Hexamethylenetetramine, A Versatile Reagent in Organic Synthesis

Blažzević, Nikola; Kolbah, D.; BELIN, B.; Šunjić, Vitomir; Kajfež, F.

doi:10.1055/s-1979-28602

Cited by 179 publications

(92 citation statements)

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“…Because their evolutions are correlated, the counter ion of HCOO − at 300 K seems to be the HMT cation. Indeed HMT could be formed at lower temperature, and because it is a base similar to NH 3 , it could react with HCOOH giving a salt [HCOO − ][C 6 H 12 N 4 H + ] (Blazevic et al 1979). At temperatures higher than 300 K, the reverse acid-base reaction release the HMT and HCOOH.…”

Section: Thermal Formation Of Hmtmentioning

confidence: 99%

New insight into the formation of hexamethylenetetramine (HMT) in interstellar and cometary ice analogs

Vinogradoff

Duvernay

Danger

et al. 2011

A&A

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Aims. We investigate the purely thermal formation of hexamethylenetetramine (HMT, C 6 H 12 N 4 ) in interstellar ice analogs from nonphotolysed ice and compare our results with those for the formation from photolysed ice. Methods. We use Fourier transform-infrared spectroscopy to follow residue formation from VUV irradiation of H 2 CO:NH 3 ice mixture in different concentration ratios. We also report the warming of the H 2 CO:NH 3 :HCOOH ice mixture.Results. We present the characterization of organic residues obtained at 330 K from VUV irradiation of H 2 CO:NH 3 ice mixtures. The organic residues contain compounds related to polyoxomethylene (POM, [-CH 2 -O-] n ) and HMT (C 6 H 12 N 4 ). We report, for the first time, the formation of HMT from the warming of an interstellar ice analogs, H 2 CO:NH 3 :HCOOH, without any energetic processing (i.e. photons or particles). New insights into HMT formation mechanism are proposed. These results strengthen the hypothesis that HMT is present in interstellar grains or in comets, where it may be detected with the COSAC instrument of the Rosetta mission.

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Section: Thermal Formation Of Hmtmentioning

confidence: 99%

New insight into the formation of hexamethylenetetramine (HMT) in interstellar and cometary ice analogs

Vinogradoff

Duvernay

Danger

et al. 2011

A&A

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“…The intermolecular correlations (Canut & Amoro Â s, 1958) between these rigid bodies lead to rather strong TDS in inter-Bragg space. On the other hand the situation is compounded by the tendency of U to start subliming at as low as 330 K (Birkedal, 1996) and, above 468 K, to chemically (Blaz Ïevic Â et al, 1979) and thermally (Klipping & Stranski, 1958) decompose.…”

Section: Introductionmentioning

confidence: 99%

Urotropin azelate: a rather unwilling co-crystal

Bonin

Welberry

Hostettler

et al. 2003

Acta Crystallogr Sect B

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Urotropin (U) and azelaic acid (AA) form 1:1 co-crystals (UA) that give rise to a rather complex diffraction pattern, the main features of which are diffuse rods and bands in addition to the Bragg re¯ections. UA is characterized by solvent inclusions, parasite phases, and high vacancy and dislocation densities. These defects compounded with the pronounced tendency of U to escape from the crystal edi®ce lead to at least seven exotic phase transitions (many of which barely manifest themselves in a differential scanning calorimetry trace). These involve different incommensurate phases and a peritectoid reaction in the recrystallization regime (T h b 0X6). The system may be understood as an OD (order±disorder) structure based on a layer with layer group Pcc2 and cell a o 9 4.7, b 9 26.1 and c 9 14.4 A Ê . At 338 K the layer stacking is random, but with decreasing temperature the build-up of an orthorhombic MDO (maximal degree of order) structure with cell a 1 = 2a o , b 1 = b, c 1 = c and space group Pcc2 is begun (at $301 K). The superposition structure of the OD system at T = 286 (1) K with space group Bmmb and cell a = 2a o , b = b and c = ca2 owes its cohesion to van der Waals interactions between the AA chains and to three types of hydrogen bonds of varied strength between UÐU and UÐAA. Before reaching completion, this MDO structure is transformed, at 282 K, into a monoclinic one with cell a m = Àa o c/4, b m = b, c m = À2a o ca2, space group P2 1 ac, spontaneous deformation $2, and ferroelastic domains. This transformation is achieved in two steps: ®rst a furtive triggering transition, which is not yet fully understood, and second an improper ferroelastic transition. At $233 K, the system reaches its ground state (cell a M = a m , b M = b, c M = c m and space group P2 1 ac) via an irreversible transition. The phase transitions below 338 K are described by a model based on the interaction of two thermally activated slip systems. The OD structure is described in terms of a three-dimensional Monte Carlo model that involves ®rst-and second-neighbour interactions along the a axis and ®rst-neighbour interactions along the b and c axes. This model includes random shifts of the chains along their axes and satisfactorily accounts for most features that are seen in the observed diffraction pattern.

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“…This property stimulated chemists to utilize their potential in the design and development of molecular probes for biological evaluations. Ubiquitous presence of this nucleus in the psychopharmacologically active agents and in molecules active against HIV infection, for example, TIBO (1) [14][15][16][17] and FDA approved dipyrido diazepine analogue nevirapine (2) [18][19][20][21][22][23][24] in Figure 1 provided an impetus for an enormous research effort to be directed towards the development of their structural analogues of medicinal importance [25,26].…”

Section: Introductionmentioning

confidence: 99%

A Simple and Advantageous Synthesis of the Privileged 1,4-Benzodiazepine Nucleus

Jain

Kishore

2014

Advances in Chemistry

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A novel domino approach has been described for an easy access of the privileged nucleus of 5-carbomethoxy substituted 1,4-benzodiazepin-2-ones 4(a-i) from an in situ methanolic hydrolysis of an incipient species formed from the interaction of 1-chloroacetylisatin 2(a-i), hexamethyldisilazane, and n-butyl lithium. The reaction is believed to take place through a consecutive series of intramolecular reactions in a cascade to first generate a highly reactive carbene intermediate 3(a-i) from 1-chloroacetylisatin and n-butyl lithium which is simultaneously trapped by hexamethyldisilazane before undergoing its in situ hydrolysis with methanol to initiate its concomitant cyclocondensation to produce 4(a-i) in high yield and purity.

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Hexamethylenetetramine, A Versatile Reagent in Organic Synthesis

Cited by 179 publications

References 0 publications

New insight into the formation of hexamethylenetetramine (HMT) in interstellar and cometary ice analogs

New insight into the formation of hexamethylenetetramine (HMT) in interstellar and cometary ice analogs

Urotropin azelate: a rather unwilling co-crystal

A Simple and Advantageous Synthesis of the Privileged 1,4-Benzodiazepine Nucleus

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