Furfuric acid

This work also suggests other research and development directions needed to bring the price of ethanol down to an automotive fuel level. We need a lower capital cost hydrolysis process which can produce a concentrated sugar solution. We also need a fermentation process adaptable to concentrated sugar solutions to lower alcohol purification costs. Finally we need to recover and include by-product values - lignin, furfural, acids, methanol, etc. -in our income. 

Carbon tetrachloride, carbon dioxide, water Ammonium nitrate and other ammonium salts Ethyl or methyl alcohol, glacial acetic acid, acetic anhydrite, benzaldehyde, carbon disulfide, glycerin, ethylene glycol, ethyl acetate, methyl acetate, furfural Acids... 

Elix JA, Evans JE, Parker JL (1987) A One Step Synthesis of the Depsidone Furfuric Acid Evidence for an Artefact in the Isolation from a Lichen. Aust J Chem 40 2129... 

Molisch s test A general test for carbohydrates. The carbohydrate is dissolved in water, alcoholic 1-naphthol added, and concentrated sulphuric acid poured down the side of the tube. A deep violet ring is formed at the junction of the liquids. A modification, the rapid furfural test , is used to distinguish between glucose and fructose. A mixture of the sugar, 1-naphthol, and concentrated hydrochloric acid is boiled. With fructose and saccharides containing fructose a violet colour is produced immediately the solution boils. With glucose the appearance of the colour is slower. 

Fumaric acid is conveniently prepared by the oxidation of the inexpensive furfural with sodium chlorate in the presence of a vanadium pentoxide catalyst ... 

C. Fumaric acid from furfural. Place in a 1-litre three-necked flask, fitted with a reflux condenser, a mechanical stirrer and a thermometer, 112 5 g. of sodium chlorate, 250 ml. of water and 0 -5 g. of vanadium pentoxide catalyst (1), Set the stirrer in motion, heat the flask on an asbestos-centred wire gauze to 70-75°, and add 4 ml. of 50 g. (43 ml.) of technical furfural. As soon as the vigorous reaction commences (2) bvi not before, add the remainder of the furfural through a dropping funnel, inserted into the top of the condenser by means of a grooved cork, at such a rate that the vigorous reaction is maintained (25-30 minutes). Then heat the reaction mixture at 70-75° for 5-6 hours (3) and allow to stand overnight at the laboratory temperature. Filter the crystalline fumaric acid with suction, and wash it with a little cold water (4). Recrystallise the crude fumaric acid from about 300 ml. of iif-hydrochloric acid, and dry the crystals (26 g.) at 100°. The m.p. in a sealed capillary tube is 282-284°. A further recrystaUisation raises the m.p. to 286-287°. 

Furfural condenses with acetic anhydride and potassiuiu acetate to give furylacrylic acid (compare Perkin reaction, Cinnamic Acid, Section IV, 124) ... 

The acid may also be prepared by the condensation of furfural with malonic acid in the presence of pyridine fiiiylmalonic acid is intermediately formed, which is decomposed upon heating In the presence of the base ... 

Method 2. Place 48 g. (41 -5 ml.) of freshly-distilled furfural, 52 g. of dry malonic acid (1), and 24 ml. of dry pyridine (2) in a 500 ml. round-bottomed flask, fitted with a reflux condenser. Heat the flask on a boiling water bath for 2 hours, cool the reaction mixture and dilute with 50 ml. of water. Dissolve the acid by the addition of concentrated ammonia solution, filter the solution and wash the filter paper with a... 

Sodium peroxide Glacial acetic acid, acetic anhydride, aniline, benzene, benzaldehyde, carbon di-sulflde, diethyl ether, ethanol or methanol, ethylene glycol, ethyl acetate, furfural, glycerol, metals, methyl acetate, organic matter... 

Alkylfurans, halofurans, alkoxyfurans, furfuryl ester and ethers, and furfural diacetate [613-75-2] behave similarly. Furans containing electron withdrawing constituents, for example, furfural, 2-furoic acid, and nitrofurans, fail as dienes even with very strong dienophiles. 

Furfural was first isolated in the eady nineteenth century. Dobereiner is credited with the discovery. He obtained a small amount of a yellow "oil" (too Htde to characterize) as a by-product in the preparation of formic acid (8). Other chemists found that the same "oil" having a charactedstic aroma could be obtained by boiling finely divided vegetable materials such as oats, com, sawdust, bran, etc, with aqueous sulfuric acid or other acids (9,10). The oil was present in the Hquid resulting from condensation of the vapors produced during heating. The empirical formula was determined by Stenhouse... 

It was not until the twentieth century that furfural became important commercially. The Quaker Oats Company, in the process of looking for new and better uses for oat hulls found that acid hydrolysis resulted in the formation of furfural, and was able to develop an economical process for isolation and purification. In 1922 Quaker announced the availability of several tons per month. The first large-scale appHcation was as a solvent for the purification of wood rosin. Since then, a number of furfural plants have been built world-wide for the production of furfural and downstream products. Some plants produce as Httie as a few metric tons per year, the larger ones manufacture in excess of 20,000 metric tons. 

Furfural can be classified as a reactive solvent. It resiniftes in the presence of strong acid the reaction is accelerated by heat. Furfural is an excellent solvent for many organic materials, especially resins and polymers. On catalyzation and curing of such a solution, a hard rigid matrix results, which does not soften on heating and is not affected by most solvents and corrosive chemicals. 

Furfural can be oxidized to 2-furoic acid [88-14-2] reduced to 2-furanmethanol [98-00-0] referred to herein as furfuryl alcohol, or converted to furan by decarbonylation over selected catalysts. With concentrated sodium hydroxide, furfural undergoes the Cannizzaro reaction yielding both 2-furfuryl alcohol and sodium 2-furoate [57273-36-6]. 

Acetals are readily formed with alcohols and cycHc acetals with 1,2 and 1,3-diols (19). Furfural reacts with poly(vinyl alcohol) under acid catalysis to effect acetalization of the hydroxyl groups (20,21). Reaction with acetic anhydride under appropriate conditions gives the acylal, furfuryUdene diacetate... 

Furfural is a resin former under the influence of strong acid. It will self-resinify as well as form copolymer resins with furfuryl alcohol, phenoHc compounds, or convertible resins of these. Conditions of polymerization, whether aqueous or anhydrous, inert or oxygen atmosphere, all affect the composition of the polymer. Numerous patents have issued relating to polymerization and to appHcations. Although the resins exhibit a degree of britdeness, they have many outstanding properties a number of appHcations are discussed under "Uses."... 

Strong inorganic acid can be used as a reaction catalyst, or if the temperature is raised high enough, sufficient acetic acid is produced by the heat to cataly2e formation of furfural. 

The flash point of furfural is 143°F by Tag Closed Cup. Because of its chemical reactivity, furfural should be kept away from strong acids, alkaHes or strong oxidi2ing chemicals. When furfural is stored for long periods in contact with air, there is a gradual darkening of color, increase in acidity, and formation of a soluble polymer. 

Useful thermosetting resins are obtained by interaction of furfural with phenol. The reaction occurs under both acidic and basic catalysis. Other large uses of furfural together with phenol are in the manufacture of resin-bonded grinding wheels and coated abrasives (5). 

Furfural reacts with ketones to form strong, crosslinked resins of technical interest in the former Soviet Union the U.S. Air Force has also shown some interest (42,43). The so-called furfurylidene acetone monomer, a mixture of 2-furfurylidene methyl ketone [623-15-4] (1 )> bis-(2-furfurylidene) ketone [886-77-1] (14), mesityl oxide, and other oligomers, is obtained by condensation of furfural and acetone under basic conditions (44,45). Treatment of the "monomer" with an acidic catalyst leads initially to polymer of low molecular weight and ultimately to cross-linked, black, insoluble, heat-resistant resin (46). 

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