For 2,5-dimethylfuran

The copolymerization of furan and 2-methylfuran with dienophiles such as maleic anhydride leads to polymer structures with furan pendent functionality. Furan, 2-methylfuran, and 2,5-dimethylfuran have been copolymerized with acrylic monomers (51,52) and acrylonitrile (52,53). The furan ring of furan, 2-methylfuran, and 2,5-dimethylfuran participates as a diene in a free radical copolymerization with acrylonitrile. The initial step for furan and for 2,5-dimethylfuran is the attachment of an acrylonitrile radical at the 2-position, but for 2-methylfuran, the attack is at the-5-position. Propagation proceeds by the attack of the furan radical on an acrylonitrile molecule, to leave one olefinic bond in the structure derived from the furan ring. If this bond is in the 4,5- or 2,3-position, it may be involved in a second additional reaction by the return of the propagating chain. 

A quick look at the most promising biofuels leads to the conclusion that ethanol and butanol are those where the use of biotechnology could play an important role. The same cannot be said for hydrogen and biodiesel, since these caimot be obtained directly by biotechnological processes, nor for 2,5-dimethylfuran, since chemistry is vital for the development of its derivatives. 

CH3COCH2CH1COCH3. Colourless liquid which becomes yellow on standing b.p. I9PC. Obtained by boiling 2,5-dimethylfuran with dilute sulphuric acid. It readily condenses with a variety of substances to give derivatives of furan, thiophen and pyrrole, and is a solvent for cellulose acetate. 

Hexanedione [110-13-4] (acetonylacetone) is one of the most widely used 1,4-diketones. It is a colorless high boiling Hquid prepared by the hydrolysis of 2,5-dimethylfuran (332,333), by oxidation of 2,5-hexanediol (334) or 5-hexen-l-one (335), and from allylacetone (336). Its main use is in solvent systems and as a raw material for chemical synthesis. It is reportedly not highly toxic (336). 

Treatment of 10-bromodibenz[fe,/]oxepin with potassium rm-butoxide at 100 C in dioxane results in elimination of hydrogen bromide to give 10,11-didehydrodibenz[6,/ oxepin. This highly strained alkyne intermediate can be trapped with dienophiles, for example, with 2,5-dimethylfuran to give 4.160... 

Heating of hexane-2,5-dione 1487 with TCS 14, Nal, and triethylamine for 36 h, to form 1488, followed by addition of triflic acid and heating to 140 °C affords, on distillation, a mixture of 2,5-dimethylfuran 1489 and HMDSO 7 containing 90%... 

Moore and Hemmens [119] studied the photosensitization of primaquine and other antimalarial agents. The drugs were tested for in vitro photosensitizing capability by irradiation with 365 nm ultraviolet light in aqueous solutions. The ability of these compounds to photosensitize the oxidation of 2,5-dimethylfuran, histidine, trypotophan, or xanthine, and to initiate the free radical polymerization of acrylamide was examined in the pH range 2 12. Primaquine does not have significant photochemical activity in aqueous solution. 

Generated from diacetyl peroxide, methyl radicals attack 2-methylfuran at position 5 preferentially if both 2- and 5-positions are occupied as in 2,5-dimethylfuran there is still little or no attack at the 3(4)-position. If there is a choice of 2(5)-positions, as in 3-methylfuran, then that adjacent to the methyl substituent is selected.249 These orientation rules are very like those for electrophilic substitution, but are predicted for radical attack by calculations of superdelocalizability (Sr) by the simple HMO method. Radical bromination by IV-bromsuccinimide follows theory less closely, presumably because it does not occur through a pure radical-chain mechanism.249... 

Yoshida has studied anodic oxidations in methanol containing cyanide to elucidate the electrode processes themselves.288 He finds that, under controlled potential ( 1.2 V), 2,5-dimethylfuran gives a methoxynitrile as well as a dimethoxy compound (Scheme 57). Cyanide competes for the primary cation radical but not for the secondary cations so that the product always contains at least one methoxy group. On a platinum electrode the cis-trans ratio in the methoxynitrile fraction is affected by the substrate concentration and by the addition of aromatic substances suggesting that adsorption on the electrode helps determine the stereochemistry. On a vitreous carbon electrode, which does not strongly adsorb aromatic species, the ratio always approaches the equilibrium value. 

The use of silica-supported Lewis acids as catalysts for the Diels-Alder reactions of 2,5-dimethylfuran leads to fairly good yields of adducts [28]. Solid supports such as... 

Moreno described the cycloaddition of 2,5-dimethylfuran (42) catalyzed by silica-supported Lewis acids under solvent-free conditions in closed Teflon vessels using a commercial microwave oven (Scheme 9.11) [28, 52]. Under these conditions coordination of the silica-supported catalyst with the oxygen bridge favors ring opening, thus leading to the aromatic compounds in one step. The use of Si (71) gave the best results for aromatic compounds. 

Exposure to other chemicals can influence the metabolism of -hexane. The effect of oral pretreatment with methyl ethyl ketone (MEK) on the metabolism of inhaled -hexane was investigated in male Fischer 344 rats (Robertson et al. 1989). Groups of 2-4 rats were given MEK (1.87 mL/kg, approximately 1,500 mg/kg) by gavage for 4 days prior to a single 6-hour inhalation exposure to w-hexane (1,000 ppm). Animals were sacrificed at 0, 1, 2, 4, 6, 8, and 18 hours after exposure ended, and samples of blood, liver, testis, and sciatic nerve were obtained and analyzed for -hexane, MEK, and their metabolites. Significant increases in the levels of the neurotoxic metabolite 2,5-hexanedione and 2,5-dimethylfuran (derived from 2,5-hexanedione) were found in blood and sciatic nerve of rats pretreated with MEK. Levels of 2,5-hexanedione in blood were approximately 10-fold higher than control immediately after -hexane exposure in rats and fell rapidly to approximately 2-fold after 6 hours. In sciatic nerve, increases in 2,5-hexanedione were approximately 6-fold at 2 hours and 3-fold at 4 hours. Similar patterns were found with 2,5-dimethylfuran. 2,5-Hexanedione was not detected in the testis of non-pretreated rats levels were measurable but very low in pretreated rats (0.3-0.6 g/g compared to... 

In a study of workers exposed to -hexane (Mutti et al. 1984), the post-exposure alveolar excretion of -hexane was about 10% of the total uptake, and was in 2 phases a fast phase with a half-life of 11 minutes and a slow phase with a half-life of 99 minutes. Urinary metabolite concentrations were lowest at the beginning of the shift, highest at the end of the shift, and still elevated the next morning. Half-life for urinary excretion of total -hexane metabolites (2,5-dimethylfuran, 2-hexanol,... 

The analogous 2,3-dihydro-2,5-dimethylfuran (11.171, R = R = Me) was formed in rats from 5-hydroxyhexan-2-one (11.170, R = R = Me), itself a primary metabolite of hexan-2-one [178], These studies are relevant in the search for the toxic metabolites of alkanes and ketones responsible for... 

There are photocalorimetric enthalpy data for two other ozonides, both coming from sensitized photochemical dioxygenation reactions in non-polar solvents . This study reports the enthalpies of the reactions of 2,5-dimethylfuran and 1,3-diphenylisobenzofuran to their corresponding endoperoxides to be exothermic by —45 20 and —92 25 kJmoU (the latter value is an average of the values given for different solvents). From... 

Dimethylfuran has been chosen as a substrate for the photooxygenation reactions. This substrate yields the ozonide of 1,2-dimethyl cyclobutadiene which undergoes a facile cleavage by the alcoholic solvent to the corresponding 2-alkoxy-5-hydroperoxy-2,5-dimethylfuran derivative.104,105... 

Compound 156 (prepared by reaction of tetrabromocyclopropene and 2,5-dimethylfuran) underwent dipolar cycloaddition with phenyl azide to produce the fused triazole 157. The reaction was carried out in dichloromethane at room temperature over 2 days. This lower reaction temperature allowed for the isolation of the adduct 157, which was established by X-ray crystallographic analysis to be the product of ct>-selective addition. Heating triazole 157 in benzene at reflux for 2 h resulted in ring expansion producing a 1 1 mixture of compounds 158 and 159 (Scheme 16) <2004JOC570>. 

Bierbach, A., I. Barnes, and K. H. Becker, Rate Coefficients for the Gas-Phase Reactions of Hydroxyl Radicals with Furan, 2-Methyl-furan, 2-Ethylfuran, and 2,5-Dimethylfuran at 300 + 2 K, Atmos. Environ., 26A, 813-817 (1992). 

The [ 02]°. values shown in Fig. 16.4 were determined by using furfuryl alcohol (FFA, I) as a probe compound (Haag et al., 1984a). Another frequently used trapping agent for l02 determination is 2,5-dimethylfuran (2,5-DMF, II) (Zepp et al., 1977) ... 

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