84681-08-3Relevant academic research and scientific papers
Dichlorocarbene from Flash Vacuum Pyrolysis of Trimethyl(trichloromethyl)silane. Possible Observation of 1,1-Dichloro-3-Phenyl Carbonyl Ylide
Gisch, John F.,Landgrebe, John A.
, p. 2050 - 2054 (2007/10/02)
Flash vacuum pyrolysis of trimethyl(trichloromethyl)silane 3 at 500-700 deg C was shown to be a simple and efficient method for the production of :CCl2 in the gas phase.The copyrolysis of silane 3 and benzaldehyde (7) at 600 deg C led to 1,1,1-trichloro-2-phenyl-2-(trimethylsiloxy)ethane (8), a 1:1 adduct, in addition to benzal chloride (15) and α-chlorophenylacetyl chloride (16), product thought to arise from 1,1-dichloro-3-phenyl carbonyl ylide 17 as outlined in Scheme I.An orange-red material trapped at deg K could be photobleached as well as thermally bleached and had an IR band at 1650 cm-1 and a si gnificant absorption with λmax 510 nm (and a broad shoulder at a 580 nm).
Selective Formation and Trapping of Dihalocarbonyl Ylides Derived from Dihalocarbenes and Substituted Benzaldehydes
Gill, Harpal S.,Landgrebe, John A.
, p. 1051 - 1055 (2007/10/02)
The thermal decompositions of several phenyl(trihalomethyl)mercury compounds in the presence of substituted benzaldehydes 1 and dimethyl acetylenedicarboxylate (7) in dry benzene at 80 deg C resulted in 2-halo-5-arylfuran-3,4-dicarboxylates 9 in isolated yields (not optimized) that ranged from 13percent to 64percent.These products appear to be the result of selective attack by dihalocarbene on the aldehyde followed by preferential capture of the resulting carbonyl ylide by the acetylenic dipolarophile and loss of hydrogen halide.The substitution of diethyl fumarate (12) for acetylene 7 produced a mixture of the E and Z isomers of dihydrofuran 14 in a ratio of 70:30.Tetrasubstituted dipolarophiles failed to give comparable products.The intermediate dihalocarbonyl ylides were shown to undergo halogen exchange.
SEQUENTIAL TRAPPING OF DICHLOROCARBENE AND DICHLOROCARBONYL YLIDES
Gill, Harpal S.,Landgrebe, John A.
, p. 5099 - 5102 (2007/10/02)
The thermal decomposition of phenyl(bromodichloromethyl)mercury in the presence of aryl aldehydes and dimethyl acetylenedicarboxylate leads to the formation of dimethyl 2-halo-5-arylfuran-3,4-dicarboxylates by selective trapping of the intermediate dihalocarbonyl ylides.
