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1. The Wurtz synthesis
8. Synthesis of alkenes from organic halides
SET
2 R Hlg + 2 Na
:B
R CH CH2 R'
R R + 2 NaHlg
Hlg
2. The Clemmensen reduction
R CH CH R'
HHlg
E
9. Synthesis of alkenes from alcohols
R
C
R
Zn(Hg)/cc HCl
O
CH2
H2O
R
R CH CH3
C
O
R
CH3CH CH2 + HBr
CH2
R
CH3
CH3CHCH2 Cl + CH3CCH3
Cl 2
CH3
500 °C
300 °C
90 : 10
64 : 36
CH3
Br2
Cl
:
99
Br
5. Nitration of ethane
, p
CH3CH2 NO2 + CH3 NO2
SR
(CH2)
n
CH2
n= 1
Br2
n> 2
SR
CH3 CH2 CH2
R CH CH2
R
CH2CH3 + R'
+
Br
Br2
n
main product
Br
CH3CH2CH2 Br

Br
Br
Br
Br

Br
Br
AE
Br
Br
enantiomers
a racemic mixture
a bromonium ion
12. Hydration of alkenes
R CH CH2
H
AE
R CH CH3
H2O
R CH CH3
H
O
H
R CH CH3
OH
H
13. Hydrogenation of alkenes
CH CH2
AR
heterogeneous cat.: Pt, Pd, Raney Ni
homogeneous cat.: metal complexes (Rh, Ru)
H
H
14. Epoxidation of cyclohexene with peroxycarboxylic acids
BrCH2CH2CH2Br
(CH2)
CH3CHCH3
11. The reaction of cyclohexene with bromine
room temp., 1 atm
7. The reaction of cycloalkanes with bromine
CH2
AE
catalyst+H2
6. Catalytic cracking of alkanes
zeolite
500°C
Br
CH3
1
R'
H
Br
a  complex
CH3CHCH2 Br + CH3CCH3
R CH2CH2CH2CH2
R CH CH3
CH3 CH CH3
CH3
CH3 CH3 + dil. HNO3
E1
OH2
R
4. Halogenation of isobutane
SR
H2O
10. The reaction of propene with HBr
1. NH2NH2 2. KOH, 
H2ON2
AN+E
CH3CHCH3
R CH CH3
OH
R
3. The Kishner–Wolff reduction
R
H
CH2
CH Br
+ HBr
O
O
H
C
O
Ar
O
H
O
a peroxycarboxylic
acid
concerted
C
Ar
AN
ArCOOH
O
O
cyclohexene oxide
an epoxide or oxirane
1
15. The reaction of buta-1,3-diene with HBr
23. Aromatization of cyclopentadiene
CH2 CH CH CH2
HBr
CH2 CH CH CH2
Br
Br
H
AE
H
CH3 CH CH CH2
CH2 CH CH CH2
Br
H
K
H+
CH3 CH CH CH2
H
Br
H
..
H
H
H
cyclopentadienide
anion
K
H
16. The Diels–Alder reaction
H
H
C
C
24. Selective oxidation of benzene and alkylbenzenes
CHO
CH2
CH
+
C
 vagy h
CH2
CH2
O
O
CH2R
H
a concerted
reaction
oxidation
.
2 HC:
>1200 °C
3 H2
methine radical
HC CH + 2 Na
H
E+
Na
C C
+ R'Hlg
R
NaHlg
C
C
E
+ H+
H
 complex
2 complex
26. The Friedel–Crafts alkylation
R'
R
20. Selective hydrogenation of acetylenes
R'
R
Lindlar Pd/H2
C C
R C C R'
AR
H
H
E
+
E = Cl, Br, NO2, SO2OH, R, RCO,
D, CH2OH, ArN N
SN
CNa
E
E
+
1 complex
+ H2
Na
19. The alkylation of acetylene
C
benzoic acid
25. Aromatic electrophilic substitution
HC CH
18. Salt formation of acetylene
R
O
maleic anhydride O
17. Synthesis of acetylene
2 CH4
COOH
oxidation
Na/liquid NH3
H
R
C
H
C
RCHMe, RCHMe,
+
R'
OH
CH
Me
R
CH
Me
Lewis acid
Hlg
or R CH CH2
+
or H
CH
SE-Ar
R
Me
21. Hydration of acetylene
H /H2SO4
HC CH + H2O
AE
Hg2+
O
H2C CH
OH
CH3 C
tautomeric
rearrangement
27. The Friedel–Crafts acylation
R
H
O
+ R
22. Hydration of substituted acetylenes
Lewis acid (MLn)
C
Cl
RC CH + H2O
H /H2SO4
AE
Hg2+
R CH CH2
OH
SE-A
R
O
C +
Cl
C

MLn
O
HCl
MLn
R C CH3
tautomeric O
rearrangement
2
33. OH  Hlg exchange (mechanism)
28. Bromination of toluene
CH2Br
CH3
CH3
Br2, h
Br2, FeBr3
SR
SE-Ar
SN1
CH3
Br
OH + HHlg
R
+
R
Hlg
O
Hlg
H
HHlg: HCl, HBr
HHlg
terahydronaphthaline
tetraline
R
Hlg
H2O
R
COOH
phthalic acid
SN2
w = k [RHlg][:Nu ]
R

Nu
Hlg + :Nu
inversion
C

Hlg
RC
NO2
+
Hlg
:Nu
+Hlg
Nu : Hlg, HO, RO, HS, RS, CN, NO2
neutral nucleophiles: NH3, R'NH2, R'2NH
R C
SE-Ar
Nu
Hlg
NO2
50°C
Hlg
35. Mechanisms of nucleophilic substitutions
RC
HNO3, AcOH
R
XHlgn = PCl 3, PBr 3, PCl 5, PBr 5, SOCl 2
COOH
30. Nitration of naphthalene
XHlgn
OH
SN
Hlg = Cl, Br
O
naphthoquinone
O
Hlg
34. Synthesis of alkyl halides from alcohols
29. Partial hydrogenation and oxidation of naphthalene
CrO3
R
SN2 H2O
Br
Na/EtOH
R
H2O
H
main product
SN1
racemization
w = k [RHlg]
31. Sulfonation of naphthalene
SO2OH
36. Mec1hanisms of eliminations
80 °C
H2SO4
SE-Ar
140 °C
H H  eliminations
H
32. Partial hydrogenation and oxidation of anthracene
O
oxidation
H
H H
..
R C C
hydrogenation
H
+Hlg
SO2OH
HHlg
:B
R C C
HHlg
R
Hlg
 elimination
E1
R C C
Hlg
140 °C
Hlg
H
E2
H
Hlg
..
R C C
9,10-dihydroanthracene
R C C
O
9,10-anthraquinone
E1cB
Hlg
3
37. Reduction of carbonyl compounds
44. Synthesis and transformations of ethylene oxide
R
R
R CH2OH
R'= H
C O
CH OH
R' H
R'
R'
LiAlH4
R COOR'
HNu: HCl, ROH,
NH3, RNH2, R2NH
39. Synthesis of alcohols from carboxylic acid derivatives with Grignard reagent
R'
O
R
C
X
2. hydrolysis
AN
R
X = Cl: acid chloride
X = OR': ester
R'
R
C OH
R
C
O
1. R"MgHlg
AN
R=H
R' = alkyl,aryl
S
CH2 OH
CH OH
OH
R
Hlg + NaNO2
R
O
CH
H2O
H
+ R' Hlg
SN
NaHlg
O
S
O
NO2 + R
SN2
O
SN1
N O
ester of
nitrous acid
OH
R
CH
R
(CH2)2 O (CH2)2 R
..
CH
N
O
O
OH , H
H
O
N
O
R
O
CH
N
O
49. Reaction of aliphatic primary amines with nitrous acid
43. The Williamson ether synthesis
R O Na
(Ar)
N
2 R CH CH2
R
R
O
C
H3C
SN
polar,
aprotic solvent
NaHlg
..
N O ambident nucleophile
42. Inter- and intra-molecular dehydration of alcohols
2 R CH2CH2 OH
R
oxidation
R'
..
+
2. H+
S
a sulfone
H3C
FriedelCrafts alkylation
2 H2O
R
48. Nitro compound–nitronic acid rearrangement
OH
1. oxidation
R
a sulfoxide
..
:O
..
R"
electrophilic
catalyst
S
47. Synthesis of nitro compounds from organic halides
41. Synthesis of phenol
E
S
a disulfide
..
R C
SE-Ar
R
R'
R'
H+
SH
R'
R, R' = alkyl, aryl
+ CH3CH=CH2
R
oxidizing
agents
oxidation
O
R"
R'
mild conditions
strong
OH
R
R'
2. hydrolysis
CH2CH2OH
n
46. Oxidation of thioeters
R'
R'
S
O
a sulfonic acid
40. Synthesis of alcohols from carbonyl compounds with Grignard reagent
R, R' = H
HO CH2CH2 O
OH
O
R'
R = alkyl,aryl
O
45. Oxidation of thiols
CH OH
1. 2 R'MgHlg
poly(ethylene glycol), PEG
n
CH2 CH2
OH
Nu
SN
H2O
R CH2OH + R'OH
R=H
OH
O
catalytic hydrogenation (Pt/H2 or Raney Ni/H2)
or hydride reduction (NaBH4 or LiAH4)
38. Reduction of esters
CH2 CH2
HNu
[O], Ag
CH2
CH2
R O R'
(Ar)
R
NH2
NaNO2, HCl
05°C
N2
R
OH + R
O
R + alkene
4
50. Reaction of aromatic primary amines with nitrous acid
Ar
O
NaNO2, > 2 equiv HCl
NH2
57. Acid- and base-catalyzed formation of enols
Ar
05°C
N
N Cl
..
RCH
HO
an aromatic diazonium chloride
Ar
C
Ar
N2
N
Cu2Hlg2, HHlg
N X
Ar
N2
an aromatic diazonium salt
R'
R'
H
Hlg = Cl, Br
OH
H
N
N Cl
+
X
Y
SE-Ar
N
N
X
X = activating
substituent
53. The reaction of diazomethane with compounds having hydroxy function
N2
CH3O Z
R C
CH3O-Z: aryl methyl ether, methyl ester, enol methyl ether
AN
R
C O + H2O
O
R'
OH
C
R'
R'
C
OH
unstable hydrate
gem-diol
H
OH
H
C
H
H
R
R'OH
R
C
H
OR'
H
OR'
R
C OR'
OH2
H
O + R"MgHlg
OR'
CH3
OR'
C O + H
R'
Al
H
R
R'
H
Li
C
H
OLi + AlH3
H3O
R
OMgHlg
C
H 3O
Mg(OH)Hlg
R"
R'
C OH
R"
C
O
+ :CH2
R
OH
H2O
H
H
C
enolate anion H
H
CH3
C
O
O
CH2
C
H
O
H2O
OH
CH3
CH CH2
OH
C
H
O
E
HC
R'
CH2
AN
C
O
C
carbanion
O
CH3
O
:CH2
H
AN
R
AN
OH
C
H
56. Reduction of carbonyl compounds with complex metal hydrides
H
OH
61. Aldol reaction
OR'
H
R'
O
R'
C
H
CN
60. Reaction of carbonyl compounds with Grignard reagent (mechanism)
O
R
C NR"
HNR" H O
2
H R'
R'
C
R'
OR'
C
H
H2O
H2O, -OH  R
CN
C
R'
C
C O + R' OH
R
R
AN
R
R
R
E
R C
R'
R'
55. Formation of acetals
AN
OH2
H3O
HNR"
59. Cyanohydrin synthesis
C O + CN
R
H2NR"
R'
R
OH2
R C
R" = H, alkyl, aryl, OH, NH2, NHPh
54. Reaction of carbonyl compounds with water
R
C
R'
OH
O
AN
R'
CH2N2 + HO Z
RCH
slow
:OH2
C O + H2NR"
C
OH
58. Reaction of carbonyl compounds with nitrogen bases
R
HO-Z: HO Ar, HOOC R, HO CH
H
OH
H3O
R'
H
Y = deactivating
substituent
R
C
RCH
fast
C
R'
HO
fast
C
RCH
Hlg
52. Diazo coupling
Y
RCH
O
Cu2(CN)2, HCN
N
C
slow
51. The Sandmeyer reactions
O
CH3
CH CH C
H
5
62. Acid- and base-catalyzed -halogenation of carbonyl compounds
C
R
H
HO
O
R
..
CH2
C
CH2Br H
R
O
Br2
C
R
Br
O
C
R
HBr
OH
R C CH3
a
Br2
CH2
68. The Tollens test (a) and the Fehling test (b)
C
OH
Br2
CH2Br
R
CBr3
O
O
R C CH3
CHIg3
R C
HO
O
O
R
O
+ :CHIg3
C
R
+
C
OH
O
O
CH2 CH C
CH2 CH C
R
R
CN
ketoenol
tautomerization
CN
C
CH3
H
+ CH2O + Me2NH
O
R
H2O
C CH2
CH2 NMe 2
O
R
C
O + H2NR'
R
AN+E
H2O
R
C
NR'
R
R' = H, alkyl, OH
LiAlH4 or
catalyst+H2
CH
H3C C CH2
O
C CH3
O
20 %
H3C C
O
H
80 %
H
O
OH
..
R CN + (R N C:
KHlg
ambidens nukleofil
SN2
R N C:)
isonitrile
SN1
sp2
CH
R
AN
O 
R
sp3
Nu C
X
R
AN
R
hydrolysis
COOMgHlg
Mg(OH)Hlg
R
COOH
72. Nucleophilic acyl substitutions
X = Cl, OOCR', OR', OH,
R sp2
NH2, NHR, NR2
C O
:Nu = HO, R'O, R'COO;
Nu
neutral nucleophiles = H2O, NH3,
1° and 2° amines
E
O
X
X
:Nu
NHR'
73. Acid-catalyzed esterification/ester hydrolysis
O
67. Keto–enol tautomerization of pentane-2,4-dione
polar,
aprotic solvent
R MgHlg + CO2
+ C
reduction
R C
71. Synthesis of carboxylic acids from carbon dioxide
R
66. Reductive amination (reductive alkylation)
R
O
R C
..
:C N:
:C N:
65. Mannich condensation
R
+ Cu 2O
red
O
precipitate
CH2 CH2 C
R
conjugate addition
C
70. Hlg  CN exchange
O
CH2 CH C
AN
R
C
H
R Hlg + KCN
OH
HCN
O
Cu2+
reagents: CrO3/H2SO4 (Jones reagent), KMnO4, K2Cr2O7/H2SO4
HCHlg3
O
64. Reaction of HCN with ,-unsaturated carbonyl compounds
O
R
silver
mirror
R CH2 OH
HO
O
+
69. Oxidation of primary alcohols
63. The haloform reaction
HIg2
Ag(NH3)2
+ Ag
C
O
C
R
b
O
CHBr
R C
OH
H+
OH
R C
SN-Ac
OH
OH
R'OH
R C
OH
R C
OH
OH
OR'
H
H+/+H+
OH
R C
OR'
OH2
C CH3
O
H2O
OH
R C
OH
R C
OR'
OR'
H+
O
R C
OR'
6
74. Base-catalyzed hydrolysis of esters
O
O
R C
80. Transformation of esters to other acid derivatives
O
R C OR'
+ :OH
OR'
SN-Ac
R C
O
R C
+ R'O
OH
OH
+ R'OH
O
75. Hydrolysis of carboxylic acid chlorides
O
+ :OH2
R
Cl
SN-Ac
R C
Cl
Cl
R
H
OEt
OH
OEt
CH3 C CH2 COOEt
EtO
O
O
H2O
n = 1, 2
R
NH2
C
Hlg
R'
C
O
R COONa
NaCl
O
R C
O
Cl
+ R COOH
NH2
P2O5
R C
H2O
n = 1, 2
2 NH3
NH4Cl
R C
O
R C
NH2
H2O
R C
O
O
N
H
SN-Ac
X
O
+ HNR'2
R C NHR'2
O
H2NR'2
X
X: Cl, OOCR", OR"
R': H, alkil, aril
O
R C NR'2
:HNR'2
SN-Ac
X
X
R C
O
NR'2
85. Decarboxylation of 1,3-dicarbonyl compounds
O
O
( )n
84. Transformation of carboxylic acid derivatives to carboxamides
79. Direct synthesis of anhydrides
O
O
Hlg = Cl, Br
R'OH HCl
R COOR'
2 R COOH
O
SN-Ac
O
SN-Ac
78. Transformation of acid chlorides to other acid derivatives
O
O

COOH
O
or AcCl
R C
C
R C
83. Formation of lactams
( )n
POCl3, PCl3, PBr3,
PCl5, SOCl2
COOH
R'
NH3
O
( )n
H
COOH
CH3 C CH2 COOEt
77. Synthesis of acid halides
R
+ R' OH
NH2
O
R C
R'OH
SN-Ac
( )n
+ :CH2 COOEt
OEt
SN-Ac
SN-Ac
OH
OH2
O
O
R C
82. Formation of lactones
NaOEt
CH3 C
R COOR'
v. base
R COOR' + R COOH
C
76. The Claisen ester condensation
CH3 C
SN-Ac
H
O
O
C OH2
R COOR"
O
NH3
81. Transformation of anhydrides to other acid derivatives
O
R C
R" OH
R
C
C
COOH
O

R
C
H
C
O H
O
C
O
CO2
R
C
C
O
R
C
C
H
R = OH - malonic acid
R = Me - acetoacetic acid
7
86. Synthesis and structure of malonic ester sodium
NaOEt
CH2
:CH
C O
C O
HC
C O
HC
C O
EtO
EtO
COOH
EtO
HC
C O
COOEt
COOEt
EtO
EtO
COOEt
COOEt
90. Transamination
C
6
C O
O + NH2 CH
R
R'
Na
EtO
HO:
NaOEt
CH2
COOEt
COOEt
EtOH
COOEt
RHlg
:CH2
SN
Na COOEt
COOH
H
R CH
R CH
COOEt
COOH
COOH COOH
H2O
AN+E
C
COOH COOH
N CH
R
HC
N C
R
R'
R'
H2O
COOH
COOH
HC NH2 + O
R
C
R'
tautomeric
rearrangement
91. Synthesis of carboxylic acids from ethyl acetoacetate (the retro-Claisen reaction)
87. Synthesis of carboxylic acids using malonic ester synthesis
COOEt
COOH
R
OH R
CH3CCHCOOEt

RCH2COOH
CO2
CH3C
O
O
CH COOEt
CH3C
..
+ RCHCOOH
CH3COO + RCH 2COO
OH
O
H3O
RCH2COOH
88. Synthesis and structure of the anion of ethyl acetoacetate
CH3
C O
CH2
C
NaOEt
O
OEt
CH3
C O
:CH
C
CH3
CH3
CH3
C
CH
O
C
O
C
O
CH
C
O
O
OEt
OEt
92. Alcoholysis of phosgene
OEt
COCl2
C O
HC 6
C
O
SN
Me C CH COOEt
R
O
dil. acid
or base
RO
HCl
SN-Ac
RO
C O
RO
dialkyl carbonate
93. Synthesis of carbamates (urethanes)
R
1. NaOEt
2. RHlg
HCl
chlorocarbonic acid ester
alkylchloroformate
Na
89. Synthesis of ketones using acetoacetic ester synthesis
Me C CH2 COOEt
ROH
C O
SN-Ac
O
OEt
Cl
ROH
C
Me C CH COOH
RO
O
CO2
SN-Ac
Cl

AN
R'HN
O + R'NH2
C
O
R'N C
O + ROH
RO
R = alkyl
R' = H, alkyl, aryl
Me C CH2R
O
8