- Reaction of amidoximes with acetonitrile at high pressure
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Reaction of amidoximes with acetonitrile giving 1,2,4-oxadiazoles occurs at 80-100 °C under a pressure of 10 Kbar without catalysts.
- Baykov, Sergey V.,Zharov, Aleksey A.,Stashina, Galina A.,Zavarzin, Igor V.,Kofanov, Evgeniy R.
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p. 264 - 265
(2016/06/06)
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- Interaction of acetonitrile with trifluoromethanesulfonic acid: Unexpected formation of a wide variety of structures
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Interaction of acetonitrile with trifluoromethanesulfonic acid has been studied by multinuclear NMR and ESI-MS. It has been found that the interaction results in formation of a great variety of different cations and neutral compounds which is controlled by the ratio of CH3CN to TfOH. In the presence of an excess of the acid (molar ratio 1:8-14) diprotonated N-acetylacetamidine 1 is formed as the major product, which eventually transforms into protonated acetamidine 3 and acetic acid 4. At molar ratio of (1:1-2) diprotonated 2,4-dimethyl-6-methylidene-3H-1,3,5-triazine 12, tautomer of the diprotonated trimethyl-s-triazine 11, becomes the main product at an early stage of the reaction and diprotonated 1-(dimethyl-1,3,5-triazin-2-yl) prop-1-en-2-ol 15 at a later stage. In the case of a large excess of acetonitrile (4-20:1) trication 17 is formed as a result of the interaction between 11 and 12 along with some oligomers [(CH3CN) 3]n (n = 4-12). The Royal Society of Chemistry 2012.
- Salnikov, George E.,Genaev, Alexander M.,Vasiliev, Vladimir G.,Shubin, Vyacheslav G.
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supporting information; experimental part
p. 2282 - 2288
(2012/04/10)
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- N-fluorotriazinium fluorinating agents
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Novel N-fluorotriazinium electrophilic fluorinating agents have the Formula I: wherein three A moieties are independently CR, where each R is, independently, hydrogen, halogen, hydroxyl, (primary, secondary or tertiary) amino, amino, cyano, perfluorothio, hydroxysulfonyl, halosulfonyl, hydrocarbyloxysulfonyl, or a carbon-containing substituent selected from the group consisting of optionally substituted hydrocarbyl, hydrocarbyloxy, hydrocarbyloxycarbonyl, and hydrocarbylthio groups, and at least one R is neither hydrogen nor halogen; two A moieties are independently Z, where each Z is independently nitrogen or a quaternary nitrogen atom and Y is a counterion or group of counterions which are inert to chemical attack by fluorine, or adjacent triazinium moieties are linked by a common R substituent to provide an oligomer or polymer. Preferably the compounds are 1,3,5-triazinium compound in which all R are the same, optionally perfluorinated, alkyl or alkoxy groups; Z1 and Z2 are both nitrogen and Y? is triflate. Compounds of Formula I are especially useful in fluorinating carbanionic species or activated aromatic compounds.
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- Electrophilic fluorination
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N-fluorotriazinium salts, especially those of the following Formula I, are electrophilic fluorinating agents useful in fluorinating, preferably in a nitromethane solvent, carbanionic species and/or activated aromatic compounds: wherein three A moieties are independently CR, where each R is, independently, hydrogen, halogen, (primary, secondary or tertiary) amino, hydroxyl, amino, cyano, perfluorothio hydroxysulfonyl, halosulfonyl, hydrocarbyloxysulfonyl, or a carbon-containing substituent selected from the group consisting of optionally substituted hydrocarbyl, hydrocarbyloxy, hydrocarbyloxycarbonyl, and hydrocarbylthio groups; two A moieties are independently Z, where each Z is independently nitrogen or a quaternary nitrogen atom and Y is a counterion or group of counterions which are inert to chemical attack by fluorine, and oligomers or polymers thereof in which adjacent triazinium moieties are linked by a common R substituent. Preferably the cation of the salt is 2,4,6-trichloro-1,3,5-triazinium.
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- N-Fluorotriazinium fluorinating agents
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Novel N-fluorotriazinium electrophilic fluorinating agents have the Formula I: wherein three A moieties are independently CR, where each R is, independently, hydrogen, halogen, hydroxyl, (primary, secondary or tertiary) amino, amino, cyano, perfluorothio, hydroxysulphonyl, halosulphonyl, hydrocarbyloxysulphonyl, or a carbon-containing substituent selected from optionally substituted hydrocarbyl, hydrocarbyloxy, hydrocarbyloxycarbonyl, and hydrocarbylthio groups, and at least one R is neither hydrogen nor halogen; two A moieties are independently Z, where each Z is independently nitrogen or a quaternary nitrogen atom and Y is a counterion or group of counterions which are inert to chemical attack by fluorine, , or adjacent triazinium moieties are linked by a common R substituent to provide an oligomer or polymer. Preferably the compounds are 1,3,5-triazinium compound in which all R are the same, optionally perfluorinated, alkyl or alkoxy groups; Z1 and Z2 are both nitrogen and Y- is triflate. Compounds of Formula I are especially useful in fluorinating carbanionic species or activated aromatic compounds.
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- Electrophilic fluorination
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N-fluorotriazinium salts, especially those of the following Formula I, are electrophilic fluorinating agents useful in fluorinating, preferably in a nitromethane solvent, carbanionic species and/or activated aromatic compounds:wherein three A moieties are independently CR, where each R is, independently, hydrogen, halogen, (primary, secondary or tertiary) amino, hydroxyl, amino, cyano, perfluorothio hydroxysulphonyl, halosulphonyl, hydrocarbyloxysulphonyl,, or a carbon-containing substituent selected from optionally substituted hydrocarbyl, hydrocarbyloxy, hydrocarbyloxycarbonyl, and hydrocarbylthio groups; two A moieties are independently Z, where each Z is independently nitrogen or a quaternary nitrogen atom and Y is a counterion or group of counterions which are inert to chemical attack by fluorine, and oligomers or polymers thereof in which adjacent triazinium moieties are linked by a common R substituent. Preferably the cation of the salt is 2,4,6-trichloro-1,3,5-triazinium.
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- HIGH-TEMPERATURE TRANSNITRILATION OF 2-BROMOCAPROIC ACID
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Chromato-mass spectrometry and IR and PMR spectroscopy were used to study the high-temperature reaction of 2-bromocaproic, 2-iodocaproic, and 2-bromo-2-phenylacetic acids with acetonitrile.The formation of anomalous transnitrilation products (capronitrile and benzyl cyanide) is a consequence of the initial conversion of 2-halo-substituted caproic and phenylacetic acids to caproic and phenylacetic acids, respectively.
- Polivin, Yu. N.,Vinokurov, V. A.,Makarshin, S. V.,Karakhanov, R. A.,Silin, M. A.,Ageev, E. A.
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p. 1528 - 1530
(2007/10/02)
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- Lanthanide(III) Ion Catalyzed Reaction of Ammonia and Nitriles: Synthesis of 2,4,6-Trisubstituted-s-triazines
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Lanthanum and yttrium trifluoromethanesulfonates at 1 mole percent concentration, have been found to catalyze a reaction between ammonia and aromatic nitriles to yield symmetrically substituted 2,4,6-triaryl-s-triazines.The generally high yields and relatively mild reaction conditions of this procedure suggest it as an alternative to other aromatic nitrile cyclotrimerization reactions.Of the aliphatic nitriles studied, acetonitrile and cyclopropanecarbonitrile gave good yields of triazine, propionitrile and butyronitrile gave significantly reduced yields of triazines 3b and3c respectively.Rearrangement of 3a and 3b to alkylated-4-aminopyrimidines was observed.
- Forsberg, John H.,Spaziano, Vincent T.,Klump, Stephen P.,Sanders, Kathleen M.
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p. 767 - 770
(2007/10/02)
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- Electrochemical Oxidation of Allenic Hydrocarbons in Acetonitrile
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The anodic oxidation of a variety of alkyl-substituted allenes, terminal and internal ones, has been investigated in acetonitrile. All compounds studied were found to undergo 2e(-) oxidation followed by nucleophilic attack by acetonitrile and water molecules, to form products containing at least two of the following functional groups, C=C, NHCOCH3, C=O, and OH.The effect of various parameters (concentration, electrolyte, oxidation potential, temperature, and anode material) on the electro-oxidation of a model compound (nona-1,2-diene) has been studied and a general mechanistic scheme is presented and discussed.
- Becker, James Y.,Zinger, Baruch
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p. 395 - 402
(2007/10/02)
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