32864-38-3

Basic information

• Product Name: TERT-BUTYL ETHYL MALONATE
• Synonyms: ETHYL TERT-BUTYL MALONATE;TERT-BUTYL ETHYL MALONATE;T-BUTYL ETHYL MALONATE;1-tert-Butyl 3-ethyl malonate;Propanedioic acid, 1,1-dimethylethyl ethyl ester;Malonic acid 1-ethyl 3-tert-butyl ester;Malonic acid 1-tert-butyl 3-ethyl ester;Malonic acid tert-butyl ethyl ester
• CAS NO: 32864-38-3
• Molecular Formula: C₉H₁₆O₄
• Molecular Weight: 188.22
• EINECS: 251-269-8
• Product Categories: C8 to C9;Carbonyl Compounds;Esters
• Mol File: 32864-38-3.mol

Chemical Properties

• Boiling Point: 83-85 °C8 mm Hg(lit.)
• Flash Point: 189 °F
• Appearance: Clear colorless liquid
• Density: 0.994 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.189mmHg at 25°C
• Refractive Index: n20/D 1.416(lit.)
• Storage Temp.: Inert atmosphere,Room Temperature
• PKA: 11.86±0.46(Predicted)
• Water Solubility: Miscible with most common solvents. Immiscible with water.
• BRN: 1776681
• CAS DataBase Reference: TERT-BUTYL ETHYL MALONATE(CAS DataBase Reference)
• NIST Chemistry Reference: TERT-BUTYL ETHYL MALONATE(32864-38-3)
• EPA Substance Registry System: TERT-BUTYL ETHYL MALONATE(32864-38-3)

Safety Data

• Safety Statements: 23-24/25
• RIDADR: NA 1993 / PGIII
• WGK Germany: 3
• Hazardous Substances Data: 32864-38-3(Hazardous Substances Data)

Usage

Uses

Used in Polymer Industry:
TERT-BUTYL ETHYL MALONATE is used as a reagent for the synthesis of polar ester-functionalized aliphatic polysulfone, a material with remarkable thermal stability. This application is significant for creating polymers with enhanced properties for various industrial applications.
Used in Organic Synthesis:
TERT-BUTYL ETHYL MALONATE is also used as a valuable reagent in organic synthesis, where it contributes to the development of new compounds and materials with potential applications in various fields, including pharmaceuticals, agrochemicals, and materials science.

Synthesis Reference(s)

The Journal of Organic Chemistry, 39, p. 2114, 1974 DOI: 10.1021/jo00928a032

Purification Methods

A likely impurity is monoethyl malonate; check IR for OH bands at 3330 br cm-1 . To ca 50g of ester add ice cold NaOH (50g in 200mL of H2O and 200g of ice). Swirl a few times (filter off ice if necessary), place it in a separating funnel and extract with 2 x 75mL of Et2O. Dry the extract (MgSO4) (since traces of acid decompose the t-Bu group of the ester, the distillation flask has to be washed with aqueous NaOH, rinsed with H2O and allowed to dry). Addition of some K2CO3 or MgO before distilling is recommended to inhibit decomposition. Distil it under reduced pressure through a 10cm Vigreux column (p 11). Decomposition is evidenced by severe foaming due to autocatalytic decomposition and cannot be prevented from accelerating except by stopping the distillation and rewashing the distillation flask with alkali again. [Breslow et al. J Am Chem Soc 66 1287 1944, Hauser et al. J Am Chem Soc 64 2714 1942, Strube Org Synth Coll Vol IV 417 1963, Stube Org Synth 37 35 1957, Beilstein 2 IV 1884.]

InChI:InChI=1/C9H16O4/c1-5-12-7(10)6-8(11)13-9(2,3)4/h5-6H2,1-4H3

Upstream product

• 540-88-5 acetic acid tert-butyl ester 
• 4303-71-3 triphenylmethyl sodium 
• 36239-09-5 ethyl chlorocarbonylacetate 
• 75-65-0 tert-butyl alcohol 
• 541-41-3 chloroformic acid ethyl ester 
• 1071-46-1 hydrogen ethyl malonate 
• 105-58-8 Diethyl carbonate 
• 115-11-7 isobutene 
• 105-53-3 diethyl malonate 
• 1010117-23-3 diethyl 2-nitro-3-oxopentanedioate 
• 201230-82-2 carbon monoxide 
• 98684-92-5 ethyl diazoacetate 

Downstream Products

• 25022-02-0 4,4-diphenyl-acetoacetic acid ethyl ester 
• 91007-16-8 ethyl 4-ethyl-3-oxo-hexanoate 
• 872791-65-6 (2-ethyl-1-oxo-butyl)-malonic acid diethyl ester 
• 857559-51-4 4-(4-isopropyl-phenyl)-acetoacetic acid ethyl ester 
• 359828-75-4 3-oxo-4-phenyl-hexanoic acid ethyl ester 
• 86728-40-7 ethyl 3-oxo-4-(thiophen-2-yl)butanoate 
• 615-09-8 ethyl 3-(2-furyl)-3-oxopropanoate 
• 141-97-9 ethyl acetoacetate 
• 62088-10-2 4-(4-chloro-phenyl)-3-oxobutyric acid ethyl ester 
• 15971-92-3 ethyl 3-cyclohexyl-3-oxopropanoate 
• 718-08-1 ethyl 3-oxo-4-phenylbutyrate 
• 17071-29-3 ethyl 3-oxo-5-phenylpentanoate 
• 62088-12-4 4-(4-nitro-phenyl)-3-oxo-butyric acid ethyl ester 
• 91882-86-9 diethyl 2-oxohexane-1,6-dicarboxylate 

Relevant articles and documents

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.

Synthesis of α-Aryl nitriles through palladium-catalyzed decarboxylative coupling of cyanoacetate salts with aryl halides and triflates

Worth its salt: The palladium-catalyzed decarboxylative coupling of the cyanoacetate salt as well as its mono- and disubstituted derivatives with aryl chlorides, bromides, and triflates is described (see scheme). This reaction is potentially useful for the preparation of a diverse array of α-aryl nitriles and has good functional group tolerance. S-Phos=2-(2,6- dimethoxybiphenyl)dicyclohexylphosphine), Xant-Phos=4,5-bis(diphenylphosphino)- 9,9-dimethylxanthene. Copyright

NOVEL PIPERAZINE DERIVATIVES AS INHIBITORS OF STEAROYL-CoA DESATURASE

The present invention relates to piperazine derivatives that act as inhibitors of stearoyl-CoA desaturase. The invention also relates to methods of preparing the compounds, compositions containing the compounds, and to methods of treatment using the compounds.

Co2(CO)8-induced domino reactions of ethyl diazoacetate, carbon monoxide and ferrocenylimines leading to 2-(1-ferrocenyl-methylidene)-malonic acid derivatives

Novel 2-(1-ferrocenyl-methylidene)-malonic acid derivatives are obtained upon reacting ethyl diazoacetate, carbon monoxide and ferrocenylimines in the presence of Co2(CO)8 as catalyst under mild conditions. Presumably, the reaction involves three steps taking place in a domino fashion, (i) carbonylation of ethyl diazoacetate leading to a ketene derivative, (ii) [2+2] cycloaddition of the ketene with the ferrocenylimine present in the reaction mixture resulting in the formation of a β-lactam and (iii) N(1)-C(4) cleavage of the β-lactam ring. In most cases, 2-(1-ferrocenyl-methylidene)-malonic acid derivatives are obtained as a separable mixture of E- and Z-isomers in ratios depending on the structure of the imine component.

Nucleophilic substitution accompanying carbon-carbon bond cleavage assisted by a nitro group

A 2-nitrated 3-oxoester reacted with amines or alcohols to afford unsymmetrical malonic acid derivatives as a result of nucleophilic substitution accompanying C-C bond cleavage. The 2-nitrated 3-oxoester easily formed ammonium salts with amines. When the amine is liberated from the salt under equilibrium, nucleophilic amine and electrophilic keto ester locate close to each other. This intimate pair effect causes a pseudo intramolecular reaction to occur, giving rise to effective substitution under mild conditions.

Selective esterifications of alcohols and phenols through carbodiimide couplings

Esterification of carboxylic acids capable of forming ketene intermediates upon treatment with carbodiimides permits the selective acylation of alcohols in the presence of phenols lacking strong electron-withdrawing groups. The selectivity of acylations involving highly acidic phenols could be reversed through the addition of catalytic amount of acid. Esterification of other carboxylic acids was found to proceed through the formation of symmetric anhydrides and provide the opposite chemoselectivity. In both cases the relative acylation rates of substituted phenols are consistent with a reaction mechanism involving an attack of phenolate anions on electrophilic intermediates such as ketenes and symmetric anhydrides, with the carbodiimides serving both as an activating reagent and as a basic catalyst.

Design, synthesis, and evaluation of aza inhibitors of chorismate mutase

The detailed information pertaining to this panel of aza inhibitors is presented. A series of aza inhibitors (4-9) of chorismate mutase (E.C. 5.4.99.5) was designed, prepared, and evaluated against the enzyme by monitoring the direct inhibition of the chorismate, 1, to prephenate, 2, conversion. None of these aza inhibitors displayed tighter binding to the enzyme than the native substrate chorismate or greater inhibitory action than the previously reported ether analogue, 3. Furthermore, no time-dependent loss of enzyme activity was observed in the presence of the two potentially reactive aza inhibitors (7 and 9). These results in conjunction with inhibition data from a broader series of chorismate mutase inhibitors allowed a novel proposal for the mechanistic role of chorismate mutase to be developed. This proposed mechanism was computationally verified and correlated with crystallographic studies of various chorismate mutases.

Design, synthesis and antimalarial activity of novel, quinoline-based, zinc metallo-aminopeptidase inhibitors

PfA-M1, a neutral zinc aminopeptidase of Plasmodium falciparum, is a new potential target for the discovery of antimalarials. The design and synthesis of a library of 45 quinoline-based inhibitors of PfA-M1 is reported. The best inhibitor displays an IC50 of 854 nM. The antimalarial activity on a CQ-resistant strain and the specificity towards mammalian aminopeptidase N are also discussed.

Acylation through ketene intermediates

Carboxylic acids possessing a strong electron-withdrawing group in the α-position undergo facile dehydration upon reaction with carbodiimides to form the corresponding substituted ketenes that can react in situ with alcohols providing esters in a high yield. The ketene formed by the treatment of ethyl 2-methylmalonate with DCC was trapped in situ by a [4+2] cycloaddition with a second DCC molecule. The chemoselectivity of the acylation through the ketene intermediates was found to be substantially different from that of conventional acylation reagents showing a very low sensitivity toward the steric bulk of alcohols. A comparison of the sensitivity of the acylation to the steric bulk of alcohols supports the presence of a pseudopericyclic pathway for the nucleophilic addition of alcohols to ketenes derived from ethyl malonic and diethylphosphonoacetic acid.

Facile acylation of sterically hindered alcohols through ketene intermediates

Figure presented Carboxylic acids possessing strongly electron withdrawing substituents in the α-position in the presence of DCC acylate sterically hindered and chemically sensitive alcohols. The pattern of reactivity, the deuteration experiments, and the formation of a product derived from a [4 + 2] cycloaddition reaction corroborate the existence of ketene intermediates in the reaction.