20098-66-2

Upstream product

• 19329-22-7 (+/-)-5c-phenyl-4,5-dihydro-1H-pyrazole-3,4r-dicarboxylic acid dimethyl ester 
• 19329-22-7 (+/-)-5t-phenyl-4,5-dihydro-1H-pyrazole-3,4r-dicarboxylic acid dimethyl ester 
• 67-56-1 methanol 
• 19952-66-0 (1RS,2RS,3RS)-3-Phenylcyclopropane-1,2-dicarboxylic acid 
• 103548-67-0 (Dimethylsulfuranyliden)essigsaeure-methylester 
• 103-26-4 Methyl cinnamate 
• 96-34-4 methyl chloroacetate 
• 98-87-3 benzylidene dichloride 
• 624-48-6 dimethyl cis-but-2-ene-1,4-dioate 
• 624-49-7 dimethylfumarate 
• 19329-23-8 (+/-)-4t-phenyl-4,5-dihydro-1H-pyrazole-3,5r-dicarboxylic acid dimethyl ester 
• 186581-53-3 diazomethane 
• 908094-04-2 phenyldiazomethane 
• 733-14-2 Diethyl (1RS,2RS,3RS)-3-Phenylcyclopropane-1,2-dicarboxylate 

Downstream Products

• 19952-66-0 (1RS,2RS,3RS)-3-Phenylcyclopropane-1,2-dicarboxylic acid 
• 119945-23-2 C₁₁H₈O₄^(2-)*2K⁽¹⁺⁾ 
• 119908-70-2 C₁₁H₁₄N₄O₂ 

Relevant academic research and scientific papers

Cyclopropane formation by nickel-catalysed electroreductive coupling of activated olefins and unactivated gem-dibromo compounds

Cyclopropyl derivatives have been prepared with good yields by transition-metal catalysed electroreductive coupling of activated olefins and unactivated gem-dibromo compounds. This electrolysis is characterized by the use of a Fe/Ni catalyst system, acetonitrile as the solvent and a catalytic amount of triphenylphosphine as ligand. This procedure is a good alternative to the classical preparations of cyclopropyl derivatives from activated olefins (Simmons-Smith reaction, 1,3-dipolar addition of diazomethane, 1,4-addition of phosphorus and sulfur ylides).

Cyclopropane formation by copper-catalysed indirect electroreductive coupling of activated olefins and activated α,α,α-trichloro or gem-dichloro compounds

Cyclopropanes have been prepared in good yields by indirect electroreductive coupling of activated olefins and activated α,α,α-trichloro or gem-dichloro compounds (Cl3CCO2Me, PhCCl3, Ph2CCl2, PhCHCl2). This process, using a copper complex in catalytic amountss is convenient for the reagent couple activated olefin/activated polyhalide, whatever the reduction potential of each reagent relative to each other. The main advantage of our electrochemical process is that it does not require the use of hazardous, toxic, or not easily prepared reagents like diazocompounds or diazirines.

Cyclopropane formation by electroreductive coupling of activated olefins and gem-polyhalo compounds

Cyclopropyl derivatives have been prepared with satisfactory yields by electroreductive coupling of activated olefins and gem-polyhalo compounds. The reaction is efficient when the olefin is more easily reduced than the organic halide. Two types of interm

Reactions of stabilized sulfur ylides with α,β-unsaturated alkoxychromiumcarbene complexes

Reaction of stabilized sulfur ylides with α,β-unsaturated alkoxy-chromiumcarbene complexes in MeCN as solvent forms vinylenol ethers 3, cyclopropanes 4, and vinylcyclopropanes 5, depending on the reagent ratio, the temperature and the nature of the ylide. The results obtained in these reactions suggest that factors apart from steric hindrance may control the chemoselectivity of the addition. Less stable ylides would add preferentially to the carbene carbon, 1,4-addition increasing as the stability of the ylide does. For more stable ylides 1,4-addition is preferred and substitution at the β-carbon has little effect in the chemoselectivity. Methoxycarbonylmethylentriphenylphosphorane exclusively add to the carbene carbon while ethyl diazoacetate is unreactive towards α,β-unsaturated alkoxychromium-carbene complexes in the conditions studied.

184. Stereoselective Hydrolysis of Substituted Cyclopropanedicarboxylates with Pig Liver Esterase

The hydrolysis of the meso-cyclopropane-1,2-dicarboxylates 1a-3a, 4, 5a, 6a, and 9, containing various substituents at C(3), and of the rac-3-phenylcyclopropane-1,2-dicarboxylates 7a, 8a, and 10 with pig liver esterase (PLE) is described.The stereoselectivity and absolute configurations of the products were determined.An interpretation of results was attempted on the basis of a recent active-site model for PLE.

Cyclopropanediamines, 3. - Pure Diastereomers of 1,2-Cyclopropanedicarboxylic Acids and Derivatives

Efficient preparations of pure diastereomers of dimethyl 1,2-cyclopropanedicarboxylates 2, dicarboxylic acids 3, dicarbonyl dichlorides 4, and dihydrazides 5 are reported.Mixtures of diastereomers of dimethyl dicarboxylates 2a, b, d, e are obtained from α,β-unsaturated methyl carboxylates 7 and methyl α-chlorocarboxylates 8 as well as from 7c, d and the sulfur ylide 10 (2c, d).The diastereomers are separated by fractionating distillations (2a, b, c, e) or crystallization (2d) on a 100-g to 1-kg scale (d.e. >99percent).Only low yields of 2c are obtained in the reaction of methyl crotonate (7c) with methyl α-chloroacetate (8a), since 7c predominantly dimerizes to afford 12.The diesters 2 are converted into the pure diastereomeric diacids 3, dicarbonyl dichlorides 4, and dihydrazides 5. 3,3-Dimethyl-cis-1,2-cyclopropanedicarboxylic acid (cis-3f) is obtained by trans-->cis isomerization of trans-3f with the help of acetic anhydride and sodium acetate as catalyst.The configurations of 2-6 and 12 are confirmed by 1H NMR spectroscopy.Derivatives of cis-1,2-dimethyl-1,2-cyclopropanedicarboxylic acid tend to form bicyclic products.Thus, the reaction of cis-3e with phosphorus pentachloride yields mainly the cyclic anhydride 6e and only small amounts of the dicarbonyl dichloride cis-4e.Furthermore, the dihydrazide cis-5e slowly cyclizes in the solid state to give the N-aminoimide 13 and hydrazine, a reaction which is fast in solution.Pure 13 is obtained by thermolysis of cis-5e at 60-65 deg C under high vacuum.

CYCLOPROPANATION OF DIMETHYL FUMARATE AND MALEATE WITH GEM-DIHALIDES CATALYZED BY Co(0)- OR Ni(0)-COMPLEX AND ZINC.

The reaction of bis(acetonitrile)bis(diethyl fumarate)cobalt(0) with dibromomethane gave diethyl trans-1,2-cyclopropanedicarboxylate in a 67% yield based on the cobalt complex. Dimethyl cis-1,2-cyclopropanedicarboxylate was obtained in a 52% yield from the reaction of dimethyl maleate with dibromomethane in the presence of acetonitrilebis(dimethyl maleate)nickel(0) accompanied by the formation of the trans-isomer in a 14% yield. The addition of zinc gave cyclopropanes in over 100% yields based on cobalt or nickel. 3-Methyl- and 3,3-dimethyl-1,2-cyclopropanedicarboxylic acid esters were produced by the reaction of dimethyl fumarate or maleate with 1,1-dibromoethane and 2,2-dibromopropane. The yield in the cobalt catalyst system decreases with an increase of substituents of gem-dibromides, while that in the nickel catalyst system does not vary appreciably.