trans-β-Chlorovinyl Ketones and trans-(β-Acylvinyl)trimethylammonium Chlorides^1,2

Abstract

When acid chlorides were added to acetylene in the presence of aluminum chloride, irons-jS-chlorovinyl ketones were formed as shown by n.m.r. spectra. When these ketones were treated with trimethylamine in an inert solvent, a series of /3-acylvinyltrimethylammonium chlorides were formed which gave complete retention of the trans configuration. The ultraviolet and infrared spectra of these systems were examined and indicated the C-C-C=0 system to be most likely in the transoid conformation.

Photochemistry of 4- and 5- phenyl substituted isoxazoles

“…5-Phenylisoxazole (4) was prepared by reaction of 3-oxo-3-phenylpropionaldehyde oxime with acetyl chloride [33]; 4-methyl-5-phenylisoxazole (10) by reaction of 2-benzoylpropanal with hydroxylamine hydrochloride [34]; 4-phenylisoxazole (22) by condensation of N,N-dimethylformamide and phenylacetic acid in the presence of phosphorus oxychloride [36] and treatment of the resulting 3-(N,N-dimethylamino)-2-phenylpropenal with hydroxylamine hydrochloride [37]; 5-methyl-4-phenylisoxazole (23) by reaction of 3-oxo-2-phenylbutanal with hydroxylamine [35]; 5-phenyl-3-(trifluoromethyl)isoxazole (16) by condensation of 4-phenyl-1,1,1-trifluorobut-3-yne-2-one with hydroxylamine hydrochloride [38]; 3-azido-1-phenylpropen-1-one (41) by reaction of 3-chloro-1-phenyl-2-propen-1-one [39] with sodium azide in methanol [40]; 5-phenyloxazole (5) by reaction of benzaldehyde with tosylmethylisocyanide [41]; 3-phenylisoxazole (6) by reaction of benzhydroximidoyl chloride [42] with triethylamine in the presence of acetylene [43]; 4-phenyloxazole (8) by reaction of α-bromoacetophenone with formamide [44]; 4-methyl-5-phenyloxazole (11), by the reaction of benzaldehyde with α-tosylethylisocyanide [41,44]; cyanophenylacetaldehyde by condensation of benzylcyanide and ethyl formate in the presence of sodium ethoxide [45]; α-benzoylpropionitrile (15) by condensation of propionitrile and methylbenzoate in the presence of sodium methoxide [46]; 2-phenylacetoacetonitrile (26) by condensation of benzylcyanide and ethylacetate in the presence of sodium ethoxide.…”

Photochemistry of 4‐ and 5‐Phenyl Substituted Isoxazoles.

“…Synthesis of Reactants and Possible Products. (4) was prepared by reaction of 3-oxo-3phenylpropionaldehyde oxime with acetyl chloride [33]; 4-methyl-5-phenylisoxazole (10) by reaction of 2-benzoylpropanal with hydroxylamine hydrochloride [34]; 4-phenylisoxazole (22) by condensation of N,N-dimethylformamide and phenylacetic acid in the presence of phosphorus oxychloride [36] and treatment of the resulting 3-(N,N-dimethylamino)-2-phenylpropenal with hydroxylamine hydrochloride [37]; 5-methyl-4-phenylisoxazole (23) by reaction of 3-oxo-2-phenylbutanal with hydroxylamine [35]; 5phenyl-3-(trifluoromethyl)isoxazole (16) by condensation of 4-phenyl-1,1,1-trifluorobut-3-yne-2-one with hydroxylamine hydrochloride [38]; 3-azido-1-phenylpropen-1-one (41) by reaction of 3-chloro-1-phenyl-2-propen-1-one [39] with sodium azide in methanol [40]; 5-phenyloxazole (5) by reaction of benzaldehyde with tosylmethylisocyanide [41]; 3-phenylisoxazole (6) by reaction of benzhydroximidoyl chloride [42] with triethylamine in the presence of acetylene [43]; 4-phenyloxazole (8) by reaction of αbromoacetophenone with formamide [44]; 4-methyl-5-phenyloxazole (11), by the reaction of benzaldehyde with α-tosylethylisocyanide [41,44]; cyanophenylacetaldehyde by condensation of benzylcyanide and ethyl formate in the presence of sodium ethoxide [45]; α-benzoylpropionitrile (15) by condensation of propionitrile and methylbenzoate in the presence of sodium methoxide [46]; 2-phenylacetoacetonitrile (26) by condensation of benzylcyanide and ethylacetate in the presence of sodium ethoxide. 4-Deuterio-5-Phenylisoxazole (4-4d).…”

One-Pot Synthesis of (Z)-β-Halovinyl Ketones via the Cascade of Sonogashira Coupling and Hydrohalogenation

“…Similar strategies have been developing relying on transitionmetal (rhodium and iridium catalyst) (Kokubo et al, 1996;Hua et al, 2005;Kashiwabara et al, 2005Kashiwabara et al, , 2008Goossen et al, 2009;Iwai et al, 2009Iwai et al, , 2012Kashiwabara and Tanaka, 2011), or Lewis acid (Price and Pappalardo, 1950;Benson and Pohland, 1964;Martens et al, 1975;Zhou et al, 2006;Wang et al, 2010;Hosseini-Sarvari and Mardaneh, 2011;Gandeepan et al, 2012;Koo et al, 2019b). However, these developed methods usually require relatively harsh reaction conditions, such as elevated temperature, long reaction time, use of expensive ligands or catalysts.…”