copper(II) chloride and chloride anions led to the formation of the organic-inorganic hybrid 1,2-bis(diaminomethylidene)hydrazine-1,2-diium tetrachloridocuprate(II), (CHN)[CuCl], (II). Its asymmetric unit is composed of half a diprotonated 1,2-bis(diaminomethylidene)hydrazine-1,2-diium dication and half a tetrachloridocuprate(II) dianion, with the Cu atom situated on a twofold rotation axis. The planar guanidinium fragments in (II) have their planes twisted by approximately 77.64 (5)° with respect to each other. The tetrahedral [CuCl] anion is severely distorted and its pronounced `planarity' must originate from its involvement in multiple N-H...Cl hydrogen bonds. It was reported that [CuCl] anions, with a trans-Cl-Cu-Cl angle (Θ) of ∼140°, are yellow-green at room temperature, with the colour shifting to a deeper green as Θ increases and toward orange as Θ decreases. Brown salt (II), with a Θ value of 142.059 (8)°, does not fit the trend, which emphasizes the need to take other structural factors into consideration. In the crystal of salt (II), layers of cations and anions alternate along the b axis, with the minimum Cu...Cu distance being 7.5408 (3) Å inside a layer. The structures of salts (I) and (II) were substantiated via spectroscopic data. The endothermic reaction involved in the thermal decomposition of (I) requires additional oxygen. The title salts may be useful for the screening of new substances with biological activity.

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“…Only little effort was made in studying the energetic parameters of the salts of ethylenedinitramine. , Worth mentioning is the reported impact sensitivity of the silver and the lead salts. Further information on their behavior is not described.…”

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confidence: 99%

Investigation of Ethylenedinitramine as a Versatile Building Block in Energetic Salts, Cocrystals, and Coordination Compounds

et al. 2021

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Ethylenedinitramine (H 2 EDN, 1) was prepared in a simple manner and with a high overall yield by direct nitration of 2imidazolidinone using 100% HNO 3 at 0 °C and subsequent hydrolysis in water at 100 °C. The versatility of 1 allows its application as starting material for a broad range of different materials. It was used for the preparation of both various salts and cocrystalline materials incorporating varying amounts of the TATOT moiety. Furthermore, H 2 EDN was successfully applied in the concept of energetic coordination compounds (ECCs) resulting in five copper(II) and two silver(I) complexes. A reaction path for the direct precipitation or slow crystallization of 17 different salts, including several alkali, alkaline earth, silver, and nitrogenrich samples, is presented. The substances were extensively characterized by low-temperature single-crystal X-ray diffraction, elemental analysis (EA), IR spectroscopy, differential thermal analysis (DTA), and thermogravimetric analysis (TGA), proving their high thermal stability, especially of the alkali salts. In addition, 1 and all salts were characterized by 1 H, 13 C, and 14 N NMR, whereas 1 was also investigated using the beneficial 1 H− 15 N HMBC NMR spectroscopy. The sensitivities toward various mechanical stimuli according to BAM standard methods, as well as ball drop impact and electrostatic discharge (ESD) were determined using the BAM 1-out-6 method. Hot plate and hot needle tests were performed, followed by further characterization of the copper(II)-based ECCs through laser ignition experiments and UV−vis spectroscopy, offering new candidates for nontoxic, less sensitive laser-ignitable materials. Several detonation parameters were calculated using EXPLO5 (V6.05.02).

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Differential thermal analysis of nitramines, amine salts, and guanidine derivatives

Cited by 23 publications

References 0 publications

Structure and chemistry of the aldehyde ammonias. 3. Formaldehyde-ammonia reaction. 1,3,5-Hexahydrotriazine

Structure and chemistry of the aldehyde ammonias. 3. Formaldehyde-ammonia reaction. 1,3,5-Hexahydrotriazine

Formaldehyde–aminoguanidine condensation and aminoguanidine self-condensation products: syntheses, crystal structures and characterization

Investigation of Ethylenedinitramine as a Versatile Building Block in Energetic Salts, Cocrystals, and Coordination Compounds

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