Aldehydes and Ketones

OCOC-II : Special Topics

Problem Solving

Class 7
* Phenol -

Formaldehyde Resins ( Bakelite) :

OH OH OH

+ H -
di -

y
H+ -
CUZOY

+
⇐E)
{ HZOH
OH
OH
CUZOY 0,4
-
HE -
CUZOY
_

benzyl alcohol
2-
Hydroxy
or £420M 1
CHZOH
2-
Hydroxy methyl Phenol (PIN )

in or

5h n

cis
Polymerises : A linear Polymer used

paints
Novo Lac
* with KCMO on
Heating gives cross
linkage
-

polymer : Bakelite .

( NCERT)
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 OH OH

-
CUZOY
n
OR Novo Lac + HCHO
+

'

o
' ' ' { HZOH
p

Ht -
n Hzo
: condensation
Polymerisation
to Cross
or • give linkage Polymer
-

-04
Bakelite

Thermosetting
polymer
• can't be
reused

•
used in Combs
,

switches handles
,

etc . . .

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

* Melamine -

format dehyde Polymer : Condensation Polymerisation

N
HZN MHz H+ N

[]
%" NHCHZOH
nano n
N N
N
formaldehyde)
N Hz
N Hz

(Melamine)
( Resin
Intermediate
H+
N
HN NH -

cuz A-
Polymerisation
,

NH

: Melamine Polymer
ₕydᵣₒcₐᵣbₒₙₛ
(unbreakable crockery) C̲ i ̲r ̲c̲l ̲e̲
* Glucose forms Hemi -
Acetal ( 2-
forms) :

Aldehyde

6 °
i. Top Top Top

Hemi Acetal
-

Formation

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

* Glucose & Fructose
(✗
-

hydroxy
, ketone give positive
solution
Totten 's
reagent &
Fencing tests .

& hence easily

• Glucose acts as
Reducing agent is

Totten's &
oxidised by mild oxidising agents like

Feinting solutions .

• With Token's Reagent :

-
≠

oxidised
↓
Glucose
Amm >
Salt of
Gluconic Acid

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

• with
Fehluig Solution :

-
+

oxidised

Glucose

Fructose ketone also to both

•

,
being ✗ -

hydroxy responds
Tolbnlsreagent-t-ehwgsk.in .

+ Agt ( Totten 's)

+ Cuzot , ( Fetting)

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 PROBLEM SOLVING
Identify the
compounds A
,
B
,
C
,
. . . .

1.
• H

B-
Cheng
C-H § -4
CHZ
gu
CHO
CH
-94
- - - -
-

B. ✓ (base) pg
• carbanion is resonance

stabilised

* involving G- V74 = Enolate

enolate
°
on p a
◦

a. cuz
-
-
H CU -
ch = CH - E -
H
]
✓

④ (aldol condensation, (Croton aldehyde)

CUz-cu-cuz-cn-n.cn
-
Cho @Wb) ( enolate )
(Nu -
attack )
◦
% 0-4
cuz
-
ch - ch -
ch = Cn - -
U 3 Cuz Cho

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 on
en ch Cn u
cuz ch -
-
= -
= -

6
A
⊖ 2 3 4 5
z

≈ Intramolecular Aldol condos .

I
°
Ju
¢4540)
2

:(Benzene) 3

3
ˢ

≈ involving G- V74 = Enolate → on last

Page ≈
Mesitylene formation

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 2.

☒BgEgS§

"°"
Curzon + COO
-

K+
-
CHO
conc .

(B)
0312h +

C2 -1140 = CH
}
CHO CHz=cn04
¢nH2nO)
A EM
:
0312N Ctlzcn -_ Chano
-
CH -_
Chang
Naini
Tt

cu-tl3°+cnzcu=cn
OH

↓
-

& -4
COOH CN

hydrolysis ( of
ₕydᵣₒcₐᵣbₒₙₛ
-

)
CN

C̲ i ̲r ̲c̲l ̲e̲
3.

DNP
Y=o
"
orange pptt, is
present
'

(p) ↳ Hgo
NaOH
yellow
I -1-2
Me -

q,
-
is
present
0
Btk ✗
or I
No Ppt P : ketone

.ÉHIÉÉ
No Rxn NO -c=c -
bond
I 1

P : Ph me : : Csltso
g-
-

'

's ?_? to ]
%
.

PHCOOH
Corky
Q
.

OÑ +
Hzcroq
.

P: Ph - -
Me s ,
•
aldol Comden .

PH * chiral
Ph
.¥÷i
Me "^5B0
no Eph
s:
Phyc-a.cn g- ph -

THF
Me
:-<
I *
geometric
me me isomers
ₕydᵣₒcₐᵣbₒₙₛ = 4 C̲ i ̲r ̲c̲l ̲e̲
4.

(a)
?
(b)

a ETENÉ COO Et 8-

CHZCCOOET)z En + s+

base Coo Et
-

Eton • Malo noateion

< Carbanion

≈ enolate ion

Eto cn(C00Et)z tons

-

CHCCOOET)z

04 -

O
Elcb
-
Eto

P ✗ COOEE
Eton -1 C
?
ₕydᵣₒcₐᵣbₒₙₛ
COOET
C̲ i ̲r ̲c̲l ̲e̲
 hydrolysis (alkaline)
-1in
•
of ester
COOEE 1. on
C -

COO Et
2. 0

a
÷.in
COOH

13 ✗

(A) CH COO H

C- Co2)

Note : idea from knoevenegal Rxn .

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 (b)

+
"
E- + addn
"
Visualise in alkene
cncoon
2 . Meon

H+

1. Meon
L + E-
effects CHCOOH

-4 -1
( More stable
)
2-

+
CH COO H ome
EWG CH COO H

less stable )

04
13 ✗
H+ Hzot
CH Coon CHCOOH
ether
P
hydrolysis of
&
☐

2. p -
unsatd Arid B- hydoxyacid

(AIB) ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

5 .
Ha formaldehyde Cross -
Aldol)
(ketone) me

Me

⊖
Me + HzC=0
Aldol
-
' ' '
'
Me
( keto)
stable ? ?
_ ,
,
'

, 04 ,

OH I CUZOH
1
1
{Uzi _

( z
Me
ME + HCOO
-

-
-
HCHO
_
_

-2
Me
Me ↓
Cannizzaro
≈ 1,3 did -

Rxn
@ 0 d- H
)
2. HCHO
Acetal formation ?
µ
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 ' ' '
.

jui
-

.
'

. ,

OH '
i
I
{Uz ,

0+4
l I
-

'
-
nie = Hzc =
-
.

= H
-1

Me

≈ 1,3 diol
-

Acetal formation ?
I
04 Ht
C O +
a
2
cyclic
3
04 Acetal .

Me

Me
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
6.

CHzC00H

Biz
/Ht
acid
catalysed
enolisation
Br
°
"
G:p -
Br
É
guns
-

c- cuz
'

e. not Br

o
-
◦ 4 NaBH4
54
{ 4- [ 4- cuz
442 base ' H2O
Br
Br on
-

base Euan
*
Cu cuz 0h 04
Intone base du dnz
-

Correct )
ₕydᵣₒcₐᵣbₒₙₛ
answer

(wrong )) C̲ i ̲r ̲c̲l ̲e̲

7.

Note : RCOOH
Nhs
RCoÉÑH4 °
RCOIVHZ (amide)
•
CSH 140 oximes ¥=0 is
present

Me-qg-i-netBCCsHgOzNa04cnBr3ttCDJBrz@I.f.D
(A) 03

"+ NHS 0 ☐
) E neutral
(strong ) cyclic compd .

* A must have : Me
}c=c - - - . .
1.1.1
Me
.

* B must have cuz

§ group
:
- -
- - -

A: Me ^^

Me
}= c-c-c-q-c.us or
} __ c-

{ Ty
-
Me
0 Me
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 HI
§÷ÉÉ(☐
Me '
, 03
Mezo + c- c-
g # -93
c-c- c-
-

Me I
§ zn ,

° NaOH C. 54802

(D)
11 -0¥ + CHBRZ
H C c c
q, Brz
- -
- -

0 (C)
H+
O

É ↳
H d c c -0T¥,
§
- -
- -

H c c on
§
- -
- - -

H-E-s-c-c-c-n.iq
4 3 2

• 11 -420
(-420) 0
4 5

ni
3
2 (E)

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

8.
5
4 •
LiAlH4Hz0
08
&
84 32 •

(aldol) (Redn ) ( EI )

4
g
3

NABHA H+
2
6 ☐

"2°
0 +
1 OH
Nuaddn
allylic
•

•
Elcb

(E)
+

(C)

-
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
9.
4 3-
'

5
y

✗2 5
6
Lz
4 3 a
21

4
5 3 2

13
6 2 5
z

P a
4
I 3

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 "
9. Ciii ) '
2

3
4 5

CHO
L
I
2 2 CHO
z

5 (A)
3 4 CHO

µ ,,a, ,
,
.
4

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

10 .

Cisualise Retro aldol)

-

B.

0-4
/
ñ
✗
z al dol

Me 2
2
04 3

0
In 11
4 5

Me

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

11 .

NaBH4 ☐ ¥ E + F
H2O

Me 5 4 5

Ht 4 Me

Is
°
? ? + Me
• 3

OH (-420) ¥2
"

3
z ring expansion 2 1

Ketone)
H 2 1
12 03 -
"

Me _ me
3
.
.

6 7
zn
4 5
0-4
2

@1) 3

↓ o
'
É -
me
CHO
reactive ore reactive
> 4
: IMP 28 5
5
ₕydᵣₒcₐᵣbₒₙₛ
⇐ %) Me C̲ i ̲r ̲c̲l ̲e̲
 OH

] E-
]
NAB "→
me du -
me
Hao
HBV

+
042

] ÉH -
me
-

up ] In -
me

@ llylic )

CH -
Me
-

32

Br
-

] on -
me

] Cy -
Me Br

(E)
Br
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 (EI) (redn .

) (aldol)
03

12 .

Try Yourself :

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Retro aldol)
( Focus -

is i. a 19
I.
CHZO
CHO OÑ C
C4zC4z
-

CU
q
-

cryo "
+
H.ge?-c%C4z
a 11
P Totylbenzal
-
cuz ( only
product)
CH3
CHO
-0h B Ix
,
2. #
☐
CH
g-
c-
C4zC4zCH3
+ !
× ° Chg
P
HE É
Xz
ICH
,

C4zC4zCH3 0-4
- - -

] °

d- Et
cn=q
PIET
-
 0
4 2

3.
✗' ✗2
222¢ -4 Very
6 CHO
-04 3

( MD
.

±
Me 5 3 11 - - - -

6
dz Cal ) 4 13 CY
}
5
✗ ↳ More reactive 7
,

??
a CMB
COCH
-3
2
3
4 6 4 1

I 2
✗, ✗
2%0 5

Me 3 5 7
6 78
✗
3
5. (un imp -

CI) Ph -
Enz -
É -
Enz-Ph _
✗
on a
-

+
- -
-
- -
-
=

O
O
p p
(E) Ph - É - É -
Ph
inter molecular
(Benzel ) •
-

ring closure
4.
✗I
4
23
GCHO
2
22

I 3 5 -04 3 %
1-
4
,
136

✗z

✗3
Uh -
IMP

6. 4 2

21
OHC 2
3 1-
c-CU
3 3 24
1
Most Imp
5
4 13
✗
z

LI
-
Cho

cuz
Cmp)→ un -

Imp
7. 10
3
2,1 0-4 £ ' °
9
32
9
8 4 7
8
13
4 6 5 6
7
,

8.
on ¢43)zC=C4 -
CHO

(Try Yourself)

(Two Products)
22 .
HWS -
4

23 24
EH Possible Products
21 ✗2
☐

0
More
me
reactive
5 5

" 4
Me
✗
1 :
1
*, ; g-
2
3 2 3

P : 2 : Imp Piz : More

Imp

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲