1.5- diketone derivatives synthesis

A particular case of the synthesis of isoxazoles via -diketone derivatives is the preparation of 3-halogenoisoxazoles (11) from -nitroketones (9) treated with hydrogen halides. This inter-... 

The synthesis of the pyridine ring from ethyl acetoacetate, aldehydes, and ammonia proceeds extraordinarily readily. The mechanism is as follows. In the first phase the aldehydes react with the acetoacetic ester to form alkylidene bis-acetoacetic esters. The 1 5-diketone derivatives so formed undergo ring closure by introduction of a molecule of ammonia and elimination of two molecules of water ... 

From the first synthesis of rare-earth /9-diketonates in 1897 by Urbain until now, hundreds of different complexes formed by reaction between Lnni ions and /3-diketone derivatives have been described in the literature. Interest for this type of complexes comes from then-potential application in numerous and diverse domains. These complexes can be used for example as extractants in solvent-solvent extraction processes or as active compounds for the development of chelate lasers or liquid lasers. But they can also find applications in NMR as shift reagents or as electroluminescent materials in organic light-emitting diodes (OLEDs) (Binnemans, 2005b). 

A modified de-Mayo reaction (shown in Scheme 21) also served as a tool in the first synthesis of a saturated taxane framework with a geminal dimethyl group (79,80). Photocycloaddition of cyclohexene (functioning as a ring C model) to a bicyclic 1,3-diketone derivative from 85 is the key step. In the course of the cyclobutane annealing, the C-8 a ring connection is established contrary to C-3,... 

The following synthesis is an excellent general method for preparing organometallic chelate compounds and is an example of a salt-plus-salt procedure which produces a soluble jS-diketone derivative and an insoluble by-product. The advantages of such salt-plus-salt syntheses have been discussed previously. In the case considered here, the desired complex should not be prepared by the simple reac-... 

It was assumed that a methaneimine complex accepting a P-diketone carbanion is formed at the first stage of the dibenzoylmethane derivative synthesis. Two ketone groups would then undergo condensation with the remaining deprotonated primary... 

The synthesis of arsonium ylides 384 from diazocyclopentadienes 383 and tri-phenylarsine has been reexamined with respect to the efficiency of various copper-containing catalysts Whereas copper bronze gave only ca. 55 % of ylide, yields over 80% were provided by the use of Ou(II) complexes of p-diketonates derived from acetylacetone, 3-methylacetylacetone, benzoylacetone or dibenzoylmethane, as well as by bis[4-(phenylimino)-2-pentanonato-N,0-]copper(II) and Cu(II) acetate, all used in boiling benzene. The sterically more demanding complex bis(dipivaloyl-methanato)copper(II) as well as dichlorodipyridinecopper(II) proved less efficient. CopperfTI) tartrate, the dibenzo-14-crown 6/copper complex and furthermore the acetylacetonate complexes of Co, Ni, Pt and Zn were totally ineffective. When 383a was decomposed by Cu(acac)2 in the presence of pyridine or thioanisole. 

Oxadiazoles and 1,2,4-oxadiazoles are heterocyclic aromatic compounds that appear in many bioactive molecules. Previous methods for the synthesis of 1,2,4-oxadiazoles include the coupling of amidoximes with carboxylic acid derivatives, aerobic C—H oxygenation of amidoximes, or a cyclization of nitrile oxides to nitriles. Telvekar and Takale developed the preparation of 1,2,4-oxadiazoles from substituted diketone derivatives through a Beckmann rearrangement process tScheme S.3S1. When treated with diphosphorus tetraiodide in dichloromethane at room temperature, dioximes 150 formed the Beckmann products, 1,2,4-oxadiazoles 151, in excellent yields. 

The first step in the Katritzky pyridine synthesis is believed to be the Michael addition of a a-benzotriazolyl ketone 2 to the a,p-unsaturated carbonyl compound 1 to generate a 1,5-diketone derivative 4. The 1,5-diketone is not typically isolated although its formation has been confirmed via preparation under typical Michael reaction conditions in the absence of ammonium acetate. 1,5-Diketone derivatives are known intermediates in the synthesis of pyridines and undergo condensation with ammonia or its equivalent followed by cyclization to form dihydropyridine 5. Elimination of benzotriazole completes the aromatization process and generates the pyridine ring. 

Contrary to earlier observations, Saxena et al have reported the successful synthesis of even the tetrakis derivatives in the step-wise reactions of zirconium isopropoxide with acetylacetone, benzoylacetone, dibenzoylmethane and ethylaceto-acetate. Ebulliometric molecular weight determinations in benzene revealed the monomeric behaviour of all zirconium /6-diketonate derivatives except the triisopropoxide mono-j6-diketonate derivatives, which show dimeric behaviour. The bidentate character of the /6-diketonate ring in zirconium compounds has been adduced from infrared spectra which show the carbonyl bands in the lower region (1580-1601 cm ), and the hexacoordinated dimeric structure (/S-dik)(01V)2Zr(/z-0Pr )2Zr(0lV)2()8-dik), with isopropoxide bridging has been suggested for [ Zr(OIV)3()S-dik) 2] derivatives. 

The BAIL, (4-sulfobutyl)-tris-(4-sulfophenyl)-phosphonimn hydrogen sulfate was reported [141] as a catalyst for the synthesis of 2,3-disubstituted quinoxahne derivatives via the one-pot condensation reaction of various o-phenylenediamine with 1,2-diketone derivatives (Scheme 4.12). 

Other common approach towards trifluoromethylated furans is based on a cyclization of the corresponding 1,4-diketones [85]. Various methods were used for the synthesis of starting trifluoromethyl-substituted 1,4-diketones. Thus, alkylation of ethyl 4,4,4-trifluoroacetate 103 with chloroacetone produced 1,4-diketone derivative 104. The latter underwent cyclizations either directly [86] or after decarboxylation [87] yielding furans 105-107. 

An alternative cycloaddition approach to bis(benzannulated) spiroacetals has been explored by Pettus and coworkers in their synthesis of Y-rubromycin 58. Based on the [3+2]-cycloaddition of an enol ether with a p-diketone-derived zwitterion [167], early studies on simple substrates afforded the 5,6-spiroacetal in moderate yield [168, 169]. 

CgHeNj. Brown-yellow crystals m.p. 103-104 C, b.p. 256 258°C. Its solutions reduce Ag ions and it is used as a photographic developer. It is also used as a dye-precursor, for the synthesis of phenazine derivatives and for characterizing inter alia) a-diketones. 

Cydopentane reagents used in synthesis are usually derived from cyclopentanone (R.A. Ellison, 1973). Classically they are made by base-catalyzed intramolecular aldol or ester condensations (see also p. 55). An important example is 2-methylcydopentane-l,3-dione. It is synthesized by intramolecular acylation of diethyl propionylsucdnate dianion followed by saponification and decarboxylation. This cyclization only worked with potassium t-butoxide in boiling xylene (R. Bucourt, 1965). Faster routes to this diketone start with succinic acid or its anhydride. A Friedel-Crafts acylation with 2-acetoxy-2-butene in nitrobenzene or with pro-pionyl chloride in nitromethane leads to acylated adducts, which are deacylated in aqueous acids (V.J. Grenda, 1967 L.E. Schick, 1969). A new promising route to substituted cyclopent-2-enones makes use of intermediate 5-nitro-l,3-diones (D. Seebach, 1977). 

The alkylation reactions of enolate anions of both ketones and esters have been extensively utilized in synthesis. Both very stable enolates, such as those derived from (i-ketoesters, / -diketones, and malonate esters, as well as less stable enolates of monofunctional ketones, esters, nitriles, etc., are reactive. Many aspects of the relationships between reactivity, stereochemistry, and mechanism have been clarified. A starting point for the discussion of these reactions is the structure of the enolates. Because of the delocalized nature of enolates, an electrophile can attack either at oxygen or at carbon. 

The Hinsberg synthesis of thiophene derivatives describes the original condensation of diethyl thiodiglycolate and a-diketones under basic conditions which provides 3,4-disubstituted-thiophene-2,5-dicarboxylic acids upon hydrolysis of the crude ester product with aqueous acid. ... 

A useful and possibly more general alternative to the Lwowski synthesis- of 1,3-diphenylisoindoles involves condensation of a l,2-dibenzoyl-l,4-cyclohexadiene (e.g., 55) with ammonia or a primary amine. Cyclohexadiene derivatives of this type are easily prepared by Riels-Alder addition of a 1,3-diene to dibenzoylacetylene, and these adducts lead directly, and in high yield, to the corresponding isoindoles (56). The reaction is closely related to the well-known synthesis of pyrroles by condensation of 1,4-diketones with ammonia. 4,7-Dihydro- and 4,5,6,7-tetrahydroisoindoles (57 and 58) have been... 

The potential of such reaction sequences for the generation of molecular diversity was also demonstrated by the synthesis of a library of heterocycles. Epoxide ring-opening with hydrazine and subsequent condensation with (3-diketones or other bifunctional electrophiles gave rise to a variety of functionalized heterocyclic structures in high purity [34]. A selection based on the substrate derived from cyclohexene oxide is shown in Scheme 12.12. 

Yosikoshi reported the synthesis of furan derivatives by the reaction of 1,3-diketones with nitroalkenes, in which the Michael addition of the anions of 1,3-diketones and the subsequent intramolecular displacement of the nitro group by enolate oxygen are involved as key steps (Eq. 7.40).42... 

CHEC-II(1996) comprehensively outlines the most commonly used synthetic approaches applied to these types of bicyclic compounds of phosphorus, arsenic, antimony, and bismuth <1996CHEC-II(8)863>. The six classes of compounds listed in this section have received considerable attention over the review period and as such the principal synthetic methods for these compounds are discussed. Schoth et al. <2000CCR101> have reviewed the use of fluorinated 1,3-diketones, 2-trifluoroacetylphenols, and their derivatives in the synthesis of phosphorus compounds. Included in this review is the use of these reagents for the synthesis of various [3.3.1] nonfused and [3.3.0] fused phosphorus bridgehead bicyclic systems. 

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