Styrene, reaction with hydrogen bromide

A-8. Write the structures of the resonance forms that contribute to the stabilization of the intermediate in the reaction of styrene (C6H5CH=CH2) with hydrogen bromide in the absence of peroxides. 

In the presence of peroxides, hydrogen bromide adds to the double bond of styrene with a regioselectivity opposite to Markovnikov s nrle. The reaction is a free-radical addition, and the regiochemistiy is governed by preferential fonnation of the more stable radical. 

This is manifest in the reactivity of 180/180-Z1 which was generated from 3-bromo-41-f-pyran (283) by /3-elimination of hydrogen bromide with KOtBu (Scheme 6.61). Whether or not this reaction was conducted in the presence of styrene or furan, the only product identified was tert-butyl 4H-pyran-4-yl ether (284). This is in line with the relationship of the intermediate to a pyrylium ion. Thus, the addition of the tert-butoxide ion to 180/180-Zj has to be expected at the 4-position with formation of the vinyl anion 285, which is then protonated to give 284. Likewise, the attack of the nucleophile is predicted at C2and C6 leading to the vinyl anions 286, which... 

The preparation of styrene from a saturated compound is analogous to that of ethylene and its derivatives. When ethylbenzene is treated with bromine, the first product of the reaction has the structure CeHs.CHBr.CHs. This substance loses hydrogen bromide, when warmed with alcoholic potash —... 

Reetz et al. reported on catalytically active solvent-stabilized colloids in propylene carbonate, which were prepared electrochemically or by thermal decomposition of [Pd(OAc)2 assisted by ultrasound. The colloidal particles had sizes of 8 to 10 nm, as determined by TEM. After addition of aryl bromide, styrene, and base to the colloid solution, satisfactory conversions were obtained within reaction times of 5-20 h. Isolation of the particles stabilized by propylene carbonate was not possible, however [16]. The same authors also reported Suzuki and Heck reactions with electrochemically prepared Pd or Pd/Ni colloids stabilized by tetraalkylammonium, as well as polyvinylpyrrolidone (PVP)-stabilized palladium colloids prepared by hydrogen reduction (Table 1) [17]. It was assumed that the reaction occurs on the nanopartide surfaces. 

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