Chapter DISTINCTIO BETWEEN PAIRS OF COMPOUNDS

ALCOHOLS
UNSATURATION TEST DISTINCTION BETWEEN 1°, 2° AND 3°
R R
Double,/Triple bonded Compounds (C=C)/C=C) + R- -OH Lucas reagent R- -CI
Room temperature
lal
CCl, (Brown colour) ’Colourless compound R R
Br,in Br Br Tertiary alcohol Cloudiness appears
immediately
Br, R-CHCH-R
R-CH = CH-R+ (Brown) (Colourless) R R
(Alkene)
R-H-OH
Lucas reagent
R CH-C
Br Br Room temperature
Cloudiness appears
R-C=C- R+ Br, CCh R---R Secondary alcohol within five minutes
(Alkyne) (Brown) Br Br
(Colourless) R- CH, - OH
Lucas reagent
Heat
R-CH, CI
b Double/Triple bonded Compounds +
Primary alcohol Cloudiness appears
after 30 minute
Baeyer's reagent (Pink colour) Brown
HCI.
precipitate Lucas reagent is anhydrous ZnCI, + conc.
R+ KMnO,’ R- ÇH - ÇH-R+
R-CH= CH -(Cold, MnO, OH
dilute) OH ÒH Brown ppt
(Alkene)
(Colourless) H,C H-R upe of alcohols give iodoform test.
R-CC-R +KMn0, ’ MnO, +RCOOH+RCOOH
(Hot, dilute) Brown ppt. OH
NaOH
R-C=C-H+KMnO, >MnO, + RCOOH+CO,+H,0
Brown ppt. (Colourless)
HC- H -R+h Todoform lest CHI, + RCOONa
(Alkyne) (Hot, dilute) lodoform

Baeyer's reagent is cold, dilute KMnO, solution (Yellow ppt.)

having pink colour. PHENOL

Note : The above test are not given by Benzene. Phenol + ferric chloride. >Violet colouration
Although it has unsaturation. (neutral)

TEST FOR TERMINAL ALKYNE 6 O H +FeCl3H+ (Fe(OC,H)J + 3HCI

Violet colouration

Terminal alkyne
Ammonical silver Ammonical cuprous
nitrate chloride CARBONYL GROUP

Carbonyl compound +2, 4-Dinitrophenylhydrazine

White ppt. AgNO, + NH,OH
Red ppt.
Yellow/orange crystal (Brady's reagent)
NH,NO, +H,0+R-C=C-Ag NO, O,N
White ppt. R -C= CH
Terminal alkyne
Cu,Cl, + NH,OH|
>fo -NO,N-NH -NO,
NH,CI +H0+R-C=C-Cu+ All aldehydes and only aliphatic methyl ketones
Red ppt.
+ NaHSO, ’ White crystalline bisulphite.
OH
NATURE OF X-GROUP INC-X BOND C=o +NaHSO,R-¢-SO Na
R-X + aqueous KOHR-OH+KXANO AgX Aldehyde
Precipitate
If Xis Cl, precipitate will be white and for Br R OH
Hc+ NatHSO, R-¢- SO,Na'
yellow precipitate will be obtained. Methyl ketone H,
 ALDEHYDE GROUP Chloroethane and chlorobenzene
Aldehyde + Tollen's reagent ’ Silver mirror " CH,-Cl+aq. KOHC,H.-OH+KCINO
AgN) AgCl
White ppt
R--H+30H +2/Ag(NH)JRCOO" +2HO+4NH,+2Ag+ Boll No
aq. KOH AgNO,."
(silver mirror)
HNO
reaction
Aldehyde +Fehling's solution -’ Reddish brown precipitate

R-CH+2Cu +50HRCO0°+3H,0+Cu,0 Chlorocyclohexane and chlorobenzene

(Reddish brown ppt)
+ aq. KOHBoil OH+ KCI HNO

WhiteAgClpot
AgNO

H,C -C- group also give iodoform test Boil

KOH AgNO No reaction
HNO,

HC-R+L,+NaOH b9lorm lesl CHI, + RCOONa

lodoform
(Yellow ppt.) Chloroethane and bromoethane
HNO

AROMATIC ALDEHYDE GROUP C,H,-Cl+aq. KOHCH,-OH+KCI

(Chloroethane)
AaCI
White ppt.
Aromatic aldehyde + Tollen's reagent Silver mirror " C,H,-Br+ aq. KOHC,H,-OH+KBr HNO,
Aromatic aldehyde + Fehling's solution ’ Negative test (Bromoethane)
AgNO. AgBr
Yellow ppt.
Fehling's solution
Negative teste -CHO
Tollen's reagent Benzyl chloride and chlorobenzene
Ag +
Silver coo C
mirror Boil
aq. KOH -CH,+ KCI
(Benzyl chloride)
HNO.
CARBOXYLIC GROUP AgCl+ AgNO,
Carboxylic acid + Sodium bicarbonate White ppt.
effervescence + ag. KOH HNO,BoilAgNONo reaction
RCOOH + NaHCO, ’RCOONa +H,0+ Co,‘ Chlorobenzene
FORMIC ACID
Fehling's solution
+H,0 + CO, +Cu,O Ethyl chloride and vinyl chloride
HCOOH Red ppt.
Formic acid Tollen's reagent " CH,-Cl+aq.KOH lC,H,OH+KÇI
2Ag + C0, + H0 (Ethyl chloride)
Silver mirror AgCl HNO,
(White ppt.) AgNO,
AMINES (1°) " H,C=CH-Cl+aq.KOH. Boil

Carbylamine HNO,. AgNO, ’ No reaction

Primary amine + KOH + CHCI reaction
+ Isonitrile
Vinyl chloride
(Offensive smel)
Amines (1°, 2° & 3)(Hinsberg's test)
Primary amine + Benzenesulphonyl chloride n-Propyl alcohol and iso-propyl alcohol
’ Precipitate

Secondary amine +Benzenesulphonyl chlorid

KOH ’soluble
CH,CH,CH,OH +HCI ZnCH,CH,CH,u
KOH No cloudiness at room temp
’ Precipitate ’ insoluble OH CI
Tertiary amine + Benzenesulphonyl chloride ’ No
reaction HC CH-CH, ZiC,
HO HcdH-CH,
Note : Benzenesulphonyl chloride is called Hinsberg's Cloudiness within 5 minutes
reagent.
 Chemistry HandB
ALLEN
alcohol and methyl
Ethyl
alcohol (lodoform test) Propanal and propanone
CH,CH,OH+41,+6NaOH ’ CHI, + HCOONa (Tollen's and Fehling reagent)
Yellow ppt. ’ Silver mirror
Propanal + Tollen's reagent
CH,OH + 4l, +6NaOH’ No yellow ppt.
alcohol and acetone (2, 4 - DNP)
Ethul
O,N H,C-CH,-H+30H +2/AgNH),J
CH,CH,COO +2H,0+4NH,+2Age
HfoH,C!
Acetone
I- NH NO,
2.4-Dinitrophenylhydrazine
(Silver mirror)

O,N Propanal+Fehling's solution’ Reddish brown precipitate

= N-NH
NO,+ H,C CH, H + 2Cu*+ 50H
(yellow orange crystals)
2,4-DNP CH,CH,COO + 3H,0 + Cu,O+
’ No reaction (Reddisth brown ppt.)
CH,OH
Fehling's solution
Negative test
Phenol and ethyl alcohol (Neutral FeCl,) Propanone Tollen's reagent
Phenol + Neutral ferric chloride ’Violet colouration Negative test

6 -OH +FeC, ’3H + (Fe(0C,H)J +3HCI

Violet colouration
Pentan-2-one and pentan-3-one (lodoform test)
CH,CH,0OH + Neutral ferric chloride
No violet colouration
" HC- CH, CH, -CH, + I, + NaOHdolerm lest
(Pentan-2-one)
Benzoic acid and phenol (NaHCO,)
Benzoic acid + Sodium bicarbonate effervescence
CHI, + CH,CH,CH,COONa
lodoform
(Yellow ppt.)
C,H,COOH+ NaHCO, ’ C,H,COONa+CO,‘ +H,o
Phenol + Sodium bicarbonate ’ No effervescence H,C- CH,. -CH, -CH, + L, + NaOHodotrmtesNo yellow ppt.
(Phenol is less acidic than benzoic acid) Pentan-3-one

Propanal and benzaldehyde (Fehling solution)

Propanone and propanol (2, 4- DNP)
Propanal+Fehling's solution’ Reddish brown precipitate
O,N
H,C
I- NH -NO, HC-CH bH:2Cu.+50H’ CH,CH,COO +3H,0+Cu,0
H,C Fehling's
solution
2, 4-DNP
O,N Benzaldehyde + Fehling's solution ’ No precipitate

=N-NH NO,+ CH0 +2Cu'+ 550HNo reaction

Yellow orange crystals
Propanol + 2,4-Dinitrophenylhydrazine ’ No crystals
Methanoic acid and ethanoic acid
(Tollen's & Fehling solution)
Ethanal and prropanal (lodoformtest) Fehling's solution
+H,O + CO, + Cu,O
nC-C-H+L + NaOHodolorm ies CHI, + HCOONa HCOOH
Methanoic acid Tollen's reagent
Ethanal lodoform +2Ag+ CO, +H,O
(Yellow ppt:) Fehling's solution
No brown ppt.
HC -CH, H+1, + NaOH odolom tal No yellow ppt. Ethanoic acid
Tollen's reagent
Propanal No silver mirror
Chemistry HandBoOk

(lsocyaniALLEN
Ethanal and methanal (lodoform test) Methyl amine and dimethyl amine
" CH,CHO+1,+NaOH lodoform test CHI,+HCOONa " CH,NH, + CHCI,+ 3KOH
de test)
Methyl amine (alc.) CH,NC +3KCl +
Ethanal lodoform
(Yellow ppt.)
Methyl isocyanide
(Offenslve smell) 3H0
"HCHO+l,+NaOH lodoform testNoyellow ppt. "H,C-NH+CHCI,+3KOH
Methanal (alc.)’ No offensive sral
Di-methyl amine

Acetophenone and benzophenone (lodoformtest) Aniline and ethyl amine (Diazotisation)

-CH, + 1, + NaOHlodolorm test -NH,

NaNO, + HCI
Diazotisation
(Acetophenone) Aniline

CHI, +<
Yellow ppt.
-

-COONa+ N=N -OH +

Orange dye
p-hydroxy azobenzene
lodoform test
+l,+NaOH No ppt.
(Benzophenone)
" CH,CH,NH,
Ethyl amine OHCCH,CH,OH +No Orange dye

Aniline and N-methylaniline (lsocyanide test)

Benzoic acid and ethylbenzoate -NH,+CHC,+3KOH’

(alc.) -NC+3KC+3H,0
Aniline
Phenyl isocyanide
(Offensive smell)
CH,COOH+NatHCO,’C,H,COONa+CO%‘+H,0 -NH - CH, + CHCI, + 3KOH’ No offensive smell
(alc.)
N-Methylaniline
effervescence Aniline and Benzylamine (Diazotisation + phenol)
Ethyl benzoate+Sodium bicarbonate ’ No
effervescence
-OH
-NH, NaNO, + HCI
Diazotisation -GNCI.pH= 8.5- 9.5
Aniline

Benzaldehyde and acetophenone (Tollen's test) N-NoH

Orange dye
Benzaldehyde + Tollen's reagent ’ Silver mirror -CH,- NH, NaNO, + HCI
CH,-OH
Benzylamine
-CHO+30H (Tollen'
+2|Ag(NH)J
s reagent) -OH
No orange dye +
CO0+2H,0+4NH,+2Agle Glucose and fructose
Acetophenone+Tollen's reagent ’No silver mirror
Glucose+Br, +H,0 ’ Gluconic acid + 2HBr
(Brown colour) (Colourless)

Fructose + Br, + H,O ’ Brown colour

(Brown colour) (no change in colour)

 Chemistry HandBook
ALLEN
Glucose and sucrose OR
Gucose + Tollens reagent ’ Silver mirror
No blue colour
Glucose+ I,solution
Sucrose + Tollen's reagent ’ No silver mirror
Glucoseand starch Starch + L, solution ’ Blue colour

Glucose + Fehling's solution ’ Red ppt.

Starch + Fehling's solution ’ No red ppt.

IMPORTANT NOTES