7686-78-4

Basic information

• Product Name: 2-VINYLCYCLOPROPANE-1,1-DICARBOXYLIC ACID DIETHYL ESTER
• Synonyms: 2-VINYLCYCLOPROPANE-1,1-DICARBOXYLIC ACID DIETHYL ESTER;diethyl 2-vinylcyclopropane-1,1-dicarboxylate;1,1-Bis(ethoxycarbonyl)-2-vinylcyclopropane;2,2-(3-Butene-1,2-diyl)malonic acid diethyl ester;2-Ethenylcyclopropane-1,1-dicarboxylic acid diethyl ester;2-Vinyl-1,1-cyclopropanedicarboxylic acid diethyl ester
• CAS NO: 7686-78-4
• Molecular Formula: C₁₁H₁₆O₄
• Molecular Weight: 212.24234
• EINECS: 231-695-0
• Mol File: 7686-78-4.mol

Chemical Properties

• Boiling Point: 230.6 °C at 760 mmHg
• Flash Point: 101.6 °C
• Appearance: /
• Density: 1.174 g/cm³
• Vapor Pressure: 0.0652mmHg at 25°C
• Refractive Index: 1.528
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• CAS DataBase Reference: 2-VINYLCYCLOPROPANE-1,1-DICARBOXYLIC ACID DIETHYL ESTER(CAS DataBase Reference)
• NIST Chemistry Reference: 2-VINYLCYCLOPROPANE-1,1-DICARBOXYLIC ACID DIETHYL ESTER(7686-78-4)
• EPA Substance Registry System: 2-VINYLCYCLOPROPANE-1,1-DICARBOXYLIC ACID DIETHYL ESTER(7686-78-4)

Safety Data

• Hazardous Substances Data: 7686-78-4(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
2-VINYLCYCLOPROPANE-1,1-DICARBOXYLIC ACID DIETHYL ESTER is used as a key intermediate in the synthesis of Vigabatrin, a novel anti-epileptic drug. It plays a vital role in the production process due to its ability to be chemically modified and incorporated into the drug's structure, contributing to its anticonvulsant properties.
Additionally, 2-VINYLCYCLOPROPANE-1,1-DICARBOXYLIC ACID DIETHYL ESTER is used as a starting material for the development of other pharmaceutical compounds, such as antidepressants, antipsychotics, and anxiolytics. Its unique chemical structure allows for the creation of diverse molecules with potential therapeutic applications, addressing various mental health conditions and improving the quality of life for patients.

Synthesis Reference(s)

The Journal of Organic Chemistry, 23, p. 1390, 1958 DOI: 10.1021/jo01103a618Tetrahedron Letters, 17, p. 2121, 1976

InChI:InChI=1/C11H16O4/c1-4-8-7-11(8,9(12)14-5-2)10(13)15-6-3/h4,8H,1,5-7H2,2-3H3

Upstream product

• 996-82-7 sodium diethylmalonate 
• 64-17-5 ethanol 
• 821-06-7 (E)-1,4-dibromobutene 
• 996-82-7 sodium diethylmalonate 
• 39198-65-7 buta-1,3-dien-t-yl-dimethyl-sulfonium; chloride 
• 105-53-3 diethyl malonate 
• 764-41-0 1,4-dichloro-2-butene 
• 1476-11-5 Z-1,4-dichlorobutene 
• 110-57-6 trans-1,4-dichlorobut-2-ene 
• 6974-12-5 1,4-dibromo-2-butene 
• 5137-55-3 Aliquat 336 
• 103-83-3 N,N'-dimethylbenzylamine 
• 49837-05-0 (E)-1,4-ditosyloxybut-2-ene 
• 132329-46-5 (Z)-1,4-Ditosyloxy-2-butene 

Downstream Products

• 36265-86-8 1-Phenyl-5,5-diaethoxycarbonyl-pent-2-en 
• 57742-48-0 (RS)-2-Vinyl-1,1-cyclopropandicarbonsaeure 
• 86726-12-7 2-[(E)-4-(2-Hydroxy-5-methyl-phenyl)-but-2-enyl]-malonic acid diethyl ester 
• 86726-14-9 2-[(E)-4-(4-Chloro-2-hydroxy-phenyl)-but-2-enyl]-malonic acid diethyl ester 
• 86726-20-7 ethyl 6-(2-hydroxy-6-chlorophenyl)-2-carbethoxy-4-hexenoate 
• 79930-10-2 diethyl <2-(phenylethynyl)-3-butenyl>propanedioate 
• 79011-77-1 ethyl 2-oxo-5-vinyl-tetrahydrofuran-3-carboxylate 
• 92173-10-9 (4E)-ethyl 2-ethoxycarbonyl-2,4-hexadienoate 
• 7686-77-3 3-cyclopentene-1-carboxylic acid 
• 85914-66-5 diethyl (E)-5-phenylthio-3-pentene-1,1-dicarboxylate 
• 86726-11-6 2-[(E)-4-(2-Hydroxy-3-methyl-phenyl)-but-2-enyl]-malonic acid diethyl ester 
• 86726-15-0 2-[(E)-4-(2-Hydroxy-5-methoxy-phenyl)-but-2-enyl]-malonic acid diethyl ester 
• 86726-13-8 2-[(E)-4-(2-Hydroxy-3,5-dimethyl-phenyl)-but-2-enyl]-malonic acid diethyl ester 
• 82819-46-3 (E)-diethyl 2-(4-phenylbut-2-en-1-yl)malonate 

Relevant articles and documents

Copper-mediated controlled radical ring-opening polymerization (RROP) of a vinylcycloalkane

This investigation reports controlled ring-opening polymerization of a vinylcyclopropane via copper-mediated atom transfer radical polymerization which leads to predominantly 1,5 ring-opening polymerization. The Royal Society of Chemistry.

A macromonomer approach to the synthesis of poly(1,1-bis(ethoxycarbonyl)-2- vinyl cyclopropane-graft-dimethyl siloxane)

Poly(1,1-bis(ethoxycarbonyl)-2-vinyl cyclopropane (ECVP)-graft-dimethyl siloxane) copolymers were prepared using a macromonomer approach. Poly(dimethyl siloxane) (PDMS) macromonomers were prepared by living anionic polymerization of cyclosiloxanes followed by sequential chain-end capping with allyl chloroformate. These macromonomers were then copolymerized with ECVP. MALDI-ToF mass spectrometry and 1H NMR spectroscopy were used to show that the macromonomers had approximately 80% of the end groups functionalized with allyl carbonate groups. Gradient polymer elution chromatography showed that high yields of the graft copolymers were obtained, along with only small fractions of the PECVP and PDMS homopolymers. Differential scanning calorimetry showed that the low glass transition temperature (Tg) of the PDMS component could be maintained in the graft copolymers. However, the Tg was a function of polymer composition and the polymers produced had Tgs that ranged from -50 to -120 °C.

Vinyl-aziridines and cyclopropanes in Pd-catalyzed (3+2)-cycloaddition reactions with cyclic N-sulfonyl imines

Efficient palladium-catalyzed (3 + 2)-cycloaddition reactions of cyclic N-sulfonyl imines and vinyl-aziridines (or cyclopropanes) have been achieved. The reactions, with either vinylic substrate, proceed with excellent yields affording highly functionalized imidazolidine and pyrrolidine derivatives. The cycloadditions take place via the reaction of zwitterionic π-allyl palladium intermediates with cyclic N-sulfonyl imines through i) the formation of two N–C bonds in the presence of vinylaziridines (synthesis of imidazolidines) and ii) one C–C bond and one N–C bond in the presence of vinylcyclopropanes (synthesis of pyrrolidines). Following on preliminary works on the diastereoselective synthesis of imidazolidines, herein we wish to give a broader view on the subject by describing derivatization reactions and attempts towards an enantioselective version. Moreover, we describe and discuss the behavior of each vinylic substrate (aziridine or cyclopropane) on the (3 + 2)-cycloaddition reactions. Mechanistic and (intriguing) selectivity outcomes are also going to be discussed.

New fluorinated liquid crystalline copoly(vinylcyclopropane)s with unusual macromolecular structure

New liquid crystal polymers with unusual macromolecular structure were prepared by copolymerization of a fluorinated vinylcyclopropane (1) with methyl methacrylate (2). The copolymers pol(1-co-2) formed a mesophase despite the high dilution of the perfluorinated side chains along the polymer main chain. The onset of mesomorphism is attributed to the microphase separation of the incompatible fluorocarbon-hydrocarbon components.

Palladium-Catalyzed Formal (3 + 2) Cycloaddition Reactions of 2-Nitro-1,3-enynes with Vinylaziridines, -epoxides, and -cyclopropanes

A two-step Pd-catalyzed (3 + 2) cycloaddition/HNO2 elimination reaction sequence has been developed to give novel cyclic 1,3-dien-5-yne systems from Pd-stabilized zwitterionic 1,3-dipoles and 2-nitro-1,3-enyne substrates. The process is highly atom-efficient and tolerates the reaction of 2-vinyloxirane, 1-tosyl-2-vinylaziridine, and diethyl 2-vinylcyclopropane-1,1-dicarboxylate derived 1,3-dipoles with a variety of 2-nitro-1,3-enyne substrates. The stereochemistry of the intermediate (3 + 2) cycloadducts was determined by single crystal X-ray analysis. Furthermore, a selective kinetic elimination of the cycloadduct with an antiperiplanar relationship between the NO2 group and the participating hydrogen was demonstrated, allowing for efficient isolation of a single diastereoisomer of the cycloadduct.

Preparation method of aminohexenoic acid

The invention discloses a preparation method of aminohexenoic acid, which is characterized by comprising the following steps: with diethyl malonate and 1,4-dichloro-2-butene as raw materials, preparing 2-vinylcyclopropane-1,1-dicarboxylic acid diethyl ester; then carrying out a reaction on 2-vinylcyclopropane-1,1-dicarboxylic acid diethyl ester in the presence of ammonia and formamide to prepare 2-carbonyl-5-vinyl-pyrrolidine-3-amide; preparing a 4-amino-5-hexenoic acid crude product from the 2-carbonyl-5-vinyl-pyrrolidine-3-amide under an acidic condition; then preparing triisopropylsilyl-4-aminohexyl-5-alkenyl ester from 4-amino-5-hexenoic acid and triisopropylchlorosilane in the presence of triethylamine and ammonia; recrystallizing the triisopropylsilyl-4-aminohexyl-5-alkenyl ester inchloroform/methanol to obtain a purified product of the triisopropylsilyl-4-aminohexyl-5-alkenyl ester; wherein the volume ratio of chloroform to methanol is 1:7; and hydrolyzing the purified productof the triisopropylsilyl-4-aminohexyl-5-alkenyl ester under an alkaline condition to obtain the aminohexylenic acid.

A convenient approach for vinylation reaction in the synthesis of 5-vinyl-2-pyrrolidinone, a key intermediate of vigabatrin

A convenient, safe and cost-effective method for carrying out the key vinylation of 5-ethoxy-2-pyrrolidinone (8) in the preparation of 5-vinyl-2-pyrrolidinone (2) in the presence of potassium carbonate is described. This present procedure is developed by replacing inherently hazardous ethyl magnesium bromide with inexpensive and eco-friendly potassium carbonate. The reaction was performed on a multi-gram scale, with vinyl magnesium bromide as the vinylation reagent, in an 81% yield to give the 5-vinyl-2-pyrrolidinone with excellent purity and without the need for chromatography.

NaOH-Promoted Chemoselective Cascade Cyclization of Cyclopropyl Esters with Unsaturated Imines: Access to Bioactive Cyclopenta[c]pyridine Derivatives

A chemoselective cascade cycloaddition reaction is developed for green and efficient access to cyclopenta[c]pyridine derivatives. Simple and inexpensive NaOH is used as the sole catalyst for this process. The δ-carbon of cyclopropyl ester is activated as a nucleophilic carbon to initiate highly chemoselective cascade reactions. Cyclopenta[c]pyridines bearing various substituents are afforded in excellent yields. Preliminary studies on the bioactivities of the afforded products show promising antibacterial activities for potential applications in plant protections.

Photoredox catalysed allylic trifluoromethylation via ring opening of vinyl cyclopropanes using Langlois reagent

Trifluoromethylation of vinylcyclopropanes (VCPs) has been developed under mild reaction conditions to synthesize allylic trifluoromethylated derivatives with high yield and E/Z selectivity using visible light photo-redox catalysis and Langlois reagent (CF3SO2Na) as a trifluoromethylation source. Further, we demonstrate a gram scale synthesis procedure for a trifluoromethylation of vinylcyclopropane.

Palladium-Catalyzed Allylic Alkylation of Aldimine Esters with Vinyl-Cyclopropanes to Yield α,α-Disubstituted α-Amino Acid Derivatives

A synthetically useful approach for the synthesis of functionalized α, α-disubstituted α-amino acid derivatives via palladium-catalyzed 1,7 addition of readily available aldimine esters to vinylcyclopropanes is reported. This methodology was operated under mild conditions, affording α-allylic α-amino esters in good to excellent yields and excellent regio- and stereoselectivity. This transformation displays broad functional-group tolerance and enantioselective allylic alkylation has also been realized using a chiral phosphine ligand to provide the desired product. (Figure presented.).