F2 , explosive

aq. NaO

HR

OH

Alcohol

Cl2 , hu

NU

CLEO

PHILIC

aq Ag

2 OR

OH

Alcohol

ALK

AN

ES B

r2 , SU

BSTITU

TION

H2 O

(ether)R

OH

Alcohol

(Substitution reaction)

I2 , reversible reactionN

aOR

'R

OR

'E

ther (use H

IO3 , conc H

NO

3 , as oxidising agent

NH

3R

NH

2P

ri. Am

ine

HX, M

arkovnikov ruleR

NH

2 R

2 NH

Sec. am

ine

ALK

ENES

(addition of HX)

HX, + P

eroxide A

nti Markovnikov rule

R2 N

HR

3 NTer. A

mine

KC

NR

CN

Cyanide

CH

LOR

OD

ER

IVA

TIVE

SA

gCN

RN

CIsocyanide

(i) HC

l/ Anhydrous ZnC

l2K

NO

2 or NaN

O2

RO

NO

Alkyl nitrite

(ii) PC

l5A

gNO

2R

NO

2N

itroalkane(iii) P

Cl3

R'C

OO

Ag

R'C

OO

RE

ster(iv) S

OC

l2N

aI (dry acetone)R

IA

lkyl iodide

ALC

OH

OLS

BR

OM

OD

ER

IVA

TIVE

S (Substitution reactn)

(i) 48% H

Br/ conc. H

2 SO

4(R

Cl or R

Br only)

(ii) NaB

r/ conc. H2 S

O4

(iii) P + B

r2 (or PB

r3 ) ELIM

INA

TION

REA

CTIO

NS

ALK

EN

E

IOD

OD

ER

IVA

TIVE

S(D

ehydrohalogenation) , alc. KO

H(i) R

ed P4 / I2

(ii) KI / 95%

H3 P

O4

+ Mg, dry ether

RM

gXG

rignard's R

eagent

RC

l or RB

r to R

I N

aI in dry acetone(FIN

KE

LSTE

IN reaction)

REA

CTIO

N W

ITH M

ETALS

+ Na , dry ether

R-R

(alkane)

RC

l or RB

r to R

F A

gF or SbF

3 , Hg

2 F2, C

oF2

, SW

AR

TS reaction

(2n-C)

RED

UC

TION

REA

CTIO

N R

H (A

lkane)R

eagents: 1. Zn- C

u couple , alcohol2. R

ed P4 , H

I3. LiA

lH4

William

son's ether synthesis

Ethanolic solution

Hunsdiecker reaction

Finkelstein reaction

+ Cl2 or Br2, dark Nucleophilic subs. + NaOH H2O / FeCl3, Anhyd AlCl3, (very low reactivity 623 K, 300 atm dil HCl + NaCl I2 or Fe fillings. due to resonance)

C6H6

Benzene + I2, conc HNO3 or Halogenation Cl Cl HIO4 Cl2 or Br2 +

FeCl3, Anhyd AlCl3 C6H5NH2 (aniline) (minor) Cl

(major) Diazotisation NaNO2 + conc. HCl Cl Cl 273 - 298 K Nitration

conc. HNO3 / + Cu2Cl2 Electrophilic subst. conc. H2SO4

Sandmeyer's reaction (major product - (minor) NO2

para substituted) (major) C6H5N2

+Cl- Cu2Br2

Sandmeyer's reaction Cl Cl Sulphonation

KI conc. H2SO4, +

(minor) SO3H(major)

Cl Cl Friedel Crafts alkylation CH3Cl + Anhyd AlCl3 +

(minor) CH3

(major)

Cl Cl Friedel Crafts acylation CH3COCl or (CH3CO)2O +

Anhydrous AlCl3 (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)

Cl

NO2

SO3H

CH3

OHOH

(Phenol)

COCH3

RC

HO

(aldehydes) Active M

etals R

ON

a + H2

(to pri. Alcohol)

Na, K

, Mg , A

l R

ED

UC

TION

(i) H2 + N

i /Pt / P

d R

CO

R' (ketones)

or (ii) NaB

H4

Acetylation R

'CO

OR

(to sec. Alcohol)

or (iii)LiAlH

4 (i) R

'CO

OH

+ conc. H2 S

O4

(ii) R'C

OC

l / pyridine R

CO

OH

RE

DU

CTIO

N (iii) (R

'CO

)2 O / H

+

(carboxylic acids) (i)LiA

lH4 (expensive reagent)

(ii) H2 O

1o alc.

No turbidity

Lucas Test

2o alc.

Turbidity in 5 mins.

RO

H + conc. H

2 SO

4 H

Cl + A

nhyd. ZnCl2

3o alc.

Imm

ediate turbidity

RC

OO

R' (Esters)

RE

DU

CTIO

N (i) P

Cl3 or

Alkyl H

alide H

2 + Ni / P

t / Pd

(ii) PB

r3 or (iii) P

4 + I2 or (iv) S

OC

l2 or (i) A

CID

CA

TALY

SE

D H

YD

RO

LYS

IS (v) P

Cl5

(dil H2 S

O4 + steam

) M

AR

KO

WN

IKO

FF AD

DITIO

N D

ehydration A

lkene + H2 O

Alkenes of H

2 O a) conc. H

2 SO

4 , 443 K or

b) conc. H3 P

O4 or

C=C

(ii) HY

DR

OB

OR

ATIO

N O

XIDA

TION

c) Al2 O

3 , 623 K or

AN

TI-MA

RK

OW

NIK

OFF A

DD

ITION

d) A

nhyd ZnCl2

OF H

2 O 1

o alc. A

ldehyde D

ehydrogenation 2

o alc.K

etone C

u, 573 K 3

o alc.A

lkeneR

CO

Cl (Acyl C

hloride) R

ED

UC

TION

( to pri. Alcohol)

LiAlH

4 or NaB

H4

1o alc.

Aldehyde

Acid

+ HC

HO

+ H2 O

1o alcohol

Oxidation

2o alc.

Ketone (containing sam

e no. of C- atom

s)

Grignard's

+ Other aldehyde + H

2 O 2

o alc. (i) K

2 Cr2 O

7 / H2 S

O4

3o alc.

Ketone (containing less no. of C

- atoms)

Reagent

(ii) KM

nO4 / H

2 SO

4

+ Ketone + H

2 O 3

o alcohol (iii) C

rO3 /anhydrous condtn.

623 K C

H2 = C

H2

RX (Alkyl halide)

aq NaO

H or aq A

g2 O

C2 H

5 OH

+ Al2 O

3

473 K C

2 H5 O

C2 H

5

RN

H2

HN

O2 (N

itrous acid) 443 K

CH

2 = CH

2

(Primary Am

ine) (for 1

o alcohol) C

2 H5 O

H + conc. H

2 SO

4

410 K C

2 H5 O

C2 H

5

Cleavage of O_H bond

( Esterification )

Pri > Sec > TertCleavage of C_ O bond

Tert > Sec > PriD

ehydration

(containing same

no. of C -atom

s)(containing sam

e

Na, Mg, Al C6H5ONa + 1/2 H2

Acidic Nature NaOH C6H5ONa + H2O 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

dil HNO3

298 K + Nitration

conc. HNO3

+ conc. H2SO4 Picric acid

Cl2 water Br water

Cle

avag

e o

f O

_ H b

ond

Elec

trop

hilic

Arom

atic

Subs

titut

ion

OHNO2

OH

NO2

OH

NO2

NO2O2N

OHBrBrBr2 water

(polar solvent) Halogenation

NaOH H + / HCl (white ppt)570 - 620 K

Br2 in CS2

273 K +(non-polar solvent)

Friedel Crafts Alkylation NaOH H + / HCl RX / Anhyd. AlCl3 + 623 K, 320 atm

conc. H2SO4

288 K Sulphonation

NaNO2 + HCl H2O 273 - 278 K (warm) conc. H2SO4

(Diazotisation) 373 K

CH3 CH3 CH _ CH3 HOO_C_CH3

O2 H2O / H + CHCl3 + aq NaOH (air) Riemer Tiemann reaction (salicylaldehyde)

Cumene

C6H5N2+Cl- , alkali N N

Coupling reaction

4- Hydroxyazobenzene [orange dye]

NaOH (i) CO2, 398 K, 4-7atmos. (ii) H+ / H2O Salicylic acid Kolbe's reaction

Zn dust

OxidationNa2Cr2O7 / conc. H2SO4 Benzoquinone

SO3H SO3Na

Benzene sulphonicacid

Cl ONa

NH2 N2+Cl-

Br

Br

OH Br OH

Br

OH

R

OHR

OHSO3H

OH

SO3H

OHCHO

OH

ONa OHCOOH

Cle

avag

e o

f C

-O

bon

d

O

O

RCH2OH Oxidation Na (Primary alcohol) (i)KMnO4 in acidic/ alkaline/

neutral medium OR NaOH(ii)K2Cr2O7/H

+ OR Acidic (iii)CrO3 / H

+ Nature NaHCO3 or Na2CO3

RCH=CHR' (i)K2Cr2O7 / H2SO4 OR Blue litmusSubstituted alkene (ii)KMnO4 / H

+ OR(iii) KMnO4 / OH-

PCl5

RC N H2O / H+ or OH- PCl3 Nitriles Hydrolysis Cleavage of

C- OH bond SOCl2

RCONH2 H+ / H2O R'OH , conc. H2SO4

Amides (esterification)

RMgX (i) CO2 (dry ice) Grignard's reagent (ii) Hydrolysis (H2O / H+) NaOH NaOH + CaO , ,

(soda lime) [Decarboxylation]

RCOCl (i)H2O/H+ OR Acyl chloride (ii)Base followed by acidification

NaOH Kolbe'sElectrolytic method

RCOOR' (i)H+ / H2O Esters (ii)OH- / H2O followed by

acidification Dehydration P2O5 ,

(RCO)2O + H2O Anhydride Reduction

(i)LAH/ether OR(ii)B2H6

+NH3

RCONH2 RCN(amide) (nitrile)

(i)Cl2 or Br2 / Red P4 (ii)H2O - Halo carboxylic acid

[Hell-Volhard Zelinsky (HVZ) reaction]

RCOONa + H2 (g)

RCOONa + H2O

RCOONa + H2O + CO2 (g)

Red

RCOCl + POCl3 + HCl

RCOCl + H3PO3

RCOCl + SO2 + HCl

RCOOR' + H2O

RCOONa(n+1) C

R H + Na2CO3

(n- C)

RCOONa(n+1) C

R R(2n- C)

(RCO)2O + H2O

RCH2OH(alcohol)

RCOONH4

RCH_COOH

X

,P2O5

a

Reduction

Basic N

ature O

H-

(i) H

2 + Pd,P

t (H

Cl)

[Seperation &

Purification

(ii) Pd _ C

/ethanol of am

ine](iii) S

n + conc. HC

l(iv) Fe + conc. H

Cl

Acylation

(i)CH

3 CO

Cl

(ii)(CH

3 CO

)2 O Substitution

(Pyridine)

+NH

3 , alcohol B

enzoylation(i)K

CN

C6 H

5 CO

Cl

(ii) LAH

or Na(H

g) + C2 H

5 OH

[increase in no. of C-atom

s] C

arbylamine reaction O

R

Isocyanide reaction(i) LA

H(1

0 amines, C

HC

l3 + alc. NaO

H)

(ii) H2 O

TES

T FOR

PR

IMA

RY

AM

INE

S

RC

ON

H2

Br2 + N

aOH

Alkyl

H2 O

[Hoffm

ann's Brom

amide

NaN

O2 /H

Cl

amine

degradation reaction] 273-278 K

[ QU

AN

TITATIV

E E

STIM

ATIO

N]

Diazotisation

Aryl

Gabriel's Pthalim

ide synthesisam

ine D

iazonium salt

(i) KO

H(ii) R

X(iii) O

H-

C6 H

5 SO2 C

l2 S

ec. H

insberg's reagent

Fe + HC

l --> FeCl2 + H

2FeC

l2 + H2 O

--> HC

l + Fe(OH

)2(regenerated)

RXCO

NH

CO

RN

O2

RN

H3 +C

l -R

NH

2

RN

HC

OC

6 H5

Nucleophilic

RN

C + K

Cl + H

2 Opoisonous

[RN

2 +Cl -]

RO

H + N

2

[C6 H

5 N2 ] +C

l -

Pri.

Tert.

RN

HS

O2 C

6 H5

(soluble in KOH

)

R2 N

SO

2 C6 H

5(insoluble in KO

H)

No reaction R

NH

CO

CH

3 + HC

l

RN

HC

OC

H3

+C

H3 C

OO

H

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

AS BASE(Less acidic than NH3

due to resonance) HCl

H2SO4

Alkylation (RX)

CH3COCl NUCLEOPHILIC Pyridine SUBSTITUTION Acylation

(CH3CO)2O conc. H2SO4

Benzoylation

[Schotten Baumann Reaction]

Carbylamine reactionCHCl3+alc. KOH + heat

REACTION OF -NH2 GROUP

DiazotizationNaNO2 + HCl [273-278K]

Bromination Br2 + H2O + 3HBr (bromine water)

ELECTROPHILIC SUBSTITUTION

Nitrationconc.HNO3 + conc H2SO4

(288 K)47% 2%

51%

453-473 K conc. H2SO4

Aniliniumhydrogen Sulphanic ZWITTERsulphate acid ION

(CH3CO)2O Br2 H+ or OH-

Pyridine, Acylation CH3COOH (Protection of NH2 group) Bromination

ELECTROPHILIC SUBSTn (CH3CO)2O conc HNO3

(after protecting the amino group) Pyridine con H2SO4, 298K

Sulphonation

No effect

[C6H5NH3]+Cl-

Less basic than NH3due to resonance.

[C6H5NH3]2+S042-

C6H5NHR C6H5NR2 [C6H5NR3]+X-

C6H5NHCOCH3 + HCl

C6H5NHCOCH3 + CH3COOH

C6H5COCl,NaOH

C6H5NHCOC6H5 + HCl

C6H5NC + KCl + H2O

C6H5N2+Cl- + NaCl + H2O

NH2Br

Br

Br

2,4,6-Tribromoaniline[white ppt]

NO2

NH2

NO2

NH2NO2

NH2

+ +

NH3+HSO4

- NH2

SO3H

NH3+-

SO3-

NHCOCH3

Br

NHCOCH3

Br

NH2

NHCOCH3 NHCOCH3

H+ or OH-

NH2

(after protecting the amino group) Pyridine con H2SO4, 298K

Freidal Crafts Reaction No product, due to salt formation with AlCl3

C6 H

5 NH

2 + NaN

O2 + 2H

Cl

C6 H

5 N2 C

l + NaC

l + H2 O

Benzene D

iazonium C

hloride

Reaction is also know

n as Diazotization

Very useful as synthetic reagent

H3 P

O2 + H

2 O

C2 H

5 OH

273-278 K

C6 H

6+ N

2+ H

3 PO

3+ H

Cl

C6 H

6+ N

2 + CH

3 CH

O + H

Cl

H2 O

, 283 K

C6 H

5 OH

CuC

l/HC

l O

H S

andmayer's react n

p-Hydroxyazo benzene

Orange D

ye C

u/HC

l [TEST FO

R PH

ENO

L] G

atterman react n

Reactions involving retention of

Reactions involving displacem

entdiazo grp(N

2 +) [Coupling react n]

of N2 +X group

CuB

r/HB

r S

andmayer's react n

Cu/H

Br

Gatterm

an react n

C6 H

5 NH

2

OH

p- Am

inoazobenzene K

I , Y

ellow dye

[TEST FOR

ANILIN

E] , to dryness

HB

F4

Fluoroboric acid aq. N

aNO

2

CuC

N ,

or Cu/K

CN

Na + C

2 H5 O

H or LA

H

C6 H

5 N2 +X

-

OH

N N

+ Cl + H

2 O

NH

2N

N

+ Cl + H

2 O

C6 H

5 OH

+ N2

+ HC

l

C6 H

5 Cl + N

2

C6 H

5 Cl + N

2 + CuC

l

C6 H

5 Br + N

2

C6 H

5 Br + N

2 + CuB

r

C6 H

5 I + N2 + K

Cl

C6 H

5 N2 +B

F4

C6 H

5 F + N2 + B

F3

C6 H

5 NO

2+ N

2 + NaB

F4

C6 H

5 CN

+ N2

+ CuC

l

C6 H

5 CH

2 NH

2

OXIDATION CrO3 in anhydrous medium or PCC (Pyridinium chloro chromate)

1o Alcohol 2o Alcohol ROH R

DEHYDROGENATION Cu or Ag at 573K

HC = CH HCHO

Alkenes OZONOLYSIS OZONOLYSIS Alkene (i) O3 (i) O3 (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

HgSO4 HCHO can't be prepared

HCHO can't be prepared

Acid Chloride Acid Chloride RCOCl + H2 , Pd-BaSO4 poisoned with S

or quinoline (ROSENMUND REACTION)

(i) SnCl2 + HCl (ii) H2O / H+ (STEPHEN REACTION )

Nitriles RCN RCN (i) DIBAL-H (Diisobutylaluminium hydride)

(ii) H2O

Esters (i) DIBAL-H(ii) H2O

C = C

C C

CrO3Chromic anhydride

CH_OHR

(SymmetricTetrasubstituted)

+ R2Cd(Dialkylcadmium)

(i) + Grignard's reagent(ii) H2O / H+

HCN + OH- H2O / H+

(base as catalyst) Aldehydes White ppt.

NaHSO3

Ketones No.for ketones for aldehydes

HCHO 1o Alcohol

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

Ketone 3o Alcohol

Nucleophilic Addition

Aldehyde RCH RCH H+ / H2O

Alcohol + dry HCl

+ 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

(Hydrazine)

C6H5NHNH2 C = NNHC6H5

(Phenyl hydrazine) NO2

2,4-DNP C = N _ NH_ _ Red, Orange or Yellow ppt

COH

CNC

OH

COOH

CSO3H

ONaC

SO3Na

OH

Other aldehydes

OR'

OHR'OH OR'

OR'hemiacetal acetal

CH2OH

CH2OH+ Ketone

H+ / H2OC

R

R

O-CH2

O-CH2

(Hydrazone)

(Phenyl hydrazone)

NO 2,4-DNP C = N _ NH_ _ 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

or H2 + Ni/Pd/Pt Ketones 2o 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. CuSO4Fehling'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]