Page 629 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 6.21. (Continued) 603

D. Acetate pyrolyses SECTION 6.6
Unimolecular Thermal
10 j O CCH 3 Elimination Reactions
2
N C CHCH 3 575 – 600°C N C CH CH 2
76%

11 k CH O CCH 3 CH 2 CH 2
2
2
555°C +
CH O CCH 3 CH 2 CH O CCH
2
2
61% 2 2 3 24%
12 l CH 3 CH 3
400°C
CH CH
O 3 O 3
CH 3 CH O CCH 3 CH 3 CH 2
2
2

E. Xanthate ester pyrolyses

13 m CH 3 1) K
PhCHCHCH 3 2) CS 2 PhC CHCH 3
3) CH I
OH 3 CH 3 91%
4) heat
14 n
OH
1) NaH
2) CS 2 +
3) CH I
3
4) heat (total yield 41%)
15 o
–
(CH ) CH CH O Na + CS 2 heat (CH ) CH CH 2
3 2
3 2
2
–
3
) CH CH O Na – CH I (CH ) CH CH
(CH 3 2 2 3 2 2
16 p
OH 1) NaH
2) CS 2
3) CH I
3
71%
4) heat
(Continued)