Page 1067 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

1051
hv
+ – PPh 2
NH PPh
Br 3(l ) 2 SECTION 11.6
S RN 1 Substitution
Processes
Ref. 222

hv
Br + – PPh 2 PPh 2
NH 3(l ) 87%

Ref. 223

Scheme 11.8. Aromatic Substitution by the S RN 1 Mechanism

hv
1 a CH 3 Br + – PPh 2 CH 3 PPh 2
57%

Br O PPh 3
Na(Hg) H O 2
2
2 b + NaPPh 2
NH 3(l ) , 25° C 60 – 66%
Br SPh
3 c + – SPh
92%
SPh
Br
O
hv
4 d I + (C H O) PO – P(OC H ) 96%
2 5 2
2
2 5
O – O
hv
5 e Br + CH 2 CC(CH ) CH CC(CH )
3 3
2
3 3
NH 3(l) 96%
–
O O
FeSO 4
6 f F I + CH 2 C N O F CH C N O
2
NH 3(l)
64%
a. J. E. Swartz and J. F. Bunnett, J. Org. Chem., 44, 340 (1979).
b. P. G. Mabzo, S. M. Palacios, R. A. Alonso, and R. A. Rossi, Org. Prep. Proc. Int., 27, 660 (1995).
c. J. E. Bunnett and X. Creary, J. Org. Chem., 39, 3611 (1974).
d. J. E. Bunnett and X. Creary, J. Org. Chem., 39, 3612(1974).
e. M. F. Semmelhack and T. Bargar, J. Am. Chem. Soc., 102, 7765 (1980).
f. M. van Leeuwen and A. McKillop, J. Chem. Soc., Perkin Trans. 1, 2433 (1993).
222 R. A. Rossi, S. M. Palacios, and A. N. Santiago, J. Org. Chem., 47, 4654 (1982).
223
R. A. Rossi, A. N. Santiago, and S. M. Palacios, J. Org. Chem., 49, 3387 (1984).