3377-20-6

Usage

Uses

Used in Chemical Synthesis:
Diethyl methylidenemalonate is used as a reagent for synthesizing donor-acceptor cyclobutanes. This application is made possible due to its ability to undergo [2+2] cycloaddition reactions when catalyzed by copper acetate or iron trichloride. The resulting cyclobutanes have potential applications in various industries, including pharmaceuticals, materials science, and agrochemicals.

InChI:InChI=1/C8H12O4/c1-4-11-7(9)6(3)8(10)12-5-2/h3-5H2,1-2H3

Upstream product

• 87-13-8 diethyl 2-ethoxymethylenemalonate 
• 107-30-2 chloromethyl methyl ether 
• 105-53-3 diethyl malonate 
• 50-00-0 formaldehyd 
• 609-09-6 Diethyl ketomalonate 
• 20605-01-0 diethyl bis(hydroxymethyl)malonate 
• 141085-35-0 C₃H₈N⁽¹⁺⁾*C₂H₃O₂^(1-) 
• 1161393-21-0 thymidine 5'-bis[3-acetyloxymethoxy-2,2-bis(ethoxycarbonyl)-propyl]phosphate 
• 1161393-20-9 thymidine 5'-bis[3-acetyloxy-2,2-bis(ethoxycarbonyl)propyl]phosphate 
• 150194-66-4 diethyl 2-methyl-2-(phenylselenyl)malonate 
• 89317-62-4 4-O,O-t-butyl 1-ethyl 2-(ethoxycarbonyl)monoperoxybutanedioate 
• 58567-05-8 diethyl 2-hydroxy-2-methylmalonate 
• 64-17-5 ethanol 
• 76221-41-5 3,3-diethoxy-2-(ethoxycarbonyl)cyclobutene 

Downstream Products

• 854723-35-6 2,2,4-trimethyl-cyclohex-3-ene-1,1-dicarboxylic acid diethyl ester 
• 197155-67-2 diethyl 3,4-dimethylcyclohex-3-ene-1,1-dicarboxylate 
• 51592-66-6 6-Dimethylamino-5.5-dimethyl-cyclohexan-1.1.3.3-tetracarbonsaeure-tetraethylester 
• 96578-94-8 5-Ethyl-1.1.3.3-tetraethoxycarbonyl-6-dimethylamino-cyclohexan 
• 22539-80-6 diethyl (3-methylbut-2-enyl)malonate 
• 64836-82-4 4,4-dicarboethoxy-2-cyclohexenone 
• 121768-02-3 ethyl 4,8-anhydro-5,6,7,9-tetra-O-benzoyl-2,3-dideoxy-2-C-ethoxycarbonyl-D-glycero-D-talonononate 
• 29805-59-2 diethyl (cyclohexylmethyl)propanedioate 
• 118799-70-5 ethyl 3-(4'-tert-butylcyclohexyl)-2-(ethoxycarbonyl)propionate 
• 118799-66-9 ethyl 3-(4'-tert-butylcyclohexyl)-2-(ethoxycarbonyl)propionate 
• 94473-55-9 1-benzyl-4,4-bis(ethoxycarbonyl)-4,5-dihydro-1,2,3-triazole 
• 96124-28-6 Diethyl 2-methyl-3-phenylisoxazoline-5,5-dicarboxylate 
• 96124-27-5 Diethyl 2-methyl-3-phenylisoxazoline-4,4-dicarboxylate 
• 53561-63-0 diethyl (2,2-dimethylpropyl)malonate 

Relevant academic research and scientific papers

COMPOUNDS FOR SELECTIVE BINDING TO ESTROGEN RECEPTORS ALPHA/BETA RELATIVE TO GPER/GPR30

The current invention is in the field of molecular biology/pharmacology and provides novel 3-oxabicyclo [3.3.1] nonene compounds and derivatives that modulate the effects of the classical estrogen receptors alpha and beta (ERalpha and ERbeta) with little to no biological or physiological effects on the G protein-coupled estrogen receptor GPER (also known as GPR30). These compounds may function as agonists and/or antagonists of one or more of the disclosed classical estrogen receptors.

CYCLIC COMPOUNDS AND METHODS OF USING SAME

The present application relates to compounds of Formula (I), as defined herein, and pharmaceutically acceptable salts thereof which are MALT1 inhibitors. The present application also describes pharmaceutical composition comprising a compound of Formula (I), and pharmaceutically acceptable salts thereof, and methods of using the compounds and compositions for treating diseases, such as cancer, autoimmune disorders, and inflammatory disorders.

Development of a Scalable Process for the Insecticidal Candidate Tyclopyrazoflor. Part 1. Evaluation of [3 + 2] Cyclization Strategies to 3-(3-Chloro-1 H-pyrazol-1-yl)pyridine

The evaluation of [3 + 2] cyclization strategies to prepare a key intermediate, 3-(3-chloro-1H-pyrazol-1-yl)pyridine, for the insecticidal candidate tyclopyrazoflor (1) is described. Among the validated strategies, the route involving [3 + 2] cyclization of 3-hydrazinopyridine·2HCl with methyl acrylate was selected for further optimization. This route provided ready access to 3-(3-chloro-1H-pyrazol-1-yl)pyridine in three steps via cyclization, chlorination, and oxidation. Further functionalization of 3-(3-chloro-1H-pyrazol-1-yl)pyridine via nitration, reduction, and amide formation with 3-((3,3,3-trifluoropropyl)thio)propanoic acid followed by ethylation rendered 1 in a total of seven steps.

Multicomponent, Enantioselective Michael-Michael-Aldol-β-Lactonizations Delivering Complex β-Lactones

Optically active, tertiary amine Lewis bases react with unsaturated acid chlorides to deliver chiral, α,β-unsaturated acylammonium salts. These intermediates participate in a catalytic, enantioselective, three-component process delivering bi- and tricyclic β-lactones through a Michael-Michael-aldol-β-lactonization. In a single operation, the described multicomponent, organocascade process forms complex bi- and tricyclic β-lactones by generating four new bonds, two rings, and up to four contiguous stereocenters. In the racemic series, yields of 22-75% were achieved using 4-pyrrolidinopyridine as Lewis base. In the enantioselective series employing isothiourea catalysts, a kinetic resolution of the initially formed racemic Michael adduct appears operative, providing yields of 46% to quantitative (based on 50% max) with up to 94:6 er. Some evidence for a dynamic kinetic asymmetric transformation for tricyclic-β-lactone 1d was obtained following optimization (yields up to 61%, 94:6 er) through a presumed reversible Michael.

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

[1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination

A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal-functionalized 1-pyrroline derivatives was developed. The reaction involves a novel rhodium-catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1-pyrrolines. Structural diversification of the enal-functionalized 1-pyrrolines resulted in the biologically important pyrrolidine-fused oxaziridine, amino acid derivatives, and a 6-azabicyclo[3.2.1]octane motif present in polycyclic alkaloids.

METHOD TO OBTAIN METHYLENE MALONATE VIA BIS(HYDROXYMETHYL) MALONATE PATHWAY

Method to obtain methylene malonate and related monomers following a bis(hydroxymethyl) malonate pathway. A bis(hydroxymethyl) malonate intermediary is subsequently reacted (i.e., subjected to thermolysis) to provide a methylene malonate monomer species. A source of formaldehyde (e.g., formalin) is provided in the presence of a basic catalyst (e.g., calcium hydroxide), to which a malonate (e.g., diethyl malonate) is added under suitable reaction conditions to obtain the desired intermediary (e.g., dialkyl bis(hydroxymethyl) malonate). The intermediary is reacted (i.e., subjected to thermolysis) under suitable conditions in the presence of a suitable catalyst (e.g., a zeolite) to obtain a methylene malonate monomer. In an exemplary embodiment, the thermolysis reaction includes the addition of the bis(hydroxymethyl) malonate intermediary onto a heated catalyst. The reaction product is collected and purified. The disclosed methods may be performed in a continuous operation. Discrete steps may be performed by using modular units within a plant.

1,1-DISUBSTITUTED ETHYLENE PROCESS

New and improved processes for the production of 1,1-disubstituted ethylenes.

SYNTHESIS OF METHYLENE MALONATES USING RAPID RECOVERY IN THE PRESENCE OF A HEAT TRANSFER AGENT

The present invention provides a method of making a methylene malonate monomer that includes the steps of reacting a malonic acid ester with a source of formaldehyde optionally in the presence of an acidic or basic catalyst and optionally in the presence of an acidic or non-acidic solvent to form reaction complex. The reaction is optionally performed in the presence of or contacted with an energy transfer means such as a heat transfer agent, a heat transfer surface, a source of radiation or a laser such that reaction complex is substantially vaporized to produce a vapor phase comprising methylene malonate monomer which may be isolated. The present invention further provides methylene malonate monomers prepared by the method of the invention, as well as compositions and products formed from the methylene malonate monomers, including monomer-based products (e.g., inks, adhesives, coatings, sealants or reactive molding) and polymer-based products (e.g., fibers, films, sheets, medical polymers, composite polymers and surfactants).

Sc(OTf)3-catalyzed tandem [3+2] cycloaddition/nucleophilic ring-opening reaction of cyclopropane 1,1-diesters with azomethine ylides

A new Sc(OTf)3-catalyzed tandem reaction combined with a dimerized self-[3+2] cycloaddition of azomethine ylide and a nucleophilic ring-opening of cyclopropane 1,1-diester has been developed. A series of polyfunctionalized imidazolidine derivatives were synthesized by this reaction (Yield 44-77 %). In some cases, this tandem reaction was also accompanied by a cross-[3+2] cycloaddition of cyclopropane 1,1-diester with imine.