15014-25-2

Usage

Uses

Used in Chemical Synthesis:
Dibenzyl malonate is used as a reagent for the preparation of various organic compounds. It is particularly useful in the synthesis of complex molecules and pharmaceutical intermediates due to its reactivity and versatility.
Used in Pharmaceutical Industry:
Dibenzyl malonate is used as a key intermediate in the synthesis of pharmaceutical compounds. It plays a crucial role in the preparation of tetraethyl 3,3-bis(benzyloxycarbonyl)propylene bisphosphonate, which is an important compound in the development of pharmaceuticals.
Used in Organic Chemistry Research:
Dibenzyl malonate is used as a reactant in the study of direct asymmetric reactions with N-tert-butoxycarbonyl aldimines in the presence of Yb(OTf)3 and iPr-pybox complexes. This research contributes to the development of new synthetic methods and the understanding of reaction mechanisms in organic chemistry.
Used in Knoevenagel Condensation:
Dibenzyl malonate is used as a reactant in the Knoevenagel condensation reaction with 2,4-dihydroxybezaldehyde to produce benzyl umbelliferone-3-carboxylate. This reaction is an important step in the synthesis of various organic compounds and demonstrates the utility of dibenzyl malonate in organic synthesis.

Purification Methods

Dissolve the ester in toluene, wash it with aqueous NaHCO3, H2O, dry over MgSO4, filter, evaporate and distil it at high vacuum. [Ginsburg & Pappo J Am Chem Soc 75 1094 1953, Baker et al. J Org Chem 17 77 1952, Beilstein 6 IV 2270.]

InChI:InChI=1/C17H16O4/c18-16(20-12-14-7-3-1-4-8-14)11-17(19)21-13-15-9-5-2-6-10-15/h1-10H,11-13H2

Upstream product

• 105-53-3 diethyl malonate 
• 100-51-6 benzyl alcohol 
• 141-82-2 malonic acid 
• 100-39-0 benzyl bromide 
• 100-44-7 benzyl chloride 
• 40204-26-0 malonic acid monobenzyl ester 
• 501-53-1 benzyl chloroformate 
• 108-59-8 malonic acid dimethyl ester 
• 141-95-7 sodium malonate 
• 100-52-7 benzaldehyde 
• 2033-24-1 cycl-isopropylidene malonate 
• 7285-83-8 2,4,6-tris(benzyloxy)-1,3,5-triazine 
• 74254-53-8 dibenzyl ethylmalonate 

Downstream Products

• 101747-44-8 (+/-)-(trans-2-benzoyl-cycloheptyl)-malonic acid 
• 31661-15-1 dibenzyl aminomalonate 
• 65100-24-5 dibenzyl 2-bromomalonate 
• 6632-52-6 3,4,5,6-Tetra-O-acetyl-1-deoxy-D-psicose 
• 56991-25-4 2-Benzyloxycarbonyl-4-benzyloxycarbonylamino-pentanedioic acid 1-benzyl ester 5-methyl ester 
• 56926-90-0 2-Benzyloxycarbonyl-4-tert-butoxycarbonylamino-pentanedioic acid 1-benzyl ester 5-methyl ester 
• 60064-83-7 2-Benzyloxycarbonyl-4-benzyloxycarbonylamino-pentanedioic acid dibenzyl ester 
• 69246-91-9 dibenzyl (isopropylidene)malonate 
• 59735-17-0 2,2-Bis-(3,5-di-tert-butyl-4-hydroxy-benzyl)-malonic acid dibenzyl ester 
• 108-59-8 malonic acid dimethyl ester 
• 82698-89-3 4,4-Dimethyl-2-oxo-tetrahydrofuran-3-methylen-dicarbonsaeuredibenzylester 
• 75098-35-0 4,6-dichloro-2-(dibenzylmalonyl)pyrimidine 
• 50907-68-1 (trimethylsilyl)ketene acetal of dibenzyl malonate 
• 80352-62-1 2-bis(benzyloxycarbonyl)methyl-3-nitropyridine 

Relevant academic research and scientific papers

Preparation and characterisation of amorphous mesoporous aluminophosphate and metal aluminophosphate as an efficient heterogeneous catalyst for transesterification reaction

Preparation, characterisation of pure aluminophosphate and aluminophosphate modified with different transition metals (V, Fe, Co Ni & Cu) and their catalytic activity in mono/dibenzyl substituted malonates synthesis are explained. The materials were prepared by the coprecipitation method in the absence of any structure-directing species and characterized for their composition, crystalline nature, total surface acidity, specific surface area pore diameter and pore volume by different techniques. Catalytic activity of the materials was investigated in transesterification of diethylmalonate with benzyl alcohol in liquid phase. Pure aluminophosphate resulted only in benzyl ethylmalonate whereas the incorporation of transition metals favored the formation of both benzyl ethylmalonate and dibenzylmalonate. Catalytic activity parallels the surface acidity and mesoporosity of the catalysts. The effect of the molar ratio of reactants, amount of catalyst, and reaction time on the conversion of diethyl malonate and transester yield has been studied. The highest activity of iron aluminophosphate is attributed to its mesoporous nature with uniform pore size distribution, higher surface acidity and surface area. Further, the scope and generality of iron aluminophosphate as a catalyst in the transesterification was studied using various aliphatic, alicyclic and aromatic alcohols. The catalysts could be recycled by retaining most of its initial activity.

Design of sulphate modified solid acid catalysts for transesterification of diethyl malonate with benzyl alcohol

Sulphate ion modified multiwalled carbon nanotubes (S-CNTs), mesoporous carbon (S-MC), zirconia (S-ZrO2), alumina (S-Al2O3) and silica (S-SiO2) were prepared by wet impregnation technique. The physico-chemical properties of the prepared materials were inv

Enantioselective iridium-catalyzed allylic alkylation of racemic branched alkyl-substituted allylic acetates with malonates

The regio- and enantioselective allylic substitution of branched alkyl-substituted allylic acetates employing malonates has been achieved through a process that calls for Krische's πallyliridium C,O-benzoate catalyst. The protocol reported herein can be applied to a diverse set of branched alkyl substrates that are generally not well tolerated in the other two types of Ir-catalyzed allylation.

O-Benzylation of Carboxylic Acids Using 2,4,6-Tris(benzyloxy)-1,3,5-triazine (TriBOT) under Acidic or Thermal Conditions

Two methods for the synthesis of benzyl esters from carboxylic acids using the O-benzylating reagent 2,4,6-tris(benzyloxy)-1,3,5-triazine (TriBOT) have been developed. The reactions were conducted either in the presence of a catalytic amount of TfOH at room temperature (acidic conditions) or in the absence of TfOH at 180-230 C (thermal conditions). Interestingly, the O-benzylation of hydroxy carboxylic acids under the two conditions afforded different products: The dibenzylated product under acidic conditions and the hydroxy ester under thermal conditions. In addition to these results, other evidence indicated that the former reaction proceeds through an SN1-type mechanism, and the latter by an SN2-type mechanism. Two methods for the O-benzylation of carboxylic acids using TriBOT have been developed under either acidic or thermal conditions. The O-benzylation of hydroxy carboxylic acids afforded the dibenzylated product under acidic conditions and the hydroxy ester under thermal conditions. The former reaction proceeds through an SN1-type mechanism and the latter by an SN2-type mechanism.

Synthesis of coumarin-3-carboxylic esters via FeCl3-catalyzed multicomponent reaction of salicylaldehydes, Meldrum's acid and alcohols

A FeCl3-catalyzed multicomponent reaction was developed for the facile synthesis of coumarin-3-carboxylic ester derivatives in a highly atom-economic and environmentally friendly way. Using simple and cheaply available salicylaldehydes, Meldrum's acid and alcohols as the starting materials, the method needs no extra additives and features wide substrate scope, good functional group tolerance and mild reaction conditions.

Transesterification of diethyl malonate with benzyl alcohol catalyzed by modified zirconia: Kinetic study

Zirconia and its modified forms such as 10%Mo(VI)/ZrO2, 10%V(V)/ZrO2, 10%W(VI)/ZrO2 and SO4 2-/ZrO2 were prepared and characterized for their physico-chemical properties such as BET for surface area, NH3-TPD and n-butylamine back titration method for total surface acidity, PXRD technique for crystallinity and ICP-OES technique for elemental analysis. These materials were used as catalysts in liquid phase transesterification reaction of diethyl malonate (DEM) with benzyl alcohol (BA). Optimization of reaction conditions such as reaction time, reaction temperature, weight of the catalyst and molar ratio of reactants were carried out to obtain highest possible transester yield. Dibenzyl malonate (DBM) and benzyl ethyl malonate (BEM) were obtained as major products. Highest total transester yield of (88%) was obtained in the presence of 0.75 g of SZ catalyst at a molar ratio of DEM: BA = 1:3, reaction temperature of 393 K and reaction time 5 h. Kinetic studies were carried out to find out the rate of the reaction and energy of activation values for zirconia catalysts, in order to identify a facile catalyst system for this reaction. A possible reaction mechanism was proposed based on the kinetic data and it was observed that Eley-Rideal mechanism fits well for this reaction. Reactivation and reusability studies of the catalysts were also taken up.

Catalytic asymmetric conjugate allylation of coumarins

A catalytic asymmetric conjugate allylation was successfully developed to synthesize potential pharmacologically active 4-allyl-2-oxochroman skeletons. A dual activation strategy was employed by using N,N′-dioxide-Yb(OTf) 3 to activate coumarins and using (CuOTf)2?C 7H8 to activate tetraallyltin via transmetalation, respectively. Good yields and enantioselectivities were obtained under mild conditions.

Surface properties and the catalytic activity of amorphous iron aluminophosphates: Effect of fe loading

Iron aluminophosphates (FeAlP) with different percentage of iron were synthesized and characterized for their surface and bulk properties. The catalytic activity was determined in the transesterification of diethyl malonate with benzyl alcohol. Benzyl ethylmalonate and dibenzyl malonate were obtained as the only products. FeAlP with 0.025 mole % of iron was found to be distinctly different in its textural and catalytic properties. Formation of diester was found to be favored by the acid sites of intermediate strength. The presence of hydrated alumina and the polycondensed phosphates in the materials reduced the catalytic activity of iron aluminophosphates in transesterification reaction.

Synthesis of thienamycin-like 2-iso-oxacephems with optional stereochemistry

All four trans-stereoisomers of 7-(1-hydroxyethyl)-2-iso-oxacephem-4-carboxylic acids, which are the 2-iso-oxacephem analogues of Thienamycin, have been synthesized. (αR,6R,7R)- and (αS,6S,7S)-7-(1-hydroxyethyl)-3-methyl-2-iso-oxacephem-4-carboxylic acids have been prepared starting from l- and d-threonine, the configuration at the α-position was inverted by using Mitsunobu reactions providing the (αS,6R,7R)- and (αR,6S,7S)-diastereomers of the compounds above. A synthetic route to the cis-annelated analogues was also worked out.

Synthesis of caffeic acid esters

A new method for the preparation of caffeic acid esters was investigated. Ten caffeic acid esters were prepared by condensation of protocatechualdehyde with malonic acid mono-esters in moderate yield. Malonic acid mono-esters were prepared from the corresponding malonate di-esters. The conformations of compounds are trans (E) form.