ALKANE

H2/Pt, Ni, Pd Zn-Cu couple EtOH

CH2=CH2 Br—CH2—CH3
200 °C Zn/Ac. OH; Zn—NaOH
Raney Ni/250°C LiAlH4
Sabatier Sanderens Reduction Br—R (1° & 2°)
Et2O
Transfer H2N—NH2/H2O2 NaBH4
Hydrogenation CH2=CH2 Br—R (2° & 3°)
Synaddn CH4
CH3—CH3
/Pd—C/ R—CH2—CH3 1) Na/Et2O
Br—R
+CH2=CH2 CH3—CH2—CH3 R"—X
O R'2Zn
(Frankland reaction)
B2H6/ H3C C OH/H2O
CH3—CH=CH2 HI/Red P.
HO—CH2—CH3
R'—X
R2CuLi (Corey house synthesis)
(R' 1°, 2°, cyclic)
O
HI/Red P.
H C CH3
O
HI/Red P. H3C CH3
C
O
Zn-Hg/HCl (Clemmenson Reduction) O
CH3 C R HI/Red P.
NH2NH2/EtO—Na+(wolf kisner reduction) HO C CH3
NaOH+CaO/
O
H3C C OH
Kolbes electrolysis H2O Al4C3
H3C C ONa —4 Al(OH)3
O
SO2Cl2 X2
CH3—CH2—Cl CH3—CH2—X [F2>Cl2>Br2>I2]
hv hv
Cl2
CH3—CH2—Cl [5.0 : 3.8 :1]
hv
H2SO4 + SO3 CH3—CH3 Br2
(3°>2°>1°) CH3—CH2—SO3H CH3—CH2—Br [1600:82:1]
hv
HNO3 I2
CH3—NO2 + CH3—CH2—NO2 CH3—CH2—I
H2SO4/400 HIO3

Cr 2 O 3 /Al2 O 3 Cr 2 O 3 /Al2 O 3
Aromatization : ; CH 3
500°C
500°C
Isomerization :
Anh AlCl 3 Anh AlCl 3
Anh AlCl 3 CH 3 (CH 2 ) 5 CH 3 CH 3 (CH 2 ) 6 CH 3
, HCl , HCl
H Cl Isooctane
(Triptane) (2,2,3-trimethyl butane)
Combustion : Pyrolysis:
3n  1
CnH2n+2 + O 2 

 nCO 2  (n  1)H 2 O 2CH 3 — CH 2 — CH 3 
600  C

 CH 3 — CH  CH 2  CH 3 — CH 3  CH 4  H 2
2
CH 4  2O 2  CO 2  2H 2 O CH 3 — CH 2 — CH 2 — CH 3 
600  C

 CH 3 — CH 2 — CH  CH 2

CH 3 — CH 3  O  2CO 2  3H 2 O
7 + + +
2 2

CH2N2/
Insertion:
O2, Cu tube
CH2=C=O/
CH3—CH2—H CH3—CH2—CH2—H CH3—OH
200°C, 100 atm
O
MO2O3/O2 O3

CH3 C H
O=CH2
CH4 Ni/Steam

H—CN
CO2+H2
NH3/Al2O3
700°C
oxidation: CH3 CH3
KMnO4
H3C C H H3C C OH

CH3 CH3

38
 Nutshell Preparation of
ALKENE

H2SO4/  H2/Pd-BaSO4
R CH CH3 H3C C C CH3
H3PO4/ 
Lindlar Catalyst

Al2O3/
OH (cis Alkene)
X Na/Liq. NH3
Alc. KOH H3C C C CH3
R CH2 CH2 -HX
Birch Reduction
(X:Cl, Br,I) Satzeff Rule
(trans Alkene)
R CH CH2 H
Ph3P=CH2 (ylides)
X X Zn dust (CnH2n) O C R

Wittig Reaction
R CH CH2 O H
Pyrolysis

X R C O CH2 CH R
Zn dust

R CH2 CH For Higher Alkene 
X (CH3-CH2)4NOH
Hoffmann Rule
O
H  R2CuLi
R C C OK Kolbe electrolysis H2C CH Cl
R' C C OK
H
O

Elimination Reaction
E1, E2 & E1CB
B  H


H3C CH CH CH2

Y

H3C CH CH CH3 H3C CH2 CH CH2

more substituted Least substituted alkene
alkene is major product is major product

Hoffman Rule
Satzeff Rule
: In presence of bulky base
Y I,Br, Cl, OTs, OBS
in presence of base
: When more bulky groups
are present around B(C)

: When y; is N Me3/OH/ 
OH / MeO / EtO

(Alc. KOH)
6:1 (trans to cis) : SR2/B /
Y : OH/Conc. H2SO4/ 
: NR /
: OH/H3PO4/ 2

: OH/Al2O3/ O
: OH/P2O5 or ZnCl2/ : F / Base
: Pyrolysis of ester

Y : OH/ThO2/

39
 Nutshell reaction of Alkene
Cl Br
Cl2/500°C Br
CH2 CH CH2 H3C CH CH2
CCl4
OH Br
SeO2 H
CH2 CH CH2 Br2 OH
H3C CH CH2 O
H
CH2N2 + H3C CH CH2

H3C CH CH2 Br Br
Anti addition of Br2 Cl
cis  dl. dibromide
CH2
NaCl
trans meso dibromide
Al2(SO4)3
Isomerization H3C CH CH2
200-300°C Br
O2

* Regioselectively : I
(Combustion) CO2+H2O Markownikoff Rule (M.R.) KI
H3C CH CH2
Br

B2H6/THF H2O2/NaOH
H OH
Br +  (CH3 CH CH2)3B H3C CH CH2
I Br
3
H
H3C CH CH2 I H
H2O/ACOH
Cl +  H3C CH CH2 H
Br Cl
H3C CH CH2 Br H
D2O/ACOD
Cl  + H3C CH CH2 D
Cl Br
H3C CH CH2 Br
Cl  +
Cl N O OsO4/NaHSO3
H3C CH CH2 N O H O OH Syn addition)
  + cis  meso (diol)
or dil. Alk. KMnO4
H3C CH CH2
H O Cl (Bayer's Reagent) trans dl (diol)
H3C CH CH2 Cl
O
OH ½ O2/Ag/ H+/H2O18
OH
X H3C CH CH2 H3C CH CH2
X + H X or F3CCO3H
H3C CH CH3 H3C CH CH3 18
OH
HBr, HCl, HI Epoxidation
(Markownikoff Rule) (Anti addition)

OH O O
Intermediate :carbocation H+/H2O O O
(thus rearrangement occur's) H3C CH CH3 O3 H3C CH CH2
Rate EAR : R2C=CR2 > R2C=CHR > RCH=CHR > R—CH=CH2> CH2=CH2 H3C CH CH2
O O
H
Anti Markownikoff Rule H Br O O
H3C CH CH Br H2O/Zn
(Peroxide Effect) R O O R H3C C H + H C H
or Me2S
H
O H O O O
H3C CH CH2 H2O2
H
+
Hg(OAC)2 H3C C H + H C OH
H3C CH CH2
HgOAC OH LiAlH4
HgOAC H3C C H + H3C OH
HO H H
NaBH4
H3C CH CH2 (M.R.)
CO+H2
H CHO
O + CO(CO)4 H3C CH CH2
KMnO4/H
H3C C OH+CO2+H2O [O] H COOH
CO+H2O
H3C CH CH2
CH3 CH3 O CO(CO)4
[O] +


H3C C C R H3C C O + R C OH + C O
H3PO4 C O
H H3C CH CH3 H3C CH CH3
CO/H2O
OOH
Br C
NBS OH2
CH2 CH CH2 H3C CH CH3

CH3—CH=CH2

40
 Nutshell Preparation of Alkyne
Br Br H2O
(i) Alc. KOH CaC2
CH2 CH2 (ii) NaNH2

Br Electric arc/1200°C
(i) Alc. KOH Berthelots process 2C+H2
H3C CH (ii) NaNH2
Br Kolbe's electrolysis
CH COOK
Br Br
Zn dust/MeOH CH COOK
Br C C Br 150°C (i) NaNH2/or Na
H H H C C R
(ii) R-X
Zn/MeOH
HC Br 150°C
s- s+
C Br CH3MgI
H H C C R
H C C H (CnH2n-2) (ii) R-X
Alc. KOH
H2C C Cl or Isomerization
H NaNH2 R C C H
Alc KOH
or
R C C R
HCI3+6Ag+I3CH NaNH2
liq. Paraffin

Nutshell reaction of Alkyne

X H H H2/Ni
H—X H2/Ni
HX R CH CH2
R C C H R C C H R CH2 CH3
Pd/Pt
X H X H2/Pd
Markownikoff rule R CH CH R (cis)
BaSO4
Br Br Na/Liq. NH3
HBr H Br R CH CH R (trans)
R CH2 CHBr R CH CH R C C H Birch reduction
perxide perxide or (C2H2)

O O Na/Liq. NH3
H2O 2+
Hg /dil.H2SO4 R C C R R C CNa (for terminal Alkyne)
R C CH3 R C CH3 H2SO4 R C C H

Amm. CuCl Amm. AgNO3
R C CAg (white ppt.)
- +
Hg+

R—C=CCu+
Red ppt. RmgBr
O O O3
R C CMgBr+R'-H
R C C H Zn/H2O
2Cl2
Cl Cl
O O O3 R'-X
R C C H O R C C R'
R C O H + H C OH H2O2 Cl Cl C O
O
H O R C C C OH
Cl 3

AsCl3
(Lewisite) CH CHAsCl2 2+ O
Hg /ACOH Distil.
H3C CH(OAc)2 H3C C H+AC2O
O OH
HOCl HOCl B2H6/THF
H3C C CHCl2 H3C C CH Cl H O H O
H2O2/NaOH
R C C H R C C H
OXIDATION H H
Red hot
Alk. KMnO4 OO (trimerisation)
Cu/Fe
HO C C OH
 O Ahy Ni(CN)2
KMnO4/H [O]
THF/
2H C O H CO2 (tetramerisation)
H C C H

OO
SeO2 H C C H
H C C H
Alk. KMnO4 O O
CuCl2 HCl
H3C C C OH H2C CH C C H

NH4Cl
O O O
KMnO4/H [O] Cl
H3C C OH+ H C OH H3C C OH+CO2 CuCl2/NH2Cl
H3C C C H HC C C C H
air CHLOROPRENE
SeO2
O O
H3C C C H

+ O
KMnO4/H
K2Cr2O7/H+ 2 H3C C OH

H3C C C CH3 OO
SeO2
H3C C C CH3

41
 Nutshell Preparation of ALKYL HALIDE
 prolong heating 2° (R-O-H) 5 mins;
1°
White turbidity immediately (3° R-O-H)
PCl5 HCl
HCl+POCl3+CH3 CH2 Cl Lucas Reagent H3C CH2 Cl
PCl5
H3PO3+CH3 CH2 Cl HBr 48%
(3° Alkene)
3 NaBr+H2SO4
H3C CH2 Br
(3° Alkene)
PBr3 H3C CH2 OH
H3PO3+CH3 CH2 Br HI(57%)
H3C CH2 I
3
KI/H3PO4
PI3
H3PO3+CH3 CH2 I SOCl2 2
3 H3C CH2 Cl(SN )
SOCl2
HCl+SO2+CH3 CH2 Cl SNi
N
Br Br
HBr HBr
H3C CH2 CH2 Peroxide CCl4 H3C CH CH3
Cl
Br HCl
Br2/800K H3C CH CH3
H3C CH CH2

CH2 CH CH2
I
Br HI
NBS H3C CH CH3
CH2 CH CH2 CCl4 Br2/CCl4
H3C CH CH2 Br
Br
Cl2 NaI
H3C CH2 H hv H3C CH2 Cl Acetone
H3C CH2 I (Finkelstein Reaction)
Cl2
H3C COAg hv H3C Br+CO2 +AgBr (Hunsdiecker Reaction)

O AgF
H3C CH2 Cl H3C CH2 F (Swart reaction)
or Hg2F2

Nucleophilic substitution)
Finkelstein NaI OH
Reaction H3C CH2 I Aq KOH
H3C CH2 OH
Acetone
NCO
SN1 Moist Ag2O
H3C CH2 N C O KCN
3°>2°>1° H3C CH2 C N
NCS EtOH
CH3 S C N +
SN2 AgCN
H3C CH2 N C
Corey house (C2H5)2CuLi
synthesis H3C CH2 CH2 CH3
O 1°>2°>3° K+O-N=O H3C CH2 O N O
O
H3C CH2 O C CH3 H5C C OAg O
Ag-O-N=O
H3C CH2 N
+ Na2SO3
H3C CH2 SO3Na O
Na2S O
H3C CH2 S CH2 CH3 NaNO2
2 H3C CH2 N
DMF
H3C CH2 N C S AgSCN O
H3C CH2 O CH2 CH3 (R—Br1°)
CH3-CH2ONa+
O Dry Ag2O
O
C C + NaSH
(CHO C)2 CHNa CH3—CH2—Br Alc. H3C CH2 SH
H3C CH2 CH
CH3SNa
C H S H3C CH2 S CH3
NH3
O
+
Li
S excess H3C CH2 NH2 (1°)
S
H3C CH2 O CH3-CH2-NH2
S C
+ excess H3C CH2 NH CH2 CH3 (2°)
O NK
C (C2H5)2NH
Gabriel C O (CH3-CH2)3N (3°)
OH
Pthalamide + H3C CH2NH2 + Et3N +
synthesis OH H 3
O Et4NBr
C +
Alc. KOH NaN=N=N +
O H C CH H3C CH2 N N N
2 2
+
H C CNa
Wurtz Na H3C CH2 C C H
reaction H3C CH2 CH2 CH3 Et2O
H3C C CNa+
Br H3C CH2 C C CH3
Wurtz-Fittig
Reaction
H3C CH2 LiAlH4/Et2O
Na/Et2O
H3C CH2 H
AlCl3 (1°,2° not 3° R—X)
F.C. Alkylation CH2 CH3
NaBH4/EtOH---->2° & 3° not 1° R—X

Mg/Et2O
C2H5 MgBr
Zn-Cu couple / EtOH
O H3C CH3
O + Zn-dil. HCl : Na /EtOH
H3C C NHNa
H3C CH2 NH C CH3

42
 Nutshell Preparation & Properties of
DI, TRI and Tetra Halides

OH CaOCl2 O2 Cl
H3C CH H' Light
O C +HCl
Bleaching powder
Cl
O CaOCl2 Zn/HCl
CH2Cl2
H3C C CH3 Bleaching powder EtOH
Zn/Aq.HCl
O NaOH CH3Cl
H-C-ONa
Cl3C C H Zn/H2O
CH4
O Aq. KOH 
CHCl3 H C OK
Fe/HCl
CCl4 O
HNO3
3Cl2/hv Cl3C NO2(Chloropicrin) (tear gas)
CH4

H3C O AgI

OH HC C H
C H3C C CH3
H3C CCl3 OH O
OC2H5
Chloretone O—C2H5 NaOH C
 O—C2H5
H
KOH OH
H3C CH2 N C Ethyl ortho formate
CH3 CH2 NH2
Carbylamine Test Riemer Tiemann Reaction

Cl2/hv
CH4
3Cl2/AlCl3
CS2
S2Cl2
Fe/H2O
Cl2/hv
CH4
CHCl3 CCl4 H2O
COCl2
500°C
OH O
SbF5 OH C
CCl2F2 O H
(Freon) KOH/

O

OH
Aq. KOH H C C H
H3C CH -H O 3
O HCl 2
PCl5
Cl OH
H3C C H POCl3 Alc. KOH
H3C CH H C C H
2HCl Zn/dust
H C C H H3C CH CH CH3 O
Hg
2+ Cl
CN H3O+ C OH
Alc. KCN
H3C CH H3C CH
CN C OH
O
Aq. KOH CH2 CH2

Cl2/KCl4 OH OH
H2C CH2 CH2 Cl Alc. KOH
NaNH2
CH3 CH2 Cl HC CH
PCl5 Zn/MeOH
CH2 CH2 CH2 Cl HC CH O
O
C

OH OH H3O+
C
KCN/EtOH CH2 CH2 H2C OH H2C
O
CN CN H2C OH H2C
C C
O
O

43
 Comparison of S N 1 and S N 2
S N1 S N2
st
A Kinetics 1 order 2 nd order
B Rate k[RX] k[RX][Nu: — ]
C Stereochemistry Racemisation Inversion
D Substrate 3° > 2°> 1° > MeX MeX > 1° > 2°> 3°
E Nucleophile Not important Needs Strong Nu
F Solvent Good ionizing Faster in aprotic
G Leaving Group Needs Good LG Needs Good LG
H Rearrangement Possible Not Possible

Comparision of E1 and E2
E1 E2
st
A Kinetics 1 order 2 nd order
B Rate k[RX] k[RX][B: — ]
C Stereochemistry No special geometry Anti-periplanar
D Substrate 3° > 2°> > > 1° 3° > 2° > 1°
E Base Strength Not im portant Needs Strong bases
F Solvent Good ionizing Polarity not import
G Leaving Group Needs Good LG Needs Good LG
H Rearrangement Possible Not Possible

Summary of S N 1, S N 2, E1, and E2 reactions

RX M e c h a n is m N u : — /:B — Solvent Tem p.

Better Nu: —
S N2 Low
HO: — , C 2 H 5 O: —
1° Polar aprotic
Strong & bulky
E2 High
base (CH 3 ) 3 C O: —
S N2 HO: — C 2 H 5 O: — Low
Polar aprotic
E2 (CH 3 ) 3 C O: — High
2°
(S N 1) (Solvent (L ow)
Polar aprotic
(E1) (Solvent) (H igh)

S N1 Solvent Protic Low

3°
E1 Solvent Protic High

44
• Reduction
O
H   CH 3— CH 2— OH
LiAlH / H O
4 2
H3 C C NaBH 4 / EtOH

O OH
CH 3 
H C
LiAlH 4 / H 2 O
H3C C NaBH 4 / EtOH
3
CH CH 3

O
Cl  CH 3–CH 2–OH
4 LiAlH / Et O
2
H3 C C

O OH
C 2 H 5   H3C
LiAlH / Et O
H3C CH 2 C O
4 2
Na / EtOH CH 2 CH 2 + C 2 H 5 OH

O
CH 2   CH 3–CH 2–OH
LiAlH / Et O
H3O
4 2
H2C

O OH
H3C CH CH 2   H3C LiAlH 4 / Et 2 O
CH CH 2 H
H3O

• By Fermentation
C 12 H 22 O 11  H 2 O Invertase
 C 6 H 12 O 6  C 6 H 12 O 6  Zymase
 2C 2 H 5 OH  CO 2

2  C 6 H 10 O 5 n  nH 2 O 
zymase
 
sucrose Glucose Fructose

 nC 12 H 22 O 11
Diastase Maltose
H2 O 2C 6 H 12 O 6
starch

45
 'NUTSHELL REVIEW AND PREVIEW OF ALCOHOL REACTIONS'
PCl5 Na
POCl3+CH3—CH2—Cl
HCl
ALCOHOL CH3+CH2—ONa+

PCl3 CH3MgBr
H3PO3+3CH3—CH2—Cl CH4+CH3—CH2OMgBr
3 O
O
PBr3 CH3—C—OH
H3PO3+3CH3—CH2—Br Conc. H2SO4 CH3—C—O—CH2—CH3
3 CH3—CH2—OH
PI3 O
H3PO3+3CH3—CH2—I O
(CH3—C)2O
SOCl2 CH3—C—O—CH2—CH3
HCl+SO2+CH3—CH2—Cl
HCl/ZnCl2
SOCl2/ CH3—CH2Cl
SO2+CH3—CH2—Cl Lucas Reagent
Cr
HBr 48%
CH3—CH2—Br
[3° R—O—H  Alkene]
NaBr + H2SO4
(3°-Alkene) CH3—CH2—I HI
KI/H3PO4
NH3
CH2=CH2 Conc. H2SO4 CH3—CH2—NH2
170°C Al2O3

H2SO4
CH3—CH2HSO4 Al2O3
100°C CH2=CH2
620 K
H2SO4
(CH3CH2)2O
H2SO4//140°C
135°C
Na CH3—CH2—O—CH2—CH3
CH3CH2—O—CH—CH
2 3
CH3—CH2—I (1°)

CH3
OH OH
H3C–C–OH
Reagent H3C CH2 CH2 CH2 H3C CH2 CH CH3
CH3
1° Alcohol 2° Alcohol 3° Alcohol
PCC/CH 2 Cl2
PDC/CH 2 Cl2 O O .8
Jones Reagent
H 2 CrO 4 /Aq.
H 3 C CH 2 CH 2 C H H3 C CH 2 C CH 3 No reaction
Acetone

K2Cr2O7/H O O O .8

KMnO4/H+/OH/ H 3 C CH 2 CH 2 C H H3C C OH + CH 3 C OH
O O CH 3
Cu/500°C H 3 C CH2 CH 2 C H CH 3 CH 2 C CH 3 H3C C CH 2
Al(OBu t) 3 O O
Acetone H 3 C CH 2 CH 2 C H H3C CH 2 C CH 3 -
or cyclohexanone
Lucas Reagent Cloudiness appear within five min. Immediately
HCl/ZnCl 2 upon heating after 30 mins.
at normal temp. no. reaction
Victor Mayer's Te st
CH 3 CH 3
P/I 2 C H 3– C H 2– C H 2– C H 2– I H 3 C CH 2 CH I H3C C I
CH 3
CH 3
AgNO3 C H 3– C H 2– C H 2– N O 2 (C H 3 ) 3 – NO 2
H3 C CH 2 CH NO 2
CH 3 No reaction
HNO2 H3C CH 2 C NO 2
NaOH H 3C CH 2 CH NO 2
N OH
Nitrolic acid N O
46
 Dihydric Alcohol
Methods of Preparation (Antifreeze Agent)

CH2
O
CH2

CH2 OH
CH2 OH

Chemical Properties
Two 10 Alcoholic group : one OH group always react completely before other group react

2CHCOOH
3 Na Na
H2C OAc CH2 CH2 CH2 CH2

ONa
50°C 160°C
CH2OAc OH ONa ONa
Glycol Diacetate 2HNO3 Disod glycollate
CH2 ONO2 PCl5
H4SO4 PCl5
CH2 ONO2 CH2 Cl CH2 Cl

O Ethylendinitrate CH2 OH Cl OH CH2 Cl

H2C CH3CHO
HC CH3 PBr3 PBr3
CH2 OH CH2 Br
H2C CH2 Br
O Ethylene glycol
Acetal CH2 OH CH2 Br
CH2

770K
O +H2O PI3
I2
CH2 I CH2
CH2
H3C CH2 I
O CH3 CH2
H2C C O
Ketal C H3C HCl HCl
H2C CH2Cl CH2 Cl
O CH3 +
160°C
H 200°C
CH2OH CH2 Cl
O
CH2 CH2
H2SO4/
H C
HNO3
H3PO4/
CH2 OH (conc.) O O Fission of C—C bond
[O] Glycoaldehyde
CH2 CH2
CHO
O O
CHO [O]
HIO4 or (CH3COO)2Pb HCHO+H—C—H+ HO
2
COOH [O] Glyoxal
(formaldehyde)
CH2OH
COOH
Glyocollic acid [O] [O]
CHO COOH + + + HCOOH + HCOOH + H2O
K2Cr2O H or KMnO4+H (Formic acid)
Glyoxalic acid COOH
Oxalic acid

47
 Nutshell review and preview Ether & Epoxides
 
H2SO4/140°C
Cl
Cl2
2C2H5 OH

Dark
H3C CH O CH CH3
CH3—CH2—I
+ Cl
(R°1°)
H3C CH2 ONa
Cl2
Cl Cl Cl
hv Cl C C O C CCl3
Dry Ag2O
2C2H5I Cl Cl Cl
H3C CH2 O CH2 CH3

Hg(OAe)2 6O2
CH2=CH2 H3C CH2 O CH3 4CO2+H2O
C2H5OH/NaBH4

(C2H5)2OO
R O R O2/O3
uv
CH2N2/BF3 +
CH3—CH2—OCH3 HCl H
(C2H5)2O Cl—
H+/CH3—CH2—OH
CH2=CH2
dil. H2SO4
2C2H5—OH
HI/cold
CH3—CH—OH + CH3—I (HI>HBr>HCl)
HI/cold
CH3—CH2I + CH3—CH2—OH
HI/
PCl5/-POCl3
2C2H5—Cl
excess CH3—CH2I + CH3—CH2—I
O
H3C O CH3
H3C C O C2H5 + C2H5Cl
ZnCl2
O
AC2O/ZnCl2 O
C2H5Cl + 3 C OC2H5
H C CO/150°C
H3C CH2 C O CH2 CH3
BF3/500° atm
O
F3C C O O H 1/2 O2/Ag
CH3—CH=CH2 CH3—CH=CH2
O H NaOH Base catalysed Nu — addition reaction
CH3 CH CH2 Cl —

Nu
O OH
Acid catalysed Nu— addition reaction H+
O CH3 CH CH2 CH3 CH CH2
+
OH H O CH3CH CH2 Nu Nu
H3C CH CH2 CH5 CH CH2 [Nu — attact least substitution carbon]
+2 +1
Nu + +

Nu H OMgBr OH
NO— attack C + (more stable)
RMgBr H3O+
CH3 CH CH2 CH3 CH CH2

+
OH H O +
R R
H
H3C CH CH2 O OH
 H+
I H3C CH CH2 HI NH3
I CH3 CH CH2 CH3 CH CH2
OH +H+
HBr NH+ 3 NH2
H3C CH CH2 +
Br + ONa OH
C2H5ONa C2H5-OH
OH CH3 CH CH2 CH3 CH CH2
H Cl
H3C CH CH2 O C2H5 C2H5 O
Cl O OH
OH + LiAlH4 dil. HCl
H CH3 CH CH2 CH3 CH CH2
H3C CH CH2 Et2O
H2O18 H
18
OH H
OH + + O H
H H
H3C CH CH2 CH3 CH CH2
R-OH H2S
O R SH
OD +
+
O H
D H
H3C CH CH2 CH3 CH CH2
D2O C2H5SH
OD S C2H5

48
 Nutshell preview and review of Carbonyl Reaction

O A B O
H3C H3C H2N NH2
C N NH2 + C N NH2 PH 4.8 to 5.2
C C
H3C H H3C CH3
H H3C

Silver mirror O +
[Ag(NH3)2] OH H OH CH3
Test Ag+CH3 C OH H C N
Tollen's Reagent
H3C C ; H C C CN
O 3
A: CuSO4
CU2O+CH3 C OH CN
(2CuO) Fehling Sol
CH3
(Red)
NaHSO3 OH White crystal
H3C C

Bisulphite
OH OH LiAlH4/Et2O adduct
H SO Na
H3C CH CH3+H3C CH2 3
NaBH4/EtOH
CH3MgBr CH3 OH
OH OH
Al(OPri)3 H3O+
H3C C OH ; H3C C CH3
H3C CH CH3 ; CH2
PriOH H CH3
M.P.V. Reduction
CH3
Zn-Hg/HCl or C2H5OH O C2H5 CH3
H2N-NH2/EtONa/
H3C CH2 CH3 ; CH3 CH2 H
H+ H3C CH O—C2H5
CH3 O C2H5
; H3C C
+ CH3 CH3 Mg-Hg/H2O O—C2H5
H CH2 OH
H3C C C CH3 H3C C C CH3 H3C O
B H3C O
O CH3 CH2 OH
OH OH
H+
C ; C
Pinacolone
Pinacol H O H3C O
CH3
O Evaporated H2N OH H3C H3C
C
Dryness
(CH2O)n.nH2O O H O
Conc. H2SO4
PH 4.8 to 5.2 C N OH ; C N OH
nCH2 Paraformaldehyde
CH CH
Room Temperature H HC
3
A
H3C O CH3 H2N NH H3C H3C
Paraacetaldehyde
PH 4.8 to 5.2 C N N Ph ; C N NH—Ph
H3C CH O CH CH3 H H
O CH2 CH3
O Conc. H2SO4 O
Room O O O O
nCH2 H2N NH C NH2 H3C
Temp. CH2 CH2 273K (A)

H3C CH O CH CH3 C N C NH2

O Metaacetaldehyde H
Mataformaldehyde
CH3 H2N C2H5 H3C
C N C2H5 imine
Conc. H2SO4
H
(CH3)2C CH Reflux (B)
Et
H N Et2
C O H3C CH3 CH2 CH N Enamins
(CH3)2C CH Dry HCl Et
Et3N
Phorone No reaction
O O
CH2
Reduction H3C C O CH3 F3C COOH
O Bayer villiger oxidation NH3 CH NH2 O
LiAlH4/Et2O NH NH ; H C C CH2 C CH
H3C CH CH C H H3C CH CH CH2 OH 3 3
NaBH4/EtOH
CH3 Diacetone amine
O
LiAlH4/Et2O H3C NH CH3
H3C CH CH C H H3C CH CH CH2 OH
NaBH4/EtOH
Ph3P CH2
O H3C C CH2 ; H3C C CH2
NaBH4/EtOH
OH DMSO
CH CH C H H CH3
CH CH CH2
Wittig Reaction
LiAlH4/Et2O O O
NaOI +
H2C CH2 CH2 OH +
Haloform Reaction CHI3+H C ONa ; (CH3 C ONa)
O
NH2NH2/H2O2
SeO2
OO OO
H2C CH2 CH2 C H H C C H+ H3C C C H

49
 As Nucleophile : (Active H-containing comp)
GRIGNARD -REAGENT GRIGNARD REAGENT as BASE
O O H O H
R H + Mg(OH)Br
R C O H C O
R O H
H3O+ R H + Mg(OR)Br
O D O D
R D + Mg(OD)Br
(1°) R CH2 H H C H
OH H3O+ R H+ MgBr
O
O H H NH2
(2°) R CH CH H3C C H H R H+Mg(NH2)Br
3
H3O+ H N R NH R
O H O R H + Mg
R Br
R C R R C R
H N R NR2
R H3O+ R H + Mg
O O Br
NR3 No reaction
H C R H C OEt
SH

1eq. H S H
O R H + Mg
OH OMgBr Br
H3O+ H C OEt
R CH R H C R R' C C H
excess R H + R' C CMgBr
R
O
O H NH Ph
R C OEt R H+ PhNHMgBr
R C R 1eq. H O Ph
R H + PhOMgBr
O H O
O
R C R R C OEt O
NH
R excess/H3O+
RMgBr NMgBr
O R H+
O 1 eq.
R C Cl O O O
R C R
1eq.
O H O R H+ MgBr
R C Cl
R C R O O

excess/H3O+
R R C NH2
O H C N 1eq.
R H+R C NHmgBr
R C H H3O+ O O
O R C N C OEt
OH
R C R H3O+ OEt
O H3O+
R C R
O R
S O O
R S OH O
H3O+ Cl C Cl
1 eq. R C Cl
O O
1. SO3
RSO3H Cl C Cl
2. H+ R C R
2 eq.
O
OH O
O H
Cl C Cl
R CH2 CH2 R C R
excess /H3O+
H3O+ R
I I
H O R I
O R CH CH2
Br Br
R Br
R CH CH2 R H3O+ Cl C N Br
R C N + Mg
O2
Cl
R OH Cl NH2 Br
H3O+ R NH2 + Mg
Cl
CN CN CN
R4Pb 1/4 PbCl4 R CN + Mg
½CdCl2 Br
R2Cd

50
 Nutshell preview and review of Carboxylic Acids
PREPAR ATION & RE ACTION
K2Cr2O7/H
O + O O
H3O

KMnO4/H 
483 K H3C C O C CH3
H3C CH2 OH NaOH+CO 6-80 atu
H C OH
Cl
O BF3 Aq.KOH
cress
[O] CO+H2O HCOOH Cl C CH3
H3C C OH O Cl O
[Ag(NH3)2]+, 2CuO

CO H3O+ NaOI/CH+
CH3 H3C OH H C OH
KMnO4/H 200°C H3C C CH3

-CHI3
H3C CH2 CH2 C COOH
H2C OH O CO+H2O
O COOH H2C CH2
dil. HCl HC OH H C OH H3PO4
H3C C N H2C OH 110°C+H3O+ O
SOCl2+CH2N2
O CH C Cl
dil HCl, dil HNO2 H2O/Ag2O 3
H3C C NH2 O O
dil NaOH/H+ + Amdt Eistert reaction
O H3C C OH C O/H3O
H+/H2O BrMgCH3
H3C C OEt HO/H O/H+ O Special Method:
2
O H3C CH2 C OH
H2O
H3C C Cl + —
H /H4O

O

O O O O
P2O5 H O C C OH H3C C OH ; H2C C OH H3C C OH
H3C C N O C OH
O

O O Na/NaOH + NaOH
NH3/OH
H3C C NH2 H3C C ONH2 NaHCO3 H3C C ONa CH4
CaO
Kolbes
O H3C CH3
(H3C C O)2Ca 
Br2 Ag2O O electrolysis
H3C Br H3C C OAg CaCO3
CCl4
Reflux O H3C C CH3
O
P2O5/
H3C C MnO/300°C O
O O H3C C CH3
H3C C 2 2
O H3C C O
O O C2H5OH
H3C C H3C C O C2H5 [Esterification]
CH3OH>EtOH>Pri OH>ButOH
H3C C OH AlPO4 +
O H2C C O H P.ate
Ketene 973-10301C
O O O
O
O
i t O
PCl5
H C > H3C C OH > Et C OH > Pr C OH>Bu C OH
H3C C Cl SOCl2 OH
LiAlH4
H3C CH2 OH
H2O

HN3
HI/P H3C NH2 (Schimdt Reaction)

H3C CH3 H2SO4
O Cl O
Cl2/P Cl2/hv
O
h
+ H3C CH C OH H3C C C OH
N N CH2
N2+CH3 C O CH3 Cl Cl
CH2N2
Hell Volhard Zelinsky Reaction
 Reading Tollen's Reagent :
SOCl2 H OH
O H2O
Ag+CO2+H2O
CH2N2 CH3-CH=C=O H3C CH C O
2CuO
H C OH Ag2O
H O C2H5
Fehling solution
C2H5OH
H3C CH C O
O
H C OH
2CuO
Cu2O+CO2+H2O NH3
H OH
red Arndt H3C CH C O
O
2HgCl2 Eistert
H C OH Hg2Cl2+CO2+2HCl H O
Reaction C2H5NH2
O H3C CH C NH C2H5
H C OH +2Hg2Cl2 CO2+2HCl+2HgBlack ppt.
It decolorizes KMnO4/H+ O O

2KMnO4+3H2SO4 K2SO4+2MnSO4 + 3H2O + 5[O] H3C CH2 C OH

H3C CH2 C
O
O H3C CH2 C
H C OH + CO [CO2+H2O] × 5 O

2KMnO4 + 3H2SO4 + 5H—C—OH K2SO4 + 2MnSO4 + 5CO2 + 5H2O

O
Note : Formic acid does not react with NH2OH; secarbazide & phenyl / hydraze
O O O
  
O C OH CH2 C C OH
COOH
CO2
H C OH : (CH2)2 O: O
COOH C OH CH2 C C OH
O O O
O O
O O
 
C OH

C OH C OH
H2C C
CO2 O O
C OH C OH C
O C OH
O O
O

51
 O
PCl5 or PCl3 or SOCl2 Distill.
O
H3C C OH
O
A SOCl2 Ca2+ (O
O
C CH3)2
PCl3
H3C C ONa
+
Distill. C PCl5
EtO C CH3
O O O
H3C C ONa
+
POCl3
Distill
I PCl5
H3C C O C CH3

NH2
O O NH2 D H2O
O
HN3
H3C C OH H SO CH3NH2
HN C CH3 HN C CH H+/HO—
3 2 4 (Schimdt reaction)
H2O
O
NO2 C2H5OH
H3C C O C2H5
HO
C —HCl
+ O
C2H5ONa
NO2 O
NO2
H3C C OH
H —NaCl
H3C C O C2H5
O O O
H3C C O C CH3 L C2H5O C2H5
ZnCl2 H3C C O C2H5 +H3C CH2 Cl
N

O O +
O O OH
O
O C CH3
OH OH O
H3C C ONa

O
H3C C O C CH3 R AlCl 3
C
+ CH3
H2O CH2N2
H3C CH2 C OH
Arndt Estard Reaction
H3C CH C O Aq2O I
(At 60°C) O C CH3 (At 120°C)
O D
..
Fries - Rearrangement
C2H5 OH
H3C CH2 C O C2H5 O
O
NH3
E NH3
H3C C NH2
Br2
KOH
H3C NH2 Carbylamine Test
H3C CH2 C NH2
Hoffmann Bramoamide degradation
O C6H5 NH2 O
H2N C2H5
H3C CH2 C NH C2H5 H3C C NH C2H5
1° +
O Et O C2H5 H3C N C
Et2NH HN(C2H5)2
H3C CH2 C N H3C C N KOH CHCl3
Et 2°
O Acetyl Chloride C2H5
O Et3N H3C NH2
H3C CH2 C No reaction
H3C CH2 C OH H3O+
O O HNO2
NH2-NH2
H3C CH2 C H3C C NH NH2 + H3C N C O
H
O +
O NaN3
O OH
+ CH3MgBr
Curtius Reaction H C C N N N CH3MgBr


3 H3C C CH3 H O+ H3C C CH3 (3°)
3
H3C N C O CH3
H3O+ O O CH3
H3C NH2 (CH3)2Cd H2SO4
O HO NH2
H3C C CH3 H3C C C C Mesityl Oxide
(CH3)2CuLi 2
Lossen Reaction CH5 C NH O H H CH
3
O
H3O+ AcCl dry HCl

H3C NH2 H3C N C O (CH3)2C=CH—C—CH=C(CH3)2
O
Ph2Cd
H3C Ph H3C Ph HO NH2 H3C C Ph
C C PH48 O O
N
+ N Backmann Rearrangement
Ph2Cd
H3C C Ph
F3CCO3H
H3C C O
OH HO (Bayer's Villiger oxidation)
O O
Conc.
H3C NH C Ph + Ph NH C CH3 o H2C CH3
H2SO4 O C CH3 Zn-Hg/HCl
LiAlH4/Et2O AlCl3
r NH2-NH2/EtONa+

H3C CH2 OH NaBH4/EtOH

O
[or LiAl(Obu)3H/78°C] H3C C H
H2/Pd
Red P/Cl2
O
BaSO4
Quinoline-S hv Cl CH2 C Cl (H.V.2 : Reactions)

52
 Heating effect
-Hy d r o xy a c id
-Hy d r o xy a c id O OH O O
O +
C H

O H HO C + O CH 2 CH 2 C OH H2C C C OH
H HC CH 3 H

H3C CH HC CH 3 H3 C CH 3
O O CH 3 O
C OH H O C O H +
H

O O Lacitide H3C CH CH 2 C OH CH C H C OH

K e t o a c id :
H y d r o xy a c id

O O O
O O

H3C C C C OH H3C C CH 3
H 
CO 2
C
-Lactone
+
C H2
 OH
O O

OH O NaO H

O2N C C OH H3C C OH
O H2

O
H 

+
C C NO 2
 OH
O -Lactone
O H
 
HN O 2

H
+
O

O O H O

Ph CH CH C O Na Ph CH CH C H Ph3 C H2 C H

53
 Nutshell preparation of Ester
O
H2SO4

H3C C OH+CH3 CH2 OH O O
H3C C O H+CH2N2 H3C C O CH3
O
ThO2
H3C C OH+CH3 CH2 OH Vapour
O
C2H5OH
Phase esterification O H3C C O CH3
O F3CCO3H H3C C or CH3—CH2—ONa+
H3C C CH2 CH3 O CH2 CH3
O
CO
H3C O CH3 H3C C O CH3
BF3/350K
O
Bayer villiger oxidation Al(OEt)3
O H3C CH2 I H C CH3
Tischenko Reaction
H3C C OAg AgI

Nutshell chemical properties of Ester

O
H3C C
O CH2 CH3

O
O Pyrolysis
HI H2C CH2+CH3 C OH
H3C C OH -C2H5I
O
O C3H7ONa+
NH3 H3C C O C3H7
H3C C NH2 (Transesteri fication)


O

(Irreversible) O
HONa H2O
H3C CH2 OH+CH3 C ONa H3C C OH+CH3 CH2 OH
H2O +
H
O (Reversible)
C2H5NH2
H3C C NH C2H5 O
NH3
O H3C C NH2
NH2-NH2
H3C C NH NH2 O
H2N-OH
OH O CH3MgBr H3C C NH-OH
CH3MgBr
H3C C CH3 H3O+
H3C C CH3 O
(CH3)2CuLi
CH H3C C CH3
O
DIBALH
Bui2AlH
H3C C H+CH3-CH2-OH
OH OH LiAlH4
H3C CH2 + H3C CH2 O OH
Et2O Na/xylene
H3C C CH CH3 Acyloin Condensation
O PCl5 H3O+
H3C CH2 Cl + H3C C Cl O O
EtONa+
EtONa
O O H3C C CH2 C OC2H5
Zn
C2H5O C CH2ZnBr Et O H2C C O C2H5 Claisen condensation
2 Br2
Br
O O
O O O
Reformat sky reaction C Ph EtO C Ph Darzen
CH2 CH C CH3 CH3 C H C CH3
CH3 CH3 reaction
H3C C C
+ O O H C OEt
O O ZnBr Ph C CH C OC2H5 N O
N Knoevengel Reaction
C2H5O C CH2 C Ph H Br OH O
H
-Br CH2 C C CH3 CH2 CH C CH3
H2O NH4Cl
EtO C CH3 EtO C CH3
O O C H C C H C
O OH
C2H5O C CH2 CH Ph Ph CH CH C OC2H5 O O O O
 OH/H2O Micheal addition
+
O H
Ph CH CH C OC2H5 H
+
O O
O H O 
Ph CH C H Ph CH CH C O
Ph CH2 C H

54
Amino Acid :
O O
O O
NH 2
 H 
HO C NH C +
H3C CH OH NH
CH CH 3 H3 C CH CH CH 3
C OH H2N NH 2
C NH
O
O
O

 OH H 
NH 2 O O + C O
H3C CH CH 2 C OH H3C CH CH C OH NH 2
NH
55
 METHOD OF PREPAR ATION OF AMINE
• Hoffmann's Ammonolysis
H 3C C H 2I C 2 H 5I +
NH 3 H 3C C H2 I (C 2 H 5) 4 NI
H 3 C CH 2 Br H 3 C CH 2 NH 2 (CH 3 CH 2) 2 NH (C 2 H 5) 3 N
-HX

Good yield 1° Amine (If NH3 1° excess) / Not suitable for Aryl Amine)
Reactivity - R-I > R-Br > R-Cl
• Gabriel / Phthalimide Synthesis :

O O O O
C C C C OH
N H3 K OH H2O
O N H CH 3-I N CH 3 + H 3 C NH 2 +
H
C C C C OH
O O O O

2° & 3°  can't be prepared : Aromatic amine can't prepared Eschweiler Blarke synthesis
• Reduction H OH
Na/EtOH R 2 NH + C O R 2 N CH 2
H3C C N LiAlH /Et O H3C CH2 NH2
2 4
H H
+

+ N a/EtO H
H3 C N C LiAl H /Et O H 3 C C H 2 NH 2 R 2 N CH 3
4 2 R2 N CH 2
O C H
LiAlH 4 /Et 2 O
R C H N OH R C H 2 NH 2 O

or N a/Et O H Formic acid act as
or B 2 H 6 /T HF reducting agent by transferring R 2 N CH 2
a hydride to the electron-deficient
• Hoffmann Boroamide Degradation : carbon & is oxidized to CO 2
O Br 2 H 2O
R e d u c ti v e A m i n a ti o n L e u c k a rt r e a c ti o n


H 3 C C NH 2 H3C N C O HO H 3 C NH 2 O
KOH O NH 2
NH 4 H C O
• Schimdt Reaction : Ph C CH 3  Ph C CH 3
O + O
HN 3 + H 2SO 4 H 3O O NMe 2
R C OH R N C O R NH 2 H C NMe 2
Et C Et (DM F)/ Et CH Et
• Lossen Reaction

O H 2 N OH
+ O +
H3O NaN 3 / H3O
R C Cl R N C O R NH 2 R C Cl R N C O R NH 2
H3C C Cl
+
O H 2N
NH 2 H 3O
HONO + H+
R N C O R NH 2

Fe/HCl +
R NO2 Sn/HCl R NH2 H/H 2 O
R N C O R NH 2
SnCl2+HCl HO/H 2 O

+ O Cl-NH 2
+ H/H 2 O
R N C R NH 2 + H C OH R Mgx R NH 2
Sn/HCl

56
 CHEMICAL PROPERTIES OF AMINES
..
Reagent R NH 2 (1°) R 2 NH(2°) R3N (3°)
NH 2

+ +
+ + Cl
1 . HCl R3N NH 3 Cl
R NH 3 Cl R 2 NH 2 Cl
H
+
2 . C H 3 —B r R—NH—CH3 R 2 NH—CH 3 R 3 N CH 3 Br NH CH 3

O O O O
3. No reaction
H 3 C C Cl R NH C CH 3 R2N C CH 3 NH C CH 3

O O O O
4. No reaction NH C CH 3
(CH 3 C) 2 O R NH C CH 3 R2 N C CH 3

O
R N SO 2 Ph
R2 N S Ph NH SO 2 Ph
5 . Ph—SO 2 Cl H soluble No reaction
NaOH O NaOH

[R N SO 2 Ph]Na+ Insoluble

+
6 . Carbylamine Test R N C No reaction No reaction +
N C
CHCl3/KOH (:CCl2)
+ +
7 . HNO=O /H + R—OH+ N 2 +HC l R 2 N –N =O R 3 N HON = O N 2 Cl  OH
(0°— 5°C)

8. Hoffmann Mustard Oi l Te st

S S S KOH
C S
1. – NH
C S R NH C SH R 2 N C SH 2

/HgCl 2 R–N=C=S + HgS No reaction No reaction HC l

Ph N C S + Ph-NH 2
2 . Hoffma nn Te st
COOEt CONH R O C NR 2 O C NH Ph
COOEt CONH R COOEt No reaction O C NH Ph
Oxamide (solid) Oxamic ester (liquid)

R'MgX R'–H+R–NHMgBr R"H+R 2 NMgBr No reaction R'H+PhNHMgBr

O N R NR 2 No reaction N Ph

Cl
O C (RNH) 2 C=O (R 2 N) 2 C=O No reaction Ph–N=C =O
Cl
O R
O O
Ph–N=C =O Ph NH C N No reaction
Ph NH C NH R R Ph NH C NH Ph
Oxidation R –C H 2 – NH 2 R 2N H R 3N



KMnO 4 R–CH=NH H3O RCHO R 2 N–NR 2 No reaction
H 2 SO 5 R–CH 2 –NH–OH R 2 N–O–H R 3N = O
R C N OH
OH
R 2 CH–NH 2 :
KMnO 4 
R 2 C=NH H 3 O  R C=O
2
H 2 SO 5 KMnO4
R3C NH2 R3C NH2

57
 Nutshell preview and review of Nitro and Nitrite

CH3
AgNO2 CH3 CH CH2 CH3
H3C I C2H5OH
O HNO3+H2SO4:675K
NaNO2
H3C I DMF or DMSO
H3C N CH3 CH3
O
CH4
H2SO4+HNO3
CH3 C CH2 CH3 + CH3 C CH CH3
675K
O NO2 H NO
AgNO2 2
H2C C OH NaOH/boil CH3 CH3
Cl CH3 CH CH2 CH2 NO2+ CH2 CH CH2 CH3

CH3 NO2
CH3 CH+CH3-CH2+CH3-NO2
NO2

LiAlH4  CH2=CH2
H3C NH2 Et2O
H2/Pt Zn/HCl
H3C NH2 H3C NH2
H2/Rany Ni Fe/HCl
Br O O Sn/HCl
NaOH NaOH
HC C CH2 NO2 Br2
H3C N Zn-NH4Cl
Br2
H2O H3C NH OH
Br OH O
Br
NaOH/
O
NaOH
H3C C CH2 NO2 NO2 CH CH CH3
H3C C OEt H3C C H

O O
O
NaOH/
OH 50%
NaOH
Ph CH CH NO2 H2C N H2SO4 H C H+H2O
Ph C H O

O O O
R CH2 N R2CH N R3C N
2° O O
1° O 3°

HNO2 HNO2 HNO2

R C N O R C NO2 No Reaction
Victor-mayers Test
NO2 N O
Nitrolic Acid Pseudonitriol
NaOH
NaOH

Blue
red

58
 Nutshell Preparation of Benzene

COONa+ MgBr
NaOH+CaO+  H2O
+
BENZENE N2Cl
OH
CH3CH2OH: or H3PO2
Zn/ or NaOH + SnCl2/Na2SnO2

Cr2O3
SO3H Al2O3 (500)
CH
H /H2 O/ 3
+ Red hot Cu tube
CH

Electrophilic Substitution Reactions

E H C H2/Pt
H
+
E+ REDUCTION
+
NO2
Cl
NO2+
Cl2/U.V. Cl Cl
Rate
HNO3 + H2SO4 (BHC)
C6H6C6D6C6T6
Cl Cl
[Nitration] SO3H Cl
SO3
BENZENE
Rate O3 CHO
C6H6>C6D6>C6T6 H2SO4 or H2SO4+SO3 3 OZONOLYSIS
[Sulphonation] Zn/H2O CHO
CH3
O2

Friedal craft CH3+ CO2+H2O
Alkynation CH3Cl+AlCl3 +
I CuCl2+I2
O CH3 OXIDATION
C
+
I
CH3—C=O O
Friedal craft
Alkynation C
CH3C Cl+AlCl3 O2/V2O5 HC
O Maleic anhydride
I2+2Cu2+2I++2Cu+
O HC
COOH 450
C
CO2 or O
AlCl3
I2/HNO3
OH
HIO3 or H2O2
O H O2/V2O5
C
CO + HCl 250
Gatterman Koch
Aldehyde Synthesis AlCl3
CrCl3 Reduction (C6H6)2Cr
CHO AlCl3/Al2O3
Gatterman
aldehyde HCN+HCl+ZnCl Na
synthesis H3O+ Birch Reduction
liq. NH3
O Ni/H2
C Cl C NH2/AlCl3 
NH2
O
O Ph O=CH2
C O
H2SO4
C
Ph C Cl+AlCl3 H2

CH2-Cl H2C OH O CH3-CH=O H

C
H C H+HCl H2SO4
ZnCl2 CH3
HCl ZnCl2
O
HgOAC (CH3)3C C Cl
Hg(OAC)2 CMe3
AlCl3

59
 Nutshell Preparation of Toluene

TOLUENE
Zn/dust

NaOH+CaO HO CH3
CH3

HOOC CH3 +

CH3Cl + AlCl3
H2O/H+
HO3S CH3
(O, P &M)
Al2O3+Cr2O3
H
+ C2H5OH, H3PO2/H2O/ 500
Cl N N CH3
SnCl2+NaOH CH3Br
(O, P &M)
AlBr3 (low temp)

Nutshell Review and Preview of Toluene Reactions

Electrophilic Substitution Reactions OXIDATION COOH

CH3 KMnO4
Cl OH
Cl2
+ H3C Cl AlCl3 TOLUENE H O
CH3 CH3 C
CrO2Cl2
NO2+ H C H2SO4 ETARD
3 NO2 REACTION
H2SO4+SO3

CHO
CH3 H2SO4
SO3H + H3C SO3H CrO3+AC2O
H2SO4+SO3
H3O+
CH3 OXIDATION CHO

OXIDATION
O2N NO2
HNO3(F)+H2SO4 CH3 COOH O2/V2O5/N2
(TNT)
T 80°C KMnO4 450°C

CH3 NO2 CHO

CH3 COOH
CH3 CH3-Cl/ACl3 O2/MnO2
+ H3C CH3 CH3 COOH
500°C
O KMnO4
CH3 CHO
H3C C Cl
H3C C
AlCl3 O2/MnO2/40
O CH3 COOH Conc. H2SO4(65%)
CH3 O

NO2 H3C C O NO2 CH2Cl CH=CH2

AC2O+N2O5
KMnO4 KMnO4
OH
CCl3 CHCl2 COOH
H2C Cl
CH2NH2 CH2OH
Cl2 Cl2 Cl2
hv hv KMnO4 KMnO4
hv

 Aq KOH  Aq KOH
OH
 Aq KOH
Oxidation O O
COOH CHO CH2OH
CH3

C C
KMnO4 OH
OH O
CH3 OH
C C
O O
OH NO2 NO2
KMnO4
COOH COOH
A B A KMnO4
OH A B A
OH
COOH COOH
CMe3

If  is absent
KMnO4 
OH
Me3C COOH CH3COOH

60
61
 Nutshell Review and Preview Phenol Reactions
NaHCO3
No effervences
NaOH +
Na2CO3 ONa
H CH2 O CH2 CH
O
O Na+ O CH3
CH2CH CH2 CH2 CHCH2 Cl
200°C
NaOH CH3I
Claisen
OH
Rearrangement O O
60°C OH O CH3
H3C C Cl
O C CH3
CH2N2
BF3
Fries C H
Rearrangement O CH3
NH2
Zn
H—O
NH3 PHENOL 
C CH3 120°C ZnCl2/300 Cl
O
PCl5
+ FeCl3 + (Ph O)3PO
3HCl+ [(Ph3O)6Fe]3-3H Neutral
(major)
Violet Colour O
O
Ph C Cl
O C Ph
Schotten Baumann Reaction
Reaction due to Bezene Ring
OH
O2N NO2 OH
(Oxidized P) Conc. HNO3+H2SO4 Br2
+ H2O
Br Br 2,4,6-Tribromophenol

NO2 OH OH
OH OH
Ph Br
NaNO2
HNO3 Br2 +
H2SO4
CS2 OH
93%
7% O2N SO3H OH
OH Br
NO2 N O O2N NO2
NO2
SO3 H + NO2
Conc. H2SO4 HNO3/H2SO4
H2O Blue
Blue NaOH Red PhOH
acess Green 100 SO3H
H2SO4
OH NO2
OH O SO3H
1 Br2 /NaOH Br
OH 125°C
C 2 H2O/H
+

Kolbes OH
Schimdt CO2/NaOH
OH OH
Reaction
H
+ CH2=O CH2OH
250°C + NaOH

COOH MeOH Bakelite
OH
HO C CCl4 CH2OH
O KOH OH O
CHCl3
KOH
C
NaOH H Riemer Tiemann Reaction


N N OH
N NCl
OH O OH
HCN+HCl
CH3 ZnCl2/H3O
C
H
Acetone + Gatterman
HO C OH Conc. HCl Reaction
AC
O CH3 O CHO
C OH C (major)
ACCl OH O
O O
Asprin C CO2/NaOH C
OH 125°C
O O NaOH
O Phenophithalein (Pink colouration)
MeOH
C + CrO2Cl2
OMe H O O (Benzoquinone)
Oil of wintergreen
K2S2O8
HO/H2O
HO OH [Elb's persulphate Oxidation]

air/O2
OH
Ph OH O O HOPh+ O O H2/Ni
Phenoquinine (red)

OH O OH O
CO2/NaOH
C Ph-OH C
125°C/H+ OH O
POCl3

CO2/KOH
O Phenyl salicylate
+ HO C
H OH (major products)

62
 Nutshell Review and Preview of Aniline
CHEMICAL PROPERTIES
+
+ H2SO4 +
NH3 SO42— Anilinium
H-Cl
NH3Cl Sulphate
2
+
HAuCl4 +
+ NH3 AuCl4 Anilinium
NH3 PtCl62 H2PtCl6 Chloroaurate
2
Anilinium chloroplatinate NH2 +
O
+
O H3C C Cl NH3
C CH3 or AC2O Anilinium Picrate

NH CH3
PhSO2Cl Ph N +
SO2 NH ANILINE CH3 Ph NMe3I
CH3
O
CS2/ NH C
N C S O
Schotten Baumann Reactions
C Cl O
Phenyl isothiocyanate
H Cl NH C NH
Ph-C=O Diphenyl Urea
N CH Na
+
+
NHNa
Benzalaniline [Schiffis base]
NH2 CHCl3 +
Br/CCl4 N C Carbylamine Test
Br KOH
H2N Br + Cl-Ph
NH
CuCl2/200°C
NH2
Br2/H2O NaNO2/HCl +
Br Br N2Cl— +2H2O
NH2 0-5°C
NH2
NaCr2O7
Br Aniline Black
+ Conc. H2SO4
HNO3+H2SO4
NO2 NO2 K2Cr2O7/H+
O O
NH2 O
O
NH2 NO2 H3C C Cl
F3C C OH
+ HNO3+H2SO4/H3O+ NO2
Conc. HNO3
H2SO5
N O
NO2 H2SO4
H2N SO3OH
180°C
NH3
Ni/H2
200°C 100 atm
Cl
+ CuCl+HCl
O C H CH2=NOH N NCl
HO—/H2O CuBr+HCl Br
Reaction with CS2
OH CuCN+HCN CN
HO N N SH
NH2 HN C S
NH2 KI I O AgNO2
H2N Cu powder C S or HgCl

N N
N C S+HgS
Cl Black
H NH-CH3 Cu/HCl
N-Phenyldithiocarnic Phenyl isothiocyanate
H3C H N N
Br O
OH Cu/HBr S
OH C S
N C N
F Solid H H
N N N
B-NaP HBF4 KOH

C2H2OH/ H3PO2/
HCl
NO2
NaNO2 N C S+ NH2,HCl
SnCl2/NaOH
OH
Cu2O
  
NH-NH2

SnCl/HCl

63
 Nutshell Preparation of Nitro Benzene
NH2
NO2 O
HNO3 +H2SO4 conc.
F3C C O O H
N O
N2O5/AC2O HNO3 H2SO5 
N NCl
NITRO NaNO2/Cu powder
BENZENE 

Nutshell Sulphonic Acid

BENZENE SULPHONIC ACID
SO3H
H2SO4
H2SO4+SO3 SO3H
200-245°C
H2SO4 / 180°C SO3H
Cl-SO3-OH/Mole (1) H2SO4
SO3H SO3H
SO3H CCl4 280-300°C
SO3H
HNO3
H2SO4 
SO3H Br2/Fe
NO2 
O Na Br
OH
+ NaOH HOH+H
H
Fused 150-200°C

NeBr
NaNH2 fused
NC
H2N Fused
NaSH

O SH
HO C O fused
H C ONa

Br
PCl5 NaCN
fused
+
SO3Na
O
+ O
SO2 H3C C ONa +
AlCl3 + H3C C ONa

64
 Nutshell Preparation of Benzaldehyde
CH2Cl
CO+HCl + Anh. AlCl3 (CH2)6N4/EtOH
Gatterman KOCH Aldehyde Synthesis H3O+ O Cl
HCN+HCl+ZnCl2/H2O
C
Pb(ONO2)2/HNO3
O H
Gatterman Aldehyde Synthesis C H2Pd-BaSO4-Quionoline-S
Rosenmund's Reduction
CH3 CrO2Cl2/H3O(Etard) H2C OH
CrO3/AC2O/H3O Br
CrO3/ N or MnO2
O +
N2Cl
BENZALDEHYDE Mg/H C OC2H3

CH2=N-OH
H O+2

Nutshell Review and Review of Benzaldehyde Reactions

O OH OH OH

Cl2
C Cl H C CN H C C
O
H H H H C N H3O+
2NH3
C N C N C OH

Ph O H OH
C +
O H C SO3Na
KCN
CH C
EtOH NaHSO3
OH
Benzoin Condensation HNO3
H
H2N OH
Benzylic acid rearrangement C N OH
OO
+ KOH
H2N NH
H
C C OK C C O
C N NH2
Ph O O2N
O O2N
AC2O/ACO H2N NH NO2 H
Perkin condensation CH C OH
KOH C N N NO2
H
O O
H O
C Oct CH2(COOEt)2
H2N NH C NH2
Knoevengel Reaction CH C C N N C NH2
H
C Oct Zn/HCl
O LiAlH4/Et2O CH2OH
Reformatsky Reaction Br O

O
CH C OEt
CH CH C OEt z ZnH2O/NH4Cl O C ONa+ CH2OH
CH3NO2 NaOH
CH CH NO2 50% +
Cannizzaro Reaction
O O
H2N
H3C C CH2
NaOH/
CH CH C CH3 CH N Ph Schift base

Tollen's Reagent
+Ve Test
Me2N Schift Reagent
Conc. H2SO4
Pink color
HC Fehling Soln.
No reaction
Malachite green 2Me2N H
H
M32N PCl5
C Cl
O C H
Cl
Conc. H2SO4
H2SO4/
[O]/Air
C OH
SO3H
O
CHO OH
PhMgBr
H O+
C
F-HNO3 3
H
H2SO4
NO2 1.AlH4
2.H+
CH2 OH
CHO
Cl2/AlCl3

Cl

65
 NUTSHELL PREPARATION OF BENZOIC ACID
CH3

MgBr MNO4/OH O=CCl2/AlCl3

H3O
O OH
CO /H O
O Cl
C C
COOH 2 3

H3O
Zn
C N 
O C OC2H5

H3O
OH H3O CCl3
Benzoic
H2C X
Acid
aq.KOH
KMnO4/OH 

SO3Na+
O
+
H C ONa
fused

NUTSHELL REVIEW AND PREVIEW OF BENZOIC ACID REACTIONS

O C Cl O C ONa
PCl5 NaOH/
PCl3 or SOCl2 NaHCO3
O OH

O O P2O5 O O
Ca(OH)2
 
2+
C OC C C O Ca Ph C Ph

NH3/
Soda lime O

P2O5
C NH2 C N
Hunsdiecker Reaction
Br COOAg LiAlH/HO
4 2
CH2OH
Br2/CCl4 Ag2O
Reflux
N3H/HSO
NH2 Schimdt Reaction
2 4

 
O
N2O C
BENZOIC O
C2HOH
5
C O C2H5
O
(i) SoCl2
ACID H+
CH2 C OH
(ii) CHN 4 2

Arndt Eistert (iii) HO/Ag

2 2O
Reaction
COOH
COOH
Cl2/FeCl3 conc. HNO3
 conc. H2SO4
Cl
NO2
COOH
COOH
Br2/FeBr3 conc. H2SO4
 
SO3H
Br

OH OH O OH
Br Br C O2N NO2
Br2 OH FINO3
H2O -CO2

Br NO2

66