REACTION CHART FOR ALKANES

GMP GR
H , Ni
(1) R–C  CH 2  (1) X , h or UV light or 400 C
2         
 RX
200300C
or
R–CH=CH2 Sabatier senderens
(2)  R-N
Nitration
reaction

(2) R–X Cu

Zn 

HCl
Sulphonati on H S O
Re d P  HI , LiAlH 4 (3) 2
       2
7  Alkyl Sulphonic acid

(3) RX Na
,dry ether

Wurtz reaction Reed reaction
(4) SO2 + Cl2    RSO2Cl
h
(4) RX  Zn

Frankland 's reaction
R–H
AlCl / HCl
(5) RX     R 2CuLi
 or (5) 3 branched
Isomerisation
alkanes
( Corey  House reaction 
) 

4
R–R
 HOH or ROH or
(6) R–Mg–X      CnH2n+2 (6) Pyrolysis
or NH3 or RNH 2   Alkenes + CH4 or C2H6
500 700 C

Cr or Mo or V oxide
       
(7) R–OH, R–CHO Re
dP / HI
 (7)  Al2O 3 500C Aromatic com-

R  C  R , RCOCl, RCOOH pound

||
O CH N
2
  2

Zn  Hg / Conc. HCl
(8) step up reaction
Higher alkane
(8) R CR    

Clemenson 's reduction
||
O O
2
(9) 
 CO2 + H2O

H 2 N  NH 2
       

(9) R CR Wolf / Kishner reduction
Combustion
||
O
or
(RCH2CH2)3B H O
2

(10) RCOONa NaOH  CaO



(11) RCOONa Kolbe

 'selectrolytic synthesis
  
 REACTION CHART FOR ALKENES
GMP GR
H Ni
(1) 2, R–CH2–CH3
(1) R–H Pyrolysis
 200300 C

(2) X
2 R–CHX–CH2X
Ni, H
2
(2) R–C  CH 
R–CH=CH2 (3) 
 R–CHX–CH3
HX
200300C
or (4) HBr
CnH2n   R–CH2–CH2Br
, Peroxide

(3) R–CH2–CH2–X alc

. KOH
 (5) HOCl
 R–CH(OH)–CH2Cl
 HX
dil. H SO
(6)  HO R–CH2(OH)–CH3
2 4
Zn dust
 
 2
(4) R–CH2–CH for higher alkene
X 2 (7) 
1/ 2O2
Ag,300C

R  CH  CH 2
(5) | | Zn
dust

 (8) 
CH 2 N 2

X X
(9) BH
3  (RCH2CH2)3B
(6) CH2=CHCl CuR 2
 R  CH  CH 3 R  CH 2  CH 2
CO  H
(10)  
2 
HCo ( CO ) 4
| + |
conc. H SO CHO CHO
(7) R–CH2–CH2–OH  24  O
 H 2O (11) 
2
CO2 + H2O


(8) R  C  O  CH 2  CH 2  R Pyrolysis
 R  CH  CH 2
|| (12) Os
 O4
 | |
O
OH OH
RCHCH 2 COOK
(9) |
Kolbe's electrolytic synthesis

COOK
(13) Bayer
  R  CH

reagent
|
 CH 2
|
1% alkaline KMnO 4
(10) (RCH2CH2)4 N+OH¯ 
 OH OH

(14) strong R  C  OH + CO + H O
 oxidant
 || 2 2

(15) Priles 

Per acid
 chalev's reaction

O H O

3

2

(16) Ozonolysis +
O

(17) 200
2
Polyalkene
C high P
Cl
(18) 
2 Substitution product
500 C

Al (SO )
(19) 200
2    Isomerisation
4 3
300 C
(20) acetic  R–CH2=CH–COCH3
 anhydride

Methyl alkenyl ketone
(21)   Higher alkane
Alkane
 REACTION CHART FOR ALKYNES
GMP GR
(1) CH2Br–CH2Br alc . KOH or NaNH 2
 
H2
(1)  C2H4, C2H6
Ni
(2) CH3–CHBr2 alc. KOH , NaNH 2
     X2
(2)  C2H2X4
HBr
(3) CHCl3 Ag
powder
  (3) 
 CH BrCH Br
3 2
 Peroxide
C2H2
(4) CHBr2–CHBr2 Zn
dust

 HBr
(4) No   CH –CHBr
 Peroxide 3 2

CHBr (5) HOCl

 Cl2CHCHO
(5) || Zn
 (6) HCN , Ba ( CN ) 2
CHBr  2  CH2=CHCN
(7) 3    CH3CH(OCOCH3)2
CH COOH , Hg
(6) CH2=CH–Cl alc. KOH , NaNH
    2  Hg 2 , 80C , dil. H SO
(8)      4  CH CHO
2
HC  COONa Kolbe's electrolytic synthesis 3
( Kucherov 's reaction )
(7) ||       
HC  COONa (9) Conc

. H 2SO 4
 CH3CH(HSO4)2


2

H O (10) AsCl
3  CHCl=CHAsCl2
(8) CaC2
C2 H5OH / H 2O
electric arc ,1200C
    
 (11)     CH CHO
(9) 2C + H2 Berthelot 's process
HgSO 3
4

CO  HOH
(10) CH3–CCH i ) Na (ii ) R X
(   (12)    CH =CH–COOH
Ni( CO ) 2 4
(10) CH3–CCH (i ) CH 3MgI (ii ) R X
     CO  EtOH
(13)    CH =CH–COOEt
Ni ,160C 2

(14) NaNH
 2  NaCCNa
AgNO3  NH 4OH
(15) (     AgCCAg
Tollen 's Re agent )
(16) Cu Cl  NH OH
22 4   CuCCCu
Combustion
(17)     O
2  CO2 + H2O
CHO
(18) Bayer
 Reagent

 |  HCOOH
CHO
O
 3
(19) Ozonolysis H O

2
 HCOOH
Trimerisat ion
(20)    benzene
(Re d hot iron tube )

Trimerisation
(21)    C8H8or 1,3,5,7-cyclo octa tetraene
[ Ni ( CN ) 2 ]
Dimerisati on
(22)    butenyne
[ Cu ( NH 3 ) 2 ]
s
(23) 



CH OH
(24)  3 
( BF  HgO )
methylal
3
 Reaction Chart of Grignard reagent (R–Mg+X–)

HOH or ROH

2
or Ph–OH

2 NH H

O2 ,H2 O
CdC
N
SO2,H

l imi
or R 3 or R


CS H

2 O,
l2
ted
2 ,H O lim gBr

NH

S,H

 H2 ite 2
,

X
d
HO

R–
CO C SiCl
H limit 4 H
2 ,H 
RCHO,H2
O ed – CH=C 2
ClCH 2
O R–Mg–X R–Mg–X
RCOR,H2O PbCl2 ClCH2 OR
Me–CH-CH2,
limited
H2O Ph
O HCO
H2 Cl 2 CH
O CH 2, OEt Zn ted
3O 

2C
l
HC (½

- i

Cl–
CH 2 lim
q.) 2 O

OO e
N,H

RCO

CN
(½ e t,H

2
Et q.)

Cl
RC

,H 2

I2
OEt

Br2
OO

O
RC

? R–OH
H RH
RSO 2 RH R2Cd RSH
S
HOH or ROH

OH R2Hg
2

R–C–SH
or Ph–OH

RCH 2
2 NH N

O2 ,H2 O

R–R
H
SO2,H

CdC


or R 3 or R

CS
2 O,

O Hg
l2

2 ,H O OH
NH

S,H

R 2CH R Si Br


 H2
O,
X

R–C–OH 2
R–

4
H R–CH2CH=CH2
CO HC SiCl H
2 ,H 
RCHO,H2
O 4 –CH=C 2
ClCH 2
R–CH2 –CH–Me O R–Mg–X PbR4 R–Mg–X
Me–CH-CH2, RCOR,H2 O PbCl 2 ClCH2OR
RCH2OR
HO H2O R Cl
O HCO 3 CO CO
O H 2,
H2 OEt H Cl 2
Zn OE
3O

C
HC (½

- t
Cl–

CH 2
eq.) 2 O

OO e
N,H

RCO

CN
(½ Et,H

R–COOEt
2

R–CH2–CH2–OH
Et q.)

R2Zn
Cl

R–CHO
RC

,H 2

I2
Br2
OEt H
OO

O
RC

R2 –C=O OH RCl R–CN

OH R–CH2
O RBr R–I
R–C–R
R–C
R
R
 + H 2O, 
N 2 Cl¯ OH + N2 + HCl

H3PO2 + H2O + H3PO3 + HCl

CuCl + HCl Cl + N2
(Sandymeyer)

CuBr + HBr Br + N2
(Sandymeyer)
Cu,  Cl + N2
(Gattermann)
CaCN + HCN CN + N2

KI I + N2 + KCl

HBF4 +
N2 BF4¯ F + N2 + BF3

(Belzschimen)
NaNO2/Cu
NO2

+ N2 + NaCl + H2O
NaOH
diphenyl

NH2
N=N NH2
p-amino azobenzene
(dye)
 ALCOHOL

GMP GR
HX or PX or PX
(1)  
3 5
 RX
H  / H 2O or KI +H 3PO 4 or SOCl2 or SO 2Cl2
(1) Alkene  
aq. NaOH or aq. KOH
  (2) Re
d P /HI
 RH
(2) RX
or aq. K 2 CO 3 or moist Ag2 O NH3
(3)    1º , 2º , 3º amines
dil. H2 SO 4
(3) R - O - R  
 H S
(4) 

2
 R - SH Thiol
dil. H2SO 4 ThO 2
(4) RCOOR  

RCOOH
(5) Na
 RONa
HNO 2
(5) 1º amine    CH MgX
(6)  
3
 CH4
Exception - (Methyl amine gives
R' OR
CH3-O-CH3 or ether) ald.R'CHO
(7) 
 C Acetal
NaH
(6) Aldehyde or ketone   dry HCl
Darzon reduction H OR
(1º alc.) (2º alc.)
Na / EtOH
R-OH
(7) Acid or  
 R' OR
Bouveault Blanc reduction
Ketone R'COR '
Acid derivative (8)     
 C Ketal
dry HCl
R MgX R' OR
(8) HCHO or [Link] ketone  

H2 O
R'COZ
(1º alc) (2ºalc) (3º alc.) (9)  
 R'COOR ester (Z = OH,Cl, OCOCH3)
O2
(9) RMgX 
 (10) H
2 SO 4
 ROSO2OH (Alkyl hydrogen sulphate)
H2O

CH2  CH2
(11) HNO
 3
 RONO2 (Alkyl nitrate)

(10)CH3MgBr   
O (12) PhSO
 2 Cl
 RSO2Ph (Alkyl benzene sulphonate)

H3 O  CH
(13)  CH
  H3C - CH (OR)2 Acetal
(11) Sugar Fermentation
 
 (14)  CH
2N2
 R - O - CH3 Ether
O

CH 2  CH 2
(15)       RO - CH2 - CH2 - OH
Alkoxyalkanol
(16)  CH 2  CO
  ROCOCH3 Ester
(17) Dehydration
 Alkene
Catalytic dehydrogenation
(18)    Aldehyde or ketone
10 or 20 alcohol , Cu or ZnO , 300 0 C
Formation of EtOH by fermention - Exception - 3º alc  Alkene
Crystallization
 
(1) Cane sugar  Molasses [ O]
Aldehyde[
(19) 1ºalc.   O]
Acid (same no. of C-atom)
Sucrose
O HCrO 4
Invertase
  Invert sugar (20) 1º or 2ºalc. 
 Aldehyde or ketone + Cr+3 (green)
hydrolysis ( orange )

zymase O, HCrO 
  EtOH (21) 3º alc  
4
 No reaction (No. green colour)
Fermentation ( orange)

Diastase
(2) Grain  Starch   Maltose
HOH

Maltase Zymase
  Glucose  
hydrolysis Fermentation

EtOH
 Chemical properties
HCN R OH
C
R CN
Methods of preparation
NaHSO3 R OH
Ozonolysis C
Alkenes R SO3Na

dil. H2SO4 
H /H2O R OH
Alkynes C
HgSO4 R OH

Hydrolysis
Gem-dihalides
Dry HCl/ROH R OR
C
R OR
Cu
Alcohols
300ºC
H2N–Z R
PCC C=N–Z
R–CH2–OH (Ammonia R
derivatives)

H /K2Cr2O7 
R–CH–R OH
 H containing
OH carbonyl compounds
Carbonyl Compounds give Aldol reaction
MnO
R–COOH [Aldehydes, Ketones] 
300ºC OH
Aldehydes without
Dry distillation H give cannizaro
(RCOO)2Ca reaction

Zn–Hg
Grignard reagent Alkane
Esters
Conc. HCl

Grignard reagent
Alkyl cyanide LiAIH4
Alcohol
H
Pd/BaSO4
RCOCl
Oxidation
SnCl2/HCl Acids
RCOCl
Hydrolysis
RMgX
Alcohols

Tischenko
Ester
reaction
 REAGENTS THEIR USES
(1) X2/CCl4/CS2/CHCl3/CH2Cl2 Anti addition of X2 on multiple bond.
X2 = Br2, Cl2

OH OH

(2) Br2 + CCl4 / CS2/CH3COOH 

Br

(3) Br2/CCl4,  Hunsdiker reaction

O
R – C – O – Ag  R – Br
(one ‘C’ less product)

(4) I2 / CCl4 Birnbaun Simmonini reaction

O O
R – C – O – Ag  R – C – O – R

(5) Br2/KOH or NaOH /  Hoffman Bromamide degradation

O
R – C – NH2  R–NH2
Amide into Amine with one ‘C’ less

(6) X2 + NaOH or NaOX Haloform reaction

(7) Br2 / h; Cl2/h ; I2 / HgO or HIO3 /  Halogenation of alkane

R – H  R – X
Cl
Cl Cl
* h
+ Cl2(excess) 
Cl Cl
Cl
(8) X2 / red P ; X2 = Br2, Cl2 HVZ reaction
CH3–COOH  CH 2  COOH
|
X
(9) Cl2 / FeCl3 ; Br2 / FeCl3 ; I2 / HIO3 ; Halogenation of aromatic compound
X

Br2 / Fe ; HOCl ; Br2 + H2O 

 REAGENTS THEIR USES
M
M Br Br

* 2 
Br H 2O

Br
M = –OH , –NH2

(10) Br2 + H2O ; Interhalogen compound ; Anti addition on alkene

Br2 / aq. Brine solution;
NOCl (Tilden reagent); HOCl

(11) HOCl Addition on lakyne

Alkyne  Enol l Carbonyl compound
* HOCl oxidised aldehyde into
carboxylic acid

(12) HBr, HCl, HI Hydrohalogenation of alkene and alkynes

according to Markovnikov’s rule

(13) HBr / peroxide; CBrCl3, CIBr3, CBrF3, Addition of alkene and alkyne according
CHCl3, CHI3, RSH, COCl2 to Antimarkovnikov’s rule

(14) (i) O3 ; (ii) Zn / H2O ; Me2S ; Ph3P Reductive ozonolysis of alkene and alkyne

(15) O3 / H2O or O3 / H2O2 Oxidative ozonolysis of alkene and alkyne

(16) Cold dilute alkaline KMnO4 or Hydroxylation of alkene

dil.KMnO4 or Bayer’s reagent ; (preparation of syndiol on alkene)
OsO4 / NaHSO3

(17) Peroxy acids ; RCO3H; mcpBA; H2S2O8; Epoxydation of alkene (Prielshavie

reaction)
H2SO5 (Carro’s acid)

(18) Hydrolysis of epoxide in acidic and Anti-diol formation

basic medium

(19) conc. H2SO4; H3PO4/; Al2O3/; Dehydration of alcohol into alkene

POCl3 / ; ThO2 / 

(20) N-Bromo succinimide (NBS) Allylic substitution

N-Chloro succinimide (NCS) CH 2  CH  CH 2  CH 2  CH  CH 2

| |
Br2 at low concentration H X
X2 at high concentration ,
t-Butyloxy chloride (Me3COCl) / h or 
SO2Cl2 / h or 
 REAGENTS THEIR USES

(21) H / H2O or H3O or dil. H2SO4 Hydration of alkene

(i) (CH3COO)2 Hg / H2O
(ii) NaBH4

(i) B2H6 / THF

(ii) H2O2 / OH¯

(i) (Sia)2BH / THF

(ii) (H2O2/OH¯)

(i) 9-BBN / THF

(ii) H2O2 / OH¯

(22) HgSO4 / dil. H2SO4 or Hg2+ Hydration of alkyne (Kucherov reaction)

(23) Mg Hg + H2O ; Zn–Hg + H2O Vicinal diol (Pinacol) formation by

Na – Hg + H2O compound having ketone group
* Pinacol conc
 .H 2SO 4
 Pinacolone
or H 3PO 4 / 

(24) conc. H2SO4 Sulphonation of aromatic compound

(25) HNO3 + HClO4 ; conc. HNO3 ; Nitration of aromatic compound

solid N2O5 ; NO2F + BF3 ; AcONO2 ;
HNO2 / HNO3

(26) Anhydrous AlCl3 (i) Isomerisation of alkane

Alkane  Branched alkane

(ii) Friedal craft’s alkylation

R

+ RX  + HX

(iii) Friedal craft’s acylation

OH OH
O
COR
+ R – C – Cl  +

COR
(iv) Fries recation
 REAGENTS THEIR USES
OCOR OH OH
COR
AlCl
3  +

COR

(27) SbCl5 / , H;AlCl3 / , H Semipanacol - pinacolon rearrangement

AgNO3 / , H

(28) CHCl3 + NaOH /  ; H3O Riemer Tiemann reaction

OH OH

CHO
+ CHCl3 + NaOH 
H3O

(29) CHCl3 + NaOH ,  Isocyanide test or Carbylamine test


R–NH2+CHCl3+ NaOH R–N  C +NaCl+H2O

OH OH
COOH
(30) CCl4 + NaOH, H3O + CCl4 + NaOH 

H 3O

(31) CO2 + NaOH , H3O Kolbe Schmidt reaction

OH OH
COOH
H3O
+ CO2 + NaOH

(32) NaOH + CaO,  Sodalime decarboxylation

O
(3 : 1) R – C – OH  R–H + CaCO3 

(33) N3H + conc. H2SO4 Schmidt reaction

O
conc.H SO 4
R–C–OH + N 3 H   2 R –
NH2+CO2+H2O+N2

O O
(34) CH2N2 (diazomethane) R–C–OH + CH2N2  R–C–OCH3 + N2
 REAGENTS THEIR USES
(35) Fused NaOH, high temperature, Dow process
Cl OH

high pressure 

(36) NaNO2 / HCl or HNO2 Diazotisation of Amine

(37) NaNO2 / HCl,  Aniline into diazonium chloride

(38) CuCl, CuBr, CuCN, H2O, H3PO2 Diazonium chloride into chlorobenzene,
Bromobenzene, Benzonitrile, Phenol, Benzene
respectively.

(39) Na /dry ether Wurtz reaction

2R – X  R – R
Fittig reaction

2 X
Wurtz-fittig reaction

X + RX + R + R–
R

(40) Cu /  Ulmann’s reaction

2 I

(41) Ag /  CHCl3  HC  CH

(42) Zn dust Phenol to Benzene

(43) Zn dust,  ; NaI / Acetone Dehalogenation of Antivicinal dihalide

Cl
|
H 2 C  CH 2  H2C = CH2
|
Cl

(44) Alc. KOH; NaNH2 Dehydrohalogenation

(45) Aq. KOH Alkyl halide into Alcohol

(46) PCl5 / P2O5 / P4O10 / POCl3 /  Dehydration of amides into nitriles

 REAGENTS THEIR USES
(47) PCl5 R–OH  R–Cl
R–O–R’  R–Cl + R’–Cl + POCl3
OH

 Ph3PO4 (major)

R R Cl
O 
R R Cl

(48) SOCl2 Darzon method

Alkyl alcohol  Alkyl chloride

(49) HI Ether convert into alcohol and ALkyl halide

(50) HCN Carbonyl compound into cyanohydrin

(51) aq. KCN R–X + aq. KCN  R–CN (cyanide)


(52) AgCN R–X + AgCN  R  N  C (isocyanide)

(53) KNO2 R–X + KNO2  R–O–N=O (Alkyl nitrite)

(54) AgNO2 R–X + AgNO2  R–NO2 (Nitro Alkane)

(55) Moist Ag2O R–X + Moist Ag2O  R–OH

(56) Dry Ag2O R–X + Dry Ag2O  R–O–R

Q. Reagents which are used in distinguish tests :

(1) HCl + anhydrous ZnCl2 Lucas test (To distinguish 1°,2°,3° alcohols)

(2) AgNO3 + NH4OH (Tollen’s reagent) Tollen’s test to identify aldehyde

(3) Fehling solution Fehling test

Only aliphatic aldehyde gives this test (red ppt.)

(4) Benedict solution Benedict test

Only Aliphatic aldehyde gives this test

(5) 2,4-DNP 2,4-DNP test

Test for ketone and aldehyde
 REAGENTS THEIR USES
(6) Hinsberg reagent Hinsberg test
C6H5SO2Cl to differentiate 1°, 2°, 3° amine

(7) CHCl3 + NaOH Carbylamine or Isocyanide test

(for primary amine)

(8) NaNO2 + HCl Libermann’s Nitroso test for phenol

(9) Beilstein test / Flame test Test of alkyl halide

Alkyl halide give blue green colour flame when
heated with Cu wire

(10) Victor Mayer test To differentiate

(i) 1°, 2°, 3° Alcohol
(ii) 1°, 2°, 3° Alkyl halide
(iii) 1°, 2°, 3° Nitro Alkane

(11) Test of Methanol

OH OH O
COOH 
C–OMe
MeOH
 /H
 (Oil of winter green)

(12) Test for carboxylic acids :

(i) Litmus test
(ii) With Na Metal
(iii) Reaction with NaOH
(iv) With NaHCO3

(13) Test of Phenol :

(i) With Na Metal
(ii) With NaOH
(iii) With aqueous FeCl3