632-56-4

Usage

Uses

Used in Pharmaceutical Industry:
TETRAETHYL 1,1,2,2-ETHANETETRACARBOXYLATE is used as a chemical intermediate for the synthesis of double-ring molecules, which are essential in the development of new pharmaceutical compounds. Its unique structure allows for the creation of complex molecules with potential therapeutic applications.
Used in Organic Chemistry:
In the field of organic chemistry, TETRAETHYL 1,1,2,2-ETHANETETRACARBOXYLATE is used as a reagent in the preparation of various organic compounds. Its ability to form double-ring molecules makes it a valuable asset in the synthesis of complex organic structures.
Used in the Synthesis of TAPT and TAPT·4HCl·EtOH·0.5H2O:
TETRAETHYL 1,1,2,2-ETHANETETRACARBOXYLATE is also utilized in the synthesis of TAPT (1,4,8,11-tetraazatricyclo[7.3.1.05,13]tridecane) and its hydrochloride salt, TAPT·4HCl·EtOH·0.5H2O. These compounds have potential applications in various fields, including pharmaceuticals and materials science, due to their unique chemical properties and structures.

Purification Methods

Recrystallise the ester twice from EtOH by cooling to 0o. [Mochizuki et al. Bull Chem Soc Jpn 64 1750 1991, Weinges et al. Angew Chem 93 1008 1981, Beilstein 2 IV 2415.]

InChI:InChI=1/C14H22O8/c1-5-19-10(15)9-14(11(16)20-6-2,12(17)21-7-3)13(18)22-8-4/h5-9H2,1-4H3

Upstream product

• 996-82-7 sodium diethylmalonate 
• 64-17-5 ethanol 
• 10222-01-2 2,2-dibromo-3-nitrilopropionamide 
• 5401-62-7 1,2-dibromocyclohexane 
• 176246-53-0 ethyl (E)-2,3-dibromo-2-phenylpropenoate 
• 60-29-7 diethyl ether 
• 6174-95-4 1,1,2,2-tetracarboethoxy-ethylene 
• 2259-30-5 tert-butylmagnesium bromide 
• 506-68-3 bromocyane 
• 996-82-7 sodium diethylmalonate 
• 857570-93-5 γ-bromo-aconitic acid triethyl ester 
• 1114-30-3 diethyl 2,3-dibromosuccinate 
• 558-13-4 carbon tetrabromide 
• 5447-97-2 2-bromo-2-nitropropane 

Downstream Products

• 6174-95-4 1,1,2,2-tetracarboethoxy-ethylene 
• 7605-64-3 tetraethyl cyclopropane-1,1,2,2-tetracarboxylate 
• 80213-18-9 tetraethyl cyclobutane-1,1,2,2-tetracarboxylate 
• 5464-22-2 tetramethyl ethane-1,1,2,2-tetracarboxylate 
• 3474-99-5 1,2,1',2'-Tetraphenyl-3,5,3'5'-tetraoxo-dipyrazolidinyl-(4,4') 
• 113563-35-2 tetraethyl ester of 1-ethoxyethane-1,1,2,2-tetracarboxylic acid 
• 87497-77-6 2,5-dibenzyl-3a,6a-diethoxycarbonyl-1,4-dioxo-octahydropyrrolo<3,4-c>pyrrole 
• 140652-74-0 1,2,3,4,5,6,7,8-Octahydro-2,2,3,3,6,6,7,7-octa(ethoxycarbonyl)-anthracen 
• 114014-90-3 1,1'-bis(4-phenyl-3,5-dioxane) 
• 114014-91-4 2,3-dibenzyloxymethylbutane-1,4-diol 
• 114052-49-2 3,4-dibenzyloxymethyl-1,6,9,12-tetraoxacyclotridecane 
• 114014-93-6 3,16-bis(4-phenyl-3,5-dioxacyclohexyl)-1,5,8,11,14,18,21,24-octaoxacyclohexacosane 
• 114052-48-1 3,4,17,18-tetrabenzyloxymethyl-1,6,9,12,15,20,23,26-octaoxacyclooctacosane 
• 109773-71-9 2-phenyl-5-(2-hydroxy-1-hydroxymethylethyl)-1,3-dioxane 

Relevant academic research and scientific papers

Atom-economic thiophosphoroselenenylations of C–H acid esters and amides

Three improved thiophosphoroselenenylation procedures of CH-acids, including derivatives of malonic and acetyl-, phosphono-, 4-nitrophenyl- and 3-pyridylacetic acids, have been described and compared to previously reported thiophosphoroselenylation of diethyl malonate using bis(disopropoxyphosphinothioyl)diselenide alone or with the aid of methyl iodide. The use of iodine makes it possible to utilize both equivalents of the selenenylating agent. The procedures work well for the majority of nucleophiles in a pKa range between more acidic malononitrile or Meldrum acid and less acidic phenylacetates. The reaction carried out on diethyl malonate in boiling rectified ethanol yields selenoacetate, which cannot be obtained by direct phosphoroselenenylation. Crystal structure of one of the selenomalonamides confirms the stabilization effects of both carbonyl oxygens on selenium atom. The P-Se bond splitting, using TBAF in 3-molar excess in the presence of alkylating agent yields the respective C,Se-dialkyl derivatives.

Visible-light-induced photocatalyst-free C-3 functionalization of indoles with diethyl bromomalonate

A visible-light induced green and efficient method is developed for the synthesis of α-indolyl diethyl malonates. The reaction proceeds without any photocatalysts or ligands in a green solvent in a short time. Moreover, the reaction mechanism has been clearly studied by control experiments, spectrophotometric studies and density functional theory (DFT) calculations. The results showed that the photocatalyst-free transformation may proceed via an XB-promoted radical process. The EDA complex formation of diethyl bromomalonate with a base is the main reason for the reaction initiation.

Reaction of N-chloroamines with carbanions derived from ethyl acetoacetate and diethyl malonate

Carbanions derived from ethyl 3-oxobutanoate and diethyl malonate reacted with an equimolar amount of N-chloro-N-ethylethanamine, N-chloromorpholine, or N-chloropiperidine to give diethyl 2,3-diacetylbutanedioate and tetraethyl ethane-1,1,2,2-tetracarboxylate in 68–83% yield. The possibility of heterocoupling of ethyl 3-oxobutanoate and diethyl malonate carbanions by the action of N-chloro-N-ethylethanamine and the effect of the molar reactant ratio on the selectivity of oxidative homo- and heterocoupling were studied.

Catalytic Access to Alkyl Bromides, Chlorides and Iodides via Visible Light-Promoted Decarboxylative Halogenation

Herein is reported the catalytic, visible light-promoted, decarboxylative halogenation (bromination, chlorination, and iodination) of aliphatic carboxylic acids. This operationally-simple reaction tolerates a range of functional groups, proceeds at room temperature, and is redox neutral. By employing an iridium photocatalyst in concert with a halogen atom source, the use of stoichiometric metals such as silver, mercury, thallium, and lead can be circumvented. This reaction grants access to valuable synthetic building blocks from the large pool of cheap, readily available carboxylic acids.

Sequential fullerenylation of bis-malonates-efficient access to oligoclusters with different fullerene building blocks

A method for the sequential fullerenylation of bis-malonates with parent C60 and C2v-symmetric pentakis-adducts is reported. This approach relies on the finding that (a) chloromalonates can be used for the nucleophilic cyclopropanation of [6,6] double bonds of C60, and (b) chloromalonates, in contrast to bromomalonates, do not undergo base-catalyzed halogen exchange reactions. For the proof of concept, we synthesized a heptafullerene by using a divergent approach based on a fullerene hexakis-adduct with six bis-malonate addends in octahedral positions, each of which is suitable for an additional cyclopropanation of a fullerene building block. A sequence for the selective fullerenylation of bis-malonates with C60 and its exohedral C2v-symmetric pentakis-adducts has been developed. This method enables the straightforward synthesis of highly functional fullerene derivatives such as the heptafullerene 1.

Bromophilic substitution/carbophilic substitution cascade reactions of α,α-dibromo-2-methoxyacetophenone with C-, N- and O-nucleophiles

α,α-Dibromo-2-methoxyacetophenone reacts, under mild reaction conditions, with C-, N- and O-nucleophiles via a bromophilic substitution/protonation/carbophilic substitution cascade process to afford α-monosubstituted-2-methoxyacetophenones in moderate to good yield. The only exception from this reaction pathway is the reaction with the anion derived from malononitrile in which 2-aroyl-1,1,3,3-tetracyanopropene is obtained.

Asymmetrie synthesis of (+)- and (-)-wuweizisu C stereoisomers and their chemosensitizing effects on multidrug-resistant cancer cells

Total syntheses of the dibenzocyclooctadiene natural product wuweizisu C in its (-)-form [(S)-1] and its (+)-form [(R)-l] were achieved in 19 steps, starting from commercially available gallic acid. In the key step, the asymmetric biphenyl axis was constructed by an oxazoline-mediated Ullmann reaction to provide either the P or Mbiaryl product in 68% yield and >99% de, depending on the configuration of the oxazoline. The efficiency of this total synthesis was excellent, as the syntheses of (S)-1 and (R)-1 from, intermediate 7 each proceeded in 13 steps with an overall yield of 6.8%. (S)-1 and (R)-1 were evaluated as chemosensitizers for multidrug-resistant cancers.

Efficient selective formation of C-C single bonds and C=C double bonds by NBS-promoted oxidative coupling of β-keto esters

A new application of NBS, which results in the oxidative coupling of β-keto esters to selectively form C-C single and C=C double bonds, can be controlled by the amount of NBS and t-BuOK employed. This methodology adds a new entry to C-C single and C=C double-bond formation between active methylene groups under mild conditions with high selectivity. Copyright Taylor & Francis Group, LLC.

Alkylation of 3,4-dibromo-4-methyltetrahydropyran with diethyl malonate as a key to understanding the electronic nature of chemo- and regioselectivity of molecules

The reaction of 3,4-dibromo-4-methyltetrahydropyran with diethyl malonate in the presence of sodium butoxide leads to formation of the corresponding cross-coupling product rather than of tetraethyl ethane-1,1,2,2-tetracarboxylate (product of dehydrodimerization of diethyl malonate) which is formed in the presence of sodium ethoxide. An explanation was proposed, which may be regarded as a key to understanding the nature of the driving force for one- and two-electron transfer, as well as chemo- and regioselectivity of organic molecules. 2005 Pleiades Publishing, Inc.