Carbohydrates furfural

Determination of xylan is frequently made by estimation of furfural production. Data so obtained, even when appropriately corrected for furfural that arises from uronic acid, may be high if araban is present in the polysaccharide preparation. In the absence of interfering carbohydrates, furfural estimation may lead to accurate xylan values. 

A number of very reactive compounds can be obtained from carbohydrates. Furfural, a furan, is one such compound that is produced by reacting a pentose carbohydrate under acidic conditions. Bill McKillip (Chapter 29) gives an excellent overview of furan resin chemistry and the use of furans for the production of polymeric materials such as adhesives. Furans, in particular furfural,... 

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. 

Molisch s Test. Dissolve about 01 g. of the carbohydrate in z ml. of water (for starch use 2 ml. of starch solution ), add 2-3 drops of a 1 % alcoholic solution of i-naphthol (ignoring traces of the latter precipitated by the water) and then carefully pour 2 ml. of cone. H2SO4 down the side of the test-tube so that it forms a heavy layer at the bottom. A deep violet coloration is produced where the liquids meet. This coloration is due apparently to the formation of an unstable condensation product of i-naphthol with furfural (an aldehyde produced by the dehydration of the carbohydrate). 

In the acid hydrolysis process (79—81), wood is treated with concentrated or dilute acid solution to produce a lignin-rich residue and a Hquor containing sugars, organic acids, furfural, and other chemicals. The process is adaptable to all species and all forms of wood waste. The Hquor can be concentrated to a molasses for animal feed (82), used as a substrate for fermentation to ethanol or yeast (82), or dehydrated to furfural and levulinic acid (83—86). Attempts have been made to obtain marketable products from the lignin residue (87) rather than using it as a fuel, but currently only carbohydrate-derived products appear practical. 

When heated with a strong acid, pentoses and hexoses are dehydrated to form furfural and hydroxymethylfurfural derivatives respectively (Figure 9.20), the aldehyde groups of which will then condense with a phenolic compound to form a coloured product. This reaction forms the basis of some of the oldest qualitative tests for the detection of carbohydrates, e.g. the Molisch test using concentrated sulphuric acid and a-naphthol. 

By careful choice of both the reaction conditions and the phenolic compound used, it may be possible to produce a colour that is characteristic of a particular carbohydrate or related group, so giving some degree of specificity to the method. Thus, Seliwanoff s test uses hydrochloric acid and either resorcinol or 3-indolylacetic acid to measure fructose with minimal interference from glucose. The colour produced by pentoses with orcinol (Bial s reagent) or p-bromoaniline is sufficiently different from that produced by hexoses to permit their quantitation in the presence of hexoses. However, none of the methods based on the formation of furfural or its derivatives can be considered to be entirely specific. 

In order to gain some information about the fundamentals of the hydrothermal carbonization process, the hydrothermal carbonization of different carbohydrates and carbohydrate products was examined [12, 13]. For instance, hydrothermal carbons synthesized from diverse biomass (glucose, xylose, maltose, sucrose, amylopectin, starch) and biomass derivatives (HMF and furfural) were treated under hydrothermal conditions at 180 °C and were analyzed with respect to their chemical and morphological structures by SEM,13 C solid-state NMR and elemental analysis. This was combined with GC-MS experiments on residual liquor solutions to analyze side products... 

The wood pyrolysis is attractive because forest and industrial wood residues can be readily converted into liqtrid products. These liqtrids, as erode bio-oil or slurry of charcoal of water or oil, have advantages in transport, storage, combustion, retrofitting and flexibility in production and marketing (Demirbas, 2007). In the first step of pyrolysis of carbohydrates dehydration occtrrs and at low temperatures dehydration predominates. Dehydration is also known as a char-forming reaction. Between 550 and 675 K volatile products, tar, and char are formed. The volatile products are CO, CO, H O, acetals, furfural, aldehydes and ketones. Levoglucosan is the principle component in tar. 

Scheme 6 Fructose can be transformed into 5-hydroxymethyl furfural (HMF) via acid-catalyzed dehydration. Solid acid catalysts applied to facilitate the reaction are zeolites, ion-exchange resins and solid inorganic phosphates. With sporadic success, notably with inorganic phosphates, other carbohydrate sources such as inulin can also be transformed into HMF.

In order to detect furfural degradation products of possible carbohydrates in the rock specimens (4), a 25-gram sample of crushed rock was treated with excess 6N hydrochloric acid, and 25 ml. of the resulting solution was collected by boiling into the empty cup of a Soxhlet extractor. Scanning the distillates... 

Of the substances studied the most abundant in the Paleozoic rocks of the area are furfurals presumably derived from carbohydrates, higher molecular weight hydrocarbons, and in a few samples, amino acids. Acid and base soluble, low boiling substances having some properties of heterocyclic compounds, phenols, and organic acids exist in smaller amounts. 

Absorption spectra of the phenol-sulfuric acid solutions tested for total sugars show that 5-hydroxymethylfurfural from hexoses is more common in the uppermost Silurian and Devonian samples than in the earlier deposits. Furfurals from pentose sugars evidently form the bulk of the residual carbohydrates in these samples, however. There is no definite evidence as to the marine or terrestrial origin of the hexose products in the samples. 

Frederick M. Swain The furfurals are believed to be represented by polymeric carbohydrate compounds in the rocks and to have been produced by distillation of the rock samples with hydrochloric acid (6). 

Furfural occurs in many essential oils and is produced in small quantities in many organic reactions,1 particularly those involving the decomposition of various carbohydrate materials. Pentoses when subjected to the action of hydrochloric acid are decomposed to give practically quantitative yields of this aldehyde.2 It is well known that carbohydrate materials such as corn cobs, wood, bran, etc., when heated with steam under pressure or distilled with dilute hydrochloric or sulfuric acids, yield appreciable quantities of furfural.3 Particularly good yields, however, are obtained from ordinary corn cobs, and this material therefore appears best for the production of large amounts of furfural in the laboratory. Improvements in the production of furfural from carbohydrate material have appeared recently in the patent literature 4 but those do not appear as satisfactory as the ones described.5... 

Pentosans. These compounds are polysaccharides which may he considered as anhydrides of pentose sugars, after the manner of the hexosans. sucrose, starch, from glucose, fructose. When pentosans or pentoses are heated with hydrochloric ot sulfuric acid, furfural C fljO CHO is formed, and addition of aniline produces a red color. Pentosans are present in gummy carbohydrates, in bran of wheat seed, and in woods. 

PENTOSAN. A complex carbohydrate (hemicellulose) present with the cellulose in many woody plant tissues, particularly cereal straws and brans, characterized by hydrolysis to give five-carbon-atom sugars (pentoses). Thus the pentosan xylan yields the sugar xylose (HOH,C CHOH CHOH CHOH CHO) that is dehydrated with sulfuric acid to yield furfural (C5H4O2). 

The Dreywood100 anthrone reagent, which gives a positive qualitative test for a large variety of carbohydrates, as well as for furfural and its 5-hydroxymethyl derivative, gives a negative test for 2-desoxyribose.101... 

Furoic acid (furan-2-carboxylic acid, or pyromucic acid) is used as a bactericide, and the furoate esters are used as flavoring agents, as antibiotic and corticosteroid intermediates. It is obtained by the enzymatic or chemical/catalytic aerobial oxidation of furfural (2-furalaldehyde) the latter is the only unsaturated large-volume organic chemical prepared from carbohydrates today. D-Xylose and L-ara-binose, the pentoses contained in the xylan-rich portion of hemicelluloses from agricultural and forestry wastes, under the conditions used for hydrolysis undergo dehydration to furfural. 

As a consequence of bottle aging, carbohydrate conversions can occur, although slowly at cellar temperature, to form the caramel-like 2-furfural aroma for example, in aged Madeira wines. Rapp and Giintert (86MI141) have shown that such carbohydrate decomposition in Riesling wines leads to 2-furfural 9,2-acetylfuran 10, ethyl furan-2-carboxylate 11, 2-formyl pyrrole 12, and 5-hydroxymethylfurfural 13. 

Furosemide can also be synthesized starting with 2,4-dichlorobenzoic acid (formed by chlorination and oxidation of toluene). Reaction with chlorosulfonic acid is an electrophilic aromatic substitution via the species -S02C1 attacking ortho and para to the chlorines and meta to the carboxy-late. Ammonolysis to the sulfonamide is followed by nucleophilic aromatic substitution of the less hindered chlorine by furfurylamine (obtained from furfural—a product obtained by the hydrolysis of carbohydrates). 

Wheat pentosans were dehydrated to furfural with concentrated HC1, and the furfural was dissolved in dibutyl ether in preparation for GC (Folkes, 1980). This method is claimed to be specific, accurate, and precise for pentoses and pentosans (Folkes, 1980), because 5-hydroxymethylfurfural is not produced, as is the case in hexose decomposition. Previously, furfural was distilled and analyzed colorimetrically. Alkalization increases the yield of 1-, 2-, and 3-carbon, vapor-phase compounds at the expense of anhydro sugars and furans (Ponder and Richards, 1993). Hydrolysis-GC is adaptable to the estimation of DP (Morrison, 1975) applicability to carbohydrates is limited to oligomers with DP = 6 (Traitler et al., 1984). 

A few years later it was confirmed that the degradation of carbohydrates with acids gave rise also to furfural (II). This had been obtained fifty years earlier by Dobereiner by the action of sulfuric acid and manganese dioxide on sugar but its significance was not realized at the time. Furfural however was obtained only from pentoses, under normal acid conditions. 

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