Most of what we know about the structure of atoms and molecules comes from studying their interaction with light (electromagnetic radiation). Different regions of the electromagnetic spectrum provide different kinds of information as a result of such interactions. Electronic Spectroscopy: Theory Electronic Spectroscopy: Application Electronic Spectroscopy: Interpretation Rotational Spectroscopy of Diatomic Molecules Photoelectron Spectroscopy: Application Photoelectron Spectroscopy: Theory
If E is a strong electrophile, as in the first equation, it will attack the nucleophilic oxygen of the carboxylic acid directly, giving a positively charged intermediate which then loses a proton. If E is a weak electrophile, such as an alkyl halide, it is necessary to convert the carboxylic acid to the more nucleophilic carboxylate anion to facilitate the substitution. The reaction is easily followed by the evolution of nitrogen gas and the disappearance of the reagent's color.
The stereoselectivity of Brønsted acid addition is sensitive to experimental conditions such as temperature and reagent concentration. The selectivity is often anti, but reports of syn selectivity and non-selectivity are not uncommon. Of all the reagents discussed here, these strong acid additions (E = H in the following equation) come closest to proceeding by the proposed two-step mechanism in which a discrete carbocation intermediate is generated in the first step.
We can account both for the high stereoselectivity and the lack of rearrangement in these reactions by proposing a stabilizing interaction between the developing carbocation center and the electron rich halogen atom on the adjacent carbon. The positive charge is delocalized over all the atoms of the ring, but should be concentrated at the more substituted carbon (carbocation stability), and this is the site to which the nucleophile will bond.
Since boron is electron deficient (it does not have a valence shell electron octet) the reagent itself is a Lewis acid and can bond to the pi-electrons of a double bond by displacement of the ether moiety from the solvated monomer. Indeed, this hydride shift is believed to occur concurrently with the initial bonding to boron, as shown by the transition state drawn below the equation, so the discrete intermediate shown in the equation is not actually formed.
The resulting amine substituent strongly activates an aromatic ring and directs electrophilic substitution to ortho & para locations. (iii) The activating character of an amine substituent may be attenuated by formation of an amide derivative (reversible), or even changed to deactivating and meta-directing by formation of a quaternary-ammonium salt (irreversible). (iv) Conversion of an aryl amine to a diazonium ion intermediate allows it to be replaced by a variety of different groups (includin…
The radical addition process is unfavorable for HCl and HI because one of the chain steps becomes endothermic (the second for HCl & the first for HI). RCH 2 (CH 3 )CH· + CH 3 CH=CH 2 —> RCH 2 (CH 3 )CH-CH 2 (CH 3 )CH· + CH 3 CH=CH 2 —> RCH 2 (CH 3 )CHCH 2 (CH 3 )CH-CH 2 (CH 3 )CH· —> etc.
A non-catalytic procedure for the syn-addition of hydrogen makes use of the unstable compound diimide, N 2 H 2 . This reagent must be freshly generated in the reaction system, usually by oxidation of hydrazine, and the strongly exothermic reaction is favored by the elimination of nitrogen gas (a very stable compound).
If, for example, we wish to carry out an S N 2 reaction of an alcohol with an alkyl halide to produce an ether (the Williamson synthesis), it is necessary to convert the weakly nucleophilic alcohol to its more nucleophilic conjugate base for the reaction to occur. If a 1:1 ratio of amine to alkyl halide is used, only 50% of the amine will react because the remaining amine will be tied up as an ammonium halide salt (remember that one equivalent of the strong acid HX is produced).