Furfuryl alcohol, derivatives

Bromomethyl-5-methylthiophene gives normal displacement products with amines but it is isomerized on attempted reaction with copper(I) cyanide (Scheme 59) 48MI30200. Whereas 2-hydroxymethylthiophene reacts normally with hydrogen halides to give 2-halomethylthiophenes, reaction of 2-hydroxymethylfuran (2-furfuryl alcohol) with hydrochloric acid results in formation of laevulinic acid (151). 2-Furfuryl alcohol derivatives are... 

Several cases of spontaneous ignition after exposure to air of fine coke particles removed from filter strainers on a petroleum refinery furfural extraction unit have been noted. This has been associated with the use of sodium hydrogen carbonate (bicarbonate) injected into the plant for pH control, which produced a pH of 10.5 locally. This would tend to resinify the aldehyde, but there is also the possibility of a Cannizzaro reaction causing conversion of the aldehyde to furfuryl alcohol and furoic acid. The latter, together with other acidic products of autoxidation of the aldehyde, would tend to resinily the furfuryl alcohol. Pyrolysis GLC showed the presence of a significant proportion of furfuryl alcohol-derived resins in the coke. The latter is now discarded into drums of water, immediately after discharge from the strainers, to prevent further incidents. 

Conversion of furfuryl alcohol derivatives 48 to pyranones 49 (Achmatowicz oxidative ring expansion) is employed in the synthesis of spiroketal moiety of a natural product and cyclopentenones <00TL6879>. 

Scheme 23 Transformation of furfuryl alcohol derivatives into pyranones...

Lalyatis, D.S. Tung, J., and Foley, H.C.. Poly(furfuryl alcohol)-derived carbon molecular sieves Dependence of adsorptive properties on carbonization temperature, time, and poly(ethylene glycol) additives, Ind. Eng. Chem. Res., 30(5). 865-873 (1991). 

Uses. Furfural is primarily a chemical feedstock for a number of monomeric compounds and resins. One route produces furan by decarbonylation. Tetrahydrofuran is derived from furan by hydrogenation. Polytetramethylene ether glycol [25190-06-1] is manufactured from tetrahydrofuran by a ring opening polymeri2ation reaction. Another route (hydrogenation) produces furfuryl alcohol, tetrahydrofurfuryl alcohol, 2-methylfuran, and 2-methyltetrahydrofuran. A variety of proprietary synthetic resins are manufactured from furfural and/or furfuryl alcohol. Other... 

Uses. Furfuryl alcohol is widely used as a monomer in manufacturing furfuryl alcohol resins, and as a reactive solvent in a variety of synthetic resins and appHcations. Resins derived from furfuryl alcohol are the most important appHcation for furfuryl alcohol in both utihty and volume. The final cross-linked products display outstanding chemical, thermal, and mechanical properties. They are also heat-stable and remarkably resistant to acids, alkaUes, and solvents. Many commercial resins of various compositions and properties have been prepared by polymerization of furfuryl alcohol and other co-reactants such as furfural, formaldehyde, glyoxal, resorcinol, phenoHc compounds and urea. In 1992, domestic furfuryl alcohol consumption was estimated at 47 million pounds (38). 

Other furan compounds, best derived from furfural, are of interest although commercial volumes are considerably less than those of furfural, furfuryl alcohol, furan, or tetrahydrofurfuryl alcohol. Some of these compounds are stiU in developmental stages. Apphcations include solvents, resin intermediates, synthetic mbber modifiers, therapeutic uses, as well as general chemical intermediates. 

Some of the typical conditions of polycondensations used for aliphatic and aromatic monomers are not suitable for furan derivatives, e.g., the melt polycondensation of 2,5-furan dicarboxylic acid chloride with 2,5-b/s(hydroxymethyl) furan at about 80 °C only yields a black insoluble product5. The hydrochloric acid liberated in the reaction is clearly responsible for the charring of the furanic diol which like its simpler homologue furfuryl alcohol, resinifies rapidly in acidic media (see below). 

Compounds which are rather unstable. Typical members of this class are 2-furaidehyde, 2-furfuryl alcohol and 2-alkyl furans, the latter being more resistant than the former. The action of acids or oxygen on these derivatives produces appreciable resinification, but, if properly purified and stored in vacuo, they are indefinitely stable25 16s. ... 

Another example of an enzymatic one-pot multiple Diels-Alder reaction is illustrated in Table 4.20 [83]. Racemic furfuryl alcohols 130 in the presence of ethoxy vinyl methyl fumarate 131 and enzyme TOYOBO-LIP undergo enzymatic acylation followed by kinetic enzymatic resolution to give the acyl derivatives 132 which then affords the adducts 133 and 134 by intramolecular Diels-Alder reaction 3-methyl-furfuryl alcohol 130 (R = Me) in acetone gives the best results. 

As we found that furan and thiophene substituted oximes can be used as substrates for the INOC reactions (Eq. 5) [29b] similarly, furan substituted nitro alkane 134 is also a good substrate for INOC reactions (Eq. 13) [40]. The furfuryl derivative 134, prepared via Michael addition of furfuryl alcohol to 4-methoxy- -nitrostyrene, was subsequently transformed without isolation of the intermediate nitrile oxide 135 to the triheterocyclic isoxazoline 136 as a 5 1 mixture of isomers in high yield. 

Euran Furan resins are thermosetting polymers derived from furfuryl alcohol and Furfural. The cure must be carefully controlled to avoid the formation of blisters and delaminations. To obtain optimum strength and corrosion resistance, furan composites must undergo a postcure schedule at carefully selected temperatures depending upon the laminate thickness. Equipment made with furan resins exhibits excellent resistance to solvents and combinations of acids and solvents. These resins are not for use in strong oxidizing environments. 

Among the various derivatives of biomass, furanic compounds obtained from furfural are important (200,0001 year-1). A new family of furanic diethers has been obtained by alkylation of 2,5-furandimethanol or furfuryl alcohol under microwave irradiation with PTC solvent-free conditions [83] (Scheme 8.59). 

Resinous adducts, 10 394 Resinous odor, 3 229t Resins. See also Epoxy resins Lacquer resins Novolac resins Phenolic resins Resole resins Thermoplastic resins acidic cation-exchange, 12 191 advanced materials, 1 693 antilipemic agents, 5 141 aromatic glycidyl amine, 10 372—373 chromatographic, 14 383-384 for coatings, 7 95-107 derived from furfuryl alcohol, 12 271— 272... 

The furfuryl alcohol used for the treatment is derived from com cobs or sugar cane residues. 

Reaction of 56 with thiols in dichloromethane gives the analogous alkyl-thiomethyl and cycloalkylthiomethyl derivatives [e.g., treatment with ethanethiol gives A -(2-hydroxyethylthiomethyl)vinblastine (57)] (75). Compound 56 is also a useful intermediate for the preparation of N-1-furanyl derivatives. For example, treatment of 56 with furfuryl alcohol in methylene chloride in the presence of trace acid gives N -[(5-hydroxy-methyOfurfuryl]vinblastine (58). 

Furfuryl alcohol is oxidized directly to 2,3-dideoxy-DL-pent-2-eno-pyranosid-4-nlose (325, R = H) by treatment with m-chloroperoxy-benzoie acid.236 A variety of substituted furfuryl alcohols have thus been converted into over 60 enediulose derivatives (345) in connection with studies of their antimicrobial activity.211 It was later found that pyridinium chlorochromate may be applied in this reaction, instead of a peroxy acid.237... 

Treatment of nonfluorinated benzylic alcohols with sulfur tetrafluoride results in extensive polymerization. However, at low temperatures and in the presence of a hydrogen fluoride scavanger, such as triethylamine or pyridine, sensitive substrates such as benzylic alcohols,47 furfuryl alcohol (6), and 2-phenylcthanol (8)48 give the expected fluoro derivatives, albeit in low yield. 

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