Molecular rearrangements. 14. Photolysis and thermolysis of phenylpropionanilides

Highly Powerful and Practical Acylation of Alcohols with Acid Anhydride Catalyzed by Bi(OTf)3

“…The following acetates are commercially available: 1 , 4 , 5 , 7 , 8 , 19 , and 28 . The following alcohols have been reported as acylated forms: acetate; 2 , 3 , 9 , 11 , 12 , 13 , 14 , 15 , 16 , 20 , 21 , 22 , 24 ,3e and 25 : benzoate; 1 , 31 , 32 , 33 3e and 34 : pivalate; 1 , 2 , 3 , 7 , 8 , 19 , 21 , 31 , 35 , and 38 …”

“…Propargyl alcohol (25) was synthesized by reaction of cyclohexanone with magnesiumphenyl acetylide prepared from phenylacetylene and methylmagnesium bromide. Homoallyl alcohol (27) was prepared from the reaction of phenylbutanone with allylmagnesium bromide. Other alcohols were prepared according to literature methods: 10, 13 26, 14 29, 15 and 30.…”

Production of Amidinyl Radicals via UV–Vis-Light Promoted Reduction of N-Arylthiophene-2-carboxamidoximes and Application to the Preparation of Some New N-Arylthiophene-2-carboxamidines

“…50 Besides, thiophene-2-carboxamide 8, m/e 127, and aniline (9I−IV), m/e 93, 127, 107, and 123, respectively, were afforded through the interaction of former radicals with ammonia, which was abundant in the reaction medium. 51 It is worth mentioning that another pathway involves the homolysis of the C−N bond (route ii) via a tautomeric form of target compounds (I−IV) as reported by Tiemann and Kruger 52 to form thiophene-2-iminoxyl and anilino radicals. Thiophene-2-carbonitrile 10, m/e 109, was formed through further photofragmentation thiophene-2-iminoxyl, whereas the aniline derivatives (9I−IV), m/e 93, 127, 107, and 133, respectively, were formed by the abstraction of hydrogen radical from a suitable source in the reaction medium.…”

“…A new route for photofragmentation of N -arylthiophene-2-carboxamide ( 3I–IV ) is the homolysis of the C–C bond (route iii) via the α-cleavage “Norrish type I reaction” which lead to N -aryl formamidyl and 2-thienyl radicals. , The N -arylformamidyl radicals may couple with hydrogen radical in the reaction medium to afford N -aryl formamides ( 6I–IV ), m / e 121, 155, 135, and 151, respectively, which follow by oxidative dehydrogenation to form phenyl isocyanates ( 7I–IV ), m / e 119, 153, 133, and 149, respectively. , 2-Hydroxythiophene 5 was formed by the interaction of 2-thienyl radical with hydroxyl radical, which was readily available in the reaction medium . Besides, thiophene-2-carboxamide 8 , m / e 127, and aniline ( 9I–IV ), m / e 93, 127, 107, and 123, respectively, were afforded through the interaction of former radicals with ammonia, which was abundant in the reaction medium …”

Investigation of Thermolysis Products of Some N‐Arylthiophene‐2‐carboxamidoximes by Analytical and Spectroscopic Analyses

“…On the other hand, Scheme explains further fragmentation of N ‐arylthiophene‐2‐carboxamides ( 5 a‐d ) under the same conditions through homolysis of C‐N bond pathway ( ii ) to form thiophene‐2‐carboxylic acid ( 7 ) m/e 128, thiophene‐2‐carboxamide ( 9 ) m/e 127 and 2,2′‐thenil ( 8 ) m/e 222 through thienyl and anilino derivatives radical pairs. The earlier products ( 7, 8 and 9 ) were formed from the coupling of thienyl radical with hydroxyl, dimerization of thienyl radical and reaction of N ‐arylthiophene‐2‐carboxamides ( 5a‐d ) with ammonia which abundant in the reaction medium, successively (Table ).…”