Chapter 24

Organic
Name Reactions

Aldol Condensation
O O O O OH O
 
OH H+ OH
H–C–CH2 H–C–CH2 C–CH3 H–C–CH2–CH–CH3 ∆ H–C–C=C–CH3
H H H H

Claisen Condensation
–
O O O O O O HO
–
EtO H+
H3C–C–OEt EtO–C–CH2 C–CH3 EtO–C–CH2–C–CH3 CH3–C–C–C–OC2H5
OC2H5 OEt H

Perkin Condensation
O
H H H O
O H3C–C–ONa
⊕

C + H–C–C C–CH3 C=C–C–OH

O H
O O H
Cinnamic acid

Benzoin Condensation

O O OH
KCN
2 C–H EtOH
C–CH Benzoin

Haloform Reaction

OH O O
1 NaOI 1 NaOH 1
H3C–CH–R H3C–C–R I2
CHI3+R –C–ONa⊕
Carbylamine Test
H
H .. Cl CHCl3  Cl ⊕ 
OH
R–N C KOH R– N–C
⊕
R–N≡C Isocyanide
H Cl Cl
H

Reimer Tiemman Reaction

H
O OH H
OH O C=O
+ CCl4 CHCl3
C–OK KOH KOH

(Salicylaldehyde)
(Salicylic acid)

Kolbe’s Schimdt Reaction

O–H OH O
NaOH 125ºC C
OH (Salicylic acid)
CO2/H+
major

Hoffmann Bromamide Degradation

O
Br2
R–C–NH2 KOH R–NH2+K2CO3

Curtius Reaction
O
NaN3
R–C–Cl ∆,H3O
+ R–NH2

Schimdt Reaction
O
⊕
HN3 H 3O
R–C–OH H2SO4
R–N=C=O R–NH2

Cannizzaro Reaction

O O O O O O
50% slow
R–C–H NaOH
H3C–C–H C–H RDS
H–C–OH+H–C–H H–C–ONa++CH3–OH
H–O H H

Bayer villiger oxidation

O
(i) F3C–C–OO–H O
O (peracid)
C (ii) H
+ H3C–C–O
H
Cumene

O–O–H
CH3–CH–CH3 CH3–C–CH3 OH
O
O2 HCl
130ºC
+ CH3–C–CH3
Cumene
hydroperoxide

Pinacol-Pincolone rearrangement

Cl

+
H+
C C –H2O
Cl C C
OH OH OH
Ph
–H+
Cl C–C–Ph
O Ph

Birch Reduction

O
OR(+M) O–R C–OH COOH

Na/ Na/ Na/

liq. NH3 ; liq. NH3 ; liq. NH3

Na/
R H Na/
R–C≡C–R liq. NH3 C=C ; R–C≡C–H liq. NH3 R–C≡CNa+
H R (Acid-base reaction)

Gabriel Synthesis

O O O O
C C C C
NH3 KOH CH3–I
O N–H NK+ N–CH3
C C C C
O O O O
O
C–OH
+CH3NH2
C–OH
O
 Name Reactant Reagent Product

Clemmensen
Aldehyde & Ketone Zn-Hg/conc. HCl Alkane
Reduction

–
N2+Cl OH NH2 Azo Dye
Coupling NaOH (phenol)
Reaction + or (Detectionof OH or
HCl (Aniline)
NH2 gr)

.. NaNO2 + HCl + –
Diazotization NH2 N≡NCl
(0º – 5ºC)

O
Etard reaction H3C CrO2Cl2/CS2 H
(Benzalde hyde)

Fitting Reaction Halo benzene Na/Dry ether Diphenyl

Friedel Craft
+ R–X Anhydrous AlCl3 Alkyl Benzene
alkylation

O
Friedel Craft
+ R–C–Cl or (RCO)2O
Anhydrous AlCl3 Acyl Benzene
acylation

Gattermann
HCN+HCl/ZnCl2/
aldehyde C6H6 + Benzaldehyde
H 3O
synthesis

Gattermann-
C6H6 (CO + HCl) anhy AlCl3 Benzaldehyde
Koch reaction

Hell-Volhard- carboxylic acid having a-halogenated

Br2/red P
Zelinsky reaction a-hydrogen atom carboxylic acid

Hoffmann
primary aliphatic amine CH3CH2–N=C=S+HgS
mustard oil HgCl2/D
+ CS2        (black)
reaction

Hunsdiecker Ag salt of carboxylic

Br2/CCl4,80ºC alkyl or aryl bromide
reaction acid

Kolbe electrolytic alkali metal salt of alkane, alkene and

electrolysis
reaction carboxylic acid alkyne

Mendius reaction alkyl or aryl cyanide Na/C2H5OH primary amine

 Name Reactant Reagent Product

Rosenmund H2,Pd/BaSO4
acid chloride aldehyde
reduction boiling xylene

Sabatier- Ranye Ni/H2,

Unsaturated
Senderens Alkane
hydrocarbon 200–300ºC
reaction

CuCl/HCl or CuBr/
Sandmeyer + –
C6H5N2Cl HBr or CuCN/KCN, Halo or cyanobenzene
reaction
heat

Gattermann + –
C6H5N2 Cl Cu/HX(HBr/HCl) Halobenzene
Reaction

benzolytated product
O
Schotten-
(phenol or aniline or O–C–CH3
Baumann NaOH + C6H5COCl
alcohol) O
reaction
NH–C–CH3

Stephen reaction alkyl cyanide (i) SnCl2/HCl (ii) H2O Aldehyde

Williamson sodium alkoxide or

alkyl halide Ether
synthesis sodium phenoxide

Wurtz-Fitting
alkyl halide + aryl halide Na/dry ether alkyl benzene
reaction