20434-13-3

Upstream product

• 24648-07-5 2-Phenyl-1,3,3-trichlorocyclopropene 
• 6262-42-6 1,2,3,3-tetrachlorocyclopropene 
• 71-43-2 benzene 
• 1600-39-1 2-hydroxy-3-phenylcyclopropenone 

Downstream Products

• 137124-26-6 2-Pentafluorophenylamino-3-phenyl-cycloprop-2-enone 
• 137124-29-9 2-Phenyl-3-piperidin-1-yl-cycloprop-2-enone 
• 137124-25-5 2-phenyl-3-(N-phenylamino)cyclopropenone 
• 61077-48-3 2-(diisopropylamino)-3-phenylcycloprop-2-en-1-one 
• 34251-46-2 N,N-diisopropylphenylacetamide 
• 102459-18-7 N,N-dibenzyl-2-phenylacetamide 
• 32907-84-9 N-methyl-N-(phenylethynyl)aniline 
• 2431-96-1 N,N-diethylphenylacetamide 
• 717-78-2 2-(diethylamino)-3-phenylcycloprop-2-en-1-one 
• 1600-39-1 2-hydroxy-3-phenylcyclopropenone 

Relevant academic research and scientific papers

Efficiency Enhancement of a Photocatalytic Decarbonylation of an Aminocyclopropenone by Benzothiophene Substitution

To improve the efficiency of the photocatalytic decarbonylation of cyclopropenones, the effects of substituents on cyclopropenone were explored. A benzothiophene-substituted aminocyclopropenone exhibited significantly improved decarbonylation efficiency t

Phototriggered Dehydration Condensation Using an Aminocyclopropenone

A phototriggered dehydration condensation using an aminocyclopropenone has been developed. The UV irradiation of an aminocyclopropenone generated a highly reactive ynamine in situ and the dehydration condensation of a carboxylic acid and an amine coexisting in the reaction solution smoothly proceeded to afford an amide. This reaction is completely controllable by the ON/OFF states of a UV lamp.

Development of a catalytic platform for nucleophilic substitution: Cyclopropenone-catalyzed chlorodehydration of alcohols

Cyclopropenone makes the switch: 2,3-Bis-(p-methoxyphenyl)cyclopropenone is a highly efficient catalyst for the chlorodehydration of 20 diverse alcohol substrates (see scheme; X=Cl). With oxalyl chloride as catalytic activator, this nucleophilic substitution proceeded through cyclopropenium-activated intermediates and resulted in complete stereochemical inversion in substrates with chiral centers.

Highly efficient photochemical generation of a triple bond: Synthesis, properties, and photodecarbonylation of cyclopropenones

UV irradiation of alkyl-, aryl-, and heteroatom-substituted cyclopropenones results in the loss of carbon monoxide and the formation of quantitative yields of corresponding alkynes. The quantum yield of the photochemical decarbonylation reaction ranges from 20% to 30% for alkyl-substituted cyclopropenones to above 70% for the diphenyl- and dinaphthylcyclorpopenones. Rapid formation (5 ns) and then a somewhat slower decay (ca. 40 ns) of an intermediate in this reaction was observed by using laser flash photolysis. The DFT calculations allowed us to identify this intermediate as a zwitterionic species formed by a cleavage of one of the carbon-carbon bonds of the cyclopropenone ring. The latter then rapidly loses carbon monoxide to produce the ultimate acetylenic product. Despite their high photoreactivity, cyclopropenones were found to be thermally stable compounds with the exception of hydroxy- and methoxy-substituted cyclopropenones. The latter undergo rapid solvolysis in hydroxylic solvents even at room temperature. The application of this reaction to the in situ generation of the enediyne strucutre was illustrated by the photochemical preparation of benzannulated enediyne 12.

Flash photolytic generation of primary, secondary, and tertiary ynamines in aqueous solution and study of their carbon-protonation reactions in that medium

A group of nine phenylynamines (PhC≡CNH2, PhC≡CNHCH(CH3)2, PhC≡CNHC6H11, PhC≡CNHC6H5, PhC≡CNHC6F5, PhC≡CN(CH2)5, PhC≡CN(CH2CH2)2O, PhC≡CN(CH2CH2CN)2, and PhC≡CN(CH3)C6F5) were generated in aqueous solution by flash photolytic decarbonylation of the corresponding phenylaminocyclopropenones, and the kinetics of their facile decay in that medium were studied. This decay is catalyzed by acids for all ynamines-primary, secondary, and tertiary-and also by bases for primary and secondary ynamines. Solvent isotope effects and the form of acid-base catalysis show that the acid-catalyzed path involves formation of keteniminium ions by rate-determining proton transfer to the β-carbon atoms of the ynamines. The ions generated from primary and secondary ynamines then lose nitrogen-bound protons to give ketenimines, and the ketenimines obtained from secondary ynamines are hydrated to phenylacetamides, whereas that from the primary ynamine tautomerizes to phenylacetonitrile. Keteniminium ions formed from tertiary ynamines have no nitrogen-bound protons that can be lost, and they are therefore captured by water instead, and the amide enols thus produced then ketonize to phenylacetamides. The base-catalyzed decay of primary and secondary ynamines also generates ketenimines, but protonation on the β-carbon is now preceeded by proton removal from nitrogen. Rate constants for β-carbon protonation of PhC≡CNHCH(CH3)2 and PhC≡CN(CH2)5 by a series of carboxylic acids give linear Bronsted relations with exponents α = 0.29 and 0.28, respectively, whereas inclusion of literature data for protonation of PhC≡CN-(CH2)5 by a group of weaker acids gives a curved Bronsted relation whose exponent varies from 0.25 to 0.97. Application of Marcus rate theory to this curved Bronsted relation produces the intrinsic barrier ΔG((+))(o) = 3.26 ± 0.19 kcal mol-1 and the work term w(r) = 8.11 ± 0.15 kcal mol-1.