Page 1016 - Advanced Organic Chemistry Part B - Reactions & Synthesis

992 1) NOCl
2) hν
CHAPTER 10
OH N OH
Reactions Involving (CH ) CH 3 HO
2 3
2 3
Carbocations, Carbenes, (CH ) CH 3
and Radicals as Reactive
Intermediates Ref. 380
These reactions depend on the proximity of the alkoxy radical to a particular hydrogen
for selectivity.

Problems
(References for these problems will be found on page 1287.)

10.1. Indicate the major product to be expected in the following reactions:
+
(a) PhCH 2 N(C 2 H 5 ) 3 Cl (b) O
+ CHCl 3 C 7 H 10 Cl 2 Δ
NaOH, H 2 O + CH 3 OCN 3 C 12 H 19 NO 2
(c)
n-BuLi (d)
CH 3 CH 3 80°C
C 7 H 12 F 2
+ CFCl 3 + PhHgCF 3 C 9 H 14 F 2
–120°C
CH 3 12 h
CH 3
(e) O
(f)
CH 3 CH 3 Rh 2 (OAc) 4
NaOCH 3 C 13 H 18 O 3
C 6 H 10 + N 2 CHCCOC(CH 3 ) 3
CH NNHTs
CH 3
O
(g) O (h) O
PhCHCCH 2 CH 3 + CH 3 O – C 11 H 14 O 2 CCl + CH 2 N 2 C 6 H 4 N 2 O 2
O
Cl
OH
(i) (j) H 5 C 2
Δ
N N C 5 H 10 (two products) NaH
nitrobenzene C 14 H 24 O 2
H C(CH 3 ) 3 ArSO 2 O
OH
H 5 C 2 CH 3
(k)
(CH 3 ) 2 C CHCH 2 [CH 2 H 1) Hg(O 3 SCF 3 ) 2 /PhN(CH 3 ) 2
2) NaCl
C 20 H 34 O 2
CH 3 CH 2 CH 2 ] 3 O 2 CCH 3
3) NaBH 4
O
(l)
(m)
CH 3 CO
N (CH 3 ) 3 SiO 3 SCF 3 C 11 H 19 N CH 3 K + – OC(CH 3 ) 3
10 mol % ArSO 2 O C 11 H 16 O
C 5 H 11
OH
Si(CH 3 ) 3
(n)
O (o) CH 3
N
Rh 2 (O 2 CCH 3 ) 4
(CH 3 ) 2 CHCH 2 CH 2 CCCO 2 CH 3
C 9 H 14 O 3 PCl 5 C 14 H 16 N 2
N
N 2
CH 3
OH
380
E. J. Corey, J. F. Arnett, and G. N. Widiger, J. Am. Chem. Soc., 97, 430 (1975).