Short Notes SKC
Short Notes SKC
Short Notes SKC
R
& > (Ph) CH
& > PhCH
& & (iii) R–SO3H > R–COOH > > R–OH
(Ph)3 C 2 2 > CH2 = CH - CH2 >
F F F
1
BASIC STRENGTH µ Kb µ pK OH
b
C H
(viii) 6 4 Phenol > m > p > o
SK
R
PbS¯
(C) DISTILLATION UNDER REDUCED PRESSURE Black ppt.
(Vacuum distillation)
When liquid boils at higher temperature and it may Halogen Na + X NaX + HNO3 + AgNO3
decompose before b.p. is attained.
SI D (i) White ppt. soluble in aq. NH3
Example (i) Concentration of sugar juice
NaX confirms Cl.
(ii) Recovery of glycerol from spent lye.
(iii) Glycerol (ii) Yellow ppt. partially soluble in
aq. NH3 confirms Br.
(D) STEAM DISTILLATION (iii) Yellow ppt. insoluble in
When the substance is P = P1 + P2
C
immiscible with water and Vapour Vapour Vapour aq. NH3 confirms I.
steam volatile. pressure pressure pressure
of of water Nitrogen As in test for nitrogen; instead of
Example : Na+C+N+S
Organic and green or blue colour, blood red
(i) Aniline is separated liquid D
SK
PRACTICAL ORGANIC
CHEMISTRY
UNSATURATION TEST DISTINCTION BETWEEN 1°, 2° & 3° ALCOHOLS
R R
(a) Double/Triple bonded Compounds (C = C)/(C º C)+ Lucas reagent
Br2 in CCl4 (Brown colour) ® Colourless compound • R – C – OH Room temperature R – C – Cl
R R
Br Br Tertiary alcohol Cloudiness appears
CCl4 immediately
• R – CH = CH – R + Br2 R – CH – CH – R
(Alkene) (Brown) (Colourless)
R R
Lucas reagent
Br Br • R – CH – OH Room temperature R – CH – Cl
CCl4 Secondary alcohol Cloudiness appears
• R – C º C – R + Br2 R–C–C–R within five minutes
(Alkyne) (Brown)
Br Br •
Lucas reagent
R – CH2 – Cl
(Colourless) R – CH2 – OH Heat
Primary alcohol Cloudiness appears
(b) Double/Triple bonded Compounds + after 30 minute
R
Baeyer's reagent (Pink colour) ¾® Brown precipitate Lucas reagent is anhydrous ZnCl2 + conc. HCl.
HALOFORM REACTION IN ALCOHOL
• R – CH = CH – R + KMnO4 R – CH – CH – R + MnO2 OH
SI
(Alkene) (Cold, dilute) Brown ppt
OH OH • H3C – CH – R type of alcohols give iodoform test.
(Colourless)
R – OH + KX
HNO3
AgX OH
R – X + aqueous KOH AgNO3 R
Precipitate C=O + NaHSO3 R – C – SO–3Na+
H3C
If X is Cl, precipitate will be white and for Br yellow Methyl ketone CH3
precipitate will be obtained.
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Ethanal and methanal (Iodoform test) Aniline and N-methylaniline (Isocyanide test)
Iodoform test
• CH 3CHO + I2 + NaOH CHI 3 + HCOONa
• N H 2+C H C l 3+3KO H N C +3 KC l+3H 2 O
Ethanal Iodoform (alc.)
(Yellow ppt.) A niline P heny l isoc ya nide
(O ffe nsiv e sm ell)
Iodoform test
• HCHO + I2 + NaOH No yellow ppt.
Methanal • NH – CH3 + CHCl3 + 3KOH No offensive smell
(alc.)
N-Methylaniline
Acetophenone and benzophenone (Iodoform test)
O Aniline and Benzylamine (Diazotisation + phenol)
Iodoform test
• C – CH3 + I2 + NaOH
+ – OH
(Acetophenone) NaNO 2 + HCl
• NH2 Diazotisation
N2Cl
Mild
0–5°C
CHI3 + COONa Aniline Basic
(Yellow ppt.) Medium
N=N OH
Orange dye
O
Iodoform test
• C + I2 + NaOH No ppt. NaNO2 + HCl
• CH2 – NH2 CH2 – OH
(Benzophenone) Benzylamine
OH
R
Benzoic acid and ethylbenzoate No orange dye
•C6H5COOH + NaHCO3 ® C6H5COONa + CO2+ H2O Glucose and fructose
effervescence
• Ethyl benzoate + Sodium bicarbonate
SI
• Glucose+ Br2 + H 2 O ® Gluconic acid + 2HBr
® No effervescence ( brown ) ( colorless )
NaNO2 + HCl + – OH
• NH2 Diazotisation
N2Cl
Mild
Aniline 0–5°C
basic
medium
N=N OH
Orange dye
p-hydroxy azobenzene
NaNO 2 + HCl
OH
• CH3CH2NH2 CH3CH2OH No Orange dye
Ethyl amine
GRIGNARD REAGENT
REACTION
GRIGNARD REAGENT as Nucleophile
O O
O OH
C O R C OEt
R C O H RMgX in excess/H O+ R C R
H 3O + 3
R
O O
H C H R C Cl O
(1°) R CH2 R C R
H 3O + 1eq. RMgX
OH
O O
O H OH
H3C C H R C Cl
(2°) R CH CH R C R
3 H3O+ RMgX in excess/ H 3O +
R
O
O H O
R C R R C N
(3°) R C R R C R
R
H 3O + H 3O+
R
O O
O OH
H C OEt
H C R R CH2 CH2
G.R. 1eq.
SI H 3O +
–d +d
OH OMgBr
Å
O RMgBr O
O
H
H3O + R CH CH2
H C OEt
R CH R H C R RMgX inH
R CH CH2 R
RMgX in excess 3O
+
R
O
O
C
R C OEt O2
R C R R O H
1eq. RMgX H 3O+
O
C OEt O
O H O H
OEt + H 3O + Cl C Cl
SK
(3° Alc.) R C R R C R
RMgX in excess /H 3O +
G.R. (excess)
R R
O
O
Cl C Cl 1 eq. Cl C N Br
R C Cl RMgX
R C N + Mg
Cl
O
O
Cl C Cl 2 eq. Cl NH 2 Br
R C R R NH2 + Mg
RMgX
Cl
O
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GMP Reactions
2 C2H5 OH
ETHER
H 2SO 4 /140°C Cl2
[Williamson continuous etherification]
Dark
(NSR) [SN2]
+
H3C CH2 ONa
CH 3—CH 2—I HCl
[Williamson synthesis] [3°[R–X] ® Alkene]
H3C CH2 O CH2 CH3 Cold
(NSR) [SN 2]
H3C CH2 O CH3
Dry Ag2O HI/cold
2C2H5I R O R
(NSR)
CH 2N 2/BF3 , D HI/D
CH3—CH2—OH
excess
SO3Na GMP R
SI
CH3
(i) NaOH (i) O2 + D H3C C H
Å
(ii) H (ii) H Å/H2O
(–CH3COCH 3)
other product
+
N2Cl
C
H2O/D OH
Cl
SK
MgBr H 2O
(i) O2/60°C/D
Industrial method
+
(ii) H 2O/H PHENOL
H
COOH
OH NaOH+CaO/D O 2, V2O5
300°C
NO2
CH
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Comparision Comparision
of of
SN1 and SN2 E1 and E2
R
H Rearrangement Possible Not Possible
H Rearrangement Possible Not Possible
SI
Summary of SN1, SN2, E1 and E2 Reactions
RX Mechanism Q Q Solvent Temp.
Nu / B
Better NuQ
S N2 Low
C
E2 NuQ/Base — High
Primary (1°) Secondary Tertiary (3°)
(2°)
SN2 + E2
Strong nucleophile SN2 >>E2 (if weak base, E2
SN2 favored)
Mostly SN1 at
Weak nucleophile
Mostly SN2 Mostly SN2/SN1 low T mostly
weak base
E1 at high T
Weak nucleophile
Mostly E2 Mostly E2 E2
strong
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–NH – OH
HC ºCNaÅ
R
H 2N–Z
C=N–Z C (Acetylinic alcohol)
–NH NO2 CºCH
NO 2
–NHCONH 2 Cl PCl5 or SOCl2 RMgX OH
C
C
SI (Alcohol)
Cl R
C (Chloretone)
CH3 CH3 CH3 CCl3
C –– C Mg–Hg CH3
CH3 CH3 H2 O
C= O
OH OH CH3 [O]
(Pinacol) CH3COOH+[HCOOH]
SK
CO2+H2O
TESTS
(Given by Aliphatic and aromatic aldehyde) (Given by Aliphatic aldehyde) (Red-Brown ppt.)
CARBOXYLIC ACID
(i)
Å
(ii) H
R
SI
C
SK
(Schimdt Reaction)
/CH3–CH2–CH3
Hell Volhard Zelinsky Reaction
COOH
COOH Conc HNO 3+ConcH2 SO4
R COOH
(1) KMnO 4–KOH/D No Friedel craft reagent NO2
(2) H Å reaction COOH
Br2+FeBr3
R[1°/2° Alkyl group,
C=C, CºC, CH 2–OH,CHO,COCH3 etc]
Br
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AMINES
PREPARATION
+
NH 3(Excess) H/H2O
H3C CH2 X R N C O
-HX HO / H2O
O [Aminolysis]
R NH2
R
SI or SnCl2 +HCl
REACTION
+ – HCl CHCl 3,KOH
R-NH3 Cl R-NC
(Salt) (Carbylamine test)
C
CH3NH 2
CH3Br [NSR] HNO2 /H +
R-NHCH 3 RCH2NH 2 R-OH
SK
CH3COCl [SNAE]
O
R-NHCOCH3 Base (Acylation)
N–R
TEST
Reagent R–NH2(1°) R2NH(2°) R3N(3°) NH2
R N SO2 Ph
Ph–SO2Cl R2N–SO2–Ph
H soluble
(Hinsberg NaOH NaOH
No reaction NH SO2 Ph
reagent)
[R N SO2 Ph]Na+ Insoluble Soluble in base
soluble
S S S
C=S R NH C SH R2N C SH Ph—NH
No reaction
D/HgCl2 HgCl2 D HgCl2 D Ph—NH
Mustard
oil test R–N=C=S+HgS No reaction
[1]
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BENZENE DIAZONIUM CHLORIDE
REACTION
OH Cl
Cu/HCl
HO N N
pH = 8–10
Gatterman
reaction
Orange dye
NH2
NH2
Cu/ HBr Br
Coupling reaction
H 2N N N
pH = 4–5
Yellow dye
H NH-CH3
C2H 5OH/D or H 3PO 2/ D
OH OH
OH
+
H2O/H
N N NH2
pH = 8–10 283K
Red orange dye
Cl
CuCl/HCl KI I
+
Sandmeyer reaction
N NCl
R
Br F
CuBr/HBr HBF 4
D
+ –
CN N 2BF 4
CuCN/KCN
SI N O2
HBF4 NaNO 2
Cu/ D
ANILINE
C
REACTION
SK
+ NH2
H-Cl Br2/H2O Br Br
NH3 Cl
or Br2/CS2
O Br
NHCOCH3 NHCOCH3 NH2
(CH3–C)2O
+ Na HNO3,H2SO4 OH or
NHNa
Pyridine
Å
288K H
(Group Protection)
NO2 NO2
O NH2 NH2 NH2 NH2
O C Cl
Conc.HNO3 NO2
NH C
Base Conc. H2SO4 + +
Schotten Baumann Reaction [51%] NO2
NO2 [47%] [2%]
O
C Cl O NH2 NH2
O (i) H3C
NO2
Cl C Cl
NH C NH +
(ii) HNO3+H2SO4/H3O +
Diphenyl Urea
(Group Protection) NO2
Å
NH2 NH3
+ CHCl3 (1) Conc. H2SO4
N C Zwitter Ion
KOH (2) 453-473K
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Friedel crafts reagent
No reactions
SK
C
SI
R
SK
C
SI
R
SK
C
SI
R
SK
C
SI
R
SK
C
SI
R
SK
C
SI
R
SKCLIVE
R
SI
C
SK
SKCLIVE
R
SI
C
SK