Heterocyclic compounds furan

Five-membered heterocyclic dienes (1) are a very important class of organic heterocyclic compounds. Furan, thiophene and pyrrole derivatives are the best known, but numerous compounds have been described in which E is a main group or transition element. 

The seventh volume of Advances in Heterocyclic Chemistry includes surveys of four groups of heterocyclic compounds furans (P. Bosshard and C. H. Eugster), dithiolium salts (H. Prinzbach and E. Futterer), 1,3,4-oxadiazoles (A. Hetzheim and K. Mockel), and diquinolylme-thanes (G. Scheibe and E. Daltrozzo). Further chapters deal with applications of mass spectrometry to heterocycles (G. Spiteller), an area which has expanded very rapidly of late, and the halogenation of heterocycles (J. J. Eisch). Finally, a summary is given of reviews in the heterocyclic field, classified by subject (A. R. Katritzky and S. M. Weeds), which it is hoped may be of assistance in literature surveys. 

The seventh volume of Advances in Heterocyclic Chemistry includes surveys of four groups of heterocyclic compounds furans (P. Bosshard and C. H. Eugster), dithiolium salts (H. Prinzbach and E. Futterer),... 

Firmenich R., G., R-E. and F-H. (Firmenich Cie) (1969g) Sulphur-containing derivatives of 5-membered heterocyclic compounds (Furanes and thiophenes). Br. Patent. 1156474. 

The five-membered ring heterocyclic compounds furan, thiophene, pyrrole, and... 

A six-membered hemiacetal ring is indicated by the infix -pyran-, and a five-membered hemiacetal ring is indicated by the infix -furan-. The terms furanose and pyranose are used because monosaccharide five- and six-membered rings correspond to the heterocyclic compounds furan and pyran, respectively. 

Additives have been developed to improve the cathode cyclability performance of lithium batteries (33). Benzene derivatives (biphenyl and o-terphenyl) and heterocyclic compounds (furan, thiophene, N-methylpyrrole and 3,4-ethylenedioxythiophene), which have lower oxidation potentials than those of electrolyte solvents have been tested. The functional electrolytes used are shown in Figure 2.4. 

Cyclic compounds that contain at least one atom other than carbon within their ring are called heterocyclic compounds, and those that possess aromatic stability are called het erocyclic aromatic compounds Some representative heterocyclic aromatic compounds are pyridine pyrrole furan and thiophene The structures and the lUPAC numbering system used m naming their derivatives are shown In their stability and chemical behav lor all these compounds resemble benzene more than they resemble alkenes... 

In general, the solubility of heterocyclic compounds in water (Table 33) is enhanced by the possibility of hydrogen bonding. Pyridine-like nitrogen atoms facilitate this (compare benzene and pyridine). In the same way, oxazole is miscible with water, and isoxazole is very soluble, more so than furan. 

Dimethyl acetylenedicarboxylate gave first a similar adduct (2) which then added further molecules of furan yielding (3) and subsequently (4). Between 1931 and 1940 the reactions of acetylenedi-carboxylic acid and its dimethyl ester with a number of nitrogen containing heterocyclic compounds were examined, and structures were proposed for the products. Apart from an unpublished investigation of the products from pyridine and dimethyl acetylenedicar-... 

Heterocyclic compounds carrying hydroxyl groups may be compared with phenols. Thomson has reviewed the tautomeric behavior of phenols often both tautomeric forms of polycyclic compounds such as naphthols can be isolated. Early work on hydroxy-thiophenes and -furans was also reviewed by Thomsond but until recently their chemistry has been in a somewhat confused state. A pattern is now beginning to emerge, at least for the a-substituted compounds, which appear to exist as A -oxo derivatives and to attain equilibrium slowly with the corresponding A -oxo forms. For the a-hydroxy compounds, the equilibrium generally favors the A -oxo form. 

The German ending -an should be translated -ane if it is the name of a hydrocarbon (or parent heterocyclic compound) which is fully saturated otherwise, -an. Examples methane, menthane, tolan, furan, pentosan. 

The wide variation in the entropy factors for both the substituted phenyl and heterocyclic compounds and in particular for the methoxyphenyl and furan derivatives was considered to be strong evidence for solvent effects being predominant in determining the activation entropy. Consequently, discussion of the substituent effects in terms of electronic factors alone requires caution in this reaction. Caution is also needed since rates for the substituted phenyl compounds were only determined over a 20 °C range. The significance of entropy factors has also been indicated by the poor correlation of the data of the electrophilic reactivities of the heterocyclic compounds, as derived from protodemercuration, with the data for other electrophilic substitutions and related reactions572. 

Heterocyclic compounds, too, have nonequivalent positions, and the principles are similar, in terms of mechanism and rate data is available. Furan, thiophene. 

A review is available of the synthesis of polyhydroxyalkyl substituted heterocycles, including furans, by condensations of aldose and ketose sugars with / -dicarbonyl compounds.Ih... 

Cycloaddition of furan (5) has again been performed successfully under pressure and solvent-free conditions [12, 44], Usually, however, the cycloaddition of furan and heterocyclic compounds requires a Lewis-acid catalyst to give good yields. 

The formation of oxygen-containing heterocyclic compounds is also a consequence of the Maillard reaction. Amines and amino acids have a catalytic effect upon the formation of 2-furaldehyde (5), 5-(hydroxy-methyl)-2-furaldehyde (11),2-(2-hydroxyacetyl)furan (44),2 and 4-hy-droxy-5-methyl-3(2//)-furanone (111) (see Ref. 214). This catalytic effect can be observed with several other non-nitrogenous products, including maltol. The amino acid or amine catalysis has been attributed to the transient formation of enamines or immonium ions, or the 1,2-2,3 eno-lization of carbohydrates. Of interest is the detection of A -(2-furoyl-... 

The double bonds in certain heterocyclic compounds, such as furans, Af-acylpyrroles and A-acylindoles are also susceptible to photoaddition of carbonyl compounds to form oxetanes (equation 106) (77JHC1777). A wide range of carbonyl compounds can be used, including quinones, a-diketones, acyl cyanides, perfluorinated aldehydes and ketones and esters. A remarkable case of asymmetric induction in oxetane formation has been reported from optically active menthyl phenylglyoxylate and 2,3-dimethyl-2-butene the oxetane product obtained after hydrolysis of the ester group had an optical purity of 53% (79AG(E)868). 

Paal-Knorr synthesis It is a useful and straightforward method for the synthesis of five-membered heterocyclic compounds, e.g. pyrrole, furan and thiophene. However, necessary precursors, e.g. dicarbonyl compounds, are not readily available. Ammonia, primary amines, hydroxylamines or hydrazines are used as the nitrogen component for the synthesis of pyrrole. 

Unsaturated aliphatic compounds and heterocyclic compounds may also be metabolized via epoxide intermediates as shown in Figure 4.6 and chapter 5, Figure 14. Note that when the epoxide ring opens, the chlorine atom shifts to the adjacent carbon atom (Fig. 4.6). In the case of the furan ipomeanol and vinyl chloride, the epoxide intermediate is thought to be responsible for the toxicity (see below and chap. 7). Other examples of unsaturated aliphatic compounds, which may be toxic and are metabolized via epoxides, are diethylstilboestrol, allylisopropyl acetamide, which destroys cytochrome P-450, sedormid, and secobarbital. 

Heterocyclic compounds range from those, such as furan which is readily halogenated and tends to give polyhalogenated products, to pyridine which forms a complex with aluminum chloride that can only be brominated to 50% reaction (23). 

The ion (97), acting as an electrophilic reagent, can also attack another molecule of the heterocyclic compound. Thiophene with benzaldehyde or chloral gives the dinuclear product (100 R = Ph, CC13). Pyrrole and furan react with acetone to form tetranuclear derivatives of type (101 Z = NH, O). Pyrroles with a single free position react analogously to thiophene e.g. two molecules of 3-ethoxycarbonyl-2,4-dimethylpyrrole with formaldehyde afford the dipyrromethane (102). 

Benzo[c]furans (isobenzofurans) 2 constitute a unique class of heterocyclic compounds. They belong to a class of 7r-excessive heterocycles... 

A theoretical understanding of furan and its congeners followed in the wake of the progress with the benzene problem, but for the five-membered heterocyclic compounds Bamberger s centric formula was always the most reasonable one, as Kekule structures could not be written at all. It is not now clear to what extent the heterocycles were really regarded as benzene analogues, but a remark made by Hantzsch, that coumarone is the furfurane of the naphthalene series was certainly percipient. Furan is variously said to be aromatic, superaromatic or not aromatic at all, for the debate continues. 

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