CHAPTER

02 G.O.C

Electrophiles are electron deficient species. (B) Stability of free radical

E.g. H⊕, R⊕, NO⊕2, X⊕, PCl3, PCl5 (Ph)3C > (Ph)2CH > CH2 = CH – CH2 > PhCH2 > (CH3)3C
⊕
(NH4 and H3O⊕ are not electrophile) > (CH3)2CH > CH3CH2 > CH3
Nucleophiles are electron rich species. (C) Stability of carbanion
$ $ $ .. ..
E.g. Cl$, C H3, OH, RO$,C N, NH3, RO .. H, CH2= CH2, (Ph)3 C > (Ph)2 CH > Ph – CH2 > CH2 = CH – CH2 >
CH≡CH
CH3 > CH3 CH2 > (CH3)2 CH > (CH3)3 C
Relative electron withdrawing order (–I order)
⊕ ⊕ ⊕ Reactivity towards nucleophile (NAR)
–NF3 > –NR3 > –NH3 > –NO2 > –CN > –COOH > –X > – (1) HCHO > CH3CHO > (CH3)2CO
OR > –OH > –C≡CH > –NH2 > –C6H5 > –CH = CH2 (2) CCl3CHO > CHCl2CHO > CH2ClCHO
Relative electron releasing order (+I order)
 ™ Reactivity order towards acyl nucleophilic substitution
–N H > –O > –COO > 3° alkyl > 2° alkyl > 1° alkyl > reaction
–CH3
Acid chloride > anhydride > ester > amide
Relative Stability Order ™ Order of electronic effect
(A) Stability of carbocation Mesomeric > Hyperconjugation > Inductive effect
⊕ ™ Stability of alkene ∝ no. of a-hydrogen
⊕ ⊕ ⊕ ⊕
> (Ph)3 C > (Ph)2 C H > Ph – C H2 > CH2 = CH – C H2 R 2 C=CR 2 > R 2 C=CHR > R 2 C=CH 2 > RCH=CHR >
trans form
⊕ ⊕ ⊕ ⊕ ⊕ RCH=CHR > RCH=CH 2 > CH 2 =CH 2
> (CH3)3 C > (CH3)2 C H > CH3 C H2 > C H3 > CH2 = C H cis form
1
⊕ ™ Heat of hydrogenation ∝
> CH ≡ C Stability of alkene