3377-21-7

Usage

Uses

Used in Pharmaceutical Industry:
Dimethyl methylenemalonate is utilized as a key intermediate for the synthesis of various pharmaceuticals, leveraging its reactivity in chemical reactions to facilitate the production of complex organic molecules required in medicinal compounds.
Used in Agrochemical Industry:
In the agrochemical sector, dimethyl methylenemalonate serves as an intermediate, contributing to the synthesis of a range of agrochemicals that are vital for agricultural applications.
Used as a Reagent in Organic Synthesis:
Dimethyl methylenemalonate is employed as a reagent in organic synthesis, where its ability to participate in diverse chemical reactions aids in the creation of a multitude of organic compounds.
Used as a Solvent in Chemical Processes:
dimethyl methylenemalonate also functions as a solvent in various chemical processes, providing a medium for reactions to occur, which is essential for the smooth operation of numerous chemical procedures.

InChI:InChI=1/C6H8O4/c1-4(5(7)9-2)6(8)10-3/h1H2,2-3H3

Upstream product

• 609-02-9 methyl-malonic acid dimethylester 
• 108-59-8 malonic acid dimethyl ester 
• 6773-29-1 dimethyl diazomalonate 
• 33757-46-9 8-(N-propionylamino)quinoline 
• 50-00-0 formaldehyd 
• 3298-40-6 mesoxalate de methyle 
• 628-51-3 diacetoxymethane 
• 64-19-7 acetic acid 
• 1338951-12-4 dimethyl 3,3-dimethyl-2-(diphenylmethylideneamino)cyclobutane-1,1-dicarboxylate 
• 116279-88-0 11,11-bis(methoxycarbonyl)-9,10-endoethano-9,10-dihydroanthracene 
• 87167-72-4 dimethyl 2-methyl-2-phenylselenopropanedioate 
• 60-29-7 diethyl ether 
• 2373-51-5 chloro-methylsulfanyl-methane 

Downstream Products

• 13138-07-3 (5-phenyl-2-thioxo-[1,3,4]oxadiazol-3-ylmethyl)-malonic acid dimethyl ester 
• 51013-62-8 3-phenyl-4H-isoxazole-5,5-dicarboxylic acid dimethyl ester 
• 1256966-48-9 5-methyl-7-phenylpyrazolo[1,5-d][1,2,4]triazin-4(5H)-one 
• 1256966-46-7 C₁₆H₁₈N₄O₅ 

Relevant academic research and scientific papers

Lithium perchlorate-, acetic anhydride-, and triphenylphosphine-assisted multicomponent syntheses of 4-unsubstituted 2,5-dioxooctahydroquinoline-3- carboxylates and 3-carbonitriles

Lithium perchlorate and acetic anhydride were the key additives for the multi-component reaction between 3-aminocyclohex-2-enones, formaldehyde, and malonates yielding adducts that were annulated under acidic conditions to afford bicyclic 2,5-dioxooctahydroquinoline-3-carboxylates. When methyl cyanoacetate was subjected to the same reaction conditions in the presence of a catalytic amount of triphenylphosphine, the bicyclic 2,5-dioxooctahydroquinoline-3- carbonitriles were obtained in a one-flask reaction.

Synthesis and Properties of Carbaporphyrin and Carbachlorin Dimethyl Esters Derived from Cyclopentanedialdehydes

Norbornenes with two ester substituents were prepared by Diels-Alder cycloadditions of cyclopentadiene with dimethyl fumarate and dimethyl 1,1-ethylenedicarboxylate. Oxidation with potassium permanganate gave good yields of related diols that were oxidatively ring-opened to afford cyclopentane dialdehydes. MacDonald-type "3 + 1" condensations with a tripyrrane, followed by oxidation with DDQ in refluxing toluene, gave carbaporphyrin or carbachlorin products in good yields. The macrocyclic products were highly diatropic and produced porphyrin-like UV-vis spectra. The carbaporphyrin was converted into silver(III) and gold(III) organometallic derivatives. Reaction with methyl iodide in the presence of potassium carbonate gave mono- and dialkylation products, and treatment of the former with Ni(OAc)2 or Pd(OAc)2 afforded nickel(II) and palladium(II) complexes. The free base carbaporphyrin and carbachlorin, and the nickel and palladium complexes, were characterized by X-ray crystallography. The carbachlorin also reacted with silver(I) acetate to give a silver(III) derivative. Carbaporphyrins and carbachlorins underwent deuterium exchange at the meso-positions with deuteriated TFA, and this observation indicates that protonation is occurring at the bridging carbons. The new route to carbaporphyrins and carbachlorins has enabled detailed studies on the properties of these systems and provides the foundations for future investigations.

Total Synthesis of the Meroterpenoid Manginoid A as Fueled by a Challenging Pinacol Coupling and Bicycle-forming Etherification

The manginoids are a unique collection of bioactive natural products whose structures fuse an oxa-bridged spirocyclohexanedione with a heavily substituted trans-hydrindane framework. Herein, we show that such architectures can be accessed through a strategy combining a challenging pinacol coupling and bicycle-forming etherification with several additional chemo- and regioselective reactions. The success of these key events proved to be highly substrate and condition specific, affording insights for their application to other targets. As a result, not only has a 19-step total synthesis of manginoid A been achieved, but a potential roadmap to access other members of the family and related natural products has also been identified.

Tandem Diels-Alder and retro-ene reactions of 1-sulfenyl- and 1-sulfonyl-1,3-dienes as a traceless route to cyclohexenes

A pericyclic approach for the synthesis of six-membered ring structures is described. The method employs 1,3-dienes with a 1-sulfur substituent in a tandem sequence of Diels-Alder and retro-ene reactions. In this pairing of [4 + 2] cycloaddition and 1,5-sigmatropic rearrangement, 1-sulfenyl-1,3-dienes engage in Diels-Alder reactions with electron-deficient dienophiles. Subsequently, the sulfenyl group of the cycloadducts is oxidized and unmasked to form allylic sulfinic acids, which undergo sterospecific reductive transposition via sulfur dioxide extrusion. The sequence can also include an inverse electron demand Diels-Alder reaction by using a 1-sulfonyl-1,3-diene. This combination of two pericyclic events offers novel stereocontrolled access to cyclohexenes that are inaccessible via a direct [4 + 2] cycloaddition route.

Mild Darzens Annulations for the Assembly of Trifluoromethylthiolated (SCF3) Aziridine and Cyclopropane Structures

We report mild new annulation approaches to trisubstituted trifluoromethylthiolated (SCF3) aziridines and cyclopropanes via Darzens inspired protocols. The products of these anionic annulations, rarely studied previously, possess attractive features rendering them valuable building blocks for synthesis platforms. In this study, trisubstituted acetophenone nucleophiles bearing SCF3 and bromine substituents in their α position were shown to undergo [2 + 1] annulations with vinyl ketones and tosyl-protected imines under mild reaction conditions.

Rh-Catalyzed Annulation of Benzoic Acids, Formaldehyde, and Malonates via ortho-Hydroarylation to Indanones

A three-component reaction from readily available low-cost materials of benzoic acids, formaldehyde, and malonates for the preparation of indanones by rhodium catalysis is reported. The annulation is initiated by an ortho-hydroarylation of benzoic acids, and a Lewis acid is not required. The solvent has a significant influence to the reaction, and 2-substituted or nonsubstituted indanones are obtained by the change of solvent.

Tandem Remote Csp3-H Activation/Csp3-Csp3 Cleavage in Unstrained Aliphatic Chains Assisted by Palladium(II)

We report here a proof-of-concept for the cleavage of unstrained remote Csp3-Csp3 bonds at room temperature assisted by a directing group, opening up new possibilities to use aliphatic carboxylic acids as suitable alkenyl coupling partners. This strategy involves the Pd-mediated Csp3-H activation directed by a tethered 8-aminoquinoline group, followed by a concerted asynchronous carbene insertion into the Pd-C bond, and an unexpected β-carbon-carbon bond splitting. The insertion of a coupling partner into a Pd-C bond is a novel route to promote C-C bond cleavage, which in contrast to most common methodologies does not rely on the use of strained carbocycles.

Three-Dimensional Tetrathiafulvalene-Based Covalent Organic Frameworks for Tunable Electrical Conductivity

The functionalization of three-dimensional (3D) covalent organic frameworks (COFs) is essential to broaden their applications. However, the introduction of organic groups with electroactive abilities into 3D COFs is still very limited. Herein we report the first case of 3D tetrathiafulvalene-based COFs (3D-TTF-COFs) with non- or 2-fold interpenetrated pts topology and tunable electrochemical activity. The obtained COFs show high crystallinity, permanent porosity, and large specific surface area (up to 3000 m2/g). Furthermore, these TTF-based COFs are redox active to form organic salts that exhibit tunable electric conductivity (as high as 1.4 × 10-2 S cm-1 at 120 °C) by iodine doping. These results open a way toward designing 3D electroactive COF materials and promote their applications in molecular electronics and energy storage.

A facile method for the synthesis of fused perhydropyrano[2,3: -b] pyrans promoted by Yb(OTf)3

A stereospecific three-component domino reaction between glycals, alkylidene malonate and aldehydes catalyzed by Yb(OTf)3 is described. Multi-substituted cis-fused perhydropyrano[2,3-b]pyran derivatives were obtained with high diastereoselectiv

Process for preparing 1,1-disubstituted ethylenic monomers

The present invention relates to a process for preparing 1,1-disubstituted ethylene monomers having general formula (I) from a compound of general formula (II) and an active methylene compound of general formula (III) using a catalytic amount of an ammonium or iminium salt in homogeneous phase or supported on a solid substrate. Said process allows the direct synthesis of the monomers and finds application in the preparation of a wide variety of monomers. The products obtained are reactive monomers of high purity which find application in the field of fast curing adhesives.