1560-95-8Relevant academic research and scientific papers
Process for hydrogenation of carboxylic acids and derivatives to hydrocarbons
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Page/Page column 7-8, (2008/06/13)
A process for hydrogenating a carboxylic acid and/or derivative thereof having a carboxylate group represented by the general formula R1COO-, which process comprises feeding hydrogen and the carboxylic acid and/or derivative thereof to a reactor and maintaining conditions within the reactor such that hydrogen reacts with the carboxylic acid and/or derivative thereof to produce a product stream comprising carbon dioxide, carbon monoxide, methane and hydrocarbons represented by general formulae R1H and R1CH3, characterised in that the molar ratio of R1H : R1CH3 is above a pre-determined value and/or the mole ratio of the sum of carbon dioxide, carbon monoxide and methane to carboxylate groups is above a pre-determined value.
Geminal dialkylation, alkylative reduction and olefination of aliphatic aldehydes. Reaction of gem-bistriflates with higher order dialkylcyanocuprates
Garcia Martinez,Osio Barcina,Ruiz Diez,Subramanian
, p. 13231 - 13238 (2007/10/02)
gem-Dialkylation or alkylative reduction of α-unbranched aliphatic aldehydes 1 is advantageously achieved by reaction of the corresponding gem-bistriflates 2 with di-n-alkylcyanocuprates or di-sec- and di-tert-alkylcyanocuprates respectively. The reaction of α-branched gem-bistriflates 2 with dialkylcyanocuprates in the presence of boron trifluoride affords the olefins 6 in good yield.
Azo Anions in Synthesis: α-Amino Carbanion Equivalents from t-Butyldiphenylmethylhydrazones
Baldwin, Jack E.,Adlington, Robert M.,Newington, Ian M.
, p. 176 - 178 (2007/10/02)
α-Amino carbanion equivalents (=C(1-)NH2) and α-hydrazino anion equivalents (=C(1-)NHNH2) are readily accessible from the C-alkylation products of t-butyldiphenylmethylhydrazones; these azoalkanes can be efficiently transformed into amines, hydrazines, and also alkanes under mild reaction conditions.
AZO ANIONS IN SYNTHESIS. USE OF TRITYL- AND DIPHENYL-4-PYRIDYLMETHYLHYDRAZONES FOR REDUCTIVE C-C BOND FORMATION.
Baldwin, Jack E.,Adlington, Robert M.,Bottaro, Jeffrey C.,Kolhe, Jayant N.,Newington, Ian M.,Perry, Matthew W. D.
, p. 4235 - 4246 (2007/10/02)
The lithium salts of trityl- and diphenyl-4-pyridylmethyl-hydrazones of both aldehydes and ketones react with electrophiles (alkyl halides, aldehydes, ketones, crotonates) at low temperature to form C-trapped azo compounds; these intermediates decompose homolytically with loss of nitrogen below room temperature and can be diverted in a synthetically useful way to alkanes, alkenes, alcohols or saturated esters.
SELECTIVE MIXED COUPLING OF CARBOXYLIC ACIDS (I). - ELECTROLYSIS, THERMOLYSIS AND PHOTOLYSIS OF UNSYMMETRICAL DIACYL PEROXIDES WITH ACYCLIC AND CYCLIC ALKYL GROUPS
Feldhues, Michael,Schaefer, Hans J.
, p. 4195 - 4212 (2007/10/02)
14 unsymmetrical diacyl peroxides (R1CO2-O2CR2 with R1: undecyl; R2: e.g. methyl, propyl, pentyl, nonyl, 2-methylpropyl, 2-propyl, 2-pentyl, cyclopropyl, cyclobutyl, cyclohexyl) are prepared in 85 to 92 percent yield.Square pulse electrolysis of dodecanoyl octanoyl peroxide (1i) affords the unsymmetrical coupling product octadecane (4) in poor yield and selectivity.Thermolysis or photolysis in solution produces preferentially 4, but also considerable amounts of disproportionation products.At -78 deg C the neat peroxides are photolysed selectively to the mixed dimers.With straight chain and β-branched alkyl groups high yields are obtained (63 - 76 percent), with cycloalkyl groups medium yields (42 - 56 percent), and with α-branched diacyl peroxides moderate yields (20 - 33 percent).A comparison of the mixed Kolbe-electrolysis with the low temperature photolysis of the neat peroxide demonstrates the superiority of the latter method in small scale conversion with regard to yield and selectivity.
