1761-67-7Relevant articles and documents
Kinetic and Theoretical Study of the Nitrate (NO3) Radical Gas Phase Reactions with N-Nitrosodimethylamine and N-Nitrosodiethylamine
Maguta, Mihayo Musabila,Stenstr?m, Yngve,Nielsen, Claus J.
, p. 6970 - 6977 (2016)
The reaction rates of (CH3)2NNO and (CH3CH2)2NNO with NO3 radicals were determined relative to formaldehyde (CH2O) and ethene (CH2CH2) at 298 ± 2 K and 1013 ± 10 hPa in purified air by long path FTIR spectroscopy. The reactions are too slow to be of importance at atmospheric conditions: k NO3+(CH3)2NNO = (1.47 ± 0.23) × 10-16 and k NO3+(CH3CH2)2NNO = (5.1 ± 0.4) × 10-16 cm3 molecule-1 s-1 (1σ error limits). Theoretical calculations, based on CCSD(T?)-F12a/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ results, predict the corresponding imines as the sole primary products in nitrosamine reactions with NO3 and OH radicals.
Photolysis of Dimethylnitrosamine in the Gas Phase
Geiger, Georg,Huber, J. Robert
, p. 989 - 995 (1981)
Photodecomposition of dimethylnitrosamine in the gas phase ( 1 Torr) has been investigated following irradiation into the S1(n?*) 0(363.5 nm) and S2(??'*) 0(248.1 nm) transitions at room temperature.With a quantum yield of unity, excitation into the S1 state yields the fragments (CH3)2N and NO which then recombine leaving no photoproducts.The addition of O2 results in only one photoproduct, (CH3)2NNO2.Irradiating into the S2 state, the products CH2=N-CH3, (CH2=N-CH3)3, CH2=NOH, N2O, NO, H2, and N2 were identified by capillary gas chromatography mass spectrometry.In the presence of N2 as a buffer gas the photoproducts are only CH2=N-CH3, (CH2=N-CH3)3, N2O, and H2.For both excitation conditions a mechanism is proposed involving cleavage of the N,N-bond as the main primary photolytic process.
Electron diffraction study of thermal decomposition products of trimethylamine: molecular structure of CH3-N=CH2
Fujiwara, Hideo,Egawa, Toru,Konaka, Shigehiro
, p. 217 - 226 (1995)
Structural studies of thermal decomposition products of trimethylamine have been performed by gas electron diffraction aided by mass spectrometry.Trimethylamine vapor is heated in a quartz tube shortly before the nozzle tip which is kept at room temperature.When the temperature inside the quartz tube is 515 deg C, N(CH3)3 simply decomposes into CH4 and short-lived CH3-N=CH2.However, more complicated reactions, which include CH3-N=CH2->CH4+HCN, take place at the reaction temperature of 535 deg C.The zero-point average structure of N-methylmethyleneimine (CH3-N=CH2) has been determined by a joint analysis of electron diffraction data and rotational constants, and then compared with ab initio calculations.Principal structural parameters are as follows: rz(N=C)=1.279(6) Angstroem, rz(N-C)=1.458(8) Angstroem and Θz(CNC)=116.62(12) deg.The molecular structure of trimethylamine has been determined much more precisely than that given in the literature.
Ultraviolet photoelectron studies of dehydration and dehydrohalogenation reactions of β-substituted alcohols using H-ZSM-5 and the formation of unstable intermediates
Alaee,Westwood
, p. 3818 - 3821 (1994)
Dehydration of 1,2-ethanediol and 2-aminoethanol and dehydrohalogenation of 2-chloro- and 2-fluoroethanol over H-ZSM-5 at 200-350°C was followed under low-pressure (ca. 25 mTorr) flow conditions using ultraviolet photoelectron spectroscopy as a direct on-line monitor. This circumvents the necessity of separations since the effluent from the reactor can be monitored immediately after leaving the catalyst bed. Under these conditions all precursors are consumed, leading to the final product acetaldehyde, except in the case of 2-aminoethanol where dehydration gives, in high yield, the unexpected N-methyl isomer of methylenimine, an unstable molecule. A postulated mechanism for this result, applicable also to the formation of acetaldehyde in the other β-substituted alcohols, suggests the intermediacy of three-membered cyclic species, namely, ethylenimine and ethylene oxide or their protonated analogs.
Too Short-Lived or Not Existing Species: N-Azidoamines Reinvestigated
Banert, Klaus,Pester, Tom
, p. 4033 - 4039 (2019/04/10)
Treatment of N-chlorodimethylamine with sodium azide in dichloromethane does not lead to N-azidodimethylamine, as thought for more than 50 years. Instead, surprisingly, (azidomethyl)dimethylamine is generated with good reproducibility. A plausible reaction mechanism to explain the formation of this product is presented. The reaction of lithium dibenzylhydrazide with tosyl azide does not result in the creation of an N-azidoamine, which can be detected by IR spectroscopy at ambient temperature, as it was claimed previously. Additional experiments with diazo group transfer to lithium hydrazides show that intermediate N-azidoamines are very short-lived or their formation is bypassed by direct generation of 1,1-diazenes via synchronous cleavage of two N-N bonds.
Matrix-IR spectroscopic investigations of the thermolysis and photolysis of diazoamides
Wentrup, Curt,Bibas, Herve,Kuhn, Arvid,Mitschke, Ullrich,McMills, Mark C.
, p. 10705 - 10717 (2013/11/19)
Matrix photolysis of N,N-dialkyldiazoacetamides 1a-d at 7-10 K results in either the formation of C-H insertion products (in case of N,N-dimethyl and N,N-diethyl diazoamides) or almost exclusive Wolff rearrangement to ketenes (in the case of the cyclic di
Nickel-catalyzed transfer semihydrogenation and hydroamination of aromatic alkynes using amines as hydrogen donors
Reyes-Sanchez, Adan,Canavera-Buelvas, Farrah,Barrios-Francisco, Rigoberto,Cifuentes-Vaca, Olga L.,Flores-Alamo, Marcos,Garcia, Juventino J.
experimental part, p. 3340 - 3345 (2011/08/22)
The transfer hydrogenation of diphenylacetylene to yield cis- and trans-stilbenes was achieved using a variety of amines as hydrogen donors and the complex 1 ([(dippe)Ni(μ-H)]2) in catalytic amounts (0.5% mol). The use of nucleophilic amines such as pyrrolidine in neat conditions afforded the hydroamination of diphenylacetylene, in moderate to high yields. Cyclization of 2-ethynylaniline also was carried out under similar conditions, with 1 in catalytic amounts, but in low yield, mainly due to the formation of homocoupling products of the starting material. The hydrogenation of diphenylacetylene by using other nitrogenated compounds such as aromatic N-heterocycles was addressed to give a metal-mediated process, using 1 in stoichiometric amounts.
A small molecule that mimics the metabolic activity of copper-containing amine oxidases (CuAOs) toward physiological mono- and polyamines
Largeron, Martine,Fleury, Maurice-Bernard,Strolin Benedetti, Margherita
supporting information; experimental part, p. 3796 - 3800 (2010/09/06)
Primary aliphatic biogenic amines have been successfully oxidized using a quinonoid species that mimics the metabolic activity of copper-containing amine oxidase (CuAO) enzymes. Especially, high catalytic performances were observed with aminoacetone, a threonine catabolite, and methylamine, a metabolite of adrenaline, and with the primary amino groups of putrescine and spermidine which are both decarboxylation products of ornithine and S-adenosyl-methionine. Furthermore, contrary to flavine adenine dinucleotide (FAD)-dependent amine oxidase enzymes, no activity was found toward secondary and tertiary amines.
GASEOUS DIELECTRICS WITH LOW GLOBAL WARMING POTENTIALS
-
, (2010/12/31)
A dielectric gaseous compound which exhibits the following properties: a boiling point in the range between about ?20° C. to about ?273° C.; non-ozone depleting; a GWP less than about 22,200; chemical stability, as measured by a negative standard enthalpy of formation (dHf0); a toxicity level such that when the dielectric gas leaks, the effective diluted concentration does not exceed its PEL; and a dielectric strength greater than air.
Retro-Ene Reactions in Acylallene Derivatives
Bibas, Herve,Koch, Rainer,Wentrup, Curt
, p. 2619 - 2626 (2007/10/03)
Allenic esters and amides 4 undergo a retro-ene reaction to vinylketene (6) and an aldehyde or imine (5) under the conditions of flash vacuum thermolysis (FVT). The same products are obtained by FVT of cyclobutenones 7 via electrocyclic ring opening to alkoxy- or aminovinylketenes 3 and 1,3-rearrangement of ketenes 3 to allenes 4. All the intermediates and products were characterized by matrix isolation IR spectroscopy, and in the case of 4c the reaction was also monitored by online mass spectrometry. A lower temperature for the retro-ene reaction of 4c, eliminating an imine, than for 4a, eliminating formaldehyde, is in agreement with a lower calculated activation barrier (167 and 181 kJ mol-1, respectively, at the G2(MP2,SVP) level of theory). The allenic amide 11 undergoes an analogous retro-ene reaction to the (unobserved) vinylketene 13, the latter isomerizing to cyclohexenylacrolein 16 in a 1,5-H shift (calculated barrier 125 kJ mol-1; G2 (MP2, SVP)).
