Hexane-2,5-dione, reaction with

Tlie bifunctional sulfenyl chloride 213 was obtained by chlorination of 144 in good yield, although excessive chlorination led to the saturated compound 214 (94CB533). A series of compounds 215-220 were obtained from 213 by reactions with secondary amines ferf-butyl methyl ketone hexane-2,4-dione 2,6-dimethylcyclohexanone diethyl malonate and acetylacetone, respectively. 

What we need is an amine— ammonia in this case—and a diketone. If the two carbonyl groups have a 1,4 relationship we will get a pyrrole out of this reaction. So hexane-2)5-dione reacts with ammonia to give a high yield of 2,5-dimethyl pyrrole. 

The amino group in 1018 can be condensed with 1,4-dicarbonyl compounds for example, with hexane-2,S-dione, the Ar-(pyrro 1 -1 -yI)pyridini 11 m 1019 is formed, or with aldehydes, imines 1020 are formed. Reaction with aryldiazonium salts forms aryl azides and pyridine, presumably via ArN=NNPy+. Nitrous acid and At-aminopyridinium cations yield pyridine and N20. 

The related Mannich reaction is not common. Under the usual acidic reaction conditions TV-substitution occurs, but this is a reversible reaction in the presence of base. Therefore, in basic medium, C- substituted products accumulate, and all positions can be substituted. 2-Methylimidazole gives 1,4,5-tri, 4,5-di- and 4-mono-substituted products. The observation that with formaldehyde and hydrochloric acid histamine gave (98) is at variance with the apparent requirement for basic medium. Since 1-substituted imidazoles do not react it is likely that the imidazole conjugate base is the reactive species. Unless imidazoles contain activating substituents they are not very susceptible to reaction with aldehydes (except HCHO) and ketones. An exception appears to be the product (99) of interaction between imidazole and hexane-2,4-dione. An activated compound such as 4-methylimidazoline-2-thione gives the 5-dimethylamino compound (100) imidazoline-2-thione gave only the (V-hydroxymethyl product under the same reaction conditions. Imidazolin-4-ones with a free 5-position readily form benzylidene derivatives (B-76MI40701). 

The reaction of N-aminoazonium salts with aliphatic and aromatic aldehydes in the absence of base gives the Schiff base type compounds 28.151,153-156 Some aliphatic ketones also react with N-aminoazonium salts.40,155 Hexane-2,5-dione reacts with N-aminopyridinium perchlorate to give l-(l -pyrrolyl)pyridinium cation 29 together with some of the bisper-chlorate 30.157 Certain esters such as diethyl malonate and ethyl cyano-acetate react with N-aminopyridinium salts in the presence of base to give the corresponding N-acylimines 31.48 However, the reaction of ethyl aceto-acetate and acetylacetone with N-aminoazonium salts in the presence of base gives 1,3-dipolar cycloaddition products (Section IV,C,1).36,154,158 The reaction of ethyl acetoacetate with 1-alkyl-l,2,4-triazole 4-imine affords zwitterionic triazolo[4,3-/>]pyridazines 32.139,159... 

Condensation of 5,6-methylenedioxyindole (661) with hexane-2,5-dione gave the carbazole 662 which was formylated and condensed with amino acetal. The resulting Schiff base 663 was reduced with sodium borohydride in methanol to give an amine. Tosylation followed by reaction with 6 N hydrochloric acid in dioxane at room temperature gave 8,9-methylenedioxyellipticine (660 Scheme 45). The overall yield was low. 

To extend this powerful new dihydrofuran synthesis to more complex systems, related reactions with branched /1-dicarbonyl systems were investigated [20]. hi a similar fashion, the cfs-fused furanoids 40 and 41 were prepared from hexane-2,4-dione (37), ethyl isobutyryl acetate (38), and 2. These targets are important chiral synthons, since there are many natural products bearing ethyl and isopropyl residues on furanoid rings. The flexibility of this method was also tested with the aromatic /3-diketone 39 yielding furanoid 42, which is an important system for tetralone synthesis (Scheme 8). 

Acetylformoin (3-hydroxy-hexane-2,4,5-trione CH3-CO-CH(OH)-CO-CO-CH3) is a suspected major product of the OH initiated oxidation of 3-hexene-2,5-dione, itself a product of the OH initiated oxidation of p-xylene. This compound has been synthesised in its isomeric enediol form 3-hexene-3,4-diol-2,5-dione. The rate coefficients for the reaction with OH radicals was found to be (2.7 0.7) X 10 ° cm s" The residual FTIR spectrum of its OH initiated photooxidation was found to be identical to that obtained from the OH initiated oxidation of 3-hexene-2,5-dione, the major product has been tentatively identified as hexane-3,3-diol-2,4,5-trione (CH3 CO-C(OH)2-CO-CO-CH3). These results suggest that acetylformoin readily enolises and then rapidly reacts with OH radicals to give products of the type observed for the OH initiated oxidation of 3-hexene-3,4-diol-2,5-dione. 

Fluorescence Eu La203, Y2O3 By reaction with ethanolic 1,1, l-trifluoro-5,5 dimethyl hexane-2,4-dione 2 pg/ml Beltyukova and Kravchenko (1982)... 

A suspension of 17a,21-dihydroxypregna-4,9(ll)-diene-3,20-dione 21-acetate (0.77 g) and iV-bromoacetamide (0.3 g) in anhydrous methylene dichloride (40 ml) is added over 2-3 min with stirring to a mixture of anhydrous hydrogen fluoride (10.19 g), and anhydrous tetrahydrofuran (18 g) in a polyethylene bottle at —80° (acetone-dry ice). After 1 hr at —80° the reaction mixture is kept for a further 1 hr at 0° and then added cautiously to an excess of an ice-cold solution of sodium carbonate. Extraction with methylene dichloride and crystallization from acetone-hexane furnish 9a-bromo-ll -fluoro-17a,21-dihydroxypregn-4-ene-3,20-dione 21-acetate (0.69 g), mp 205-208°, raised by several crystallizations from acetone-hexane to 215-217° [aju 142° (CHCI3) max 240-242 mju (e 15,500). 

An ethereal solution approximately 2.5 molar in methyllithium is prepared from 17 ml of methyl iodide and 4 g of lithium metal in 200 ml of anhydrous ether. A mixture consisting of 150 ml anhydrous ether, 3 g (10 mmoles) of 3jS-hydroxy-5a-androstane-ll,17-dione and 60 ml (0.15 moles) of the above methyllithium solution are stirred at room temperature for 40 hr. The reaction mixture is diluted with 100 ml of water and the ether is removed by distillation. Filtration of the chilled aqueous phase yields 2.6 g (77%) of 1 la,17a-dimethyl-5a-androstane-3a,l l/ ,17j5-triol mp 149-154°. Recrystallization from acetone-hexane yields pure material mp 164-166° [a] —5° (CHCI3). 

Preparation of cholesta-5,7-diene-ia,3/3-diol a solution of 500 mg of the 1,4-cyclized adduct of cholesta-5,7-dien-3/3-ol-ia,2a-epoxideand 4-phenyl-1,2,4-triazoline-3,5-dione in 40 ml of tetrahydrofuran is added dropwise under agitation to a solution of 600 mg of lithium aluminum hydride in 30 ml of THF. Then, the reaction mixture liquid Is gently refluxed and boiled for 1 hour and cooled, and a saturated aqueous solution of sodium sulfate is added to the reaction mixture to decompose excessive lithium aluminum hydride. The organic solvent layer is separated and dried, and the solvent Is distilled. The residue Is purified by chromatography using a column packed with silica gel. Fractions eluted with ether-hexane (7 3 v/v) are collected, and recrystallization from the methanol gives 400 mg of cholesta-5,7-diene-la, 3/3-diol. 

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