Std.

XII FLOW CHARTS IN ORGANIC CHEMISTRY 2013 - 2014

STUDENTS NAME : BRANCH : COLLEGE : BATCH : ROLL NO :

2013 MT EDUCARE LTD. (MTEL)

No Part of this book may be reproduced or copied or transmitted in any form without the prior permission of MTEL. Mumbai

HALOALKANES & HALOARENES

Preparation of Haloalkanes : 1) Halogenation R H + Cl2 R H + Br2 2) Hydrohalogentation CH2 = CH2 + HX * Addition of hydrogen halide on unsymmetrical alkane follows Markownikoffs rule. (i.e. the negative part of reagent gets added to unsaturated carbon that carries lesser number of hydrogen). * Addition of HBr follows peroxide rule also. (Anti Markownikoffs rule). 3) From Alcohols R OH + HX R OH + PX3 R OH + PCl5 R OH + SOCl2 4) Borodine Hunsdiecker Reaction R COOAg + Br2 5) Halogen exchange R X + NaI (X = Cl, Br) R X + AgF
(swarts reaction) NaX (Finkelstein reaction) NaX D D D Reflux Pyridine H2O H3PO3 POCl3

RX (Alkyl halide)

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HALOALKANES AND HALOARENES

Reaction of Haloalkanes :

1)

R COOAg (silver salt of acid)

AgX

R COOR (Ester)

2)

With alkali :aq. NaOH aq. NaOH NaX KX AgX

R OH R OH (alcohol) R OH

moist Ag2O

3)

R X + Na metal (Wurtz synthesis)

Dry ether

NaX

RR (alkane)

4)

With alkoxide :R ONa (Williamsons synthesis)

NaX

ROR (Ether)

RX Alkyl halide

5)

Cyanide :alc. NaCN alc. AgCN

NaX AgX

R CN (eyanide) R NC (isocyanide)

6)

Ammonia NH3
HX

R NH2 (Amine)

7)

Grignards reagent :Mg (Dryether) R Mg X Alkyl magnesium halide

KX, H2O

8)

Elimination Reaction alc. KOH CH2 = CH2

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HALOALKANES AND HALOARENES

Preparation of Haloarenes : 1) By electrophilic substitution CH3

+ X2 Fe(dark) or FeCl3 or BCl3 (X = Cl.Br) 2HX

CH3 X +

CH3

2) Sandmeyers reaction

Cu2Cl2

(X Cl)

NH2

N2+Cl
Cu2Br2 X = Br

Halo arene

KI

X=I

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HALOALKANES AND HALOARENES

Reaction of Haloarenes : Halogenation : + 2Cl2 Cl anhydrous FeCl3

HCl

Cl Cl + Cl (Major)

Nitration :HNO3 conc. H2SO4 D

H2O

Cl NO2 +

Cl

NO2 (Major) Sulphonation conc. H2SO4 Cl D

H2O

Cl SO3H +

Cl

SO3H (Major) Chloro benzene

CH3Cl

Cl Anhydrous AlCl3
HCl

Cl CH3 + CH 3 (Major)

Friedel crafts

Cl
CH3COCl

Cl COCH3 + COCH 3 (Major)

Anhydrous AlCl3

HCl

Wurtz fittig reaction R X + 2Na Dry ether

2NaX

Alkyl benzene

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ALCOHOLS, PHENOLS & ETHERS

Preparation of Alcohols : 1) From alkyl halide R X + NaOH(aq) R X + KOH(aq) R X + Ag2O(moist) 2) Alkenes CH2 = CH2
cold and conc. CH3 CH2 H2SO4
HOH D

D D D

NaX KX AgX

OSO3H (Addition of HOH follows Markownikoffs Rule) Can undergo 1,2-methyl or 1,2-Hydride shift. Except ethanol, it gives 20 or 30 alcohol. CH3 CH CH2
B2H6 H2O2 OH

(H3C CH2 CH2)3 B

(Anti-Markownikoffs rule)

3) Reduction R CHO (Aldehydes) O RCR

(ketones)

+H2 Ni D +H2 Ni D

R OH (Alcohol)

O R C OH
(Acids)

+ 4 [H]

LiAlH4

H2O

O R C OR
(Esters)

+ 4 [H]

LiAlH4

ROH

4) Grignards reagent H H C = O + R Mg X H R C = O + R Mg X O R C R + R Mg X
(30 alcohol) (20 alcohol) (10 alcohol)

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ALCOHOLS, PHENOLS & ETHERS

Reaction of Alcohols : 1) Metals :

Na K Al

(10 > 20 > 30)

H2 H2 H2

R-ONa R-OK (R-O)3Al

2) Esterification:
R - COOH R - COCl (R - CO2)O
0

H+ Pyridine Pyridine
0 0

H2O HCl RCOOH

R-COOR R-COOR (ester) R-COOR

3) Hydrogen halides : (3 > 2 > 1 )

10 HCl 2 3 HBr HI (10, 20, 30) (10, 20, 30)
0

Anhyd. ZnCl2, D Anhyd. ZnCl2 Room Temp. NaBr + H2SO4

R-Cl R-Cl R-Cl (alkylhalide) R-Br R-I

H3PO3

NaI + H3PO4
PCl3 PCl5 SOCl2

R-OH (alcohol)

4) Phosphorus hlide and SOCl2 :

R-CI R-CI R-CI R-Br R-I

HCl, POCl3 SO2, HCl H3PO3 H3PO3

PBr3 PI3

Red P. (Br2) Red P. (I2)

5) Dehydration : (30 > 20 > 10)

10 H3SO4 20 30 10 Al2O3 20 30 95% H2SO4 60% H2SO4 20% H2SO4 623 K 523 K 423 K 443 K 373 K 363 K

Alkenes

Alkenes

6) Oxidation :
10 2
0

(10 > 20 > 30) Aldehydes Ketones

[O] [O]

Carboxylicacid Carboxylicacid (less carbon)

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ALCOHOLS, PHENOLS & ETHERS

Preparation of Phenol :

1) From chlorobenzene :Cl

NaOH, 300atm, 623 K (Dows process)

ONa
HCl

Cl
+ HOH
,

Ca3(PO4)2

698 K

(Raschings process)

2) From Benzene sulphonic acid SO3H

NaOH H2O

SO3Na
NaOH , 573 K Na2SO3 , H2O

ONa
HCl NaCl

OH 3) From cumenc (isopropyl benzene) O OH H3C CH CH3 + O2 cumene

Mn-naphthenate or Co-naphthenate Alkaline dil Na2CO3 at 403 K

Phenol

H3C C CH3
dil H2SO4 distillation CH3COCH3

cumene hydroperoxide

(Commerical method) 4) Diazotisation Method NH2

NaNO2 + 2 HCl 273 278 K NaCl H2O

+ N2Cl
H2O + dil H2SO4 HCl , N2 D

Aniline

Benzene diazonium chloride

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ALCOHOLS, PHENOLS & ETHERS Reactions of Phenol :

Br2 inCS2 273 K HBr

OH Br + OH
Br2 water (Redcolour) Room. Temp HBr

OH

Bromination Br Br

Br

(white ppt) Br OH OH NO2 + NO2 NO2 2, 4, 6 - Trinitrophenol (Picric acid) NO2 OH SO3H

dil HNO3 2H2O

Nitration OH
conc. HNO3 conc. H2SO4 3H2O

O2N

OH Sulphonation

conc. H2SO4 298 K H2O

OH Phenol
conc. H2SO4 373 K H2O

SO3H Reimer - Tiemann Reaction ONa

CHCl3 + NaOH

ONa CHCl2
2NaOH

ONa CH(OH)2
H2O

ONa CHO
HCl

CHO

NaCl

Kolbes Reaction ONa

NaOH (i) CO2 (ii) H
+

OH COOH salicylic acid

With Zn dust
Zn D

+ ZnO Benzene O

Oxidation
K2Cr2O7 dil H2SO4

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ALCOHOLS, PHENOLS & ETHERS

Preparation of Ethers : 1) From Alcohols R OH + R OH R OH + R OH (Only with primary alcohols) Used for simple ethers. 2) Williamsons Synthesis (Labolatory method) R X + Na OR Used for simple as well as Mixed ethers.
D
NaX

conc. H2SO4 413 k (Acid catalysecl Dehydration) Al2O3 513 523 k (catalytic dehydration)

H2O

H2O

ROR ether

3) From Alcohols and cliazomethane : R OH + CH2N2 Used to prepare alkylmethyl ether.

HBF4 N2

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ALCOHOLS, PHENOLS & ETHERS

10

Reaction of Ether : With hydrogen Iodide (HI)

cold HI cold HI (simple ether) (mixed ether)

R I + R OH R OH + RI

* If one alkyl group is 10 or 20. Lower alkyl group forms alkyl halide. (SN2) * If one alkyl group is 30. 30 alkyl halide is formed. (SN1). R O R Ether R = R = simple ether R R = mixed ether
D

Hot HI

(simple ether)

H2O

2RI R I + RI

Hot HI

(mixed ether)

H2O

Hydrolysis
H2O H2O dil H2SO4, Pressure dil H2SO4, Pressure (simple ether) (simple ether)

2R OH R OH + R OH OCH3 Br + (Minor) Br (Major) OCH3 + CH3 (Major) OCH3 + COCH3 (Major) OCH3 + NO2 OCH3

Br2

in CH3COOH

OCH3
Friedel crafts

CH3Cl . AlCl3

OCH3 CH3 (Minor)

Anisole

CH3COCl . AlCl3

OCH3 COCH3 (Minor)

conc. HNO3, H2SO4 (Nitration)

OCH3 NO2

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ALDEHYDES, KETONES & CARBOXYLIC ACID

Aldehydes and Ketones Preparations :

C=C

O3 / H2O / Zn

CC

H2O / HgSO4

Cl C=C Cl (Geminal dihalide)

aq. NaOH

CH OH (10 20 alchol)

oxidation PCC. or collins reagent

CH = O (Aldehyde or ketone)

RCN

(i)

R MgX

+ (ii) H3O

O R / Ar C Cl
H2 / Pd + BaSO4 Rosenmund reduction

O CO O CO C
D Dry distillation

ONLY ALDEHYDES : O R C N + 2(H)

SnCl2 / HCl H2O +

RCH (Aldehyde)

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ALDEHYDES, KETONES & CARBOXYLIC ACID

12

Aldehydes and Ketones Reactions :

.. H CN / OH cat.

OH C CN OH C R OH C SO3Na OH C OH

(i)

R MgX

(ii) H3O + NaHSO3

H2O/H

2 RO H / H ( H2O)
+

OR C OR

CH = O (Aldehyde or ketone)

H O CH2 H O CH2 ( H2O) H +

O CH2 C O CH2 a, b unsaturated aldehydel ketone

aldol reaction dil . NaOH H2N Z ( H2O) H2 Pd or H Zn Hg

+

..

.. C=NZ

LiAlH4

CH OH

HCl

CH2

NH2 NH2

KOH

CH2

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ALDEHYDES, KETONES & CARBOXYLIC ACID

13

Preparation of Carboxylic acids : 1) Oxidation

K2Cr2O7/dil H2SO4

R CH2 OH

R CHO

K2Cr2O7/dil H2SO4

C6H5 R

Alkaline KMnO4

COO K

dil HCl

2) Hydrolysis

(I) dil HCl

(ii) dil NaOH

R CN

HOH . HCl

R CONH2
NH4Cl

3) From Dry ice

Dry ether H-OH , dil HCl

R - COOH carboxylic acid

O = C = O + R Mg - X (CO2)

4) From acyl chloride and acid anhydride

H2O , OH

R COCl
H2O

(R CO)2 O

5) From esters (by hydrolysis)

dil H2SO4 , D R OH

R COOR

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ALDEHYDES, KETONES & CARBOXYLIC ACID Reaction of Carboxylic acids :

Reaction involving cleavage of O H bond Na or NaOH or Na2CO3 Reaction involving cleavage of C OH bond
SOCl2 (D) D D SO2 , HCl H3PO3 POCl3

14

R COONa

(A)

formation of acyl chloride

PCl3 PCl5

R CO Cl

(B)

R OH (formation of ester)

O
, conc. H2SO4 H2O

RCOR

(C)

P2O5 (formation of anhydricle) NH2 ,

(R CO)2 O

(D) R-COOH R = alkyl or arul group

R CO NH2

Reactions involving COOH group

LiAlH4 , ether , H3O+ (formation of 10 alcohol , reduction)

R CH2 OH

NaOH , CaO , D (Decarboxylation)

RH

Substitution reactions in the hydrocarbon part

(i) X3 , reaction P , (ii) H2O (Hell-volhard-zelinsky reaction)

R CH COOH X (a - halo carboxylic acid) COOH

Nitration (For aromatic acids)

conc. HNO3 , conc. H2SO4

NO2

(m substituion)

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ALDEHYDES, KETONES & CARBOXYLIC ACID

15

PREPARATION AROMATIC ALDEHYDES : CH3

CrO2Cl2, CS2 H3O+

(Toluene)

CH3

Cl2 /hv

(Toluene)

CHO

(Benzaldehyde)
CO, HCl Anhydrous AlCl3

(Benzene)

O CCl (Benzoyl chloride)

H2 PdBaSO4

AROMATIC KETONES : O CN
PhMgBr / Dry ether H3O
+

(Benzophenone) O
Anhydrous AlCl3 D

O + CH3 C Cl

C CH3

(Acetophenone)

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