Chem., 27, 60 (1962). Comparable lactone absorptions for related systems are reported. (17) The ir and nmr data were identical with those of an authentic sampie of this compound prepared according to the procedure described by R. Criegee, E. Vogel, and H. Hoger, Chem.E l e c t r o p h i l i c bromination, iodination, a n d chlorination o f phenylallene a n d i t s derivatives were carried o u t u n d e r various reaction conditions. Products were exclusively monoadducts a n d t h e ratios o f 1,2 t o 2,3 adducts were determined b y pmr spectroscopy. B r o m i n a t i o n in m e t h a n o l gave exclusively a 1,2-bromomethoxide a t -70" w h i l e it resulted in t h e f o r m a t i o n o f t h e 2,3 a d d u c t as w e l l a t 0". B r o m i n a t i o n in carbon disulfide yielded b o t h 1,2-a n d 2,3-dibromides a t -70" but t h e former rearranged completely t o t h e l a t t e r a t 0". T h e fraction o f a 1,2 a d d u c t decreased w i t h t h e electron-donating a b i l i t y o f a substituent o f phenylallene derivatives in t h e b r o m i n a t i o n in m e t h a n o l a t 0". I o d i n a t i o n t e n d e d to give more 1,2 a d d u c t a n d chlorination less 1,2 adduct. T h e former reaction gave exclusively a 1,2 a d d u c t in m e t h a n o l even a t 0". T h e p r o d u c t ratios are considered t o be determined by t h e s t a b i l i t y o f t h e i n i t i a l l y f o r m e d 1,2-halonium i o n a n d t h e r e a c t i v i t y o f a nucleophile.We have previously investigated the hydrochlorination2 and the sulfenyl chloride addition1 of phenylallene and its derivatives. It was concluded that the hydrochlorination involves the rate-determining protonation a t the central carbon to form a perpendicularly twisted vinylbenzyl cation which easily leads to a conjugated cinnamyl cation by the bond rotation.2 That is, the reaction takes place uia Hf HOAc + C6H;CH=C=CH2
Phenylallen (I) wird der Halogenierung, z.B. in Gegenwart von Methanol, unterworfen und hierbei werden bei niederen Temperaturen die 1,2‐Acldukte (II) erhalten, die bereits bei Raumtemperatur in 2,3‐Addukte (III) übergehen.
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