Classification Tests for Carboxylic Acid and Derivatives

Mary Catherine Sarte, John Emmanuel Sy, Allurie Umel,

Franklin Yap, Mary Christine You
Introduction
Carboxylic acids derivatives are simply roups
o! compounds that contain a carbonyl roup but
"ith an electroneative atom attached to the
carbon# $he di!!erence in the structure leads to a
ma%or chane in reactivity# $he reactions o! these
roups o! compounds involve nucleophilic
substitution# Althouh there are abundant kinds
o! carboxylic acid derivatives, the experiment
only !ocuses on the common ones& acid halides,
acid anhydrides, esters and amides#
Carboxylic acids and their derivatives are
usually seen in industrial processes and most
bioloical path"ays# Esters can be seen as !ats
and "ithin the cell membrane# Esters are also
present in pleasant smellin li'uids that are
responsible "ith the !rarant odor o! !ruits and
!lo"ers# Amides are also present in animal
protein and also in industrial products such as
nylon# Acid chlorides and acid anhydrides are
used in the synthesis o! carboxylic derivatives#
$hese are not usually !ound in nature because o!
its hih reactivity property#
(ne property o! carboxylic acids is that they
are acidic# )ecause o! these, carboxylic acids are
mostly made to react "ith bases such as *a(+ to
yield a "ater soluble metal carboxylates#
Carboxylic acids and their derivatives react "ith
nucleophiles "hich yields a !ormation o! alcohol#
$he initially !ormed intermediate product expels
one o! its substituents "hich is oriinally bonded
to the carbonyl carbon !ormin a ne" carbonyl
compound# $he reaction is called nucleophilic acyl
substitution reaction#
$he procedure !or acyl halides, acid anhydrides,
esters and amides is hydrolysis# +ydrolysis is
simply the reaction "ith "ater to yield a
carboxylic acid# Also !or acetyl chloride is
alcoholysis& Schotten,)auman -eaction# .t is the
reaction "ith an alcohol to yield an ester# $he
alcohol used here "as ethanol# Aain !or acetyl
chloride and acetic anhydride, the reaction used
"as aminolysis& anilide !ormation# Aminolysis is
the reaction "ith ammonia or amine to yield an
amide# .n this case, aniline "as the ammonia and
anilide, an amide, "as produced# +ydroxamic
acis test "as used !or ethyl acetate and
acetamide#
$hrouh this experiment, students are able to
visuali/e, throuh the di!!erent reactions, the
necleophilic acyl substitution reaction !or
carboxylic acids and it derivatives# $he di!!erent
classi!ication tests !or such are also observed#
Experimental
A. Hydrolysis of Acid Derivatives
Acyl halides and Acid anhydrides
0 ml o! "ater "as placed in a test tube# 01
drops o! the sample, in this case acetyl chloride
and acetic anhydride, "as added in a drop "ise
manner# A "armin e!!ect "as noted# $he !irst
resultin mixture "as divided into t"o portions#
$o the 0
st
, 0 ml o! 23 A*(4 "as added#
5recipitation "as observed# $o the second
mixture, 0 ml o! saturated *a+C(4 "as added#
An evolution o! as "as observed#
Esters
2ml o! 263 *a(+ solution "as added to 0 ml
o! ethyl acetate# $he mouth o! the test tube "as
covered and the test tube "as heated in a boilin
"ater bath !or about 6 minutes# $he mixture "as
then neutrali/ed "ith 013 +C7 solution# 8ith a
"a!tin motion, the odor o! the solution "as
noted#
Amides
0ml o! ben/amide "as treated "ith 6ml o! 013
*a(+ solution# $he solution "as then heated to
boilin# 8hile heatin, the test !or the reaction o!
as evolution "as done by holdin a piece o!
moist red litmus paper over the heated test tube#
B. Alcoholysis: Schotten-Baumann Reaction
A mixture o! 01 drops o! acetic acid, 0ml
ethanol and 6 drops o! conc# "as "armed
over a "ater bath !or 2 minutes# $he odor o! the
ester !ormed "as noted#
Abstract
Carboxylic acids are mainly oranic compounds containin at least one carboxyl roup# .ts eneral !ormula
is represented by the !ormula -,C((+# .ts derivatives, on the other hand, is de!ined as oranic compounds
containin a carbonyl roup "ith an electroneative atom 9oxyen, nitroen or haloen: attached to the
carbonyl carbon# Amon these carboxylic acid derivatives, acyl halides are the most reactive and amides
the least# -eactions o! carboxylic acides also yield esters, salts and acyl chlorides# $he experiment done is
to test "hether the substance is positive !or carboxylic acid and derivatives# $he reaents used are acyl
chloride representin acyl halides; acetic anhydride representin acid anhydrides; ethyl acetate
representin esters and acetanamide and ben/amide representin amides# Speci!ic tests "ere per!ormed to
speci!ic compounds# Yieldin a positive results indicate the presence o! the carboxylic acid roup#
.n another test tube, a mixture o! 1#6ml
ethanol, 0ml "ater, and 1#2ml o! acyl halide or
acid anhydride "as prepared# 2ml o! 213 *a(+
solution "as then added# $he test tube "as
covered "ith para!!in "ax and "as shook !or
several minutes# An odor o! the !ormed ester and
a !ormation o! t"o layers "ere noted#
C. Aminolysis: Anilide Formation
A !e" drops o! acetyl chloride or acetic
anhydride "as added to 1#6ml o! aniline# $he
mixture "as trans!erred to a ne" test tube
containin 6ml "ater# $he !ormation o! a
precipitate "as noted#
D. Hydroxamic Acid est
$he preliminary test "as done by mixin 2
drops o! the sample, 0 ml o! <63 ethanol and 0M
+C7# A drop o! 63 FeCl4 solution "as added to
the mixture and the color produced "as noted# .!
a color other than yello" "as obtained, the test
cannot be used# (ther"ise, another test "as
conducted as !ollo"s&
2 drops o! the sample "as added to 2ml o!
alcoholic *+2(+ +C7 and 0ml o! =(+# $he
solution "as heated in a boilin "ater bath !or 2
minutes# $he mixture "as cooled# 0ml o! 36
FeCl4 "as then added# A deep burundy
precipitate "as observed#
Results and Discussions
A. Hydrolysis of Acid Derivatives
8ith the addition o! A*(4 to acetyl chloride, a
"hite precipitate "as !ormed and there "as no
evolution o! as# For acetic anhydride, there "as
no precipitate but there "as an evolution o! as#
8ith ethyl acetate, an alcoholic scent "as
observed "hen added "ith *a(+ and then the
odor "as one "hen neutrali/ed "ith +C7# For
ben/amide, in the addition o! *a(+ and "hen the
mixture "as heated, an evolution o! as "as
noted and the red litmus paper tested turned to
blue, indicatin that it "as a basic solution#
B. Alcoholysis: Schotten-Baumann Reaction
8hen 1#6ml o! ethanol, 0ml o! "ater and 1#2ml
o! acetyl chloride "as prepared, "ith the addition
o! 213 *a(+ solution, a !ruity odor and a
solution "ith layers "as noted#
C. Aminolysis: Anilide Formation
8hen1#6ml o! aniline "as added to the sample,
a "hite crystalline precipitate "as observed,
indicatin the presence o! acetanilide#
D. Hydroxamic Acid est
$he preliminary test "as no loner per!ormed
because the reaents used in this experiment
"ere already iven# >oin a preliminary test "ill
surely yield a positive result !or the t"o reaents#
For the actual test, both ethyl acetate and
acetamide yielded a deep burundy precipitate
"hich "as an indication o! a positive result#
As said, carboxylic acids and derivatives, "hen
reacted "ith a nucleophile, the reaction is termed
as nucleophilic acyl substitution reaction# .t is
similar "ith the reaction o! aldehydes and
ketones but their di!!erence is that in the
product# An intermediate product normally !orms
and it expels one o! its substituents oriinally
bonded "ith the carbonyl carbon, leadin to a
ne" carbonyl compound#
$he usual nucleophilic acyl substitution reaction
beins "ith the addition o! a polar bond to ive
an intermediate, the alkoxide ion# $he
intermediate !ormed is protonated to ive an
alcohol# .n carboxylic acid derivatives, the
intermediate !orms expels a livin roup to ive a
ne" carbonyl compound# $hese di!!erent
behaviors to"ards the reactions are because o!
the di!!erence in structure# Carboxylic acid
derivatives have an acyl carbon bonded to a
roup ?Y that can leave as a stable anion# 8hen
the addition o! nucleophile occurs, the roup
leaves and a ne" carbonyl compound is !ormed#
$he di!!erence o! carboxylic acid derivative
substitution and aldehyde addition is that
aldehydes don@t have leavin roups, there!ore,
no substitution takes place but only addition#
$he rate o! the overall reaction involves the
addition step and the elimination step# )ut the
addition step is usually the rate determinin step#
$he more the electron poor the CA( is, the
more readily it reacts "ith nucleophiles# +avin
said this, usually acid chlorides are the most
reactive compounds because o! its
electroneative ion, chlorine# Amides, on the
other hand are the least reactive compound#
$hese di!!erences in reactivity usually result to
the conversion o! a more reactive acid into a less
reactive one#
-eactions involvin carboxylic acid derivatives
include hydrolysis, alcoholysis, aminolysis,
reduction and Brinard reaction#
+ydrolysis is the addition o! "ater to !orm
carboxylic acids# $his is seen in the reaction&

$here is an intermediate product in "hich
underoes loss o! +C7 to yield the product# $his
is seen in esters, amides and acid chlorides#
Alcoholysis is the reaction "ith an alcohol to
yield amides# $his is seen in acyl chloride
reactions# $he best kno"n method is
the Schotten,)aumann reaction, "hich involves
conversion o! the acid to the acid chlorides&

Aminolysis is the reaction o! amines to yield
amides# $he amine used in the experiment is
aniline and the product !ormed "as anilide# $he
reaction is as !ollo"s&
-eduction is the reaction "ith hydride reducin
aent to yield an alcohol# Esters are usually
involved here "hich has a primary alcohol as a
product# $he reaction is as !ollo"s&
Brinard reaction is the reaction o! an
oranomanesium reaent to yield an alcohol#
Esters are also the ones involved here convertin
them into tertiary alcohols# $he reaction is as
!ollo"s&
$hese are the reactions involve in the
experiments !or the classi!ication o! carboxylic
acids and derivatives# 5ositive observations in
these tests are usually in the !orm o! precipitates#
Some exhibit evolution o! as#
Refferences
)ay'uen A#C#, Cru/ C#, >e Buia -#, 7ampa
F#, 5ena B#, Sarile A#, $orres 5# 9211D:
!a"oratory #anual in $r%anic
Chemistry. Manila 5hilippines& US$
5ublishin +ouse#

McMurry J# 92101: Foundations of $r%anic Chemistry.
Cenae 7earnin Asia 5te# 7td#
5avia >#7#, 7ampman B#M#, =ri/ B#S#, 92116:
&ntriduction to $ra%nic !a"oratory echni'ues(
A Small Scale A))roach. *
nd
ed. Australis&
)rokkesECole
http://chemistry2.csudh.edu/rpendarvis/carb
oxder.html#struct
www.wikipedia.com