UNIT-IALDEHYDES AND KETONES (13 Hrs)

Structure and reacti vity of carbonyl group - relative reactivities of aldehydes and

ketones - mechanism of nucleophilic addition reaction (HCN, NaHSOs, Grignard reagent)

-mechanism of aldol condensation, crossed aldol condensation,

Knoevenagal reaction. Study of the following reacti ons - Wolff-Kishner reduction, Wittig

reaction, Meerwein Ponndorf Verley

reduction.
Preparation, properties and uses of chloral, acrolein, crotonaldehyde and sucecinaldehyde.

UNIT-II CARBOXYLIC ACIDS & ACID DERIVATIVES (12 Hrs)

Structure of carboxylic acid and carboxylate anion - relative strengths of

monocarboxylic acids effect of substituents on acidity Hel - Volhard - Zelinsky

reaction- action of heat on hydroxy acids- preparation, properties and uses of lactic acid and
citric acid-dicarboxylic acids: action of heat on dicarboxylic acidls - preparation, properties

and uses of oxalic acid and succinic acid

Acid anhydrides - Amides -Preparation, properties and structure of urea -Esters-

mechanism of esterificati on and ester hydrolysis.

UNIT-III ORGANOMETALLIC COMPOUNDS AND ORGANO SULPHUR

COMPOUNDS Hs)
Preparation, structure and synthetic uses of Grignard reagent-preparation and reactions
of methyl lithium, diethyl zinc and tetraethyl lead-Reformatsky reaction
Preparation and properties of thioalcohols and thioethers sulphonal-mustard gas and

sulphones

Page 7

UNIT-IV REACTIVE METHYLENE COMPOUNDS & TAUTOMERISM

(11 Hrs)

Reactivity of methylene groups preparation and synthetic uses of diethyl malonate

and ethyl acetoacetate. Tautomerism - definition - various types, keto - enol, amido

imido, nitro-acinitro and oxime - nitrosotautomerism.

UNIT-V ALICYCLIC cOMPOUNDS 13 Hrs)

Nomenc lature -general methods of preparation - spectroscopic properties -chemical

properties relative stabilities of cyclo alkanes 3aeyer's strain theory-Sachse-Mohr

theory Coulson and Moffit's concept conformations of eyclohexane and
monosubstitutedcyclohexanes - largering compounds synthesis and structure of civetone

and muscone (structure elucidation not necessary).

 uumben ezpeet 50me 3t/nun and
Lower

Lexsstable

Notue mehylene Compoun ds

gha ercempu!
CoOC, 1H 5
CH,
CDOC H diethyl melbnat (DEM)
CH COo C, H5
ethyt acaro a catat CEAA)
Co CH3
CN
CH CH
CocHa
CN
dicyand mehane CDCH 3

n
ce
Olcayl acetone
achve
mehyune Compound
compound the malh oup
CH s
epenated b 2Canbony
Canbony roup
huulhple bond elactron poup Or or

me
thylne hydrogn withdraon
withdnalon gq 9wupinTneTha achve
acedic un
ochve
nesonance natune
natue duz due the
hu
stabilasatuon
Elhyl acalo ate tala
(EAA)
CH- cH-
Etu oceBo acatooc,H s
-

-
CH--CH--Oc Hsa
CH-
ethylaca to acelatu wn
CH--DC, HE< CHg-c =CH
-C-OczH
elc
ekc CH3--CH=-0cHy
OaADnancosstabizatron
tabilzaftonmeemorne t3ableabla
 ne

Nene Hj oion
n oill
Loill be
prodluLce d ond
Ond h e the
ethu)
acé tattjate ton Stable by he
tresonanca
aion s above

aeretore eth aceBo acekot s Ocidic nato c

alsp eeplaun by kelo- enol -

tautomarim
Ch3--H
CH 3-C CH
=
-
oC2H
-

ethyla ce to

neut ral
dcatal
(ketofovm eHhuy acoto acehat eno jorm)
acidic

Prepanalion o Efhy aceto acetat

1,elaisen reachon C
Clasen condonsalion Yeachon)
C2HbNa
2CH CooC, H CH3 CO CH- CooC,Hs+ C2HsD H
Ethy acautate EAA

Cive tone

0 CCH2),- eH
(CH2), CH

trans civeton
CcH2),- c -H

OH,),
H

Synthers civeton
COOC H3 PA/A
CHL)- 0 =c

coo (CH) coocHs

 anhehc picoluen
app icalion
Aceto acehc esten (o)
acelo a ate tata
t etat

. C H 3 -CD CHCH Co0c C2H 50a

-

f a u p

aton
a na l o n
Can boxuuic arid
with
wi th Sodium ethoide (CaH, dNa)
C2 H5
CaH5
co CHCObC,H5 CH
Hg-
- CH- cooc,Hy
C4 2 14- Cuco4
Joid yaalase

Sgn
hesis
ketone

C2 H 0 N a
C2HsO CH3-CO - H
CH-CD-CH2- COOC2 H5
cOOC,lH 5

kebohydreu
shs CH 2 CO - C H
COohHs

+ C2 H504
+ CO2
ClgCOCHzc, H5
Suthevis ikeloh
C2HaOnba
CaHa (0-CHccoc,
CH3-
CH2-Ce-CH,-CooC2H5
keto hy dnolysa
CoCH2
CHCocl CH 3 C0-
CH- CooCHy

CH2CoCH2CD CH3

diketohe
Synhexa. diol:
LAH
oH
CH
CH3C CH 2 CoOC2 H
CH3-C4- CH,-CH 2 -0H
-

Ffhy aceto acefat AlH

Synfhess ketoacid
CH3-C- CH, CH2 coOH
PR
 Na0C2 r u - l CH - CoO C2 Hy
_ cH,-CooC2 H5
-C
) CH3
CH2 CoOH
cH-C-CH-CooC2 H5
CH-CbOH

Co
CHz-C-CH-CoDL CH c-CH- ctjeCoOH

cHa-COOH valeric C i d
Y-ket
, sUsed to s hasuy hetroayetie co p o u n d

cH-cOC,H5 +DN- 4, CHt3-c-pu

CH- 2

co
, 11
OH N14 O
AD
1
CH
C -OC2Hs

NH
c OO Matfuy Ura cil
CH
11
CH
NH

Oun hes
Mulh
1)H20/H
2)A/20aCP3
CH- CH - COoc, Hs
cH3
CH-C- CHa - Coo C, He Na DC2 Hs -CH co0 Hs

) H2D/A" cu-coo,A,CHs CH, Br

CH3
CH--
CH C3
A (cO2
 ctH
CH3-- CHCE, -CH2
CH3
 Oinea
O i n
m e d

Adwe methylane Compbund

CH2 CEnn, C=D, = N ,N02

CEN

Phepanahon:
t9iethuy melonate
Coo
CaH0H Coo@
CH,CN + Ha0+ H a CH > CH
- Ket - 2H20

COOk HA
CoOH cooC2 Hs
Pot-cyano Melonic aud 9ie ky malona
acetatt

Syntheh c appieations r
A Syn the mono Cob oryic a cidl

n-Valeuc acid
coOC Hs
CDO2 H s CH 3CH B CH
ACH, CH, -CH2 -

Na CH

coDCzH
-nWaBr
coOC2Hs
Sooliam melonte Psten
-CaHsH KOH
CoOH
COok
Contrele
CHgCH,CH, CH He CH CHCH, CH
CoDH cook
CO2

CHa CHa CH 2 CH, CODH

n-valerie a i d

. DsD but yric acid

CHs cooc Hs

coDC CH 3T
C 3
2naD
cooC Hs
CooC2
esten
Si sodio melohic
 HC
C Cook
C 2 Hs OH
kel
ctl3 Cook
COO
cH 3
CooH
contrelledA
CoOH
cO cH
CH3
Dso buturie aald

3-pheny POpDnic add

COOC2 H5 ,CH2
C Hs CH, Br CooC2 H
N aC H

coOC2 H5

odiorme lonc sben

ko HH20

CH,CH CooK
+2C HOH
ontrolladA CH5CH COOH
cOok
-CO2 2k
COoH
C HCH 2 COo

c acid
propioni
3-pheny)
acid
dicanbocy lie
Synthes
Sucejnicacid cooC H
CH
CoOC2 1H
NaCt CooC 2 H
cOOC2HS +Ta CoOC2H
CooC2H ual
naP cH

Na CH
CoOC H
cooc2Hs kOH
COok
CODH
CH CH
codH HO
CooH
cook
CH .CDOR

CH cO0 K
0

cooH
 COD H
contoleda CH 2
CHg-CO0
e soil
CD SucciniC a c i d coO C2 Hs
ts of

blutarnic acid CH
cobc2H

CooC2HS CH 2
a a
NacH coOC2Hr
ras tCHTI -2 Na?
cODC2 H CH
the
CooCaHs
NacH
COOC2 hs
CooC Hs
K DH

CoOR
CoOH
C CH C0OK
Controlled A Cbo
CH 2 Cook

cH
C b o y

2k
c02 CH eook
C0OH
CH CoO
cH2
CH-C0OH

utarie aaid

3 Adipie acad
Cobl2Hs
Na CH
CooC Py +CH2 Br

CobC -2NaBr
va cH CHBr

CoOCt
 Synthees n
wnsatuntunate d acid Cknoeve naqal
Yeacio

COOC 5 COOC H5
CH=Ot H2 c CH2CH=
CH
cOOC2H5
H2D cooC Hs
CDOH COOK k DH
H CHCH= c
CHCH=C
-2kcl cook
2 tonhro lled
A
COoH
CH3CH= C
H
d-B-wnsalin alhd acd

Synthesis keto acios

cooC s
CoOC2H CH2CO- H c
Na He
CHgCoCl+
Ta cooc 24
coO2 s
Rontrolod
Controlo d
kotHo
LDO) COok
CH 2 -CO- He
,00-CH CHCD-CH
H COOH
Scook

.8unhesus keore
1. Acetone

COoC H
CD O Cg Hs
CH CO-Hc
CHaCOCl a Ple - Na C
cooC 2 Hs
cODC2 Hs
COo k HC CooH
kDeHO CH3CD-HC
CH3Co-CH
Coot
cobk
 PIRATION

ContTolle dA
CH 3 O CH3
acetone

ketone
Ethyl me thyl CoC
Cooc H5 CHaCH2 -CD-HC
Coc)+Da He
CH CH - Na c
CooC Hs

Synhesthesis heBrocyele componds

CO NH
CooC2 HUH CH 2
CH
HrDH -2C2 Hs OH
OcHN
CooC2 H
melornc acid
 Compoun d
Synthenu Alicyelie
cooc Hs
Cooc,HS
CH, B3Y CH CH
+NaCH
cooC2tls
cHBY Co OC2Hs CH, BY

Ctne di brenmids
co OC2Hs
cH2 CNA
-CaHe OH
cooC,Hs
C2 Hs 0No
CH,BY
Co Ok
C Ha cO0c H Kolt ct2
Ctl 2 Coo X
CH2 CooC2 ts

,Coo H CH
CH2 CH C00t7

cH COO cH

CH, Brr cooC2H

cH tNacH

Ycooc, H
cHBY coo H
CH2 CH
C2 H 0na
CH CoocHs
CH, BY
CH2 coo Hs
cH cNa

CH,BT CooC s
 coOc ts
CHa
CH o CH CHa Coek
CH
cooCH
ch Coo k

CH CoOH
ch
cH COOH

cHa
CH2 -Coo H

cta
23.05.22
autbmenusm Same pasts

phenomenon whene a 8unale che mica

Compolund erot un two DY more mtorn Conventable

stucwes tha arne duenen! n tems the

he

elalwe PostDN t One atomic nucleous hudoqun

the wo

And hee types omens

D compouwnd LsLally
phee un the numbe electvo n and paolons
1hey also exsi in dynamie egubiuruum ohen the
heonduon occuws beween these there
oompounols fhe
s ony raunen
pootong
lauloneus m s auo enmod as dem
automeris m takes plaunde in he phese) ee
Cabylst

CH2 CH HC C-C)2
ocelou
Cketo 4om) Cenoorm)
 1. keto eno) aulomesm
aamido -

imi do taulo mores m

2 nutTo -
a hit ro taleouim

h ifJ0 tutomeusm
4-62ime

R R2 OH

1. R, C C
Rg R, - éE C- R

th ohemical
keto enol tatomerBm Taje)o
Rui biriwm
uubirium bekveon k dlo 4orm (c=o) ContaUnu
Jorm dlouble bond
hudogen and he eno
a compoune
ovehent adacet -C =cDp
Sent
to
to be
kdo and eno 4ovm ahe

tOutomers )each o hen

Reacie n U WOLUn Cketo 4orm
NOH
NH2OH CH 2 c _cH2 COOC2 H;
CH-C- CH, Coo Cz H5
th a Ceto acolale
Kelo o r m EAA
 ONa
ha
CH2C = CH cod C2Hs CH3-C
CH-Coo C, H,
enolJoTm EAA

Amido-Dmi olo tautomonum

OH
C N-H
C= -
H
amido imido form

benzamids and wea

n ths tOuto enism

hmiornauoh 1 a
pouolo
po Ton
akes place om N eoup fo the
C=O0xygen
C Hg2 11
CH5 NH2 -NH C, Hs +HD
anudo oTm) N ehuyben2arnid
OH
chAg0 pC2 Hs
CH C = NH+HT
tmidD 403m) -ethy beneammde
 3) Nitro-AciniBap taulo meusmn
e OH
CH-cH, - N CH CH-N

(nilao)oTm) Cacnit7ojoTm)
Mechanibm
R Base R
,CH-N .N
Aaid R
R
so
O4
R R
R' N
C N
R >D
6TH R CH - NH2 + 2H20
R-CH2-ND
o4 oH
13T2
CLHEC - N
3)CHs- CH = N
SD BY B7
o
4J0xime nitroso automerum

-HC- N=D -C N - OH

(nitso6D) (Oxime
Mec hanusm
R
Bo -N-Ob
, C
CH N = O
Acid R
R

Cni roso rm)

N-b
Acid
R ,C= N-OH
worls

R Base

yerence behoeen Fautomansm and Keoran

Oaulomenus m Resonan ce

h tautbmes Can be 1.Re8ohanco hybrid

seponated Strucu haWe ho
Independent esk tan ce

a.In NMR 6pectYepm thone Dn nMR

pectrom here
s 6penat ignal s he 8epahat siqo a)
4oY au to mos 40r Res onan a

in th
autmers eat due t They deper only
olierence th ponton placo ment y elecron

e atom and electovn

 dypeenea)n th Ohe pooi rion nulei dbjon
6. h
yobitton
An 1oh not moYe that b.3

ahgsteDC) Angstrbhe.
oypa only io

.dionomic eguubivigm No e - t p t dlanomic

Rist eguubivium
D desno involwe h Dinvolves în th
vauoluon y bond length yaiatto n bond Lengh
1DhebhDb lowe han Wes han he ehe

the eneprgy he moetule he mole cul

benz