14035-96-2

Usage

Uses

Used in Flavor and Fragrance Industry:
Dimethyl propylmalonate is used as a flavoring agent for providing a sweet, fruity, and slightly floral aroma to various food and cosmetic products, enhancing their sensory appeal.
Used in Pharmaceutical Industry:
Dimethyl propylmalonate serves as an intermediate in the synthesis of pharmaceuticals, contributing to the development of new medications and therapeutic agents.
Used in Agrochemical Industry:
In the agrochemical sector, dimethyl propylmalonate is utilized as an intermediate, playing a role in the creation of compounds used in agricultural applications to protect crops and enhance yields.
Used in Organic Synthesis:
Dimethyl propylmalonate is employed as a building block in organic synthesis, facilitating the construction of complex organic molecules and contributing to the advancement of chemical research and development.
It is crucial to handle dimethyl propylmalonate with caution due to its potential hazards, such as harmful effects if swallowed or inhaled, and its ability to cause skin and eye irritation.

InChI:InChI=1/C8H14O4/c1-4-5-6(7(9)11-2)8(10)12-3/h6H,4-5H2,1-3H3

Upstream product

• 67-56-1 methanol 
• 616-62-6 n-propylmalonic acid 
• 18795-82-9 2-propylidene malonic acid dimethyl ester 
• 187737-37-7 propene 
• 18424-76-5 dimethyl malonate sodium salt 
• 102127-54-8 Bicyclo<1.1.0>butan-2,2-dicarbonsaeuredimethylester 
• 97935-32-5 dimethyl 2-methyl-1,1-cyclopropanedicarboxylate 
• 106-94-5 propyl bromide 
• 108-59-8 malonic acid dimethyl ester 
• 40637-56-7 dimethyl allylmalonate 
• 107-08-4 1-iodo-propane 
• 95124-07-5 dimethyl (prop-2-yn-1-yl)malonate 

Downstream Products

• 137628-82-1 2,4,6-Tri-n-propyl-1,3-cyclohexandion 
• 87711-72-6 (E)-methyl 2-benzylidenepentanoate 
• 357336-20-0 brivaracetam 
• 63095-51-2 (+)-(R)-4-propyl-4,5-dihydrofuran-2(3H)-one 
• 875125-87-4 (R)-2-(hydroxymethyl)pentanoic acid 
• 97-61-0 2-Methylpentanoic acid 
• 5650-75-9 2-propylacrylic acid 
• 875125-89-6 (S)-2-(hydroxymethyl)pentanoic acid 

Relevant academic research and scientific papers

A Biocatalytic Route to the Novel Antiepileptic Drug Brivaracetam

An asymmetric synthesis of the novel antiepileptic drug Brivaracetam 1 is described. The stereochemistry of the 4-n-propyl substituent is introduced by a biocatalytic resolution of (rac)-methyl 2-propylsuccinate 4-tert-butyl ester 4. The selection of the resolution substrate and the screening of enzymes were carried out from our in-house screening platform. The development and scale-up of the best conditions, including solvent media, pH control, workup, and enzyme supply, led up to a successful demonstration conducted at 1 kg scale in a 10 L vessel. The chiral intermediate (R)-2-propylsuccinic acid 4-tert-butyl ester 6 was reproducibly obtained in 42% yield and 97% ee all along the development. The control of the stereochemistry via the biocatalytic resolution allowed the production of Brivaracetam 1 within the required commercial quality specifications.

Stable Zero-Valent Nickel Nanoparticles in Glycerol: Synthesis and Applications in Selective Hydrogenations

Small (mean diameter, ca. 1.2 nm) and well-dispersed zero-valent nickel nanoparticles (NiNPs) stabilized by cinchona-based alkaloids and TPPTS (tris(3-sulfophenyl)phosphine trisodium salt), were synthesized from the organometallic precursor [Ni(cod)2] in neat glycerol under hydrogen pressure. NiNPs were fully characterized ((HR)-TEM, EDX, XPS, XRD, IR, magnetization), both at solid state and directly from the corresponding colloidal solutions in glycerol due to its negligible vapour pressure. NiNPs dispersed in glycerol were applied in hydrogenation reactions, in particular in semihydrogenation of alkynes to give (Z)-alkenes under satisfactory conditions (3 bar H2, 1 mol% Ni, 100 °C), showing remarkable activity and selectivity. The catalytic phase was recycled at least ten times without loss of activity, affording in each case metal-free organic products. Other functional groups such as nitro, nitrile and formyl groups were efficiently hydrogenated to the corresponding anilines, benzylamines and benzylalcohols respectively (77–95% yields). (Figure presented.).

Synthesis of Enantiomerically Enriched 2-Hydroxymethylalkanoic Acids by Oxidative Desymmetrisation of Achiral 1,3-Diols Mediated by Acetobacter aceti

The stereoselective desymmetrisation of achiral 2-alkyl-1,3-diols is performed by oxidation of one of the two enantiotopic primary alcohol moieties by means of Acetobacter aceti MIM 2000/28 to afford the corresponding chiral 2-hydroxymethyl alkanoic acids (up to 94 % ee). The procedure, carried out in aqueous medium under mild conditions of pH, temperature and pressure, contributes to enlarge the portfolio of enzymatic oxidations available to organic chemists for the development of sustainable manufacturing processes.

Ketenimines from Isocyanides and Allyl Carbonates: Palladium-Catalyzed Synthesis of β,γ-Unsaturated Amides and Tetrazoles

The reaction of allyl ethyl carbonates with isocyanides in the presence of a catalytic amount of Pd(OAc)2provided ketenimines through β-hydride elimination of the allyl imidoylpalladium intermediates. The insertion of the isocyanide into the π-allyl Pd complex proceeded via an unusual η1-allyl Pd species. The resulting ketenimines were hydrolyzed to β,γ-unsaturated carboxamides during purification by flash column chromatography on silica gel or converted in situ into 1,5-disubstituted tetrazoles by [3+2] cycloaddition with hydrazoic acid or trimethylsilyl azide.

Unprecedented hydrogen transfer from water to alkenes and alkynes mediated by TiIII and late transition metals

We describe how alkenes and alkynes can be hydrogenated under mild conditions by hydrogen transfer from water mediated by titanocene(III) and a substoichiometric quantity of one of the late transition metals usually employed as hydrogenation catalysts. This process proceeds presumably by H-atom transfer from TiIII-coordinated water to the late transition metal partner (depicted in the drawing above), a mechanism in support of which we provide theoretical and experimental evidence.

1,3-Stereoinduction in radical reactions: Radical additions to dialkyl 2-alkyl-4-methyleneglutarates

Tin hydride-mediated radical additions to a series of α-methylene-glutarates 1, furnishing 2;4-dialkyl-substituted glutarates 3 are reported. The diastereoselectivity of hydrogen transfer to the intermediate adduct radicals 2, possessing a stereogenic center in γ-position, was disappointing in the temperature range of -78 to 80 °C. However, the reactions proved to be able to proceed with excellent 1,3-diastereoselectivities under chelation-controlled conditions, depending on the steric impacts of 2- and 4-alkyl substituents as well as on the ester-alkyl moiety and choice of Lewis acid. Using MgBr2·OEt2 as additive, syn-selectivities of 98:2 were achieved upon initial tert-butyl radical addition at -78 °C. High anti-diastereoselectivities were observed in the MgBr2·OEt2-controlled pathway at 70 °C when smaller alkyl radicals such as cyclohexyl, ethyl, and methyl were applied. Interesting and uncommon temperature dependences were observed in the temperature range of -78 to 100 °C, revealing strong entropic effects in the transition states. A model that accounts for the opposed stereochemical outcomes under chelation-controlled conditions is presented.

Electrochemically induced oxidative rearrangement of alkylidenemalonates

Alkylidenemalonates capable of double bond migration being electrolyzed in methanol or ethanol in the presence of alkali metal halides in an undivided cell equipped with Fe cathode are transformed into 2-alkyl-3,3- dimethoxyalkane-1,2-dicarboxylates in 70-90% yield via electrochemically induced oxidative rearrangement. Acidification of the reaction mixture after the electrolysis leads to the formation of 2-alkyl-3-oxoalkane-1,1- dicarboxylates. In the case of isobutylidenemalonate, the electrolysis intermediate dimethyl 3,3-dimethyl-2-methoxy-cyclopropane-1,1-dicarboxylate was isolated in 70% yield.

Electrochemical Cyclodimerization of Alkylidenemalonates

Electrolysis of dimethyl alkylidenemalonates RCH=C(COOMe)2 (R=n-Alk, Ph) in an undivided cell in MeOH in the presence of alkali metal halide as mediator, leads to the formation of cyclic dimers, i.e., 3,4-disubstituted 1,1,2,2-cyclobutanetetracarboxylates.The reaction proceeds via the reductive coupling of two substrate molecules at cathode and the cyclization of a hydrodimer dianion by its interaction with an active form of a mediator, an anode-generated halogen.

Samarium(II) iodide promoted reductive ring opening reaction of cyclopropane-1,1-dicarboxylic esters. Synthesis of substituted 5-Pentanolides from carbonyl compounds and dimethyl cyclopropane-1,1-dicarboxylate

Dimethyl cyclopropane-1,1-dicarboxylate is readily subjected to reductive ring opening reaction with samarium(II) iodide in the presence of tris(dibenzoyl-methiodo)iron(III). The generated organosamarium intermediate is trapped by aliphatic ketones to aff

Electrochemical cyclodimerization of alkylidenemalonates into 3,4-disubstituted cyclobutane-1,1,2,2-tetracarboxylates

Alkylidenemalonates being electrolyzed in methanol in undivided cell with glassy carbon, carbon or lead cathode in the presence of sodium iodide or sodium bromide are transformed into 3,4-disubstituted cyclobutane-1,1,2,2-tetracarboxylates.