Page 665 - Advanced Organic Chemistry Part B - Reactions & Synthesis

640 Scheme 7.3. (Continued)

CHAPTER 7 G. Ketones from nitriles, thioesters, amides, and anhydrides
O
Organometallic
Compounds of Group I 14 n C N CCH 3
and II Metals H 2 O
+ CH 3 MgI
HCl
52 – 59%
15 o O
H 2 O
CH 3 OCH 2 C N + PhMgBr PhCCH 2 OCH 3
HCl 71–78%
16 p
H H H H
S S O + S S O
CH 2 CH 2 CS N BrMgCH 2 CH 2 CH 3 CH 3 CH 2 CH 2 CCH 2 CH 2 CH 3
CH 3 93%
17 q O O
PhCCH 2 Cl
PhMgBr + ClCH 2 CNCH 3
92%
OCH 3
18 r O O
HC CCH 2 CH 2 CNCH 3 + CH 2 CHMgBr HC CCH 2 CH CCH CH 2
2
OCH 3
19 s O
PhC CMgBr + (CH 3 CO) 2 O PhC CCCH 3
80%
H. Carboxylic acids by carbonation

20 t CH 3 CH 3
H 2 O
CO 2 H
CH 3 MgBr + CO 2 CH 3
H +
86 – 87%
CH 3
CH 3
21 u
H 2 O
CH 3 CH 2 CHCH 3 + CO 2 CH 3 CH 2 CHCH 3
H + 76 – 86%
22 v MgBr CO 2 H
1) active Mg
2) CO 2
+
Cl 3) H , H 2 O CO 2 H
60 – 70%
I. Amines from imines
23 w
H 2 O
PhCH NCH 3 + PhCH 2 MgCl PhCHCH 2 Ph
96%
CH 3 NH
J. Alkenes after dehydration of intermediate alcohols
24 x
H 2 SO 4
PhCH CHCH O + CH 3 MgBr PhCH CHCH CH 2
25 y H + 75%
2 PhMgBr + CH 3 CO 2 C 2 H 5 Ph 2 C CH 2
H 2 O
67–70%
(Continued)