Chalcones conversion

These conclusions were supported by the results obtained in a study of the reactions of various types of acetylenes with TTN (94). Hydration of the C=C bond was found to occur to a very minor extent, if at all, with almost all of the compounds studied, and the nature of the products formed was dependent on the structure of the acetylene and the solvent employed. Oxidation of diarylacetylenes with two equivalents of TTN in either aqueous acidic glyme or methanol as solvent resulted in smooth high yield conversion into the corresponding benzils (Scheme 23). The mechanism of this oxidation in aqueous medium most probably involves oxythallation of the acetylene, ketonization of the initially formed adduct (XXXV) to give the monoalkylthallium(III) derivative (XXXVI), and conversion of this intermediate into a benzoin (XXXVII) by a Type 1 process. Oxidation of (XXXVII) to the benzil (XXXVIII) by the second equivalent of reagent would then proceed in exactly the same manner as described for the oxidation of chalcones, deoxybenzoins, and benzoins to benzils by TTN. The mechanism of oxidation in methanol solution is somewhat more complex and has not yet been fully elucidated. 

The conversion of the bitter flavanone glycosides into those of the corresponding chalcones by alkali-catalyzed fission of the pyrone ring, and of the dihydrochalcone glycosides by hydrogenation thereof (see Scheme 1)... 

Scheme 1.—Conversion of a Flavone Glycoside into the Corresponding Chalcone and Dihydrochalcone Analogs.

The subsequent Claisen-Schmidt reaction was originally performed on a 10-pmol scale using 20-fold excess of both acetophenone and LiOH to achieve complete formation of the chalcone 8. This result could be verified on a small scale however, employing the same conditions on a 35-mmol scale resulted in no conversion even after 22 h, as revealed by IR spectroscopy. By cleaving a resin sample with 20% TFA in dichloromethane, only -formylbenzamide 11 was detected by HPLC. This result may be explained by the low solubility of LiOH in DME under dry/aprotic conditions. Therefore, a small amount of EtOH was added, which initiated a fast reaction (Chiu et al. 1999) and the formation of the desired chalcone 8 together with 20% of the Michael adduct 10 (Fig. 2). This was confirmed by sample cleavage from the resin and LC-MS analysis. Short reaction screening resulted in considerable im-... 

The final conditions were scaled up with no problems chalcone 8a and guanidine (liberated from its hydrochloride with sodium ethoxide) were heated in dimethyl acetamide while bubbling air through the mixture to form pyrimidine 9a. After complete conversion (16 h), the product was cleaved from the support (20% trifluoroacetic acid in DCM). Pure 4-(2-amino-6-phenyl-pyrimidin-4-yl)bcnzamidc 1 was obtained as its trifluoroacetate salt upon evaporation of the filtrate and recrystallisation of the residue from ethanol/water in 56% overall yield based on the solid phase attached 4-carboxybenzaldehyde 6a. 

The stereoselective Michael addition of the anion derived from diethyl acetyl-aminomalonate with chalcone has been found to be most effective under soliddiquid two-phase conditions in the absence of an added solvent [62]. For optimum overall conversion and enantiomeric excess (56% with 60% ee), A-benzyl-V-methyl-... 

Payne rearrangements have been effectively demonstrated using derivatives of the epoxy chalcone products. Conversion of the epoxy ketone 2 to the 2,3-... 

Oxidative rearrangements resulting in the formation of heterocyclic compounds are relatively less explored, although some of them are quite important. A basic reaction is the conversion of a chalcone to 3,3-dimethoxy-l-phenylpropanone (Eq. 2) (85TL2961). This process may be adapted to heterocyclic synthesis. 

Although conversion 226 to 228 is quite general, the presence of a methoxyl group at the para position of ring A of the chalcone 226 changes the course of this process. The chalcone 226a, for example, on treatment... 

Oxidation of chalcone phenylhydrazone 13 leads to a pyrazole and the expelled proton catalyses formation of a pyrazoline from the chalcone phenyl-hydrazone [43]. The latter undergoes further anodic oxidation (p. 308). In the presence of pyridine as a proton acceptor, the pyrazole becomes the major product. A further example of oxidative cyclization is the conversion of a-oximino phenylhydrazones to 1,2,3-triazole-l-oxides 14 [44]. 

The strong basic sites associated with surface OH groups are responsible for the catalytic activity of the activated Ba(OH)2 in organic reactions, such as the Michael addition (285). The authors showed, for example, that the Michael addition of diethyl malonate to chalcone catalyzed by activated Ba(OH)2 yielded 95% of the Michael adduct. When Ba(OH)2 was selectively poisoned with TBMPHE, a conversion of only 5% was observed, however when Ba(OH)2 was poisoned with DNB a conversion of 58% was obtained. The small poisoning effect of DNB indicates that only a small number of reducing sites with basic character (e.g., 0 ) can act in the process as basic sites. Thus, it was concluded that the basic sites responsible for the catalytic activity must be surface OH groups on the Ba(OH)2 H2O. 

Although it has long been thought, based on genetic mutant and biochemical evidence, that aurones are derived from chalcones, the biosynthetic mechanism has only recently been clarified, and some aspects of the enzymatic process still await in vivo proof An mRNA from A. majns, specifically expressed in the petal epidermal cells, has been shown to encode a recombinant protein with aureusidin synthase (AUS) activity.AUS is a variant polyphenol oxidase (PPO) that can catalyze conversion of either 2, 4, 6, 4-etrahydroxychalcone (naringenin chalcone) or 2, 4, 6, 3,4-pentahydroxychalcone to... 

The oxidative rearrangement of chalcones is a valuable route to isoflavones which has been thoroughly investigated. Initially, the conversion was achieved in two distinct steps. Epoxidation of a 2 -benzyloxychalcone, carried out by conventional techniques, is followed by treatment with a Lewis acid, such as boron trifluoride etherate, which brings about the rearrangement. 

The reaction of 2 -benzyloxychalcone dibromides (605) with ammonia gives a chalcone aziridine (606). Following conversion to the (V-benzoyl derivative, acid hydrolysis removed the protecting group at C-2 and a 3-aminoflavanone results (Scheme 230) (73ACH(76>95). 

I mines.2 Bis(dichloroaluminum)phenylimide (1) is useful for conversion of ketones as well as aldehydes to imines because the by-product is a stable dialu-minoxane (equation I). In addition the reagent converts acid chlorides into amides. The reagent is particularly useful for preparation of the anil (3) of chalcone (2). 

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