- Synthesis of glycidyl-5-(carboxyethyl-1H-tetrazole)polymer and 1,2-bis(5-carboxyethyl-1H-tetrazolyl)ethane as polymeric precursor
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The synthesis of the nitrogen-rich glycidyl-5-(carboxyethyl-1H-tetrazole) polymer (4) by the reaction of glycidyl azide polymer (GAP) and ethyl cyanoformate (2) is described. Moreover, the polymer precursor 1,2-bis(5-carboxyethyl-1H-tetrazolyl)ethane (3), containing two tetrazole moieties, was obtained by reacting compound 2 and 1,2-diazidoethane (1). The substances were characterized by using vibrational spectroscopy (IR), mass spectrometry, as well as multinuclear NMR spectroscopy. Compound 3 was additionally characterized by single-crystal X-ray diffraction measurements. The thermal stability of 3 was determined by differential scanning calorimetry, which reveals that this compound is a highly stable molecule. Synthesis of highly thermally stable energetic nitrogen-rich polymers incorporating tetrazole heterocycles and the corresponding polymer precursor is reported. Complete structural and spectroscopic characterization including IR and multinuclear NMR spectroscopy and mass spectrometry, as well as single-crystal X-ray diffraction analysis of 1,2-bis(5-carboxyethyl-1H-tetrazolyl)ethane, was accomplished. Copyright
- Betzler, Franziska M.,Klapoetke, Thomas M.,Sproll, Stefan M.
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- SYNTHESIS OF THE ETHYL ESTER OF THE MONONITRILE OF MALONIC ACID BY THE CATALYTIC CARBONYLATION OF THE BENZENESULFONYLOXYACETONITRILE
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A new method has been developed for the synthesis of the ethyl ester of the mononitrile of malonic acid by the carbonylation of benzenesulfonyloxyacetonitrile in absolute ethanol in the presence of cobalt carbonyl.The yield of the desired product was 30 percent with 60-90percent conversion of the starting compound.The effects of temperature, pressure, and reaction time was studied. Keywords: carbonylation, dicobalt octacarbonyl, benzenesulfonyloxyacetonitrile, ethyl ester of the mononitrile of malonic acid.
- Lapidus, A. L.,Pirozhkov, S. D.,Tumanova, A. R.,Koksharova, T. G.,Volkova, N. V.,et al.
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- Detrifluoroacetylation of 4,4,4-trifluoro-3,3-dihydroxy-2-(hydroxyimino)butan-1-ones as a convenient synthetic strategy for acyl cyanides Dedicated to Academician Valery N. Charushin on his 65th birthday.
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A reaction reinvestigation of fluorinated 1,3-dicarbonyl compounds with NaNO2 in acidic conditions revealed the formation of corresponding 1,1,1-trifluoro-3-hydroxyimino-butan-2,4-diones which predominantly isolated as hydrates. A novel synthesis of ethoxy-, alkyl-, (het)aryl substituted carbonylcyanides via acid-catalyzed detrifluoroacetylation of obtained 2-hydroxyimino derivatives of 1,3-dicarbonyl compounds was described.
- Bazhin, Denis N.,Kudyakova, Yulia S.,Nemytova, Natalia A.,Burgart, Yanina V.,Saloutin, Victor I.
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- Synthetic route to isotopically labelled-oxamate
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Since none of the available methods was suitable for the synthesis of isotopically labelled oxamate, a new procedure has been developed in our laboratory, based on the known procedures, but with substantial modifications. The method is convenient and gives reproducibly 17% yield based on KCN used. The strategy is considered suitable for labelling oxamate with 15N and 13C or 14C when starting with labelled KCN and can be easily modified for the synthesis of 18O-carbonyl-labelled oxamate. Copyright 2011 John Wiley & Sons, Ltd. Synthesis route to sodium oxamate labelled with various isotopes has been proposed. Copyright
- Siwek, Agata,Trotsko, Nazar,Wujec, Monika,Kaminski, Rafal,Paneth, Piotr
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experimental part
p. 344 - 344
(2012/06/04)
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- Theoretical, structural, vibrational, NMR, and thermal evidence of the inter- versus intramolecular hydrogen bonding in oxamides and thiooxamides
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This contribution describes the study of hydrogen bonding in secondary oxamides, monothiooxamides, and dithiooxamides by ab initio calculations, X-ray diffractions, NMR spectra, thermal analysis, and variable-temperature infrared and Raman spectroscopy. The results can all be interpreted as a function of the change in the strength and the nature of the hydrogen bonding by substituting oxygen for sulfur in the series CH3-HNCOCONHCH3, CH 3HNCSCONHCH3, CH3HNCSCSNHCH3 and by changing the steric influence of the alkyl group in a series of oxamides (RHNCOCNHR; R = CH3, C2H5, iC3H 7, tC49).
- Desseyn,Perlepes,Clou,Blaton,Van Der Veken,Dommisse,Hansen
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p. 5175 - 5182
(2007/10/03)
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- Flash vacuum pyrolysis of 3-oxo-2-arylhydrazonopropanals and related derivatives
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Flash vacuum pyrolysis (FVP) of 3-oxo-2-arylhydrazonopropanals at 500°C and 0.02 Torr yielded the corresponding derivatives of anilines, N-formylanilines, N-benzoylanilines and benzoylnitriles. Similar FVP of phenylhydrazonomalononitrile, phenylhydrazonoa
- Ibrahim, Yehia A,Kaul, Kamini,Al-Awadi, Nouria A
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p. 10171 - 10176
(2007/10/03)
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- Reaction of stabilised phosphorus ylides with nitrogen dioxide
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The reaction of the stabilised ylides 14-23 with an excess of NO2 in CH2Cl2 at room temperature gives different results depending on the structure of the starting ylide. The monacyl ylides 14-16 give the corresponding α-oxo nitriles 4 together with Ph3PO · HNO3 (24) which has been fully characterised for the first time. Under the same conditions, the ylide 18 gives 2,4-dinitrobenzonitrile (26), Ph3PO, and benzoic acid. The other ylides examined all give 24 together with a variety of other products.
- Aitken, R. Alan,Karodia, Nazira
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p. 251 - 254
(2007/10/03)
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- Process for producing cyanoformate esters
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Alkyl, aralkyl or aryl cyanoformate esters having from one to 20 carbon atoms are prepared by anhydrously reacting stoichiometric amounts of the corresponding alkyl, aralkyl or aryl haloformate and an organosilyl nitrile in the presence of a catalytic amount of a tertiary amine base, preferably 1,4-diazabicyclo?2.2.2!octane, in the absence or presence of an inert solvent. The reaction is conducted at a temperature of from about -30° C. to 70° C., preferably at from about 5° C. to 30° C.
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- Phosphane alkylenes, 55. Reactions of alkylidenetriphenylphosphoranes with nitrating reagents
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The reaction of phosphonium ylides 1 with N2O4 (2) is strongly influenced by the natur of the substituents of the starting ylide. Formation of α-nitro-α-nitrosoalkanoates 8, nitrolic acid 11, and nitriles 13 was realized. Nitration at the phenyl group of benzylidenephosphoranes 24 or at the γ-position of allylidenephosphoranes 30 accompanied by transylidation and oxidation processes leads to the formation of nitro-substituted ylides 26 and 32, respectively. Strongly basic ylides and ethyl nitrate (34) undergo complex reactions as is shown in the formation of the aziridinyl-substituted ylide 40 from ethylidenetriphenylphosphorane (9) and 34. Allylidenetriphenylphosphoranes 41 are nitrated by ethyl nitrate (34) at the γ-position affording (γ-nitroallylidene)triphenylphosphoranes 43, from which nitro dienes 45 are available. In the reaction of 1-(dimethylamino)-2-nitroethylene (46) with phosphonium ylides nitro-vinylation of the starting ylide takes place. VCH Verlagsgesellschaft mbH, 1996.
- Bestmann, Hans Juergen,Kamberger, Werner,Roeder, Thomas,Zimmermann, Reiner
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p. 845 - 851
(2007/10/03)
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- The crystal structure and vibrational spectra of potassium oxathioamidate
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The crystal and molecular structure determination of the title compound, K-SO2NC2H2, Mr = 143.21, (1) is part of a series of determinations of N-substituted oxathioamidates.The structure has been refined using single-crystal X-ray diffraction data measured at 295 K .The crystals are orthorhombic, space group Pn21a, Z = 8, with cell dimensions: a = 11.399(2) Angstroem, b = 22.131(2) Angstroem, c = 4.021(1) Angstroem, V = 1014.5(7) Angstroem3.Dcalc. = 1.875 mg m-3, Dobs = 1.600 mg m-3, F(000) = 576, μ = 13.14 cm-1.The final agreement factors for 1979 observed reflections 3?(I)> were: R = 0.062 and Rw = 0.067.The vibrational spectra confirm the geometrical differences between the two thiooxamidate molecules.KEY WORDS: Potassium oxathioamidate.
- Hereygers, Marleen L.B.F.,Desseyn, Herman O.,Perlepes, Spyros P.,Verhulst, Koen A.F.,Lenstra, Albert T.H.
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p. 181 - 188
(2007/10/02)
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- Gas-Phase Lewis Acid-Base Interactions. An Experimental Determination of Cyanide Binding Energies from Ion Cyclotron Resonance and High-Pressure Mass Spectrometric Equilibrium Measurements
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Both ion cyclotron resonance and high-pressure mass spectrometric equilibrium techniques have been used to investigate the binding energies of anions to a variety of Lewis acids.From an analysis of the enthalpy changes associated with CN- binding it is evident that in cases of relatively weak binding considerable freedom of rotational motion of CN- in the complex may be retained.Ab initio calculations and experiment suggest that binding through both the N and C sites of CN- is nearly equally favorable in some cases.In contrast to results previously obtained for Bronsted acids which showed that CN- and Cl- bind nearly identically, the present data for Lewis acids show many cases where cyanide is much more favorably bound than chloride, a consequence of enhanced covalent binding of the CN- complexes.New Kroeger Drago parameters derived for CN- support the importance of covalent binding in cyanide adducts.Correlations of binding energy of anions to Lewis acids with the anion proton affinity show excellent linear relationships which may be used to predict binding energetics for new anions.
- Larson, J. W.,Szulejko, J. E.,McMahon, T. B.
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p. 7604 - 7609
(2007/10/02)
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- 1,2λ3,3λ3-AZADIPHOSPHOLE EIN AROMATISCHES RINGSYSTEM MIT CIS-P=P-DOPPELBINDUNG 1λ3ρ3,λ3ρ3-DIPHOSPHOLE
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By reaction of 1,2,4,5-tetrazinedicarboxylates with 4 mole tert-butylphosphaethyne the title compounds are formed in an unusual reaction sequence.
- Maerkl, G.,Dietl, S.,Ziegler, M. L.,Nuber, B.
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p. 5867 - 5870
(2007/10/02)
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- Trimethylsilyl Cyanide - A Reagent for Umpolung, XI. On the Ambident Character of Substituted Allylic Anions.
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The dependence of the α/γ-ratio of alkylation products on several factors has been determined with 1-cyano-3-aryl-1-(trimethylsiloxy)allylic anions.Increasing amounts of γ-product are found in more polar solvents, with larger alkali ions, on addition of HMPT, with smaller alkyl groups in the electrophile, and especially with p-cyanophenyl groups.In contrast, temperature and leaving groups have minor effects.On substitution of the O-silyl group by O-methyl and O-ethoxycarbonyl, α-alkylation predominates strongly.The results are compared to known allylic anions.Furthermore, the isomerisation of compounds of type C to type B is described as well as a new addition reaction of cyanoformates to aldehydes.
- Huenig, Siegfried,Reichelt, Helmut
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p. 1772 - 1800
(2007/10/02)
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- Reaction of 3,4-Bis(ethoxycarbonyl)-1,2,5-oxadiazole 2-Oxide with Olefins
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3,4-Bis(ethoxycarbonyl)-1,2,5-oxadiazole 2-oxide (1) has been shown to react with several olefins in a molar ratio of 1:2, giving 5-(ethoxycarbonyl)-1-aza-2,8-dioxabicyclooctanes (2).Evidence is presented that these products arise from 1,3-dipolar cycloaddition, elimination of ethyl cyanoformate from the initial cycloadducts, and 1,3-dipolar cycloaddition of the resulting isoxazoline N-oxides with another mole of olefin.
- Shimizu, Tomio,Hayashi, Yoshiyuki,Teramura, Kazuhiro
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p. 3053 - 3058
(2007/10/02)
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- TRIBUTYLTIN CYANIDE: A FACILE CYANATING AGENT OF ACYL CHLORIDES
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Tributyltin cyanide was prepared from tributyltin chloride and potassium cyanide, and was found to be an efficient cyanation reagent for acyl chlorides to give acyl cyanides in excellent yields.
- Tanaka, Masato
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p. 2959 - 2962
(2007/10/02)
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