- Practical catalytic nitration directly with commercial nitric acid for the preparation of aliphatic nitroesters
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To pursue a sustainable and efficient approach for aliphatic nitroester preparation from alcohol, europium-triflate-catalyzed nitration, which directly uses commercial nitric acid, has been successfully developed. Gram scalability with operational ease showed its practicability.
- An, Jichao,He, Pan,Li, Wenhao,Liu, Peipei,Si, Mengyuan,Yang, Bo,Yang, Guanyu
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supporting information
p. 6612 - 6616
(2020/09/21)
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- Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(-)-myrtenol nitrate
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Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a 'halide for nitrate' substitution. Employing readily available starting materials, reagents and Horner-Wadsworth-Emmons chemistry the synthesis of easily separable, synthetically versatile 'key building blocks' (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, 'off the shelf' materials. Exploiting their reactivity we have studied their ability to undergo an 'allylic halide for allylic nitrate' substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates ('isoprene nitrates') in 66-80% overall yields. Using NOESY experiments the elucidation of the carbon-carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our 'halide for nitrate' substitution chemistry we outline the straightforward transformation of (1R,2S)-(-)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(-)-myrtenol nitrate.
- Bew, Sean P.,Hiatt-Gipson, Glyn D.,Mills, Graham P.,Reeves, Claire E.
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p. 1081 - 1095
(2016/07/06)
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- Synthesis of nitric acid esters from alcohols in a dinitrogen pentoxide/carbon dioxide liquid system
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Organic nitric acid esters have been prepared in 89-98% yield by the nitration of the corresponding alcohols and polyols with N2O5 in liquid CO2.
- Kuchurov, Ilya V.,Fomenkov, Igor V.,Zlotin, Sergei G.,Tartakovsky, Vladimir A.
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experimental part
p. 67 - 69
(2012/07/02)
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- NO donors. Part 16: Investigations on structure-activity relationships of organic mononitrates reveal 2-nitrooxyethylammoniumnitrate as a high potent vasodilator
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The vasoactive properties of 14 organic mononitrates were investigated in vitro using PGF2α-precontracted porcine pulmonary arteries. A surprisingly wide range of vasorelaxant potencies was observed (pD2: 3.36-7.50). Activities showed to be highly sensitive to the molecular structure and the substituents at the molecular carrier of the nitrate group. A correlation between lipophilicity and vasorelaxant potency could not be recognized. 2-Nitrooxyethylammoniumnitrate (1) was found to be slightly superior to the high potency trinitrate GTN.
- Koenig, Andreas,Roegler, Carolin,Lange, Kathrin,Daiber, Andreas,Glusa, Erika,Lehmann, Jochen
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p. 5881 - 5885
(2008/03/14)
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- Rate coefficients for the reactions of Cl atoms with a series of C3-C6 hydroxyalkyl nitrates at 296 ± 2 K
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Rate coefficients for the gas-phase reactions of chlorine atoms with a series of C3-C6 hydroxyalkyl nitrates of atmospheric interest have been determined at 296 ± 2 K and atmospheric pressure. The experiments were conducted using the relative rate technique combined with solid-phase microextraction (SPME) sampling followed by gas chromatography (GC) analysis with an electron capture detector (ECD). The experiments were performed in a collapsible 100 L PVF-film (Tedlar) reaction chamber. It is shown that the presence of the hydroxy group enhances the reactivity of the hydroxyalkyl nitrates toward the Cl atom as compared to the corresponding alkyl nitrates and alkyl dinitrates. The Cl atom reactivity toward the hydroxyalkyl nitrates increases with the length of the alkyl chain and with increasing separation between the hydroxy and the nitrooxy groups. Tropospheric lifetimes are calculated using the determined rate coefficients and the atmospheric implications are briefly discussed.
- Treves, Keren,Shragina, Lea,Rudich, Yinon
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p. 5902 - 5907
(2007/10/03)
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- Formation of nitrogenous compounds in the photooxidation of n-butane under atmospheric conditions
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The photooxidation of n-butane under atmospheric conditions in the presence of NOx resulted in the formation of the following nitrogenous products: peroxy acetyl nitrate 23, sec-butyl nitrate 16, n-butyl nitrate 1.3, ethyl nitrate 1.3, peroxy n-butyryl nitrate 1.3, and peroxy propionyl nitrate 0.5% of the initially added odd nitrogen. In addition, an electron capturing compound eluting at the retention time of sec-propyl nitrate was also observed accounting for 5% of initial NOx. Butan-2-one was the major product of conversion of n-butane with a yield of 37%. From product ratios it is evident that the formation of sec-butyl nitrate is favored over that of n-butyl nitrate by a factor of 2.1. The rate of reaction of sec-butoxy radicals with oxygen is equal to their decomposition rate.
- Evmorfopoulou, Efthalia,Glavas, Sotirios
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p. 1151 - 1159
(2007/10/03)
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- Separation of Diastereomeric and Enantiomeric Alkyl Nitrates - Systematic Approach to Chiral Discrimination on Cyclodextrin LIPODEX-D
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High-resolution gas chromatographic separation of all diastereomeric monomethyl-substituted cyclohexyl nitrates is shown on a nonpolar methylpolysiloxane stationary phase, and the first application of this procedure to the environmental diastereomeric analysis of alkyl nitrates is presented.Two characteristic signals in the achiral analysis of atmospheric samples could be assigned to the smallest alkyl nitrate containing two asymmetric carbon atoms, 3-methyl-2-pentyl nitrate.Retention indices in the temperature-programmed separation based on the n-alkanes were determined.The homologous series of 1-alkyl nitrates were found to be useful as ECD-visible n-alkanes.Enantiomeric separation of alkyl nitrates was achieved on heptakis(3-O-acetyl,-2,6-di-O-pentyl)-β-cyclodextrin (LIPODEX-D).The influence of the nitrooxy group and the alkyl chain length on the chiral discrimination on LIPODEX-D is discussed for 25 chiral alkyl nitrates.The absolute configurations of some alkyl nitrates were assigned by asymmetric synthesis of enantiomerically pure references.The complexity of the alkyl nitrate mixtures present in air samoles does not allow a direct chiral separation as the alkyl nitrates partly coelute on the LIPODEX-D column.Column coupling of LIPODEX-D with a polar achiral stationary phase like polyalkylenglocol (PAG) was successfully applied to solve this problem, and the chiral alkyl nitrates present in a typical air sample were separated.A systematic nomenclature for alkyl nitrates is introduced to handle the steadily growing number of branched and long-chain nitrates detected in environmental analysis. - Keywords: analytical methods; alkyl nitrates; chiral resolution; cyclodextrins; gas chromatography
- Schneider, Manfred,Ballschmiter, Karlheinz
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p. 539 - 544
(2007/10/03)
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- Formation and Thermal Decomposition of Butyl-Substituted Peroxyacyl Nitrates: n-C4H9C(O)OONO2 and i-C4H9C(O)OONO2
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The butyl-substituted peroxyacyl nitrates n-C4H9C(O)OONO2 and i-C4H9C(O)OONO2 have been synthesized in the liquid phase, prepared in-situ in the gas phase by sunlight irradiation of aldehyde-NO mixtures, measured by electron capture gas chromatography, and characterized in a number of gas-phase and liquid-phase tests. Gas-phase yields as a fraction of initial NO were 0.39 for the n-butyl isomer and 0.20 for the isobutyl isomer. The corresponding gas-phase aldehyde oxidation mechanisms are outlined. Thermal decomposition in the presence of excess NO yielded n-butanal and isobutanal as the major carbonyl products. Thermal decomposition rates at ambient temperature and atmospheric pressure are comparable to that of PAN , with k298 = 1.8E-4 s-1 for n-C4H9C(O)OONO2 and 2.4E-4 s-1 for i-C4H9C(O)OONO2. Emission data for precursor hydrocarbons indicate C4H9C(O)OONO2/PAN ambient concentration ratios of 0.19 in urban air. Atmospheric implications for the formation and removal of C4H9C(O)OONO2 are briefly discussed.
- Grosjean, Daniel,Grosjean, Eric,Williams, Edwin L.
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p. 1099 - 1105
(2007/10/03)
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- Convenient preparation of alkyl nitrates free of nitrites with potassium nitrate and boron trifluoride hydrate
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Primary and secondary alkyl nitrates free of nitrites were conveniently prepared by treating the corresponding alcohols with potassium nitrate and boron trifluoride 1.25 hydrate. This procedure was also successful for the preparation of 1-adamantyl nitrate.
- Olah,Wang,Li,Prakash
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p. 207 - 208
(2007/10/02)
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- Formation of Organic Nitro-compounds in Flowing H2O2+NO2+N2+Organic Vapour Systems. Part 3.-Effects of O2 Addition on H2O2+NO2+N2+Alkane Systems
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The effects of oxygen on the product distribution from the surface-initiated reactions in flowing mixtures of H2O2, NO2, N2 and RH, where RH=ethane, propane, n-butane and n-pentane, at 298 K have been studied.In the absence of O2, the principal products are the corresponding nitroalkane, alkyl nitrite and alkyl nitrate.In the presence of sufficiently large concentrations of O2, the predominant product is the alkyl nitrate and the only other products of significance, in some cases, are the corresponding carbonyl compounds.The variation of the product yields with / gives values for the rate-constant ratios k8/(k3+k4) for reaction at both primary and secondary radical sites:.Possible mechanisms by which the products are formed are discussed.
- Baulch, Donald L.,Campbell, Ian M.,Chappel, Jonathan M.
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p. 617 - 628
(2007/10/02)
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- Formation of Organic Nitro-compounds in Flowing H2O2+NO2+N2+Organic Vapour Systems. Part 2.-H2O2+NO2+N2+Alkane System
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The principal products from the surface-initiated reactions in flowing mixtures of H2O2, NO2,N2 and RH, where RH=ethane, propane, n-butane and n-pentane, have been identified as the nitroalkane, alkyl nitrite and alkyl nitrate.The product yields have been measured; in the case of propane the variation of the yields with total gas pressure has also been studied.Values have been obtained for the relative rates of primary and secondary H-atom abstraction from each alkane by OH and for the rate-constant ratios k3/k4 and k5/k6 at 298 K:.The trends in the product yields with the variation of pressure and change of R indicate that RO radicals are produced via reactions (4)-(6) rather than by a single-step reaction of R with NO2.
- Baulch, Donald L.,Campbell, Ian M.,Chappel, Jonathan M.
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p. 609 - 616
(2007/10/02)
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- Alkyl Nitrate Formation from the NOx-Air Photooxidations of C2-C8 n-Alkanes
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The yields of alkyl nitrates formed in the NOx-air photooxidations of the homologous series of n-alkanes from ethane through n-octane have been determined at 299 +/- 2 K and 735 torr total pressure for two different chemical systems.Alkyl peroxy radicals were generated by reaction of the n-alkanes with OH radicals (generated from the photolysis of methyl nitrite in air) or Cl atoms (from photolysis of Cl2 in air).The alkyl nitrate yields obtained from the two systems, corrected for secondary reactions, were in agreement within the experimental errors and increased monotonically with the carbon number of the n-alkane, from x-air photooxidations of the large n-alkanes.
- Atkinson, Roger,Aschmann, Sara M.,Carter, William P. L.,Winer, Arthur M.,Pitts, James N.
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p. 4563 - 4569
(2007/10/02)
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