Chromone, oxidation

Chromone, 3-hydroxymethyl-8-methoxy-antiallergic activity, 3, 707 Chromone, 7-methoxy-chlorosulfonation, 3, 708 Chromone, 7-methoxy-2-methyl-chloromethylation, 3, 708 Chromone, 2-methyl-chloromethylation, 3, 697 halogenation, 3, 709 IR spectra, 3, 596 mass spectra, 3, 613 oxidation, 3, 709 reactions... 

Chromone-2-carbaldehyde, 3-methyl-synthesis, 3, 709 Chromonecarbaldehydes Knoevenagel condensation, 3, 711 Chromone-3-carbaldehydes mass spectra, 3, 615 oxidation, 3, 709 reactions, 3, 712 Schiff bases, 3, 712 synthesis, 3, 821 Chromone-2-carbonyl chloride Grignard reaction, 3, 711 Chromonecarboxamide, N-tetrazolyl-antiallergic activity, 3, 707 Chromone-2-carboxylic acid, 3-chloro-ethyl ester... 

Spirothiopyrans 45b including a benzopyrylium ring have been prepared in one step by condensation of 2-aminovinyl-3-formyl chromone-4-thione 47 with 1,2,3,3-tetramethylindolinium salts in ethanol (Scheme 25).90 The precursor 47 is prepared from 3-carboxymethylene-2-methyl-chromone-4-thione 48. First, oxidation of 48 with pyridinium dichromate in CH2C12, and then condensation with dimethyl formamide dimethyl acetal in benzene gave compound 47. 

Chromone-3-carbonitrile oxide obtained from 3-formylchromone oxime by bromination and subsequent dehydrobromination underwent cycloaddition reactions with terminal alkenes to give isoxazolines 34 (175). 

Dipolar cycloaddition of 3-cyano-4// -1 -benzopyran-4-thione 187 with benzonitrile oxide proceeded regioselectively to give cycloadduct 188 (involving the thione function). The unstable cycloadduct fragmented to yield 3-cyano-chromone 189 and phenyl isothiocyanate (Scheme 1.32) (355). 

In an alternative strategy functionalized phenols, such as iodophenol, were involved in palladium-catalyzed carbonylation of alkynes or allenes, producing coumarin or chromone derivatives (Scheme 23) [130-133]. After oxidative addition of the iodoarene to the Pd(0) catalyst the order of insertion of either CO or the unsaturated substrate mainly depends on the nature of the substrate. In fact, Alper et al. reported that CO insertion occurs prior to allene insertion leading to methylene- or vinyl-benzopyranone derivatives [130]. On the contrary, insertion of alkynes precedes insertion of CO, affording couma-rine derivatives, as reported by Larock et al. According to the authors, this unusual selectivity can be explained by the inability of the acyl palladium species to further react with the alkyne, hence the decarbonylation step occurs preferentially [131-133]. 

Oxidation of the aromatic methyl group of chromone to the corresponding aldehyde and acid has also been reported recently (equation 24) . 

The dibenzopyranone ring system may be viewed as a chromone with an additional fused benzene ring and thus generally related to the antiasthmatic mediator release inhibitor cromolyn (see Chapter 11). Two dibenzopyranones have in fact been investigated for this indication in the clinic. Friedel-Crafts cyclization of the substituted cresyloxybenzoic acid (2-1) in sulfuric acid leads to the dibenzopyranone (2-2). The methyl group is then oxidized to a carboxylic acid by means of chromic acid. The acid is then converted to its sodium salt, xanoxate sodium (2-3) [2]. 

Chromones are readily oxidized by permanganate or dichromate with opening of the pyran ring and the formation of a salicylic acid (402). Flavones and isoflavones are also degradatively oxidized for example oxidation of munetone (403) with alkaline hydrogen peroxide yields 2-methoxybenzoic acid and 4-hydroxy-2-isopropylbenzofuran-5-carboxylic (isotubaic) acid. 

An unusual oxidative breakdown of a p-tolyl group to a carboxylic acid (688) is accomplished in moderate yield without degrading the chroman system (51JCS76) and the stability of this system to oxidation (cf. chromone, Section 2.23.9.3) is further illustrated by the conversion of an ethyl to a carboxyl group in the formation of 2,4,4-trimethylchroman-2,7-dicarboxylic acid (689) (57JCS3060). 

Salicylaldehyde also reacts with enamines to form chromans, although these have not usually been isolated but rather have been oxidized directly to a chromone (66JOC1232). The synthesis has been applied to both cyclic and acyclic enamines and to 2-hydroxy-1-naphthaldehyde. The initial intermediate undergoes an intramolecular cyclization involving participation of the neighbouring hydroxyl group. 

Several groups have described syntheses of chromones which involve the use of enamines. Reaction of salicylaldehyde with 1-morpholinocyclohexene gives the chromanol which is readily oxidized to the chromone (66JOC1232). Other examples include the use of 1-morpholino-l-phenylethylene which gives flavene, whilst N-styrylmorpholine yields isoflavone. The enamine reaction is considered to proceed in the normal manner with subsequent cyclization involving the neighbouring phenolic group (Scheme 163). 

Similarly, chromanones are converted into benzopyrylium salts in this case though the oxidant is triphenylmethyl perchlorate. Hydrolysis affords the chromone (60CB1466, 60CI(L)1192>. 

Chromium trioxide oxidizes 2-aminochroman-4-ols, available in high yield from salicyl-aldehyde and enamines, to chromones (74IJC26). 

Numerous examples of stilbene-to-dihydrophenanthrene photocyclization incorporating oxygen and sulfur heterocycles have been reported. Oxidation to the phenanthrene is usually effected by added iodine or by oxygen. Thus, irradiation of 2,3-diphenylchromone (37) results in the formation of phenanthro[9,10 -2,3]chromone (38)29 analogous photocyclizations have... 

Photodimerizations have been observed in a variety of sulfur-containing heterocycles notable examples include the photodimerization of 2- and 3-ary lbenzo[b]thiophens,287 benzo[h]thiophen 1-oxide,288 benzo[h]thiophen 1,1-dioxide,289 and its 2-bromo289 and 2-methyl derivatives.290 All four possible dimers were obtained on irradiation of thio-chromone in aromatic solvents,291 and 1-thiauracil (345) is converted into... 

Dehydrorotenone 1 can be readily transformed into rotenone 2 by reduction of the chromone to the chromanol followed by Oppenauer oxidation. Two elegant syntheses of dehydrorotenone 1 used DCC as a key reagent as follows (i) treatment of derrisic acid 3 with DCC/EtjN followed by reaction of the intermediate thus obtained with sodium propanoate in ethanol gave 1. (ii) Condensation of tubaic acid 4 with the pyrrolidine enamine derived from 5 in the presence of DCC also gave 1. 

Chromone carbaldehyde 407 reacts with o-benzoquinodimethane 408 in a Diels-Alder reaction and concomitant deformylation to give a diastereomeric mixture of tetrahydrobenzo[ ]xanthones 409. Subsequent oxidation provides benzo[ ]xanthones 410 in good yields (Scheme 67) <2002T997>. 

Chalcone, chromone, flavone, /rans-cinnamaldehyde, cyclopentenone, etc. gave the corresponding products in satisfactory yields [28], The oxidation of some disub-stituted a,j8-unsaturated cyclic ketones, however, gave predominantly hydroxylated products [29], An interesting variation was the synthesis of ds-hydroxyflavanones from 2-hydroxychalcones, e.g. [30] ... 

Benzo[fe]xanthene-6,l 1,12-triones are readily available through the photo-induced 1,4-acylation of naphthoquinone with 2-hydroxybenzaldehydes followed by oxidation <02H(57)1915>. Chromone-3-carboxaldehyde reacts with o-benzoquinodimethane in a DA reaction with concomitant deformylation to give a diastereoisomeric mixture of tetrahydrobenzo[fc]xanthones oxidation can be accomplished with DMSO/I2 <02T105>. 

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