F2, explosive aq.

NaOH ROH Alcohol

Cl2, hu NUCLEOPHILIC aq Ag2O ROH Alcohol

ALKANES Br2, SUBSTITUTION H2O(ether) ROH Alcohol

(Substitution
reaction) I2, reversible reaction NaOR' ROR' Ether
(use HIO3, conc HNO3, Williamson's ether synthesis
as oxidising agent NH3 RNH2 Pri. Amine
Ethanolic solution
HX, Markovnikov rule RNH2 R2NH Sec. amine

ALKENES HX, + Peroxide

(addition of HX) Anti Markovnikov rule R2NH R3N Ter. Amine
KCN RCN Cyanide
CHLORODERIVATIVES AgCN RNC Isocyanide

(i) HCl/ Anhydrous ZnCl2 KNO2 or NaNO2 RONO Alkyl nitrite

(ii) PCl5 AgNO2 RNO2 Nitroalkane

(iii) PCl3 R'COOAg R'COOR Ester
(iv) SOCl2 Hunsdiecker reaction
NaI (dry acetone) RI Alkyl iodide
ALCOHOLS BROMODERIVATIVES Finkelstein reaction
(Substitution reactn) (i) 48% HBr/ conc. H2SO4 (RCl or RBr only)
(ii) NaBr/ conc. H2SO4

(iii) P + Br2 (or PBr3) ELIMINATION REACTIONS ALKENE

IODODERIVATIVES (Dehydrohalogenation) , alc. KOH

(i) Red P4 / I2
(ii) KI / 95% H3PO4
+ Mg, dry ether RMgX
Grignard's
Reagent

RCl or RBr NaI in dry acetone

to RI (FINKELSTEIN reaction) REACTION WITH METALS
+ Na , dry ether R-R (alkane)

RCl or RBr AgF or SbF3, Hg2F2,CoF2 (2n-C)

to RF , SWARTS reaction
REDUCTION
REACTION RH (Alkane)
Reagents:
1. Zn- Cu couple , alcohol
2. Red P4, HI
3. LiAlH4
 + Cl2 or Br2, dark Nucleophilic subs. + NaOH OH H2O / OH
FeCl3, Anhyd AlCl3, (very low reactivity 623 K, 300 atm dil HCl + NaCl
I2 or Fe fillings. due to resonance)
(Phenol)
C6H6
Benzene + I2, conc HNO3 or Halogenation Cl Cl
Cl
HIO4 Cl 2 or Br2 +
FeCl 3, Anhyd AlCl3
C6H5NH2 (aniline) (minor) Cl
(major)
Diazotisation
NaNO2 + conc. HCl Cl Cl
273 - 298 K Nitration NO2
conc. HNO 3 / +
Cu2Cl2 Electrophilic subst. conc. H2SO4
Sandmeyer's reaction (major product - (minor) NO2
para substituted) (major)
+ -
C6H5N2 Cl Cu2Br2
Sandmeyer's reaction Cl Cl
Sulphonation SO3H
KI conc. H2SO4, +

(minor) SO3H
(major)

Cl Cl
Friedel Crafts alkylation CH3
CH 3Cl + Anhyd AlCl3 +

(minor) CH3
(major)

Cl Cl
Friedel Crafts acylation COCH3
CH 3COCl or (CH3CO)2O +
Anhydrous AlCl 3
(minor) COCH3
(major)
+ Mg, dry ether ArMgX
(Grignard's reagent)

+ Na, dry ether Ar.Ar

With Metals FITTIG REACTION (eg: C6H5.C6H5 -Biphenyl)

+ Na + RX ,dry ether Ar _ R
WURTZ FITTIG REACTION (eg: C6H5.CH3)
 Cleavage of O_H bond
RCHO (aldehydes) Active Metals RONa + H2

Pri > Sec > Tert

(to pri. Alcohol) Na, K , Mg , Al
REDUCTION
(i) H2 + Ni /Pt / Pd
RCOR' (ketones) or (ii) NaBH4 Acetylation R'COOR
(to sec. Alcohol) or (iii)LiAlH4 (i) R'COOH + conc. H2SO4
( Esterification )
(ii) R'COCl / pyridine
+
RCOOH REDUCTION (iii) (R'CO)2O / H
(carboxylic acids) (i)LiAlH4 (expensive reagent)
o
(ii) H2O 1 alc. No turbidity
o
Lucas Test 2 alc. Turbidity in 5 mins.
ROH + conc. H2SO4 HCl + Anhyd. ZnCl2 3o alc. Immediate turbidity

RCOOR' (Esters) REDUCTION (i) PCl3 or Alkyl Halide

H2 + Ni / Pt / Pd (ii) PBr3 or
(iii) P4 + I2 or
(iv) SOCl2 or
(i) ACID CATALYSED HYDROLYSIS (v) PCl5
(dil H2SO4 + steam)
MARKOWNIKOFF ADDITION Dehydration Alkene + H2O
Alkenes of H 2 O a) conc. H2SO4 , 443 K or
b) conc. H3PO4 or
C=C (ii) HYDROBORATION OXIDATION c) Al2O3 , 623 K or
ANTI-MARKOWNIKOFF ADDITION d) Anhyd ZnCl2

Cleavage of C_ O bond
OF H 2 O 1o alc. Aldehyde
o
Dehydrogenation 2 alc. Ketone
Tert > Sec > Pri
o
Cu, 573 K 3 alc. Alkene
RCOCl (Acyl Chloride) REDUCTION Dehydration
( to pri. Alcohol) LiAlH4 or NaBH4
1o alc. Aldehyde Acid
(containing same (containing same
+ HCHO + H2O 1o alcohol no. of C - atoms)

Oxidation 2o alc. Ketone (containing same no. of C- atoms)

Grignard's + Other aldehyde + H2O 2o alc. (i) K2Cr2O7 / H2SO4 3o alc. Ketone (containing less no. of C- atoms)

Reagent (ii) KMnO4 / H2SO4

+ Ketone + H2O 3o alcohol (iii) CrO3 /anhydrous condtn.

623 K CH2 = CH2

RX (Alkyl halide) aq NaOH or aq Ag2O C2H5OH + Al2O3
473 K C2H5OC2H5

RNH2 HNO2 (Nitrous acid) 443 K CH2 = CH2

(Primary Amine) (for 1 o alcohol) C2H5OH + conc. H2SO4
410 K C2H5OC2H5
 Na, Mg, Al C6H5ONa + 1/2 H2
Acidic Nature NaOH C6H5ONa + H2O
Cleavage of O_H bond

Blue litmus Turns Red

R'COOH ,conc. H2SO4 C6H5OCOR'

Esterification
Acetylation
(R'CO)2O ,conc. H2SO4 C6H5OCOR'
R'COCl , pyridine

Benzoylation C6H5OCOC6H5
C6H5COCl , Schotten-Bauman reaction

OH OH
dil HNO3 NO2
298 K +
Nitration
NO2
Aromatic

OH
conc. HNO3
Substitution

O2 N NO2
+ conc. H2SO4
Picric acid
Electrophilic

NO2

Cl2 water OH
Br Br
Br2 water
(polar solvent)
SO3H SO3Na Halogenation Br
NaOH H + / HCl (white ppt)
570 - 620 K
OH OH
Benzene sulphonic Br2 in CS2 Br
acid 273 K +
(non-polar solvent)
Br
OH OH
Cl ONa Friedel Crafts Alkylation R
NaOH H + / HCl RX / Anhyd. AlCl3 +
623 K, 320 atm
R
conc. H2SO4 OH
288 K SO3H
Sulphonation
NH2 N2 +Cl-

NaNO2 + HCl H2O

OH
273 - 278 K (warm) conc. H2SO4
(Diazotisation) 373 K

CH3 CH3 SO3H

CH _ CH3 HOO_C_CH3 OH
O2 H2O / H + CHCl3 + aq NaOH CHO
(air) Riemer Tiemann reaction (salicylaldehyde)

Cumene

C6H5N2+Cl- , alkali OH
N N
Coupling reaction

4- Hydroxyazobenzene [orange dye]

ONa OH
NaOH (i) CO2, 398 K, 4-7atmos. COOH
(ii) H+ / H2O Salicylic acid
Kolbe's reaction
Cleavage of C - O bond

Zn dust
O

Oxidation
Na2Cr2O7 / conc. H2SO4 Benzoquinone

O
 RCH2OH Oxidation Na
RCOONa + H2 (g)
(Primary alcohol) (i)KMnO4 in acidic/ alkaline/
neutral medium OR NaOH
RCOONa + H2O
(ii)K2Cr2O7/H+ OR Acidic
(iii)CrO3 / H+ Nature NaHCO3 or
RCOONa + H2O + CO2 (g)
Na2CO3

RCH=CHR' (i)K2Cr2O7 / H2SO4 OR Blue litmus

+ Red
Substituted alkene (ii)KMnO4 / H OR
(iii) KMnO4 / OH-
PCl5
RCOCl + POCl3 + HCl
+ -
RC N H2O / H or OH PCl3
RCOCl + H3PO3
Nitriles Hydrolysis Cleavage of
C- OH bond SOCl2
RCOCl + SO2 + HCl
RCONH2 H+ / H2O R'OH , conc. H2SO4
RCOOR' + H2O
Amides (esterification)

RMgX (i) CO2 (dry ice)

+
Grignard's reagent (ii) Hydrolysis (H2O / H ) NaOH NaOH + CaO , ,
RCOONa R H + Na2CO3
(soda lime)
(n+1) C (n- C)
[Decarboxylation]
RCOCl (i)H2O/H+ OR
Acyl chloride (ii)Base followed by acidification
NaOH Kolbe's
RCOONa Electrolytic method R R
(n+1) C (2n- C)
RCOOR' (i)H+ / H2O
-
Esters (ii)OH / H2O followed by
acidification Dehydration
(RCO)2O + H2O
P2 O 5 ,

(RCO)2O + H2O
Anhydride Reduction
RCH2OH
(i)LAH/ether OR
(alcohol)
(ii)B2H6

+NH3
RCOONH4
,P2O5

RCONH2 RCN
(amide) (nitrile)

(i)Cl2 or Br2 / Red P4 RCH_COOH

(ii)H2O a - Halo carboxylic acid
X

[Hell-Volhard Zelinsky (HVZ) reaction]

 Reduction Basic Nature OH- RNH2
RNO2 (i) H + Pd,Pt RNH3+Cl-
2 (HCl) [Seperation & Purification
_
(ii) Pd C/ethanol of amine]
(iii) Sn + conc. HCl
(iv) Fe + conc. HCl
RNHCOCH3 + HCl
Fe + HCl --> FeCl2 + H2
Acylation
FeCl2 + H2O --> HCl + Fe(OH)2
(regenerated) (i)CH3COCl
Nucleophilic (ii)(CH3CO)2O
RNHCOCH3 +
Substitution (Pyridine)
CH3COOH
+NH3 , alcohol
Benzoylation
RX RNHCOC6H5
(i)KCN C6H5COCl
(ii) LAH or Na(Hg) + C2H5OH
[increase in no. of C-atoms] Carbylamine reaction OR
RNC + KCl + H2O
Isocyanide reaction
poisonous
(i) LAH (10 amines, CHCl3 + alc. NaOH)
(ii) H2O TEST FOR PRIMARY AMINES

RCONH2
Br2 + NaOH Alkyl H2O
[RN2+Cl-] ROH + N2
[Hoffmann's Bromamide NaNO2/HCl amine
degradation reaction] 273-278 K [ QUANTITATIVE ESTIMATION]
Diazotisation
Aryl
CO [C6H5N2]+Cl-
Gabriel's Pthalimide synthesis amine Diazonium salt
NH (i) KOH
CO (ii) RX
(iii) OH
- Pri. RNHSO2C6H5 (soluble in KOH)
C6H5SO2Cl2 Sec.
R2NSO2C6H5 (insoluble in KOH)
Hinsberg's reagent
Tert. No reaction
 C6H5NO2 REDUCTION
(nitrobenzene) (i)H2+Ni or Pd or Pt
(ii)Sn + conc. HCl
(preferred)(iii)Fe + conc. HCl
(iv)H2 + Pd (ethanol)
(v)SnCl2 + conc. HCl

C6H5CONH2 Br2 + alc. NaOH

(Benzamide) Hoffmann Bromamide Reaction
(n+1)C
 Red litmus
No effect
Less basic than NH3
AS BASE due to resonance.
(Less acidic than NH3
due to resonance) HCl
[C6H5NH3]+Cl-

H2SO4
[C6H5NH3]2+S042-

Alkylation
C6H5NHR C6H5NR2 [C6H5NR3]+X-
(RX)

CH3COCl
C6H5NHCOCH3 + HCl
NUCLEOPHILIC Pyridine
SUBSTITUTION Acylation
(CH3CO)2O
C6H5NHCOCH3 + CH3COOH
conc. H2SO4

Benzoylation
C6H5NHCOC6H5 + HCl
C6H5COCl,
NaOH [Schotten Baumann Reaction]

Carbylamine reaction
C6H5NC + KCl + H2O
CHCl3+alc. KOH + heat
REACTION OF -NH2 GROUP

Diazotization
C6H5N2+Cl- + NaCl + H2O
NaNO2 + HCl [273-278K]

NH2
Bromination Br Br
Br2 + H2O + 3HBr
(bromine water)
Br
2,4,6-Tribromoaniline
[white ppt]

ELECTROPHILIC
SUBSTITUTION NH2 NH2 NH2
Nitration NO2
conc.HNO3 + conc H2SO4 + +
(288 K) NO2
NO2 47% 2%
51%

NH3+HSO4- NH2 NH3+-

Sulphonation 453-473 K
conc. H2SO4

Anilinium SO3H SO3-

hydrogen Sulphanic ZWITTER
sulphate acid ION

NHCOCH3 NHCOCH3 NH2

-
(CH3CO)2O Br2 H+ or OH
Pyridine, Acylation CH3COOH
(Protection of NH2 group) Bromination
Br Br

NHCOCH3 NHCOCH3 NH2

ELECTROPHILIC SUBST n (CH3CO)2O conc HNO3 H+ or OH-
(after protecting the amino group) Pyridine con H2SO4, 298K

Freidal Crafts Reaction No product, due to salt formation

with AlCl 3
 C6H5NH2 + NaNO2 + 2HCl 273-278 K C6H5N2Cl + NaCl + H2O

Benzene Diazonium Chloride

Reaction is also known as Diazotization

Very useful as synthetic reagent

H3PO2 + H2O
C6H6 + N2 + H3PO3 + HCl

C2H5OH
C6H6 + N2 + CH3CHO + HCl

H2O , 283 K
C6H5OH + N2 + HCl

C6H5OH CuCl/HCl
N N OH n
C6H5Cl + N2
OH Sandmayer's react
p-Hydroxyazo benzene + Cl + H2O
Orange Dye
Cu/HCl
C6H5Cl + N2 + CuCl
[TEST FOR PHENOL] Gatterman reactn

Reactions involving retention of

C6H5N2 +X- Reactions involving displacement
diazo grp(N2+) [Coupling reactn] +
of N2 X group CuBr/HBr
C6H5Br + N2
Sandmayer's reactn

Cu/HBr
C6H5Br + N2 + CuBr
Gatterman reactn
C6H5NH2
N N NH2
OH
p- Aminoazobenzene KI ,
+ Cl + H2O C6H5I + N2 + KCl
Yellow dye

[TEST FOR ANILINE] , to dryness

C6H5F + N2 + BF3
HBF4
C6H5N2+BF4
Fluoroboric acid aq. NaNO2
C6H5NO2 + N2 + NaBF4

CuCN ,
or Cu/KCN C6H5CN + N2 + CuCl

Na + C2H5OH or LAH

C6H5CH2NH2
 OXIDATION
CrO3 in anhydrous medium or
PCC (Pyridinium chloro chromate)
o
1 Alcohol CrO3 o
2 Alcohol
ROH Chromic anhydride R
DEHYDROGENATION CH_OH
R
Cu or Ag at 573K

HC = CH HCHO

Alkenes OZONOLYSIS OZONOLYSIS Alkene

(i) O3 (i) O3 (Symmetric
C=C Tetrasubstituted)
(ii) Zn dust and (ii) Zn dust + H2O
H2O Symmetric Disubstituted
alkene other aldehydes

HC CH CH3CHO

Alkynes HYDRATION H2O + dil. H2SO4 Alkynes

dil. H2SO4 + H2O + + HgSO4
C C HgSO4 HCHO can't be prepared

HCHO can't be prepared

+ R2Cd
Acid Chloride Acid Chloride
RCOCl + H2 , Pd-BaSO4 poisoned with S (Dialkylcadmium)
or quinoline (ROSENMUND REACTION)

(i) SnCl2 + HCl

(ii) H2O / H+ (STEPHEN REACTION )

(i) + Grignard's reagent

Nitriles RCN
RCN (i) DIBAL-H (Diisobutylaluminium hydride)
(ii) H2O / H+
(ii) H2O

Esters (i) DIBAL-H

(ii) H2O
 HCN + OH- OH H2O / H+ OH
(base as catalyst) C C
CN COOH
Aldehydes White ppt.
NaHSO3 SO3H SO3Na
C C Ketones No.
ONa OH
for ketones for aldehydes

o
HCHO 1 Alcohol

o
(i) Grignard's reagent RCHO 2 Alcohol
(ii) H2O / H+ Other aldehydes

Ketone 3o Alcohol

Nucleophilic
Addition
OR' OR'
Aldehyde RCH R'OH RCH
H+ / H2O OH OR'
hemiacetal acetal
Alcohol + dry HCl
CH2OH
+ Ketone R O-CH2
CH2OH + H2O
C
R O-CH2
H+ / H2O
Ketal

NH3 ( H+NH2- ) C = NH. (Imine)

(Ammonia)

RNH2 C = NR' (Substituted imine) [schiff's base]

(Primary amine)

NH2OH C = NOH. (Oxime)

(Hydroxyl amine)

NH2NH2 C = N.NH2 (Hydrazone)

(Hydrazine)

C6H5NHNH2 C = NNHC6H5 (Phenyl hydrazone)

(Phenyl hydrazine)
NO2
2,4-DNP C = N _ NH_ _
NO Red, Orange or Yellow ppt
(2,4-dinitrophenyl hydrazine) (2,4-DNP hydrazone) (Test for >C=O group)

C = N _ NHCONH2 (semicarbazone)
(Semicarbazide)
(NH2NHCONH2)
Aldehydes 1o Alcohol
NaBH4 or LiAlH4
o
or H2 + Ni/Pd/Pt Ketones 2 alcohol

HCHO Doesn't reduce

Reduction Zn amalgam + conc. HCl other ald. RCH3 (Alkanes)

[Clemmensen reduction]
Ketones RCH2R (Alkanes)

(i) NH2NH2 hydrazine Alkane [ RCH3 or RCH2R]

(ii) KOH or NaOH + Ethylene glycol.
[Wolf-Kishner reduction]
 Aldehydes contg. No reaction
no a - hydrogen
Aldol Condensation
dil. Alkali(catalyst) other aldehydes b - hydroxyaldehyde [aldol]
only by aldehydes & ketones
containing a- hydrogen Ketones b - hydroxyketone [ketol]

HCHO CH3OH + HCOONa

Reduction Oxidation
Cannizaro reaction product Product
only by aldehydes contg
no a- H atoms. CH3CHO No reaction
(contains a - H)

Ketones No reaction

Aldehydes Silver mirror

Tollen's reagent, heat [Test for aldehydes]
Ammonical silver nitrate soltn. Ketones No ppt.

Aldehydes Reddish brown ppt.

Oxidation Fehling's solution, heat [Test for aldehydes]
[Fehling's A =aq. CuSO4
Fehling's B = alkaline sodium Ketones No ppt.
potassium tartarate]

Aldehydes Carboxylic acid

(i) HNO3, (ii) KMnO4 + H2SO4
(iii) K2Cr2O7 + H2SO4 Ketones Carboxylic acids contg.
lesser no. of C-atoms

HCHO No effect

CH3CHO Yellow ppt CHI3

Haloform reaction
+ I2 + NaOH (NaOI) CH3COCH3 Yellow ppt CHI5
only by compounds contg.
CH3CO- group CH3CH2COCH2CH3 No effect.
[IODOFORM TEST]