Alkanes
R–H
Alkyl Halides
R–X
Reaction Map: Reactions of Alkanes, Alkyl Halides, Alkenes, Alkynes and Alcohols
Alkenes
Thiols
Sulfides
["Thioethers"]
Alkynes
Nitriles
Esters
C C RR
C NROR
R
O
R
Alcohols
ROH
Ethers
ROR
RSH
RSR
Azides
RN3
1
2
3
4
5
67
8
9
10
11
12
13
R
XX
R
XHO
R
O
R
OHHO
OO
R
Vicinal
Dihalides Halohydrins
Epoxides
Vicinal Diols Cyclopropanes
34 35
33
32
"Carbonyls"
O
HO
19
28
27
15
16
17
18
36
37
38
R
X
Geminal
Dihalides
X
26
23
25
24
20
21
22
29
30
31
55
55
52
53
54
Alkenyl halides
Alkenyl dihalides
Tetrahalides
41
42
43
44
HR
XH51
XR
XR
R R
X
XX
X
50
49
48
47
46
47
45
39 40
10
14
Alkyl Sulfonates
R–OTs
R–OMs
63
56
57
58
59
7
8
61
62
64
666768
Ring opened
products
R
HO
Nu
Disulfides
RS S R
60
65
69
1
2
Cl2, hγ
Reaction Typical
Conditions Notes [1°, 2° and 3° refers to
primary, secondary, tertiary]
Not highly selective
Br2, hγHighly selective for tertiary C–H
Name
Free radical chlorination
Free radical bromination
3RO /ROH Best for 2° and 3°, anti stereochemistryElimination [E2]
4polar solvent,
heat
Competes with SN1Elimination [E1]
5OH / H2O Best for 1° alkyl halides; 2° can compete w/ E2Alcohol Formation [SN2]
6H2O Best for 3° alkyl halides; rearr possible w/ 2°Alcohol Formation [SN1]
7Best for 1° alkyl halides; 2° can compete w/ E2Ether Formation [SN2]
["Williamson Ether Synthesis"]
8ROH Best for 3° alkyl halides; rearr possible w/ 2°Ether Formation [SN1]
"Solvolysis"
9SH SN2; best for 1° alkyl halides, 2° OKThiol formation [SN2]
10 SR SN2; best for 1° alkyl halides, 2° OKSulfide formation [SN2]
11 RCO2SN2; best for 1° alkyl halides, 2° OKEster formation [SN2]
12 N3SN2; best for 1° alkyl halides, 2° OKAzide formation [SN2]
13 CN SN2; best for 1° alkyl halides, 2° OKNitrile formation [SN2]
14 R Best for 1° alkyl halides; 2° can compete w/ E2Alkyne formation [SN2]
RO /ROH
"Solvolysis"
in
polar
aprotic
solvent
C C
Addition of H-Cl To Alkenes H–Cl Markovnikov-selective; rearr. possible
15
Addition of H-Br To Alkenes H–Br Markovnikov-selective; rearr. possible
16
Addition of H-I To Alkenes H–I Markovnikov-selective; rearr. possible
17
Radical addition of H–Br to
alkenes
HBr, hγanti-Markovnikov-selective; radical process
18
Hydrogenation of alkenes Pd/C, H2syn- selective
19
Alkene chlorination Cl2, CCl4anti- selective
20
Alkene bromination Br2, CCl4anti- selective
21
Alkene iodination I2, CCl4anti- selective
22
Chlorohydrin formation Cl2, H2Oanti- selective; Markovnikov selective, water
is solvent. Alcohol solvent gives ether
23
Bromohydrin formation Br 2, H2Oanti- selective; Markovnikov selective, water
is solvent. Alcohol solvent gives ether
24
Iodohydrin formation Cl2, H2Oanti- selective; Markovnikov selective, water
is solvent. Alcohol solvent gives ether
25
Epoxidation of alkenes RCO 3Hanti- selective; Markovnikov selective, water
is solvent. Alcohol solvent gives ether
26
(e.g. m-CPBA)
or NCS
or NBS
or NIS
Dihydroxylation of alkenes
with OsO4
OsO4, KHSO3syn- selective. KHSO3 helps remove Os
27
(e.g. m-CPBA)
Dihydroxylation of alkenes
(cold KMnO4)
KMnO4, NaOH
(cold, dilute)
syn- selective. Important to keep cold,
otherwise oxidative cleavage occurs (see 31)
28
Ozonolysis (reductive
workup)
O3, then Zn/H+ or
(CH3)2S
cleaves C=C to give two carbonyls. Alkenyl
C-H bonds remain
29
Ozonolysis (oxidative
workup)
O3, then H2O2cleaves C=C to give two carbonyls. Alkenyl
C-H bonds oxidized to C–OH
30
This "map" includes reactions typically covered in chapters covering:
•Substitution and eliimination reactions of alkyl halides
• Reactions of alkenes
• Reactions of alkynes
• Free-radical substitution of alkanes
• Alcohols and thiols
It will be expanded as subsequent chapters are covered
Please feel free to add comments or sugestions!
