2.5- Dimethyl-furan measurement

Note Values are obtained by time-resolved measurements at 1270 nm (this work), kg values are given in 10s M-1/sec. a DMF = 2,5-dimethyl furane. 

A detailed kinetic model, based on quantum chemical calculations for the initial 2,5-dimethyl furan (2,5-DMF) consumption and important reactions of intermediates, is proposed for the oxidation of 2,5-DMF. The model is validated by comparison with new measurements of 2,5-DMF shock tube ignition delay time and its pyrolysis speciation measurements (/. Phys. Chem. A, 102, 10655 (1998))." " ... 

Such nucleophilic displacements are likely to be addition-elimination reactions, whether or not radical anions are also interposed as intermediates. The addition of methoxide ion to 2-nitrofuran in methanol or dimethyl sulfoxide affords a deep red salt of the anion 69 PMR shows the 5-proton has the greatest upfield shift, the 3- and 4-protons remaining vinylic in type.18 7 The similar additions in the thiophene series are less complete, presumably because oxygen is relatively electronegative and the furan aromaticity relatively low. Additional electronegative substituents increase the rate of addition and a second nitro group makes it necessary to use stopped flow techniques of rate measurement.141 In contrast, one acyl group (benzoyl or carboxy) does not stabilize an addition product and seldom promotes nucleophilic substitution by weaker nucleophiles such as ammonia. Whereas... 

The situation in 2-acetylfuran (63, R = Me) resembles qualitatively that of the 2-formyl (63, R = H). Accurate NMR measurements (85JCS(P2)1839) at low temperature and in dimethyl ether performed on 2-acyl derivatives of furan have enabled direct detection of the two conformers. At 173K the (E)-conformer population for 2-acetylfuran amounts to 53%. 

In the fused compounds (241) and (242) the furan ring fails to react as a diene and Diels-Alder reaction with dienophiles occurs on the terminal carbocyclic rings. However, (243) and (244) afford monoadducts with dimethyl fumarate by addition to the furan rings (70JA972). The rates of reaction (Table 2) of a number of dehydroannuleno[c]furans with maleic anhydride, which yield fully conjugated dehydroannulenes of the exo type (247), have been correlated with the aromaticity or antiaromaticity of the products (76JA6052). It was assumed that the transition state for the reactions resembled products to some extent, and the relative rates therefore are a measure of the resonance energy of the products. The reaction of the open-chain compound (250), which yields the adduct (251), was taken as a model. Hence the dehydro[4 + 2]annulenes from (246) and (249) are stabilized compared to (251), and the dehydro[4 ]annulenes from (245) and (248) are destabilized (Scheme 84). 

There have been two additional experiments which verified this basic picture of the nuclear hyperfine interaction in hemins. Johnson (78) increased the spin-lattice relaxation time by performing the Mossbauer experiment under field and temperature conditions which provide a large value of H/T. At 1.6 °K and in an applied field of 30 kG, a magnetic hyperfine interaction corresponding to that expected for high spin Fe(III) and for the g-values is measured experimentally. Recently, Lang et al. have found that a portion of hemin chloride dissolved in tetrahydro-furan at 1 mM concentration displays a hyperfine interaction at 4 °K in zero applied magnetic field. Their conclusion is that a portion of the hemin is present in a monomeric form in this solvent, a situation which is not apparent to any extent in water, acetic acid, chloroform, or dimethyl sulfoxide (77) at any concentrations used. 

Raw or gently pasteurised milk (e.g. for 10 seconds at 73 °C) has a fine characteristic odour and sweet taste. Typical components present in low concentrations are dimethylsulfide, biacetyl, 2-methylbutan-l-ol, (Z)-hept-4-enal and ( )-non-2-enal. Milk pasteurised at higher temperatures and Ultra High Temperature (UHT) milk present the so-called cooked flavour, the appearance of which is the first measurable manifestation of the chemical changes that occur in heated milk. The substances responsible for the cooked off-flavour are sulfane and other sulfur compounds. Of particular importance are dimethylsulfide, dimethyldisulfide and dimethyltrisullide that are produced from proteins contained in the membranes of fat particles and from thiamine. Also relevant are alkane-2-ones (methylketones) generated by thermal decarboxylation of P-oxocarboxylic acids (mainly hexane-2-one, heptane-2-one and nonane-2-one), y-lactones and 5-lactones produced by dehydration of y- and 5-hydroxycarboxylic acids (mainly 8-decalactone and y- and 8-dodecalactones). Important carbonyl compounds include biacetyl, hexanal, 3-methylbutanal, (Z)-hept-4-enal and ( )-non-2-enal. In the more intensive thermal treatment of milk (sterilisation), products of the Maillard reaction play a role, such as maltol and isomaltol, 5-hydroxymethylfuran-2-carbaldehyde, 4-hydroxy-2,5-dimethyl-2 f-furan-3-one (furaneol) and 2,5-dimethylpyrazine. 

The rates of nitration of isothiazole (and its 3- and 5-methyl derivatives) have been measured. While isothiazole and its 3- and 5-methyl derivatives are nitrated as free bases, the 3,5-dimethyl-compound is nitrated as the conjugate acid. Isothiazoles are nitrated in the 4 position 10 times slower than benzene. The order of reactivity for nitration is pyrazole > isothiazole > isoxazole, in contrast to that of five-membered heterocycles containing one heteroatom, which for trifluoroacetylation is pyrrole > furan > thiophen. ... 

---