Beruflich Dokumente
Kultur Dokumente
+ - -
c) CH3OH + K H CH3O + H2
pKa = 15.5 pKa = 38
2) Alkali Metal Reductions give Alkoxides
a) 2 H2O + Na (Li, K, Cs) 2 Na+OH- + H2 (Violent!)
b) 2 ROH + Na 2 Na+OR- + H2
c) Reactivity: MeOH > primary > secondary > tertiary
3) Uses of Alkoxides
a) Strong base for E2 reactions
b) Ether synthesis by SN2 reactions (stay tuned!)
H+ H
ROH R O R+ + H2O
H
3) Synthesis of Haloalkanes from Alcohols
HBr H Br-
ROH R O RBr + H2O
H
a) Only I- and Br- are nucleophilic enough to work
b) Works best for primary alcohols
4) Reaction of Secondary and Tertiary ROH with H+
a) Secondary and Tertiary alcohols easily lose water to from carbocations
b) If the acid contains a good nucleophile, you get SN1 substitution
H OH H Br
3) Mechanism H+ H OH2 H
Br -
-H2O
H H H H
secondary normal product
carbocation
hydride
a) H:- and + trade places shift
b) Very fast (faster than SN1/E1) - Br H
tertiary H Br
if new C+ more stable carbon
(more stable) H H
rearranged
product
4) Orbital Picture of the Hydride Shift Mechanism
H OH H OH2 H H
H2SO4 -H2O
+
o
130 C
H H H H OH2 H H
secondary normal products
carbocation
hydride
shift
H H
tertiary H
carbon +
Me H Me H Me H Me H
secondary normal product
carbocation Alkyl
shift
- Br Me
tertiary Me Br
carbon Me Me Me Me rearranged
product
(more stable) Me H Me H
2) Hydride and Alkyl Shifts occur at about the same rate
a) Very fast if rearranged carbocation is more stable
b) Formation of tertiary carbocation is faster than secondary
4) Mechanism
O
Nu
R OH R O S R' R Nu
O