JEE MAINS CHEMISTRY- A HAND OUT ON NAMED REACTIONS

SN NAMED REACTIONSJEE CONTENT

1. SABATIER-SANDEREN'S REACTION
R-H=CH-R'+H2 R-CH-CHz-R'
2 WURTZ REACTION
R-X +R-XR-R + 2Nax (30 RX do not give this reaction]
3 FRANKLANDREACTION
R-X + R-x R-R+ZnX2 [ 19,20,3o gives this reaction]
4 COREY-HOUSE SYNTHESIS
R-X+2Li , DRY ETHER R-L + LiX
2 R-Li + Cul ’ R2CuLi + Lil
R2CuLi + R'X ’ R-R' + R-Cu + LiX (R'= alkyl, cycloalkyl ,âryl, viny etc]
5 KOLBE's HYDR0CARBON SYNTHESIS
a) 2 RCOOK + H0 FLECTROLYSIS R-R+ CO2+ H2t 2KOH
ELECTROLYSIS
b) CH(COOK)=CH(COOK) + H0 CH CH +C0+ H2+
2KOH
c) CHa(COOK)-CH<CoOK) +H 0 C H CHa +co: +H2+
2KOH
6 WITTIGREACTION
R-CH-Br
(0(PA3P) ()NaH (ú)RCOR' R'-C=CH-R

Note: If phosphonate ester is used instead of triphenyl phosphonium salt,

the reaction is Horner Wadsworth Emmonsreaction.
7. oXYMERCURATION-DEMERCURATION
Markovnikov addition of water - avoiding rearrangements

OH
1) Hg(OAc)2. H20
2) NaBH4
major No rearrangement
8 HYDROBORATION

1.B,H,
2.H,0, OH
OH
1 19%
9996

OH

1.B,H,
2. H,O, OH

859% 15%

HYDROCARBOXYLATION REACTION-KOCH-HAAF REACTION

Carboxylation of alcohols and olefins with carbon monoxide under
strongly acidic conditions.

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 JEE MAINS CHEMISTRY- A HAND OUT ON NAMED REACTIONS

The formation of tertiary carboxylic acids or esters by treatment of

alcohols or alkenes with anhydrous formic acid that functions as both an
acidic catalyst and a source of carbon monoxide is generally referred to
as the Koch-Haaf carboxylation.

or
co, H,0

co,CH3NHZHEAT ÀNKARI
a) R-CH-CH; R-CH(CONH-CHS)-CHs
0,ROHHEAT
b) R-CH=CH2 R-CH(COOR)-CH3
cO,RSH,HEAT
c) R-CH=CH2 R-CH(COSR)-CH
10. HYDROFORMYLATION OR oxO PRoCESS
R-CH=CH2+CO+ H2 Co,(CO)s R-CHz-CHz-CHO
11. PRINS REACTION
RCH=CH2 HCHO-H" HOH R-GH(OH)-CH-CHz-OH

+CH,-OH0(99

12. PRILEZHAEV REACTION

PERAOND-cHsCOOOH H,C CH, CHg

(CHs)2-C=CH-CH
13. LEMIEUX REAGENT|OSO4 - NalO, OR KMn0, - Nal0)
-Waio R-CO-R +R'CHO
Ra-C=CH-RKMno-Nalo,
Rac=CH-R' R-CO-R +CO;+H0
14 OXDATIVE 0zONOLYsIS

Ra-C=CH-R3 k
5. REDUCTIVE OZONOLYSIS
HOH-Ht
-R-CO-R +R'COOH +H202

Ra-C=CH-R nneR-Co-R +R'CHO +Zno

16. BORODINE HUNSDIECKER REACcTION
RCOOAg RX + AgX + CO2
(CHs)2-CH-CoOH UAgNO3 ()Br,cCt4A
(CHs)2-CH-Br

(CH3)-CH-COOH gs (CH3)-CH-CI
17. SIMONINI REACTION

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RCOOH ()AgNO3(),A RCOOR +C02 + Agl

RCOOH AgNO3
RCOOAg RCOOR + CO2 + Agl

18. SOMMELET ALDEHYDE SYNTHESIS (only benzyl halide)

CoHs-CH2-X (CH,)6Na H,0,H* CeHs-CHO
19. SWERN OXIDATION
DMSO
R-CH(X)-R RCOR
DMSO
RCH;X RCHO
20. FREUND REACTION
CL C1 + Z n A+ ZnCl2
Aprocess used to create alicyclic hydrocarbons by treating open ohain
dihalo compounds with sodium. When zinc is used instead of sodium,the
reaction is known as the Gustavson reaction.
21. ULMANN REACTION

Cu-Zn ALLOY OR
CoHs-X
22. BOUVEAULT-BLANC REACTION
CWcHe-CoHs OR DIPHENYL

Na-c2HSOH
RCOOR' RCH2OH +R'OH
23. PINACOL-PINACOLONE REARRANGEMENT
R-CH(OH)-CH(OH)-R R-C-c0-R
HQ
H H,C
-CH,
HjC
CH, H,C
H,C CH3
Pinacol Pinacolone
2,3-dirmethyibutane-2,3-diol 3,3-dimethylibutan-2-one

24. DAKIN REACTION OR DAKIN REARRANGEMENT

Only aromatic aldehydes having -OH or NH2 at ortho and para position
HO HO -OH
H,O,-0H

OH

NH2 NHz

Ha02-0H
25. FRIES REARRANGEMENT
Fries Rearrangement is an organic rearrangement reaction in which an
aryl ester is transformed into a hydroxy aryl ketone with the help of
a Lewis acid catalyst and an aqueous acid

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CH
L catayst
CH,
2 ag. HCI

CH,

At 160°C, ortho product is major and at 60°C, para product is major.

26. CLAISEN REARRANGEMENT
CHa
OH

CHe

Claisen|3.3] rearomatisation

The aliphatic Claisen Rearrangement is a [3,3]-sigma-tropia

rearrangement in which an allyl vinyl ether is converted thermally to an
unsaturated carbonyl compound.
The aromatic Claisen Rearrangement is accompanied by are
aromatization.

27. HOUBEN-HOESCH REACTION

The Hoesch reaction or Houben-Hoesch retction isan organic reaction in
which a nitrile reacts with an arene compound to form an aryl ketone. The
reaction is a type of Friedel-Crafts acylation with hydrogen chloride and
a Lewis acid catalyst.
OH OH
OH
CH,CN H.O
ZnCl HCL ELO HO OH efux 2hrs Ho OH
HO OH S10C 24 hrs
NH o 74%
+ NH4CI
Phloroacetophenone
28. REIMER TIEMANN REACTION
DH OH
3 NaOH A CHO
CHCl, -3 NaCi
-2 H0 HO
Phenol Saligyldehyde benzaldehyde
4hydroxy (Mincr)
(Majar)
29. VILSMEIER REACTION OR VILSMEIER-HAACK REACTION

H 1. POCL
N 2. H,0

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Vilsmeier Reaction allows the formylation of electron-rich arenes.

30. KOLBE'S
OH
REACTION (onlyat ortho
ONa
position)
OH

COOH
NaOH 1)CO,
2) H

phenol sodium phenolate 2-hydroxybenzoic acid

31. LEDRER-MANASSE REACTION
Synthesis of phenol-formaldehyde resins by polycondensation of phenols
in excess amounts of formaldehyde.

+ H,C=O Acid/Base +
6 days
o-hydroy benzyl alcohol
Phenal Methanal
H,OH
P-hydrary benryl alcohol

OH
OH OH

Hydrosymethytphenol Novalc (Linear potymer)

OH OH

CH, ÇH;

OH OH OH
Baketine (Cross tinkod polymer)
32. WILLIAMSONs SYNTHESIS
RONa + R4R-0-R +NaL
L= X SO:R"-0SO-OR"
33. WITTIG
REARRANGEMENT
Given only by benzyl and allyl ethers
CoHs-CH-0-CH, OPhLE,Na NH2 (Dw*CoHs-CH(CHs)-OH
34. OXO PROCESSOR HYDROFORMYLATION
Given only by terminal alkynes
(Co(CO)150C300 atm P.CH-CH-CH0+R -CH(CHO)-CH3
R-CH=CH2 + CO + H2
35. WACKER PROCESs
The process of oxidation of terminal alkenes to aldehydes and ketones by
using Palladium and Copper compounds as catalysts is called the Wacker
process.
Pdci2,HOH AIR CuCl
CH2 =CH2 CH3-CHO
Pdci2,HOH AIR CuCl
R-CH=CH2 R-COCHs
36. NEF CARBONYL SYNTHESIS
The conversion of nitro compounds into carbonyls is known as the Nef
Reaction.

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NO, 1) base
R 2) acid R R

NO, Ox.
R R
S ASRHEKRA R I

NO, Ox.
H
OF

37. GATTERMANN -KOCH FORMYLATION

Co + HCI AlCI
CuCI

CH3

38. GATTERMANN FORMYLATION( GATTERMANN ALDEHYDE

SYNTHESIS)
CH,

CH3

()zn(CN):-HCI(g)(i) HOH,A

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OH

OH OH

(0zn(CN)2-HCI9) (ü)HOHA
S H A N K A R I

CH

()Zn(CN)2-HCIG()HOHA

39. BAEYER -VILIGER OXIDATION

CH,C0oOH
RCHO RCOOH (Carboxylic acid)
RCOR CaH,CO00H RCOOR (Ester)
40. CLAISEN-SCHMIDT REACTION
Cross aldol condensation between aromatic aldehydeand aliphatic ketone
or mixed ketone.
CoHs-CHO + CH3-C0-CH, 109C,oM CoHs-CH(OH)-CH-CO-CHs
-HOH

CsHs-CH=CH-C0-CH
41. CLAISEN CONDENSATION
Claisen condensation proceeds when one ester with a-H's self condenses
to form -keto esters,
IntramolecularClaisen condensation is called Dieckmann cyclisation.
The Dieckmann cyclizationreaction is an intramolecular chemical process
In Organic Ghemistry wherea dicarboxylic acid ester undergoes
condensationtoforma cyclic B-keto ester under the influence of a base
H 1) NaOR
H
oR 2) H,o*
R

Clalsen Acceptor Clais en Donor

b.Ketoester

I) NaOEt
EtOH
2) H0*
Et
Diethyl hexanedioate Ethyl 2-oxocyclopentanccarboxy late
(1.6-Diester)

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42. PERKIN REACTION OR PERKIN CONDENSATION
Between aromatic aldehyde and aliphatic acid anhydride having atleast
two alpha hydrogens.
CH,COONaA
CaHs-CHo+ CHs-CO-0-c0-CH CsHs-CH(OH)-CHz-CO-0-CO-CH3
-HOH Hydrolysis
CsHs-CH=CH-CO-0-C0-CH3 CsHs-CH=CH-CO0H+ CH:COOH

CH
CHCOON OH

COUMARIN
43. KNOEVENAGEL REACTION
Between aromatic aldehyde and active methylene group
BASE,A HOH
CeHs-CHO+ H-CH-(Coo-CaHs)2CHs-CH(OH)- CH-(CO0-CH)2
CoHs-CH=C-(COO-CaHslz
44. REFORMATSKI REACTION
0zn (t)HOH,NH, CI
CoHs-CHO+Br-CH-C00-CaHs CaHs-CH(OH) CH COO-CaHs
CH-CHeCH-COO-CaHs
CANNTZARODEAgted sSem stable due to resonance)
45. INTERNAL REACTION
Alpha keto aldehydes with no alpha hydrogen can undergo this)
CaHs-CO-CHO Con Naon(u0o deH-CHOH CHO
46. CROss CANNIZZARO REACTION
In this reaction, formaldehyde is oRidizedto formic acid, while
benzaldehyde is reduced to theequivalent alcohol.
(0coneNaoH a)HOA
CeHs-CHo+ HCHO CeHs-CHOH + HCOOH
QCone Na OH (i)HOH,H*
CoHs-CHO
HINT:
+(CH)-C-CHQ FOUR PRODUCTS

() benzaldehyde reducedand tert-butyl aldehyde oxidised (two

products)
(ü) benzaldehyde oxidised and tert-butyl aldehyde reduced (two
products)
474 CANNIZZARO REACTION

C-H+ NaOH HCOONa+ CH;OH

FormaldeByde Sodium fomate Methanol

Csts H+CHs -H+ NaOH +cH,COONa +CoH;CH,0H

Benzaldehyde Soduum benzoate Benzyl alcohol
48. TISCHENKO REACTION OR TISCHENKO CONDENSATION
(An extension of Cannizzaro)
CeHs-CHONaz[Fe(co) JA
a) CsHs-CHO + (CzH_0,yAlA
CeHs-CO-0-CH2-CeHs
b) CH3-CHO + CHSCHO S[CHC0OH +CzHs-OH)
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ester formation
CHsCO0CzHs
49. BENZOIN CONDENSATION
KCN ETHANOLHOH,A
CsHs-CHO + CeHs-CHO CeHs-CO-CH(OH)-CeHs( Benzoin)
50. MICHEAL ADDITION
Conjugate addition( 1,4 addition) of enolateion into a,ß-unsaturated
carbonyl compounds is called Micheal addition.
CH30H,CH,0
CH,-CH=CH-COCHs CH-CH(OCH)-CH-C0-CH,
51. BENZILIC AcIDREARRANGEMENT
The benzilic acid rearrangement is formally the 1,2-rearrangement of 1,2
diketones to form a-hydroxy-carboxylic acids using a base. Thisreaction
receives its name from the reaction of benzil with potassium hydroxide to
form benzilic acid. AR
KOIE

benit

OH

COOH

52. KUCHEROV'S REACTION

The Kucherov reaction, also referredto as the Kucherov coupling or
Kucherov condensation, invoves the hydration of acetylenic
hydrocarbons in the presence of acatalyst, such as mercuric sulfate
HgSO4 or boron trifuoride BFa, and dilute sulfuric acid H:SO4, yielding
ketones. H
-CECHgso
-C-ç
HÖ
53. BERTHELOT SYNTHESIS
2C +H2ELECTRIC ARC 1475, CH= CH
54. BLACE REACTION(CHLOROMETHYLATION)
Anhy AICI3
CoHot HCHO + HCI CaHsCH:CI
5 REED REACTION( CHLOROSULPHONATION)
hu
CoHe +SO2+ Cl2 ’ CsH:SO:CI (propane sulphonyl chloride)
56. BIRCH REDUCTION
Synthesis of trans-alkenes using sodium in liquid ammonia
Na, NH,

CH,OH
57. PRILESCHIAEV REACTION
An alkene treated with perbenzoic acid gives an epoxide.

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CH

RCH=CHz + CeHsCooOH ’ +CeHsCOOH

58. DIEL-ALDER REACTION
When a six membered ring is formed by cyclo-addition of a 4n-electron
system with 2r-electron system. The addition product is called Diel-Alder
adduct.
Occurs in conjugated dienes.

Buadiese Ehylene
Cyclohexn
59. CURTIUS REARRANGEMENT
Acid chlorides react with sodium azide to form acyl azides. Acyl azides on
heating with water yields primary amines. This reaction involves a
rearrangement, called Curtius rearrangement.
First step is formation of acyl azide and second step is Curtius
rearrangement.

NaN3
R CI R Na Na CI

R N: RNH,
N -N Co,
AcvI Azide Isocyanate

60. ARNDT-EISTERT REACTION

R-COOH + SOCl2R-COCh+SO2+ HCI
acid chloride is converted toadiazoketone. Abase like EtsN is employed
to neutralize HCIIiberated in this step.
R-COCI +GH.NG--R-CoCHN, + HCI
The Woftrosrrangomentof diazoketone into a ketene and subsequent
conyersion of it to ahigher carboxylic acid or its derivative by using a
nucleophile.
Ag,0, A or hv, -N, Nucleophile (Nu)
R-COCHN, **>R-CH=C=O R-CH,CONu
diazoketane Wolff rearrangement ketene higher homologue
Note:
H-OH R
Acarboxylic acid

R-CH=C=0 R.OH An ester

Ketene
R-NH, NHR
1

An amide

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61. WoLFF REARRANGEMENT

Ag',or h Ag
R-CH=-C=0
Wolff re arrangement
-N,
H

Acarbene A ketene

Silver salts like PhCO,Ag, Ag,0 along with heat or light catalyze the Wolff rearrar
62. TRANSESTERIFICATION
When an ester RCOOR' is heated with an excess of another alcohol,
R"OH, in the presence of acid(H2SO4 or HCI) or a base (R"ONa) as
catalyst, a new ester RCOOR" is obtained.
It is obtained as a result of exchange of -OR' of ester with OR" ofalcohol.
Such a reaction is called transesterification reaction.

^OH
63. PINNER SYNTHESIS
When a nitrile is heated with anhydrous alcoholin presence of dry
hydrogen chloride gas, the hydrochloride of an imidateester is formed.
The later on being treated with water forms acarboxylic acid ester. This
reaction is called Pinner synthesis.
HCI CI H,0
NH,
R

64. THORPE REACTION

Nitriles containing alpha hydrogens undergo sef-condensation much like
the aldol condensation, in presence of ethoxide to form beta-imino nitriles.
The later ôn hydrolysis give beta-ketonitriles.
The reaction is called Thorpereaction.
NH,
EtONa
EtOH
R
65. MENDIUS REACTION
Primary amines can be prepared in good yield by the reduction of nitriles
either with H2 gas in presence of Raney nickel, LAH in dry ether or sodium
amalgam. The reduction of nitriles with Na and CaHsOH is called Mendius
reaction.

CH,-C=N +4 [HJ NaCHoH, CH,CH, NH,

Methyl cyanide Ethylamine
66. BORCH REACTION
When aldehyde or ketone is reacted with ammonial 10 amine/20 amines, in
presence of a reducing agent, the process is called reductive amination.

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The intermediate formed is an imine/N-substituted imines/l iminium ion

respectively. These are reduced to 1°,20,30 amines respectively by
reducing agents.
When NaBHsCN (sodium cyanoborohydride) is used as a reducing agent,
the reduction is known as BORCH reaction.
R H

Reduction
RNH,

67. ESCHWELLER CLARKE METHYLATION REACTION

The N-methylation of a primary amine or a sec. amine to a tertiary amine
RN(CHs)2 or RaN(CHs)respectively by reaction with a mixture of
formaldehyde and formic acid is called Eschweller-Clarke reaction.
This is a reductive amination procedure uses formic acid as reducing
agent.

Redssotion

68. LEUCKART REACTION

When aldehydes or ketones are heated with ammonium formate or
formamide at 1800C, primary amines areformed. Sec amines can
be obtained using N-alkylammoniumformate on N-alkyiformamide.
Tertiary amines can be formed by using NN-di alkylammoniumformate or
N,N-dialkyl formamide.
This reaction is called Leuckartreaction.
Ammonium formate serves to supplyammonia and formic acid acts
reducing agent.
NH, HCOO HN H H NH2
R. R2 Rf Rz
Rí R2
69. LIBERMANNS NITROso REACTION(a test for secondary amines)
N-Nitrosoamines when warmed with a small amount of phenol and conc.
H2SO4, produce a graen solution which on being made alkaline with
aqueous sodium hydroxide , turns deep blue. The reaction eventually
yields sodium salt of indophenol (deep blue). This reaction is known as
Libermann's nitrosoreaction.
Liebermann's nitroso reaction is a test that is given only by secondary
aliphatic or aromatic amines.
R-E-H+ HO-N= O >R-N-N-0 +H,o
R R
Nitre
itrosoamine
This nitroso amine, upon warming with phenol and concentrated sulfuric
acid (H2SO) forms a red or brown colour which first changes to blue, and
then to green.
Upon dilution, the colour changes to red, and upon further treatment with
alkali, the colour changes to violet or greenish-blue.

-OHcOConcH2S04,heat,
Rz-N-NO+ +

R¿NH

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