Reaction Map: Reactions Of Alkanes, Alkyl Halides, Alkenes, Alkynes And Alcohols

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Typical
Notes [1°, 2° and 3° refers to
Reaction
Name
Conditions
primary, secondary, tertiary]
Reaction Map: Reactions of Alkanes, Alkyl Halides, Alkenes, Alkynes and Alcohols
Free radical chlorination
Cl
, hγ
Not highly selective
2
1
Free radical bromination
Br
, hγ
Highly selective for tertiary C–H
2
2
56
Elimination [E2]
RO /ROH
Best for 2° and 3°, anti stereochemistry
3
Geminal
Vicinal
57
Vicinal Diols
Halohydrins
Alkenyl halides
Dihalides
Dihalides
Elimination [E1]
polar solvent,
Competes with S
1
Cyclopropanes
4
N
HO
OH
heat
HO
X
X
H
X
X
X
51
X
R
H
Alcohol Formation [S
2]
OH / H
O
Best for 1° alkyl halides; 2° can compete w/ E2
R
R
R
Epoxides
5
R
R
N
2
O
Alcohol Formation [S
1]
H
O
Best for 3° alkyl halides; rearr possible w/ 2°
6
N
2
55
R
"Solvolysis"
50
55
23
22
54
27
33
Ether Formation [S
2]
Best for 1° alkyl halides; 2° can compete w/ E2
RO /ROH
49
7
N
21
26
24
32
28
["Williamson Ether Synthesis"]
53
48
20
Ether Formation [S
1]
ROH
Best for 3° alkyl halides; rearr possible w/ 2°
69
25
8
N
52
"Solvolysis"
Ethers
Thiol formation [S
2]
SH
S
2; best for 1° alkyl halides, 2° OK
9
N
N
Alkenes
Alkenyl dihalides
Alkynes
35
34
R
OR
47
39
40
R
C C R
R
X
Sulfide formation [S
2]
SR
S
2; best for 1° alkyl halides, 2° OK
R
10
N
N
X
R
59
8
in
Ring opened
41
36
Ester formation [S
2]
RCO
S
2; best for 1° alkyl halides, 2° OK
products
polar
11
N
2
N
29
37
46
aprotic
47
60
7
58
HO
42
38
solvent
15
45
30
Azide formation [S
2]
N
S
2; best for 1° alkyl halides, 2° OK
12
N
3
N
R
Nu
19
43
Alcohols
16
31
Tetrahalides
Nitrile formation [S
2]
CN
S
2; best for 1° alkyl halides, 2° OK
13
N
N
R
OH
X
X
44
17
X
X
Alkyne formation [S
2]
R
C C
Best for 1° alkyl halides; 2° can compete w/ E2
14
R
R
N
Disulfides
18
61
R
S S
R
"Carbonyls"
Addition of H-Cl To Alkenes
H–Cl
Markovnikov-selective; rearr. possible
15
68
67
66
62
HO
8
O
65
Addition of H-Br To Alkenes
H–Br
Markovnikov-selective; rearr. possible
O
16
6
63
7
O
4
Alkanes
5
Addition of H-I To Alkenes
H–I
Markovnikov-selective; rearr. possible
64
Thiols
17
R–H
3
R
SH
1
Radical addition of H–Br to
HBr, hγ
anti-Markovnikov-selective; radical process
18
2
alkenes
Alkyl Halides
9
10
R–X
Hydrogenation of alkenes
Pd/C, H
syn- selective
19
2
14
Alkyl Sulfonates
Alkene chlorination
Cl
,
CCl
anti- selective
20
10
2
4
This "map" includes reactions typically covered in chapters covering:
Sulfides
R–OTs
["Thioethers"]
R–OMs
21
Alkene bromination
Br
,
CCl
anti- selective
2
4
•Substitution and eliimination reactions of alkyl halides
R
SR
• Reactions of alkenes
11
• Reactions of alkynes
22
Alkene iodination
I
,
CCl
anti- selective
2
4
• Free-radical substitution of alkanes
13
12
• Alcohols and thiols
anti- selective; Markovnikov selective, water
23
Chlorohydrin formation
Cl
, H
O
2
2
is solvent. Alcohol solvent gives ether
It will be expanded as subsequent chapters are covered
or NCS
Esters
anti- selective; Markovnikov selective, water
24
Bromohydrin formation
Br
, H
O
2
2
is solvent. Alcohol solvent gives ether
O
Please feel free to add comments or sugestions!
or NBS
Nitriles
Azides
R
O
anti- selective; Markovnikov selective, water
R
C N
25
Iodohydrin formation
Cl
, H
O
R
N
R
2
2
3
is solvent. Alcohol solvent gives ether
or NIS
anti- selective; Markovnikov selective, water
26
Epoxidation of alkenes
RCO
H
3
is solvent. Alcohol solvent gives ether
(e.g. m-CPBA)
syn- selective. KHSO
helps remove Os
27
Dihydroxylation of alkenes
OsO
,
KHSO
3
4
3
with OsO
4
(e.g. m-CPBA)
syn- selective. Important to keep cold,
28
Dihydroxylation of alkenes
KMnO
, NaOH
4
otherwise oxidative cleavage occurs (see 31)
(cold KMnO
)
(cold, dilute)
4
Ozonolysis (reductive
O
, then Zn/H
+
or
cleaves C=C to give two carbonyls. Alkenyl
29
3
workup)
C-H bonds remain
(CH
)
S
3
2
30
Ozonolysis (oxidative
O
, then H
O
cleaves C=C to give two carbonyls. Alkenyl
3
2
2
workup)
C-H bonds oxidized to C–OH

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