35234-88-9

Basic information

• Product Name: DIETHYL DICYANOFUMARATE, 97
• Synonyms: DIETHYL DICYANOFUMARATE, 97;diethyl 2,3-dicyanofumarate;2,3-Dicyanofumaric acid diethyl ester
• CAS NO: 35234-88-9
• Molecular Formula: C₁₀H₁₀N₂O₄
• Molecular Weight: 222.1974
• EINECS: 252-453-0
• Mol File: 35234-88-9.mol
• Article Data: 11

Chemical Properties

• Melting Point: 114-118 °C(lit.)
• Boiling Point: 337.3°Cat760mmHg
• Flash Point: 147.1°C
• Appearance: /
• Density: 1.23g/cm³
• Vapor Pressure: 0.000106mmHg at 25°C
• Refractive Index: 1.482
• CAS DataBase Reference: DIETHYL DICYANOFUMARATE, 97(CAS DataBase Reference)
• NIST Chemistry Reference: DIETHYL DICYANOFUMARATE, 97(35234-88-9)
• EPA Substance Registry System: DIETHYL DICYANOFUMARATE, 97(35234-88-9)

Safety Data

• Hazard Codes: Xn
• Statements: 20/21/22
• Safety Statements: 26-27-36-36/39
• Hazardous Substances Data: 35234-88-9(Hazardous Substances Data)

Usage

Synthesis Reference(s)

Synthetic Communications, 22, p. 3169, 1992 DOI: 10.1080/00397919208021130

InChI:InChI=1/C10H10N2O4/c1-3-15-9(13)7(5-11)8(6-12)10(14)16-4-2/h3-4H2,1-2H3/b8-7+

Upstream product

• 105-56-6 ethyl 2-cyanoacetate 
• 1187-46-8 ethyl bromocyanoacetate 
• 81852-22-4 ethyl cyano<thio>acetate 
• 7446-08-4 selenium(IV) oxide 
• 13280-85-8 ethyl 2,2-dibromo-2-cyanoacetate 
• 101342-43-2 methyl tricyanoethylenecarboxylate 
• 86290-00-8 diethyl 2,3-dicyanomaleate 
• 506-78-5 cyanogen iodide 
• 762-21-0 acetylenedicarboxylic acid diethyl ester 

Downstream Products

• 6174-95-4 1,1,2,2-tetracarboethoxy-ethylene 
• 92166-39-7 (E)-N-<1,2-dicyano-2-(ethoxycarbonyl)vinyl>-4-methylaniline 
• 97834-81-6 (Z)-N-<2-cyano-1,2-bis(ethoxycarbonyl)vinyl>-4-methylaniline 
• 92044-65-0 (E)-4-chloro-N-<1,2-dicyano-2-(ethoxycarbonyl)vinyl>aniline 
• 97525-68-3 (Z)-4-chloro-N-<2-cyano-1,2-bis(ethoxycarbonyl)vinyl>aniline 
• 55260-59-8 2,3-Dicyano-2-(4,4-dimethyl-2,6-dioxo-cyclohexyl)-succinic acid diethyl ester 
• 92166-59-1 N-<4-Methoxy-phenyl>-trans-α.β-dicyano-β-ethoxycarbonyl-vinylamin 
• 97833-91-5 N-<4-Methoxy-phenyl>-trans-α.β-diethoxycarbonyl-β-cyano-vinylamin 
• 93996-19-1 4-(α.β-Dicyano-α.β-diethoxycarbonyl-ethyl)-N.N-dimethyl-anilin 
• 92256-56-9 4,5-Dicyano-4,5-diaethoxycarbonyl-cyclohexen 
• 93004-40-1 N-<3-Nitro-phenyl>-trans-α,β-dicyano-β-aethoxycarbonyl-vinylamin 
• 98578-59-7 4-(α.β-Dicyano-α.β-diethoxycarbonyl-ethyl)-N.N-diethyl-anilin 
• 92870-65-0 1-Methyl-4,5-dicyano-4,5-diaethoxycarbonyl-cyclohexen 
• 89731-02-2 3-(Cyano-carbethoxy-methyl)-2-phenyl-pyrrol 

Relevant articles and documents

Ester-Substituted Electron-Poor Alkenes for Cycloaddition-Retroelectrocyclization (CA-RE) and Related Reactions

We report the reactions of electron-deficient alkenes, tetrasubstituted by carboxylic ester and cyano groups, with electron-rich (dimethylamino)phenyl-substituted alkynes. Mono- or diester-substituted alkenes exclusively undergo the [2+2] cycloaddition-retroelectrocyclization (CA-RE) reaction, well established for multicyanated ethenes, whereas tri- and tetraester-substituted alkenes also undergo a [4+2] hetero-Diels-Alder (HDA) reaction with a third product being formed, presumably by a [3+2] cycloaddition reaction followed by rearrangement. Electrochemical studies revealed cathodic shifts of the first reduction potential of the buta-1,3-dienes obtained from the CA-RE reaction as cyano groups are substituted for ester moieties. Post-CA-RE functionalization of the ester-substituted buta-1,3-dienes by transesterification, diazonium chemistry, and cross-coupling is described. The formation of a pharmacologically interesting pyrazolopyran illustrates the synthetic utility of ester-substituted CA-RE products.

An unexpected reaction of diethyl phosphite with electron-deficient dialkyl dicyanofumarates

Diethyl phosphite reacts with both dimethyl dicyanofumarate and dicyanomaleate in boiling 1,2-dichloroethane to yield, after chromatographic workup, a 1:1-mixture of the corresponding meso- and dl-dicyanosuccinates. The analogous transformation was observed in the cases of diethyl and diisopropyl dicyanofumarates. A reaction pathway via initial formation of a P-C bond followed by its hydrolytic cleavage is proposed.

Cyclopropanation of electron-deficient alkenes with activated dibromomethylene compounds mediated by lithium iodide or tetrabutylammonium salts

Reactions of electron-deficient alkenes with dibromomethylene compounds activated by cyano and ester groups were promoted by LiI or tetrabutylammonium bromide to afford the corresponding cyclopropanes in high yields.