Acetylacetone, reaction with ethyl

Alkylation of acetylacetone chelates is generally unsuccessful, but carbon—methylene bonds can be formed by chloromethylation,279 reaction with ethyl diazoacetate,287 reaction with thioacetals288 (equations 64, 65 and 66) and by the Mannich reaction (Scheme 73).279 The Mannich base can be quatemized with methyl iodide and converted by cyanide ion into a cyanomethyl-substituted chelate. 

Diaminopyridinium iodide undergoes reaction with ethyl aceto-acetate and acetylacetone to form somewhat unexpected products, the pyrido[l,2-a]pyrimidine derivatives 33 and 34, respectively.154 The initial step has been shown to be decomposition of 1,2-diaminopyridinium iodide to 2-aminopyridinium iodide which undergoes condensation with [i-dicarbonyl compounds. The reaction of 1,2-diaminopyridinium salt with 1,2-dicarbonyl compounds gives pyrido[ 1,2-A] [1,2,4]-triazinium salts 35.161... 

From Table 3, it can be seen that the reactivity of acyl acetanilide, such as BAA or AAA, is higher than that of the other reductant reported from our laboratory, i.e., acetanilide (AA), N-acetyl-p-methylaniline (p-APT), acetylacetone (AcAc), and ethyl acetoacetate (EAcAc). Moreover, the promoting activities of derivatives of acetoacetanilide were affected by the ortho substituent in benzene ring, and the relative rate of polymerization Rr) decreased with the increase of the bulky ortho substituent to the redox reaction between Ce(IV) ion and substituted acetoacetanilide. 

The Michael reaction of benzylidene acetophenone and benzylidene acetone with ethyl acetoacetate, nitromethane, and acetylacetone was studied by Musaliar and co-workers in the presence of a cetyltrimethy-lammonium bromide-containing aqueous micellar medium.50 The Michael reaction of various nitro alkanes with electrophilic alkenes is performed in NaOH (0.025-0.1 M) in the presence of cetyltrimethylam-monium chloride (CTACI) without any organic solvent (Eq. 10.23).51... 

Palladium(II) acetate was found to be a good catalyst for such cyclopropanations with ethyl diazoacetate (Scheme 19) by analogy with the same transformation using diazomethane (see Sect. 2.1). The best yields were obtained with monosubstituted alkenes such as acrylic esters and methyl vinyl ketone (64-85 %), whereas they dropped to 10-30% for a,p-unsaturated carbonyl compounds bearing alkyl groups in a- or p-position such as ethyl crotonate, isophorone and methyl methacrylate 141). In none of these reactions was formation of carbene dimers observed. 7>ms-benzalaceto-phenone was cyclopropanated stereospecifically in about 50% yield PdCl2 and palladium(II) acetylacetonate were less efficient catalysts 34 >. Diazoketones may be used instead of diazoesters, as the cyclopropanation of acrylonitrile by diazoacenaph-thenone/Pd(OAc)2 (75 % yield) shows142). 

Acetylacetone has been prepared by the reaction of acetyl chloride with aluminum chloride followed by hydrolysis,3 and by the condensation of acetone with ethyl acetate under the influence of sodium,4 sodamide,5 and sodium ethoxide,5-6-7 and by the reaction of acetone and acetic anhydride in the presence of boron trifluoride.8... 

The interaction of l-(p-arsonophenyl)biguanide and ethyl acetoacetate failed to give the expected 2-(p-arsonophenylguanidino)-4-hydroxy-6-methylpyrimidine under a variety of conditions (408), as did the corresponding reaction with diethyl malonate. Condensation did occur, however, with acetylacetone (see Section VII J5) (see also ref. 590). 

Knoevenagel adduct 239 of oxohomophthalimide 240 with malononitrile 27a in reactions with CH-acids behaves ambiguously (82CPB1215). Reactions of 239 with acetylacetone, ethyl esters of acetoacetic and ben-zoylacetic acids, as well as methyl pyruvate led to the formation of the desired spiropyrans 241. However, benzoylacetone, dibenzoylmethane, cyanacetamide, and oxindole always gave the same 242. Authors explain this feature in terms of a retro-cleavage of adducts of Michael product 239... 

Certain reactions must be catalyzed by aqueous alkali (90MI2 91USP4988812) or by sodium ethoxide, e.g., the condensation of 3-mercapto-AT and ethyl acetoacetate (68UP1), which does not proceed in acetic acid (60JOC361), in contrast with the analogous reaction with acetylacetone (60JCS1829). 

The 5-amino-l,2,3-triazoles 8 react with ethyl acetoacetate and ethyl ethoxymethylenemalonate to give 9 and 10, respectively [71JCS(C)2156]. Cyclocondensation of the aminotriazole 8a with isopropyl 2-acetyl-o-fluorocinnamate (11) gave 4,7-dihydro-l,2,3-triazolo[l,5-a]pyrimidine 12 [88JAP(K)63107983]. Condensation of 8b and 8c with acetylacetone in ethanolic piperidine afforded triazolol[l,5-a]pyrimidine derivatives 13a and 13b, respectively. When the reaction with 8b was carried out in glacial ace-... 

The synthesis of some new substituted thieno[2,3-Z>]thiophenes (369)-(372) has been achieved <93BCJ201l> in a one-pot reaction employing solid-liquid phase transfer catalysis (PTC) conditions (K2C03, benzene, tetrabutylammonium bromide catalyst) and starting from acetylacetone, CS2, and a-chloro compounds in 1 1 2 molar ratio. The reaction of acetylacetone and CS2 with ethyl chloroacetate, chloroacetonitrile, 2-(chloroacetylamino)thiazole, or chloroacetanilide was carried out under PTC conditions by stirring the reactants reaction times and temperatures were optimized. The corresponding thieno[2,3-6]thiophenes (369)-(372) were obtained in excellent yields (51-93%). 

Similar reactions of diethylaminosulfur trifluoride take place with 2,4-pentanedione (acetylacetone), with butyl acetoacetate, and with ethyl 3-oxooctanoate, giving the corresponding difluoro compounds as E/Z mixtures in the ratio of 1 1 [9]. 

Rann et al. reported the dramatic influence of a new tailor-made, task-specific, and stable ionic liquid, butyl methyl imidazolium hydroxide ([bmim][OH]), in Michael addition. They have discovered that a task-specific ionic liqnid [bmim][OH] efficiently promoted the Michael addition of 1,3-dicarbonyl compounds, cyano esters, and nitro alkanes to a variety of conjugated ketones, carboxylic esters, and nitriles withont reqniring any other catalyst and solvent (Fig. 12.21) [16]. Very interestingly, all open-chain 1,3-dicarbonyl componnds such as acetylacetone, ethyl ace-toacetate, diethyl malonate, and ethyl cyanoacetate reacted with methyl vinyl ketone and chalcone to give the usual monoaddition products, whereas the same reactions with methyl acrylate or acrylonitrile provided exclusively bis-addition products. 

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... 

The reaction of 2-amino-3-nitrosopyridines with compounds containing an activated methylene group permits unambiguous synthesis of various derivatives of pyrido[2,3-b]pyrazine. For example, the pyridine 58 reacts in the presence of sodium ethoxide with a variety of arylacetonitriles and cyanoacetic acid derivatives to provide various 2-substituted 3-amino compounds (59). " " Diethyl malonate reacts similarly to give the 2-carboxylic acid 60, its ester being presumably hydrolyzed in the alkaline reaction conditions. Ethyl acetoacetate yields the 2-acetyl-3-oxo compound 61, and acetylacetone ° provides the 2-acetyl-3-methyl compound 62. The latter condensation proceeds poorly in ethanolic sodium ethoxide, but heating the nitroso compound with acetylacetone under reflux in pyridine gives a 59% yield of the product 62. °... 

The reaction of diethyl 3,4-dimethylthieno[2,3-Z ]thiophene-2,5-dicarboxylate (117, R = Me, EWG = C02Et) with hydrazine hydrate afforded dihydrazide 231, which was subjected to various transformations. For example, the reactions with acetylacetone, ethyl acetoacetate or malononitrile (93BCJ2011) are accompanied by the closure of the exocyclic pyrazole ring to form the corresponding derivatives 232-234. The reaction of dihydrazide 231 with carbon disulfide in the presence of KOH followed by decomposition with dilute HCl or concentrated H2SO4 produces di(oxadiazole) (235) or di(thiadiazole) derivative (236). Condensation of di(oxadia-zolyl)thienothiophene 235 with hydrazine hydrate affords di(triazolyl)thienothio-phene 237. 

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