607-81-8

Basic information

• Product Name: Diethyl benzylmalonate
• Synonyms: BENZYLMALONIC ACID DIETHYL ESTER;DIETHYL BENZYLMALONATE;AKOS BBS-00006590;(phenylmethyl)-propanedioicacidiethylester;Diethyl 2-benzylmalonate;Malonic acid, 2-benzyl-, diethyl ester;Malonic acid, benzyl-, diethyl ester;Diethyl benzylmalonate,97%
• CAS NO: 607-81-8
• Molecular Formula: C₁₄H₁₈O₄
• Molecular Weight: 250.29
• EINECS: 210-142-7
• Product Categories: Pharmaceutical Intermediates;Aromatic Esters;TheMalonateRamificationProducts;Aromatics Compounds;Aromatics;C12 to C63;Carbonyl Compounds;Esters;Building Blocks;C12 to C63;Carbonyl Compounds;Chemical Synthesis;Organic Building Blocks
• Mol File: 607-81-8.mol

Chemical Properties

• Boiling Point: 162-163 °C10 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: Colourless Liquid
• Density: 1.064 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.00115mmHg at 25°C
• Refractive Index: n20/D 1.486(lit.)
• Storage Temp.: Refrigerator
• Solubility: Chloroform, Methanol
• PKA: 12.56±0.46(Predicted)
• Water Solubility: immiscible
• BRN: 615793
• CAS DataBase Reference: Diethyl benzylmalonate(CAS DataBase Reference)
• NIST Chemistry Reference: Diethyl benzylmalonate(607-81-8)
• EPA Substance Registry System: Diethyl benzylmalonate(607-81-8)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 24/25-36-26
• WGK Germany: 3
• TSCA: Yes
• Hazardous Substances Data: 607-81-8(Hazardous Substances Data)

Usage

Uses

1. Used in Organic Synthesis:
Diethyl benzylmalonate is used as a key intermediate in the synthesis of various organic compounds. Its ability to form complexes with metal ions makes it a valuable component in the development of new chemical structures and materials.
2. Used in the Synthesis of Macrocyclic Ligands:
Diethyl benzylmalonate is employed as a starting reagent for the synthesis of macrocyclic ligands, which are essential in the formation of stability constants with Cu(II), Ni(II), and Co(II) complexes. These complexes have potential applications in various fields, including catalysis and coordination chemistry.
3. Used in the Synthesis of 2-Benzyl-1,3-Propane Diol:
As a starting reagent, Diethyl benzylmalonate is used in the synthesis of 2-benzyl-1,3-propane diol, a compound with potential applications in the pharmaceutical and chemical industries.
4. Used in the Condensation with 2-Amino-Benzimidazole:
Diethyl benzylmalonate is used in the condensation reaction with 2-amino-benzimidazole, resulting in the formation of 3-benzyl-4-hydroxypyrimido[1,2-a]benzimidazole-2-one. Diethyl benzylmalonate may have potential applications in the development of new drugs and pharmaceuticals.

Synthesis Reference(s)

The Journal of Organic Chemistry, 31, p. 620, 1966 DOI: 10.1021/jo01340a523

InChI:InChI=1/C14H18O4/c1-3-17-13(15)12(14(16)18-4-2)10-11-8-6-5-7-9-11/h5-9,12H,3-4,10H2,1-2H3

Upstream product

• 996-82-7 sodium diethylmalonate 
• 100-44-7 benzyl chloride 
• 996-82-7 sodium diethylmalonate 
• 105-53-3 diethyl malonate 
• 616-75-1 2-benzylmalonic acid 
• 2021-28-5 ethyl dihydrocinnamate 
• 141-52-6 sodium ethanolate 
• 105-58-8 Diethyl carbonate 
• 55791-06-5 benzyl mesylate 
• 100-39-0 benzyl bromide 
• 92303-29-2 CH(CO₂C₂H₅)2 
• 103514-63-2 C₁₃H₂₅N₃PS⁽¹⁺⁾ 
• 82044-44-8 diethyl benzyl(prop-2'-en-1'-yl)propanedioate 
• 100-52-7 benzaldehyde 

Downstream Products

• 101268-99-9 4-benzyl-1-(1-methyl-[4]piperidyl)-pyrazolidine-3,5-dione 
• 36861-61-7 3-benzyl-pyrido[1,2-a]pyrimidine-2,4-dione 
• 101350-74-7 3-benzyl-1,2-dihydro-4-hydroxy-7-methyl-2-oxo-1,8-naphthyridine 
• 54986-54-8 2-butyl-3-hexyl-indene 
• 6943-96-0 ethyl 2-(hydroxyimino)-3-phenylpropanoate 
• 107524-40-3 benzyl-(2-methylsulfanyl-ethyl)-malonic acid diethyl ester 
• 116055-59-5 5-benzyl-2-seleno-barbituric acid 
• 23450-66-0 5-benzyl-1-methyl-barbituric acid 
• 101499-51-8 2-benzyl-octanedioic acid 
• 103034-83-9 2-benzyl-tridecanedioic acid diethyl ester 
• 361446-66-4 5-benzyl-1-phenyl-barbituric acid 
• 859200-53-6 benzyl-(3-bromo-benzyl)-malonic acid diethyl ester 
• 102663-75-2 (benzoylamino-methyl)-benzyl-malonic acid diethyl ester 
• 104958-18-1 triethyl 1,3-diphenylpropane-1,2,2-tricarboxylate 

Relevant articles and documents

Solid Molecular Frustrated Lewis Pairs in a Polyamine Organic Framework for the Catalytic Metal-free Hydrogenation of Alkenes

We report for the first time a metal-free heterogeneously catalyzed hydrogenation using a semi-solid frustrated Lewis pair (FLP). The catalyst consists of a solid polyamine organic framework and molecular tris(pentafluorophenyl)borane (BCF) that form a semi-immobilized FLP in situ in the catalytic hydrogenation of diethyl benzylidenemalonate. 11B NMR spectroscopy proves the successful hydrogen activation by the FLP. Furthermore, the B?N interactions between the polyamine and BCF are investigated by IR and solid state NMR spectroscopy. The FLP 1,4-diazabicyclo[2.2.2]octane (DABCO)/BCF, which combines the features of a FLP and a classical Lewis adduct, functions as molecular reference in both, catalysis and characterization. Furthermore, computational studies enable a better insight into the hydrogen activation through DABCO/BCF and polyamine/BCF.

Preparation of mono-substituted malonic acid half oxyesters (SMAHOs)

The use of mono-substituted malonic acid half oxyesters (SMAHOs) has been hampered by the sporadic references describing their preparation. An evaluation of different approaches has been achieved, allowing to define the best strategies to introduce diversity on both the malonic position and the ester function. A classical alkylation step of a malonate by an alkyl halide followed by a monosaponification gave access to reagents bearing different substituents at the malonic position, including functionalized derivatives. On the other hand, the development of a monoesterification step of a substituted malonic acid derivative proved to be the best entry for diversity at the ester function, rather than the use of an intermediate Meldrum acid. Both these transformations are characterized by their simplicity and efficiency, allowing a straightforward access to SMAHOs from cheap starting materials.

FRUSTRATED LEWIS PAIR-IMPREGNATED POROUS MATERIALS AND USES THEREOF

Described herein are compositions composed of frustrated Lewis pairs impregnated in porous materials such as, for example, metal-organic frameworks, and their uses thereof. These compositions may allow new applications of frustrated Lewis pairs in catalysis by sequestering and protecting the frustrated Lewis pair within the nanospace of the porous material. Also provided are methods of hydrogenating an organic compound having at least one unsaturated functional group comprising using the compositions described herein.

Manganese-catalyzed homogeneous hydrogenation of ketones and conjugate reduction of α,β-unsaturated carboxylic acid derivatives: A chemoselective, robust, and phosphine-free in situ-protocol

We communicate a user-friendly and glove-box-free catalytic protocol for the manganese-catalyzed hydrogenation of ketones and conjugated C[dbnd]C[sbnd]bonds of esters and nitriles. The respective catalyst is readily assembled in situ from the privileged [Mn(CO)5Br] precursor and cheap 2-picolylamine. The catalytic transformations were performed in the presence of t-BuOK whereby the corresponding hydrogenation products were obtained in good to excellent yields. The described system offers a brisk and atom-efficient access to both secondary alcohols and saturated esters avoiding the use of oxygen-sensitive and expensive phosphine-based ligands.

Validating the 1,2-Difluoro Motif As a Hybrid Bioisostere of CF3and et Using Matrix Metalloproteinases As Structural Probes

Matrix metalloproteinases (MMPs) are involved in a spectrum of physiological processes, rendering them attractive targets for small-molecule drug discovery. Strategies to achieve selective inhibition continue to be intensively pursued, facilitated by advances in structural biology. Herein, we harness MMPs 2, 8, 9, and 13 to validate the vicinal difluoro motif as a hybrid bioisostere of CF3 and Et (BITE) in a series of modified barbiturate inhibitors. Crystallographic analyses of representative structures reveal conformations of the vicinal difluoro motif that manifest stabilizing hyperconjugative interactions consistent with the stereoelectronic gauche effect. Detailed docking studies of a potent difluorinated probe with MMP-9 are also disclosed and indicate that the structural basis of inhibition is a consequence of the anisotropic nature of the motif. Significant selectivity of MMP 13 versus MMP-2 can be achieved by subtle chain contraction in a BITE-modified inhibitor.

Synthesis of protected α-amino acids: Via decarboxylation amination from malonate derivatives

A general and efficient strategy for the synthesis of protected α-amino acids is reported. The method uses malonate derivatives as the starting materials and Cs2CO3 as a base at 60 degrees, giving α-amino acid derivatives in moderate yields by releasing CO2. This methodology shows broad substrate scope (primary and secondary acids), excellent functional group tolerance and high efficiency to give the desired products under mild reaction conditions. It also allows the construction of β and γ-amino acids and other unnatural products.

FLP-catalysis meets hydrogen-bond activation

The potential of two chiral amidines and three non-chiral boranes in the metal-free hydrogen activation was explored. The resulting chiral amidiunium borohydride salts were investigated in asymmetric hydrogenation reactions of ketimines, activated double bonds and dehydro amioacid esters.

Enantioselective α-Amination of Acyclic 1,3-Dicarbonyls Catalyzed by N-Heterocyclic Carbene

Herein, we describe a method for the catalytic enantioselective α-amination of α-substituted acyclic 1,3-ketoamides and 1,3-amidoesters that affords the products possessing N-substituted quaternary stereocenters with a chiral N-heterocyclic carbene (NHC). The reaction is based on the utilization of an intrinsic Br?nsted base characteristic of NHC that enables the catalytic formation of a chiral ion pair comprising the enolate and the azolium ion. A series of challenging open-chain α-substituted 1,3-dicarbonyls are aminated via this method with ee's of ≤99%.

Environmentally benign nucleophilic substitution reaction of arylalkyl halides in water using CTAB as the inverse phase transfer catalyst

An environmentally benign, practically scalable and highly selective C-arylalkylation of active methylene compounds is developed using CTAB as the inverse phase transfer catalyst in water. The methodology developed is elaborated into the one-pot synthesis of quinoline derivatives and also applicable to the regioselective N-aralkyl of 2-pyridones.

Aryltrifluoromethylative cyclization of unactivated alkenes by the use of PhICF3Cl under catalyst-free conditions

A concise and catalyst-free aryltrifluoromethylative cyclization of unactivated alkenes has been developed herein. The use of PhICF3Cl as a powerful trifluoromethylating agent allows easy transformations. A set of trifluoroethylated carbocycles and aza-hereocycles were efficiently synthesized in good yield and selectivity. A broad substrate scope, mild reaction conditions, and easy operation would make this method well-suited for applications.