Page 306 - Advanced Organic Chemistry Part B - Reactions & Synthesis

278 SOCl 2
ROH RCl
100°C
CHAPTER 3 Percent Structure and
Functional Group unrearranged amount of
Interconversion R RCl rearranged RCl
by Substitution,
CH 3 CH 2 CH 2 CH 2 100
Including Protection and 99.7
Deprotection (CH 3 ) 2 CHCH 2 (CH 3 ) 2 CHCH 3
100
Cl 0.3%
(CH 3 ) 2 CHCH 2 CH 2
78
CH 3 CH 2 CHCH 2 CH 3 CHCH 2 CH 2 CH 3 , CH 3 CH 2 CHCH 2 CH 3 , CH 3 CH 2 C(CH 3 ) 2
Cl 1% Cl 11% Cl 10%
CH 3
2
(CH 3 ) 3 CCH 2
CH CH C(CH )
3
2
3 2
98%
Cl
98
CH 3 CH 2 CH 2 CHCH 3
CH 3 CH 2 CHCH 2 CH 3
Cl 2%
90
CH 3 CH 2 CHCH 2 CH 3
CH 3 CH 2 CH 2 CHCH 3
Cl 10%
5
(CH 3 ) 2 CHCHCH 3
CH 3 CH 2 C(CH 3 ) 2
Cl 95%
3.4. Give a reaction mechanism that would explain the following observations and
reactions.
a. Kinetic measurements reveal that solvolytic displacement of sulfonate is about
5
5×10 faster for 4B than for 4A.
OSO Ar OSO Ar
2
2
O
O
4A 4B
b.

H N Br H H O
2
H HOAc Br N
CH CH CO CH 3
2
2
2
S H
S
H
c.
CH
+
CH 3 ) O PF – 3
CH 3 S C H 1) (CH 3 3 6 CH SCHCH C O CHC H
2
6 5
3
O 6 5
CH 2) NaCN
3
CH 3 CH 3 CN
d.
SOCl 2
C H CH SCH CHCH SCH C H C6H CH SCH CHCH Cl
6 5
2
2
2
5
2
2 6 5
2
2
OH SCH C H
2 6 5