Page 978 - Advanced Organic Chemistry Part B - Reactions & Synthesis

954 Scheme 10.15. (Continued)

CHAPTER 10 OH O
11 k
Reactions Involving
Carbocations, Carbenes, (CH ) CONH PhI(O CCH ) O NH
2 2
2
3 2
2
and Radicals as Reactive
Intermediates CH CN,40°C
3
83%
O
12 l OH NBS
AgO CCH 3 O NH
2
OH
C H DMF 77%
7 15
OH
CONH 2 C 7 H 15
13 m PhCH 2 O C
PhCH O CNH 2
2
2
N PhI(O CCF ) N N
2
3 2
H 2 NOC O
pyridine, CH 3 CN N
N O H N O
50%
C. Schmidt reactions
NaN
14 n 3
PhCH CO H polyphosphoric PhCH NH 2
2
2
2
acid 67%
+
15 o CO H NH 3
2
NaN 3
H SO 4
2
3 3
(CH ) C C(CH 3 3 (CH ) C C(CH 3 ) 3 93%
)
3 3
16 p
NaN 3
NH
CF CO H
2
3
O O 59%
D. Beckmann Rearrangements
17 q NOH PhSO Cl O
) CNHCPh
(CH 3 ) 3 CCPh 2 (CH 3 3
NaOH 76%
O
CH 3
18 r
C NOH NHCCH 3
p-toluenesulfonyl
chloride
pyridine
H H 92%
19 s
H C polyphosphoric H 3 C
3
acid
NH
NOH
H H O 92%
20 t p-toluenesulfonyl O
O NOH chloride O
pyridine NH
91%
(continued)