7. Reaction of Amine
Gabriel pthalimide Rxn
② Hoffmann Bromamide React
's
③ Mendius Rxn
① Schmidt Rxn
⑤ Curtius Rxn
⑥ Lossen
Rearrangement
⑦ Hoffmann mustard oil test
⑧ carbylamine Rxn
⑨ Scholten Baumann Reaction
④ Heinsberg Test
④ Coupling Rxn
8. Wurtz Reaction
Coupling reaction in which higher and symmetrical alkane containing even number
of carbon is formed.
CH cant be prepared in wurtz reaction
Free radicle intermediate is formed.
Friedel craft acylation Reaction
R-
✗ + 2 Nat X-
R
deer - R-
R -12N ax
ether
so
•
4
•
dʰY
SCHg-ctlz-CHz-CG-cnz-C.kz-
Cky
-
Cha -
Choo
CH}
-
CI -12 Nat CtCH2CH3 ether
0
+ R-
§-
C , Anhyd .
Alas ,
'
R
electrophile > RC0+(Acyliniiumn ph
+ ph -
%-
gantry Akb >
9. Ozonolysis
i) Reductive ozonolysis
ii) Oxidative ozonolysis
R
c-
R i
) 03
> GO + O=
'
R
R
/ '
Rii)Ha0/Zn
Aldehyde) ketone
Alkene
R E- C- R
'
"
> R-
§
-
§
-
R
'
R-
⇐ CH
' '
> R -
§
-
§
-
H
R
Rios R
H
[ =C
Hii> Hao % C=0tO=R
•
Hack gᵗk9
R -
COOH
✗
R-E.GR
'
"
>
R-§-§
-
R
'
i> 03,304C
-
CHO
ii> H2O /Zn
10. Kucherov Reaction
Product form by Markovnikovs rule
PH
HC -=CH + H2O
H&YH+ > CHECK
333K
tbc-CHTautometi.se -
CH
,
-
Cho
10h
^
Aldehyde
in
Ctlg -
CECH +420
HE/ Ht
S Ctb-
CH
=Ch2
333k
OH
CHz-tc-cna-Tautomeri.se-
Chg-
%-
cry
ketone
11. Birch reduction
partial reduction
Stereochemistry anti addition
R
R-
C. ≤ C- R / R' Nahiqntb> c=c
"
H R
'
/R
Alkyne tears .
alkene
•
•
>
R -
CECH
Na
> R-
⇐c-Noir
-
✗
sR-c=GR
'
Liqnn}
alkyne lower Higher alkyne
F-DG
EDG
Nain
s
LiqNH3
F- DG= -
R ,
-
OR ,
-
OH ,
-
Nhzetc
ENG
ENG
"
>
F- WG= -
Nong,
-
COOH ,
-
CHO ,
-
CN ,
etc
12. Kolbes Electrolysis
Electrolysis of mono carboxylic acid and salt of Na and K.
Free radical intermediate
CH cant be prepare
pH of final solution increases due to formation of NaOH.
If mixture of Carboxylic acid taken.
ZRCOO Niet 2h20 Electrolysis s R -
R + CO2 -1 2 NaOH +
H2
NaOH / KOH
Anode cathode
•
•
•
4
•
R'COON'_a + R'
'
Coo
-
Nai
'
Electrolysis > R'_
R' + R'
'
-
R'
'
+ R
'
-
R'
'
+
2cg -12 NaOH -1ha
NaOH /KOH
13. Soda lime decarboxylation
Alkane produce contains one C atom less than the carboxylic acid (reagent)
Soda lime process
3:1 ratio and NaOH: CaO is sodalime
CO is removes so it is decarboxylation
Carbanion intermediate
Rate of carboxylation carbanion stability
Methane cant be prepared
Sebatier Senderens reaction
This reaction is carried out in presence of Ni /
R-
Cinta NaOH
> R -
H -1 Nyco,
""
"
sodium salt of
Cao ,D
Carboxylic acid)
•
1 1
00
80
•
2
⑨
•
@
Ni
CH2=CH2 -142 ☐
> CH
}
-
Ch
}
A
14. Corey - house Synthesis
Carbanion intermediate
Unsymmetrical alkanes can be prepared in good yield
Frankland Reaction
Symmetrical as well as unsymmetrical
alkane can be prepared
Methane cant be prepared
R-
X
×
>
Rryculi > Lithium dialkylcopper
> Gilman 's
reagan
'
s
gives @ )
•
•
R2culi.R-XSR-R-cuxa-t.it
•
2R✗ In
>
Ren -12×2
dry ether
sdialkylzinc >
givers
Frankland 's reagent
R2ZntR
'
-
X - R -
R' + alkane
•
•
0
15. Ulmann reaction
Fitting with copper
Fittings reaction
Wurtz - fitting reaction
✗ + Cutx
A s
Brt2Na+Br Ether
>
☐
1- 2Na -1cL -
cry
day >
CH
}
ether
16. Wurtz Reaction
Coupling reaction in which higher and symmetrical alkane containing even number
of carbon is formed.
CH cant be prepared in wurtz reaction
Free radicle intermediate is formed.
Friedel craft acylation Reaction
R-
✗ + 2 Nat X-
R
deer - R-
R -12N ax
ether
so
•
4
•
dʰY
SCHg-ctlz-CHz-CG-cnz-C.kz-
Cky
-
Cha -
Choo
CH}
-
CI -12 Nat CtCH2CH3 ether
0
+ R-
§-
C , Anhyd .
Alas ,
'
R
electrophile > RC0+(Acyliniiumn ph
+ ph -
%-
gantry Akb >
17. Friedal Craft alkylation reaction
Sandmeyer reaction
Diazotisation Reaction
+
RCIN-kbk-ec.ly/g-RBF3/BClz/ZnCk
Electrophile Rt - can
undergo rearrangement
Nili *
,
a
HCl 1- Na
"
Br
¥1342s + Na "
R-
What HNO
,
> [R -
Ñ=N_C1ᵗᵗʰ°)
> R-
OHTHCI
(NaN02t (Diazonium salt ) (Alcohol)
Nik
Hc )
Npici (unstable)
Nang-1% + NaCl -12420
@ -5°C)
(Aniline
) (Benzene-
diazonium chloride)
18. Balz - Schiemann Reaction
Hunsdiecker Reaction
pili F
+
HBE,
> +
N2↑+BFz
Fluoro boric
acid ) (Fluoro benzene)
i
R-c-on-gt-xyc.CH > R-
✗ +
coat Agx
Silver salt of ✗ =Br.CI
Carboxylic
✗
COO
-
Agt +
X2
CCK, > + CO2 +
Ag
✗ =
Bull
19. Lucas test
Lucas reagent conc. HCl and anhydrous ZnCl
Lucas reagent is used to distinguish 1 2 and 3 alcohol
Alcohol gives turbidity with lucas reagent
Carbocation formed so rearrangement occurs
Reactivity order 3 > 2 > 1 alcohol
HI > HBr > HCl
R-OHI-HXAnhyd.MG > R-
✗ + Hao
•
g
• • @
•
,
•
3.Alcohol 2° alcohol Iialcohol
Instant •
5- 10min 30min . on
warming
•
O O O
•
•
20. Reed reaction
Chlorosulponation
Free radicle mechanism
Darzens process
Swarts Reaction
Alkylfluoride is prepared
R-
H -150g -192hr - R-50201
•
⑨
R-
OH + SOCK > R -
CI -1502-1 HCl
R-CIIB.ee ASF / Hgafa / coF2 > R -
F
/ 5bF3
21. Finkelstein Reaction
Halogen exchange reaction
Alkyl Iodide is prepared
Unlike NaI ; NaCl and NaBr is not soluble in
acetone
Gattermann Reaction
⑨
•
R-
X + NAI f-cetane - R -
I + Nax
✗ =C1, Br
ÉNa↑
-
Njci
Cultic /
,
-
Bee
cult Bee s + N2↑
22. Kolbes Reaction
Rosenmund reaction
Stephens Reduction
Etards reaction
OH
ONE
pH
-
COOH
NaOH
>
it CO2 >
ii)H+
Pd /Basque > Aalr-
É-
H
Arr- É-
CI -142 Quinoline
or
sulphur
R-C=Ni)5nCk/ HCl
sR-CH=NHᵗk¥ >
RCH0tNHg↑
ii> Hao/ H+
Nitrile) Imine) Aldehyde
)
4h3 CHOGEOHCK)2 CHO
Hoot
+ Crack C52 > 9
(Toluene)
chromium Benzaldehyde
complex)
23. Gattermann koch synthesis
Gatterman Aldehyde synthesis
Witting Reaction
CHO
CO,
HCl
>
Anhyd.tt/Cb/CuCl
CHO
+ HCNTHCI Alcb s + Ntlgttlcl
(
Hydrogen) H2O
(Benzene
)
cyanide)
( Benzaldehyde)
R R R
"
HR
,
'
C- 0+6645)g+P c,
>
R
'
C=C
R
" -1
0=p@H5)z
( Aldehyde or (Alkene
) Triphenylphosphine oxide)
ketone )
24. Haloform Reaction
Mozingo Reduction
Haloform reaction is used to detect the methyl ketone group in carbonyl compound
The only aldehyde which show haloform reaction is acetaldehyde
R- §-
CH
,
X2 -1 NaOH > R-%e0Nat-CHX3X-CI.BR,I
or
Naox
(sodium salt (
Haloform)
ofcarboxylic
acid )
One 'Éless than substrate
CH
}
§
OH 0
R-CH-ctlg-2-NAOH-R-E-chg-2-NAOKR-4-ONa-ct.LI}
or
NAOI (Iodoform)
O
SH
SH
- C § Ha.
Ni
s
c Hr,
Ethane -1,2 -
did
25. Bouvedlt-Blanc Reduction
Meerwein- Pondorff - verley reduction
RCHONAIETOH sRCHaOH
Aldehyde)
Metal acid
R -
É-
r
'
"
sR-_pi
(ketone)
R-
COOET
"
> RCTKOHTETOH
(ester)
MPV reduction
OH
R R, /Ht _
'
R RIH -1
Excess Oppenaver
oxidation
26. Clemmenson Reduction
Note: It fails for acid sensitive substrate
Suitable for base sensitive substrate
Wolff kishner reduction
Note: It fails for base sensitive substrate
Suitable for acid sensitive substrate
RCHO Zn -
Hg - R -
CH
}
(Aldehyde) Hcl ( Alkane
An R - §-
R
'
Zn-
Hg > Art R-
Cha
-
R
'
HCl
7
R µ /pi/An
inna-
Nha > R-
Cha-
H /R'/An
iiotil
-
H2O
7
27. Hell-Volhard Zelinsky reaction
Aldol condensation
Formation of carbanion ( enolate )
Combination of carbanion with other aldehyde/ ketone molecule
Alpha beta - unstaurated carbonyl compound formed as a product
Aldehyde and ketones must have atleast one alpha hydrogen
i
"
R CH
,
[Oni)✗2/RedP > R-
CH-
cook
ii)H20
"
X=CbBr
4- Halocaeiboxylic
Must have acid
a-
hydrogen
Aldol reaction
QCHGCHO-dilnaokchgc.tt -
Cha
-
Cho > CH}
-
CHIH -
CHO
or
Ethanol Konoe
°
"
"
But -
2- enal
Bacon)2
1^2%1*1
,
•
@
:
28. Mixed or cross aldol condensation
Note: If we want only one product in cross aldol reaction, we take one aldehyde/ ketone which is not having
any H
CH
}
CH }
-
Cho
↳ NaOH >
cttg-CH-CH-C.no/-CHz-Chz-CH--C-CH0
+ 2) D
but -
2-enal 2-
methyl pent -
2- enal
Chg -
Cha-
Cho
simple or
self aldol product
+
CHg-ctt-f-CHO-CHzctb-CH-CHC.NO
CH
}
2-
methyl but -
2-enal Pent -
2- enal
form Imokcule
ofethanol and 1 molecule of propanol
Cross aldol product
30. Fehling solution A aq solution of CuSO
Fehling solution B Rochelles Salt ( sodium potassium salt + NaOH
Fehlings Test
Note: Ketone and aromatic aldehyde dont give Fehlings test
Only aliphatic aldehyde give Fehling test.
>
4
>
0H o- Nat
k%
%, 8
R-
CHO Fetting > RCOO
-
+ Cuyo -13420
keagantcscut) Red-brown
ppt
HCOOH
2C#
>
CO2 -1420+020
Redppt
31. Tollens Test
Tollens reagent : ammoniacal solution of silver nitrate
Only aldehyde give tollens test
Done in basic medium
AgN0ztNH4OH >
[Ag(NH3)2)0H
RCH0t2[AgNHzk7+-130h
'
> RCOO
-
+
2Agr -12420 -14MHz
ketones
Totten's
reagent
> ✗
photo
"
>
PHCOOH 1-
Agr
HCOOH
"
>
C021-H201-Agrsihffo.org
carboxylic
acid
32. 2,4 DNP Test
Both aldehyde and ketone give this test
R
R - É-
HIR + Han NH ◦
-
N°2 >
EN -
NH o
-
Noa
RIH /
Noa
N°2
2,4 -
diniteophenlyhydnazine Red,
yellow,
orange
colour ppt
33. Schiffs reagent Test
Schiffs reagent : Solution of (p- rosahiline and SO ) which is colourless
Schiff base colourless pink colour
Ketones dont give this test
Both aliphatic and aromatic aldehyde give this test
502 ,
RCHO >
Schiff's
regant
:
34. Cannizzaro Reaction
Shown by aldehyde which dont contain alpha hydrogen.
Disproportion ( oxidation and reduction both)
Product: salt of Carboxylic acid + alcohol
:
•
oxidation
HCHOTHCHO conf
KOH >
CHg0H 1- HCOO
-
Kt
(Alcohol) saltofacid
u
nod-
H present
Reduction
35. Cross or Mixed cannizzaro reaction
Here two different aldehyde are used
The compound that is more reactive toward Nucleophilic addition reaction undergoes oxidation, while the other one undergoes
reduction
Reactivity order of aldehyde : HCHO > RCHO > phCHO
0
HCHO -1 -4-
Hanako"
> HÉ-0kt -1 CH20H
D
formaldehyde Benzaldehyde oxidized deduced
product product)
HCHO 1- CHO
cone . NaOH
> HCOONA -1 CH2OH
A
•
I
00
37. Acid catalysed Hydration
This reaction follow markovnikovs rule in case of unsymmetrical alkane
Carbocation formed as intermediate so rearrangement can occur
OH attack occurs
Ht
R-
CH=CH2 Hao
> R-
CH -
CH}
Alkene GH
2°alcohol
•
•
•
38. Hydroboration Oxidation
It follow anti- Markovnikovs rule in case of unsymmetrical alkene
Syn addition of borane to alkane
No carbocation form so no rearrangement occur.
Hydroboration reduction
3R-CH=CH2i
>
BH3.tt/Fs3R-CH2-CH2-0HtHgB0goEB2H6ii)H202/0H-
•
:
3R-CH=CH2i)BH3'THE
> BR-
cha-
CH
,
OE
B2H6
iitboltioeheduction
40. Pinacole-Pinacotone rearrangement
443 443 Ctb
Hgc C
,
C -
CH
,
dit 'H2S°4 >
Hgc d-%-
cry
OH 10h ↳
Vicinal diol ketone
Pinacof
Pinacolone
Migratory optitute : H
aryl alkyl
t > 3° 2° I
-
ph-ocrb.ph ph-
N°2
41. Esterification
i) Alkylation
ii) Acetylation
a) reaction with carboxylic acid
b) Reaction with anhydride
c) Reaction with acid chloride
2 R-
OH -12 Na -
na
>
IRONER
"
¥
> R -
O-
R
O
Ar R OH + RCOOH
conc .
Has R-
"
d-OR An
Acid Alcohol
0
Arlr OH + R- É-
o -
É-
r
'
"
+
- R - É -
or An
Anhydride
Alcohol
Ar R-
OH + RCOCI Pyridine > R-
É-
o -
r An
Acid chloride alcohol
42. Schotten Baumann Reaction
Dows Process
%-
CI + Ghg OH s
É-0 -
cans
R-
CI tag. NaOH >
R-
OH Snueaction
:
ao .
NaOH
> ✗
> Partial double bond character
•
Phenly cation
formed is
highly unstable
CI gnat PH
NaOH ,
HCI
s
673K
300 atm
•
Industrial method
of preparation of phenol
43. Cumene Hydroperoxide Rearrangement
HsP04 s
+ 250°C
propene Pressure
Benzene camera
443
Hgc C -
O -
O -
H
02
9
95 -135°C
Cumene
hydroperoxide
443
Hgc C -
O -
O -
H
OH
H30+ > + CHG
- §-
Ctb
50 -90°C
Phenol )
acetone
> Industrial method
> Acetone as side product
45. Williamsons Ether Sythesis
Laboratory method
Both Symmetrical and unsymmetrical ether can be prepared
SN 2 mechanism
2 and 3 alkylhalide gives alkene
R-
ON a + R'-
✗
Sna - R -
O -
R
'
t Nax .
(Alkoxide) I-
Alkyl
halide
(Ether)
•
⑨
•
•
0 0
PH OR
ONE
+ NaOH s R -
X
>
talky halide
46. Schotten Baumann Reaction
(
Acylation ofamine
Ctb-
%-
C ,
P
CH
}
-
C -
WH R
O
R-
NH2É3CHz-
É - NHR
-
ChzOH
d-ÉÉ Chg
- % -
NHR
-
CHZCOOH
• Famine don't
give acetylation reaction
°
11
CHJNH2-ICGH-y-d-CI.PK, ,
>
Chg-
NH -
&-
Cong
47. Carbylamine reaction
Both aliphatic and aromatic primary amine give this test
Used to distinguish 1 amine from 2 and 3 amine.
2 and 3 amine don’t respond to this test
Intermediate is dichlororcarbene
Iso-
cyanide Test
R-
Ntbtctlclg -13 KOH
☐
> R-
N=c -13420 -13kt
v
Very bad ≤
Alkyl isocyanide
smell or
carbylamine
①
A •
◦
•
g
⑧ O
o
48. Hoffmann Mustard oil reaction
R-
NH2 1- Csg SR-
NH -
§-
SH Hgck
Famine r
R -
N -1=5
Isothiocyanate)
R
R2NH -1cg > R-
Ñ-
§
-
SH HGCK > No reaction
Janine
RzN 1- Csg > No reaction
Janine
49. Curtius Rearrangement
Lossen Rearrangement
Schmidt Reaction
R-
§-
el
NaN} 1h20 SR-
NH
,
-1 NaCl +
Cg↑tN2↑
A
Intermediate >
Isocyanate
R- %-
Nti -
o - É-
r
0h
'
> R-
Nha -1cg
^
+ Rcoo
-
R - É-
OH + Nztt
"2504 > R-
Ntb -1cg↑ +
N2↑
Carboxylic acid ) Hydro}%;)
R-
CHO HN3 > R-
CN + R -
NH -
CHO
42504
R-
Co-
R
' '
> R-
%-
NHR -1
N2↑
50. Mendius Reaction
Amines containing one carbon atom and more than starting amine formed as product
Hoffmann Bromide Degradation Reaction
1 amine formed with one carbon less than the product
4mole of NaOH used per Br
Aryl/ Alkyl isocynate formed as on intermediate
Migration of alkyl / aryl group from carbonyl carbon amide to nitrogen
R-
E- Nt 41h7
Na
> R -
Cha
-
Nrk
C2Hg0H
Alkyl cyanide) @amine)
O
R -
4- Nha
Baat NaOH > R-
What Naacozt 2NaBr -12420
or
Nao Bee
•
•
••
2
•
•
51. Gabriel Pthalimide Reaction
1 amine only can be prepared
Aromatic amine cant be prepared
2 and 3 amine cant be prepare
Pure aliphatic 1 amine obtained
0
11 cooing
Nhi)akk0H s 1- RNH
,
ii > R -
X
" Iii)Na0H¢q,
COO Nat
0
⑨
⑨
o o
o
52. Hinsburgs test
§ Cl
(Hinsbergreagant)
%
Benzene sulfonly chloride
R-
Nha t Ph 502cL > Ph 502 NHR
(soluble in KOH
Ra NH 1- Ph 502cL > Ph 502N R2
Insoluble in KOH
RzNH + Ph 502cL > No reaction
53. Coupling Reaction
1. Reaction with B - Naphtol
2. Reaction with Diazonium salt
,N=N
-
ph
Nhz NÉCI
-
OH
-
OH
NaN02 > 7
HCl B- naphthol
Orange colour dye
NH2 NaCl
+ skin N=N
Azodye)
54. 3. Reaction with Benzaldehyde
Nmez
H Nmea
CHO + anhyd g
CH
Zn
Ck
H NMe2 Malachite -
NMe2
Green dye
