Dimethyl Acetonedicarboxylate Research Articles

Benzannulation of arynes with dimethylacetonedicarboxylates via an insertion-fragmentation-Dieckman-aromatization cascade: Expeditious entry to naphthoresorcinols and binaphthoresorcinols

Aryne insertions into 1,3,5-tricarbonyl bearing dimethylacetonedicarboxylate (DMAD) proceeds through a 4-step cascade process to eventuate in a versatile one pot synthesis of functionally embellished naphthoresorcinols. Functional group amplifications and transformations on these entities have been explored with the intent to apply them for natural products syntheses and to access other interesting scaffolds.

Successive Michael reactions on chromone derivatives with dimethyl 1,3-acetonedicarboxylate: one-pot synthesis of functionalized benzophenones, benzo[ c]chromones and hydroxybenzoylfuroates

Chromones were reacted with dimethyl acetonedicarboxylate in the presence of DBU in THF at room temperature to furnish good yields of products, their structure depending on the substituent at 3-position. Unsubstituted chromones lead to methyl 7-hydroxy-6-oxo-6 H-benzo[ c]chromone-8-carboxylates 2, whereas by using 3-bromochromone, the methyl furoate 3c along with the unexpected furylcyclopropyl-chromene carboxylate 4c was isolated. Finally, from 3-formyl-chromones functionalized benzophenones 5 were isolated, in good yields. Plausible mechanisms are proposed.

4,4′‐Spirodichroman‐2‐ones (IV) as Unexpected Products from the Condensation of Resorcinols and Dimethyl Acetonedicarboxylate.

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4,4′-Spirodichroman-2-ones as unexpected products from the condensation of resorcinols and dimethyl acetonedicarboxylate

As a result of the reaction of resorcinols with dimethyl acetonedicarboxylate under the conditions of the Pechmann reaction derivatives of 4,4′-spirodichroman-2-one were isolated as anomalous condensation products. Their structure was demonstrated by spectral methods. A mechanism was proposed for the formation of the spirodilactone system.

Synthesis of Functionalized 4H‐Pyran and Cyclohexanone Derivatives via Three‐Component Reactions of Dimethyl Acetonedicarboxylate, Aromatic Aldehydes and Malononitrile.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Trimethyl 2-Hydroxy-2-(2-methoxy-2-oxoethyl)-4-(4-methylphenyl)-6-oxo-1,3,5-cyclohexanetricarboxylate

Aromatic aldehydes react with dimethyl acetonedicarboxylate in molar ratio 1:2 with spontaneous intermolecular Michael addition to give polysubstituted cyclohexanones [1].[...]

Trimethyl 4-(3,4-Dichlorophenyl)-2-hydroxy-2-(2-methoxy-2-oxoethyl)-6-oxo-1,3,5-cyclohexanetricarboxylate

Aromatic aldehydes react with dimethyl acetonedicarboxylate in molar ratio 1:2 with spontaneous intramolecular Michael addition to give polysubstituted cyclohexanones [1].[...]

Trimethyl 4-(4-Chlorophenyl)-2-hydroxy-2-(2-methoxy-2-oxoethyl)-6-oxo-1,3,5-cyclohexanetricarboxylate

Aromatic aldehydes react with dimethyl acetonedicarboxylate in molar ratio 1:2 with spontaneous intramolecular Michael addition to give polysubstituted cyclohexanones [1].[...]

Synthesis of Functionalized 4H-Pyran and Cyclohexanone Derivatives via Three-Component Reactions of Dimethyl Acetonedicarboxylate, Aromatic Aldehydes­, and Malononitrile

Dependent on the reaction time, the three-component condensation of dimethyl acetonedicarboxylate (1), aromatic aldehydes 2, and malononitrile (3) gives rise to 4H-pyran derivatives 5 after reflux for 15 min. Moreover, using excess of benzaldehyde and prolonged heating for 150 min afforded multifunctional cyclohexanone derivatives 8. Different substitution patterns in the phenyl nucleus of 8 can be achieved by condensation of 4H-pyran derivatives 5 with benzaldehydes 2.

Pyridazines with heteroatom substituents in position 3 and 5. 3. 2‐aryl‐5‐hydroxypyridazin‐3(2H)‐ones as potential herbicides: Synthesis and some reactions

AbstractThe coupling of dimethyl acetonedicarboxylate 1 with a variety of aryldiazonium salts 2a‐i produces the hydrazones 3a‐i which can be cyclized in boiling dichlorobenzene to yield the pyridazone esters 4a‐i, or in sodium hydroxide solution to give the pyridazone acids 5a‐f,h,i, which can be decarboxylated at elevated temperatures. The hydroxy group in 4a,d can be acylated, sulfonated or alkylated yielding compounds 8a‐n. Condensation of 4a,d with magic malonates 9a‐d produces the pyronopyridazinones 10a‐f. The reaction of 4a with hydrazine yields the hydrazide 12 via the salt 11, and with ammonia the amide 14.

ChemInform Abstract: A Convenient Synthesis of 5‐Substituted‐4‐Hydroxy‐3,4,5,6‐tetrahydro‐2H‐pyran‐2‐ones via a Chemoselective Differentiation of the Two Ester Functions of Dimethyl Acetonedicarboxylate.

AbstractDimethyl acetonedicarboxylate (I) is converted to the alkylated enamines (V) which are reduced, hydrolyzed, and saponified, yielding the 3,4‐dihydroxycarboxylic acids (VIII).

A convenient synthesis of 5-substituted-4-hydroxy-3,4,5,6-tetrahydro-2H-pyran-2-ones via a chemoselective differentiation of the two ester functions of dimethyl acetonedicarboxylate

Dimethyl acetonedicarboxylate formed the enamine 1 with benzylamine and thereby converted one of the carbomethoxy groups into a less electrophilic vinylogous urethane. Subsequent sequential alkylation of the active methylene moiety, chemoselective NaBH 4 reduction of the ester function, hydrolysis of the enamine moiety and reduction of the newly generated keto group afforded alcohols 5. Hydrolysis of the ester and lactonization gave the readily separable cis and trans lactones 8 ˜ and 9 ˜ .

ChemInform Abstract: Synthetic Anthracyclinones. Part 32. Synthesis of Daunomycinone via Intramolecular Nucleophilic Addition to 9,10‐Anthraquinones.

AbstractThe daunomycinone precursor (V) is prepared by alkylation of dimethyl acetonedicarboxylate (II) with the chloromethylanthraquinone (I), followed by hydrolysis and decarboxylation.

Synthesis of a bridged benzodiaza[l4]annulene by reaction of 4,6-bisbromomethyl-5,2,8-ethanylylidene-5H-1,9-benzodiaracycloundecine with dimethyl acetonedicarboxylate

Reaction of 4,6-bisbromomethyl-5,2,8-ethanylylidene-5H-1,9-benzodiazacycloundecine (1) under basic conditions with dimethyl acetone-1,3-dicarboxylate gives the ester (10) by 1,3-dialkylation. Oxidation of the ester (10) affords the bridged annulenone (19). The reaction of the dibromide (1) with the dimethyl ester of 2,2′-sulphinylbisacetic acid (12) or of 2,2′-sulphonylbis acetic acid (11) gives products not by 1,3-dialkylation but by gem-dialkylation.

The synthesis of [15]annulenone 4,7:10,13-dioxides and aromatic 4,7:10,13-dioxido[15]annulenium cations : Novel 14]gp ‘odd’ annulene systems

2,15 - Dimethoxycarbonyl - [15]annulenone 4,7:10,13 - dioxide ( 14) has been prepared by the condensation of cis -α,β -bis(5 - formyl - 2 - furyl)ethy]ene ( 13) with dimethyl acetonedicarboxylate. Treatment of 14 with conc H 2SO 4 led to 4,7:10,13-dioxido[15]annulenone 2,15-dicarboxylic acid anhydride ( 17), which was subsequently converted to the corresponding dicarboxylic acid ( 18) by dilute KOH. Decarboxylation of 18 gave rise to two isomeric [15]annulenone 4,7:10,13 - dioxides, i.e., the tri- cis isomer ( 7) and the mono - trans - di - cis isomer ( 8). Regarding to the ring current effects, the proton chemical shifts of these [15]annulenones were compared with those of a reference model, 4,7:10,13 - dioxido - cyclopentadecaheptaene (2.4.6.8.10.12.14) ( 3). Both of the parent [15]annulenones ( 7 and 8) have been interpreted as nondiatropic, while the anhydride ( 17) has been shown to be diatropic, sustaining an induced diamagnetic ring current. The enforced planarity and symmetrical geometry of the anhydride have been discussed. As expected, when 7, 8, 14, 17 and 18 were dissolved in CF 3COOH or conc H 2SO 4, completely delocalized [15]annulenium cations were produced, all of which proved to be diatropic. Three possible geometrical isomers of these 14π cations were established experimentally.