Page 334 - Advanced Organic Chemistry Part B - Reactions & Synthesis

306 Scheme 4.2. Addition Reactions of Other Electrophilic Reagents

CHAPTER 4 Reagent Preparation Poduct
Electrophilic Additions a
to Carbon-Carbon 1 I N C O AgCNO, I 2 RCH CHR
Multiple Bonds
I NCO
+
2 b Br N N N – HN , Br 2 RCH CHR
3
Br N 3
+
3 c I N N N – NaN , ICl RCH CHR
3
I N 3
4 d I S C N (NCS) , I 2 RCH CHR
2
I S C N
5 e I ONO 2 AgNO , ICl RCH CHR
3
I ONO 2
6 f CI SCN Pb(SCN) , Cl 2 RCH CHR
2
CI SCN
7 g RCH CHR
N CS SC N Pb(SCN) , Br 2 RCH CHR and
2
N CS SC N N CS N C S
8 h O N Cl RC CHR
HON Cl
9 i O N O CH C 5 11 ONO RC CHR
H
2
HCO H
2
HON O 2 CH
a. A. Hassner, R. P. Hoblitt, C. Heathcock, J. E. Kropp, and M. Lorber, J. Am. Chem. Soc., 92, 1326 (1970); A.
Hassner, M. E. Lorber, and C. Heathcock, J. Org. Chem., 32, 540 (1967).
b. A. Hassner, F. P. Boerwinkle, and A. B. Levy, J. Am. Chem. Soc., 92, 4879 (1970).
c. F. W. Fowler, A. Hassner, and L. A. Levy, J. Am. Chem. Soc., 89, 2077 (1967).
d. R. J. Maxwell and L. S. Silbert, Tetrahedron Lett., 4991 (1978).
e. J. W. Lown and A. V. Joshua, J. Chem. Soc., Perkin Trans. 1, 2680 (1973).
f. R. G. Guy and I. Pearson, J. Chem. Soc., Perkin Trans. 1, 281 (1973); J. Chem. Soc., Perkin Trans. 2, 1359
(1973).
g. R. Bonnett, R. G. Guy, and D. Lanigan, Tetrahedron, 32, 2439 (1976); R. J. Maxwell, L. S. Silbert, and J. R.
Russell, J. Org. Chem., 42, 1510 (1977).
h. J. Meinwald, Y. C. Meinwald, and T. N. Baker, III, J. Am. Chem. Soc., 86, 4074 (1964).
i. H. C. Hamann and D. Swern, J. Am. Chem. Soc., 90, 6481 (1968).

ambident nucleophile and both carbon-sulfur and carbon-nitrogen bond formation can
be observed, depending upon the reaction conditions (see Entry 7 in Scheme 4.2).
N N N
C C C
S S
S +
RCH CHR + RCH CHR
RCH CHR + (N CS) 2 RCH CHR
S N
C C
N S

For nitrosyl chloride (Entry 8) and nitrosyl formate (Entry 9), the electrophile
is the nitrosonium ion NO . The initially formed nitroso compounds can dimerize or
+
isomerize to the more stable oximes.