ALLEN Chemistry HandBook

Chapter
DISTINCTION BETWEEN PAIRS OF COMPOUNDS
5
UNSATURATION TEST DISTINCTION BETWEEN 1°, 2° AND 3° ALCOHOLS
B R
(a) Double/Triple bonded Compounds (C=C)/(C=C) + Lucas reagent R--C
R--OH Room ternperature
Br, in CCI,(Brown colour)’Colourless compound R R
Br Br Tertlary alcohol Cloudiness appears
immediately
R- CH = CH -R+ Br, cCh R-CH-CH -R
(Alkene) (Brown) (Colourless) R R
Br Br R-H -OH Lucas reagent
Room temperature
R-H-CI
R-C=C-R+ Br, ce R---R Secondary alcohol Cloudiness appears
within five minutes
(Alkyne) (Brown)on Br Broold
Lucas reagent
(Colourless) R-CH, - OH Heat
R-CH, -CI
(b) Double/Triple bonded Compounds + Primary alcohol Cloudiness appears
after 30 minute
Baeyer's reagent (Pink colour) Brown
precipitate Lucas reagent is anhydrous ZnCI, + conc. HCI.
" R-CH= CH-R+ KMnO, R-ÇH-ÇH-R+ MnO, OH
(Alkene) (Cold, dilute)
OH OH Brown ppt
(Colourless) H,C H-R type of alcohols give iodoform test.
R-C=C-R +KMnO,’ MnO, +RCOOH+RCOOH
(Hot, dilute) Brown ppt. OH
RC=CH+KMnO, MnO, + RCOOH+CO,+H,0 H.C- H-R+h NaOH
lodoform test CH, + RCOONa
(Alkyne) (Hot, dilute) Brown ppt. (Colourless)
lodoform
Baeyer's reagent is cold, dilute KMnO, solution (Yellow ppt.)
having pink colour. SU0 pHENOL
Note : The above test are not given by Benzene. Phenol + ferric chloride Violet colouration
Although it has unsaturation. (neutral)

TEST FOR TERMINAL ALKYNE 6OH +FeCl,3H+ (Fe(OC,H)J +3HCI

Violet colouration
Terminal alkynebirolts u
Ammonical silver Ammonical cuprous
nitrate chloride CARBONYL GROUP

White ppt. Red ppt. Carbonyl compound+2, 4-Dinitrophenyhydrazine ’

AgNO, + NH,OH Yellow/orange crystal (Brady's reagent)
NH,NO, +H,0+R-C-C-Ag+ NO, ON
White ppt. R-C=CH

+H,0+R-C=C-CuCu,C, +NH,OH
Terminal alkyne
foono
NH,CI " Allaldehydes and only aliphatic methyl ketones
Red ppt.
+ NaHS0, ’ White crystalline bisulphite.
OH
BOND R C=0+ NaHSO,R-¢-SO Na
NATURE OF X-GROUP IN C-X
KOH+R-OH+KX AgNO, AgX Aldehyde H
R-X + aqueous Precipitate
OH
white and for Br c=0+ NaHSO, R-- SO ,Na'
If X is CI, precipitate will be
H,CMethyl ketone CH,
yellow precipitate will be obtained.

137
 CH,CH,CHu
White
ppt.
AgCI
reaction
No
+
AgCWhite
ppt.
chlorobenzene
and
Chlorocyclohexane
AgCIWhite
ppt.
Yellow
ppt.
’AgBr a reaction
ANNO
HNO, reaction temp
room minutes
BolNo
reaction
HNO,
AgNO, ANO HNO,AgNO, -oC,H,-OH+KÇI alcohol HC
CHCH,
andChlHNOC,H,OH+KCI-
chlorobenzene
oroethane
AgNO,
KCI
OH+
HNO,
bromoethane
and
AgNO,
KOHCH,-OH+KCI
Chloroethane
HNO,
AgCl4
chlorobenzene
KOHCH,-OH+KBr White
ppt.
’No
AgNO,
at
cloudiness 5
within
chloride HNO, AgNO, iso-propyl
agNo,HNO,
on CH,CH,CH,OH
+HCI
Zid Cloudiness
Boil
KOH
KOH
d+a,.
AgNO,
HNO,
BolKOH- Boil
vinyl
AgCl.
ppt.) BoilHNO,,
(White No
KOH
ag.
+
Bol KOH- "H,C-CH-Cl+aq.KOH
and OHH
and HC
CH-CH,
KOH aq. aq. and KOH alcohol
-Cl+ aq, aq. aq. chloride + C,H,-Cl+aq. Vinyl
chloride chloride
Cl+aq. +
I + (Chloroethane) (Benzyl
chloride) Chlorobenzene
(Ethyl
chloride)
C,H-CI + (Bromoethane)
C,H,-Br n-Propyl
C,H, Benzyl
Ethyl
" " " "
RCOONa test
-CHO Co,‘ Cu,ORed
ppt. ysoluble
No Hinsberg's
(silverprecipitateR-C-H+2Cu
(Reddish
brown
ppt) ’
(Offensive
smell)
chloridechlorid chloride
Silver
mirror mirror) +50HRCO0+3H,0+Cu,0 mirror +
H,0 Isonitrile
+ ’
+2H,0+4NH,
+2Ag+ Negative bicarbonate
Sodium+H,0+
test GROUP
AROMATIC
ALDEHYDE + called
Reddish
brown
Silver
+ lodoform
KOH Benzenesulphonyl
insoluble
KOH
Benzenesulphonyl
iodoformCHI, (Yellow
ppt.)
’ -’ Tollen'
reagents GROUP RCOONa CO, C0,
CARBOXYLIC Carbylamine
reaction,
test)Benzenesulphonyl
ALDEHYDE
GROUP solution
reagent + + Silver
+H,0
ACID
FORMIC mirror (Hinsberg's
Precipitate
’ is
chloride
solution
Fehling's reagent2Aa(19)
AMINES
CHC
reagent
R--H+3OH°
+2|Ag(NH),JRCOO give is arm
bdbi Fehling's
’
solution also
Tollen's
-COO NaHCO,- + ’Precipitate
Benzenesulphonyl
Tollen's H.CRH,+NaOH teste
Negative +
solution
Fehling's KOH 3) +
group + +
aldehyde acid
Carboxylic + amine
+
+Fehling's aldehyde Tollen's
+ & amine amine
Chemistry
HandBook effervescence amine2°
+
Aldehyde
-C-
Aromatic
+
RCOOH (1°,PrimarySecondary reaction
Tertiary reagent.
Aldehyde Aromatic AgSilvermirror
+ HCOOH Primary
H,C acid
Formic Amines :Note
138
HandBook
Chemistry precipitate
139
mirror
Silver
’ test) test ppt. precipitate +
No
reaction Cu0
H,C-CH,-H+20u+50H-’
CH,CH,CO0+3H,0+Cu,0
NaOHlodolorm yellowsolution) precipitate ppt. +No
H, +No
brown silver
mirror
+2H,0+4NH,+2Aglt
CH,CH,CO0
mirror)
(Silver +Negative (lodoform
test +Negative
test + +
+2(Ag(NH,),|
CH,-H+30H
HC- "brown 5OHCu,04
ppt.)
No brown
Co CO
tet (Fehling No
Reddish
2Cu'+brown
lodotarm
+ +2Agt+
+ + CHI,
pentan-3-one
CH,CH,CH,COONa
+ Reddish acid +H,0 solution’
reagent) 3H,O(Reddish L, NaOH 50H
reagent solution-> + ethanoic
Fehling
solution) Fehling's
solution
solution
Fehling's Tollen' --CH, benzaldehyde
solution-> Tollen'
reagents
Propanal
and
propanone + reagents + 2Cu'+ Fehling's
solution
H + CH,CH,COO (Pentan-2-one)
+L Fehling's Tollen's
reagent
Tollen's
Fehling CH,
Propanal+Fehling's - Propanal+Fehling's + and
CH, and CH, -CH, Fehling's
+ CHO
solution
Propanone Penlan-3-one Benzaldehyde acid "Ethanoic
acid
+
and Propanal Pentan-2-one (Yellow
ppt.) - and
-H,C CH, lodoform HCOOH
Methanoic
acid
Methanoic
(Tollen's
&
(Tollen's HC-
CH, Propanal
"H,C
"
test)HCOONa violet
No H,0 acid)SrilA
colourationeffervescence
bns
-NO,1 crystals
No
’
+3HCI
’Violet
colouration bicarbonate
effervescence HCOONa ppt.
+ benzoic
(lodoform ppt. C,H,C0ONa+CO,f yellow
yellow FeCl,) Fe(0CH)J -NO,+
+ Yellow DNP) -NO,2,4-Dinitrophenylhydrazine Violet
colouration than DNP) crystals
orange
Yellow
CHI,
ppt. -NO, (yellow
orange
crystals)
’No
reaction chloride (NaHCO,) No acidic 4-DNP
2, 2,+
Propanol
4-Dinittest)
rophenyl+CHI,
hydrazi ne
ppt.)
(Yellow No
lodoform
alcohol No 4- (Neutral
’ less -4
(lodoform test
Jodolorn
’ 6NaOH’ test
(2,
CH,CH,OH+41,+6NaOH
+
chloride
’3H
ferric
’
(2,
bicarbonate
is
(Phenolpropanol
toN-
NH O,N NH..C=N- NaOHodolorm
NaOH
acetone+N-NH.NH
HoN-
methyl alcohol Neutral phenol NaHCO, propanal
2,4-DNP ferric
FeCl,
Sodium
Sodium
. -H+L
+
and +
41, and ethylNeutral + and +
CH,CH,OH + and HC--H+L,
+
H,C
+
-OH acid CGH,COOH Propanal
alcohol + alcohol Acetone C,H,OH and+ acid Propanone and
ALLEN' CH,0H Benzoic +
H,C HC
Phenol Ethanal "HC-
CH,
Phenol Benzoic H,C H,C/ Ethanal
Phenol
Ethyl Ethyl
"
test) 3HO smell OoH OoH 2HBr colour)
(socyanide Orange
+No
dye test) -NC+3KCI+3H,0
smell
phenol) 8.5-9.5
=
pH OH
-CH,- (Colourless)
+3KCI offensive (Diazotisation) (Isocyanide offensive -OH OH +
acid colour
Brown
’
isocyanide
Methyl in
change
smell)
(Offensive + Gluconic
+
CH,NC OH isocyanide
Phenyl (Diazotisation
No (Offensive
smell) No
amine (alc.)> -OH 3KOH’ (no
3KOH’ N-methylaniline Orange
dye
-N=N dye obol
No
orangele ’
HC
dimethyl H,C-NH+CHCI,amine
+3KOH NaNO
+
HCICH,CH,OH
azobenzene
p-hydroxy
odelo -NH,+CH,+3KOH
(alc.)
+
+
NNo, H,O
(alc.)
HCI
+
NaNO,
-NH,
piazotisation
N.-N=
dye
Orange (alc.) CHCL, Benzylamine Glucose+Br,
+
H,0
Glucose
and
fructose
and +CHCI, ethyl NaNO,
+
HCI2Diazotisation
NH, +
+ (Brown
colour)Br, (Brown
colour)
amine
ÇH, amine
Di-methy and and
CH, NH, "CH,-
+
+ amine
Methyl
CH,NH, Anilineotls Fructose
-NHN-Methylaniline
and
Methyl Aniline Aniline
CH,CH,NH,
"
Aniline
Benzylamine
amine
Ethyl Aniline Aniline
.
CHL+HCOONa
"
CH,COOH+NaHCO,C,H,CO0Na+CO,
mirror
‘+H,0
effervescence
effervescence
ppt.
No test)
test) mirror
silver
>No
ppt. (Tollen's +2H,0+4NH,+2Ag
Silver +2[AgNH),J
(Yellow
ppt.)
lodoform yellow test
NaOHbdoform
(lodoform -CHO+3OH
(Tollen's
reagent)
test) No
-COONat
lodoform
test
bicarbonate’ ’
(Lodoform No ethylbenzoate acetophenone
reagent
test benzophenone +l,+NaOH
bdoform bdetomtst L+ reagent
Acetophenone+Tollen's
CH,CHO+H.+NaOH
methanal +
-CH, benzoate+Sodium
Tollen's
coor
HCHO+I,+NaOH (Acetophenone)
and CHI,
+ (Yellow (Benzophenone)and and +
Chemistry
HandBook ppt.) Benzaldehyde
Acetophenone acid
Benzaldehyde
and
Ethanal Ethanal Methanal Benzoic Ethyl
" " 140
 Chemistry
HandBook
141
colour
Blue
colour
blue
No
’
solutionsolution
OR
I, L,
+ +
GlucoseStarch IMPORTANT
NOTES
mirror
’Silver
mirror
silver ppt. ppt.
’Red
red
No No
’ ’
reagent solution
reagent solution
and Tollen's
Glucose
sucrose Tollen's
Fehling's
Fehling's
Glucose
and
starch
+ + + +
ALLEN Glucose
Sucrose Glucose
Starch