CHM143L Organic Chemistry 2 Laboratory Group No.

8
3rd uarter !" 2#13$2#14 %he &'coho'ics
Factors Affecting the Relative Rates of Electrophilic Aromatic Substitution Reactions
Martin, Marilen
1
, Taeda, John aul, !", #$M1%&'()&1
*
1
(ro)essor* !choo' o) Chemica' +ngineering* Chemistry and ,iotechno'ogy* Mapua -nstitute o) %echno'ogy.
2
!tudent /s0* !ub1ect2!ection* !choo' o) Chemica' +ngineering*
Chemistry and ,iotechno'ogy* Mapua -nstitute o) %echno'ogy
ABSTRACT
This experiment visualized and determined how the substituents present in the aromatic ring, the solvents used, and the
temperature affect Electrophilic Aromatic Substitution EAS! reactions" Substituent groups on an aromatic ring can be
classified into two t#pes$ activating and deactivating groups" Activating groups donates electron densit# to the aromatic ring,
stabilizing it and ma%ing it more reactive, and in terms of regioselectivit#, the# are called ortho-para directors" &n the other
hand, deactivating groups withdraws electron densit# from the aromatic ring, destabilizing it and ma%ing it less reactive" The#
are also called meta- directors" Solvents affect the rates of EAS reactions b# means of their polarit# and temperature is also
one factor affecting the rates of the said reactions" The experiment was performed using bromine as the electrophile and
reagents such as benzene, chlorobenzene, and anisole with the additional of bromine in c#clohexane and bromine in acetic
acid" The reactions were observed in micro test tubes b# adding small amounts of the needed reagents" &bservations such as
decolorization, appearance of a ver# pale #ellow color, or a color change were considered to have a complete reaction and
from there, the time was recorded" After accumulating and anal#zing the data, the following were stated$ a! aromatic
compounds with activating groups such as phenol and p'nitrophenol were faster to react as compared to benzene and li%ewise
aromatic compounds with deactivating groups, b! the more polar the solvent is, the faster the reaction would ta%e place, and
c! as the temperature increases, the time it ta%es for the reaction to complete decreases, leading to a faster reaction rate"
(espite some errors regarding the data ac)uired, the group was able to confirm the consistenc# of the theories discussed"
*+TR&(,CT*&+
+'ectrophi'ic &romatic !ubstitution /+&!0 is
de)ined as an organic chemica' reaction in 3hich an atom*
usua''y hydrogen* or a group o) atoms attached to an
aromatic ring system is rep'aced by an e'ectrophi'e.
Common e4amp'es o) these substitution reactions are
aromatic ha'ogenation* nitration* su')onation* 5riede'$Cra)ts
&'6y'ation* and 5riede'$Cra)ts &cy'ation.
+&! has a genera' mechanism 3hich can be
obser7ed )rom the said 6ey substitution reactions
mentioned8
-igure ." /eneral 0echanism for Electrophilic Aromatic
Substitution
1 &rganic Chemistr# b# (avid 2lein
9ith one o) the pi bonds o) the aromatic ring
acting as the nuc'eophi'e* it attac6s the e'ectrophi'e present
and )orms a sigma comp'e4 3here it is de)ined as the
positi7e intermediate o) an +&!. %he ring in here
temporari'y 'oses its aromaticity and it is resonance$
stabi'i:ed due to the )ormation o) a de'oca'i:ed cation. %he
comp'e4 is then deprotonated* restoring bac6 its
aromaticity.
%his particu'ar substitution reaction can be readi'y
a))ected by the presence o) a substituent in the aromatic
system* choice o) so'7ent* and temperature.
%he presence o) substituent groups on an
aromatic ring can a))ect an +&! in t3o 3ays and these are
the regiose'ecti7ity and rate o) the substitution reaction.
%hese can be e4p'ained by means o) inducti7e e))ects or
resonance structures. -n such situations* t3o types o)
substituent groups 3ere considered. %hese are the
acti7ating groups and deacti7ating groups.
&cti7ating groups or acti7ators tend to stabi'i:e the
sigma comp'e4 by means o) donating e'ectrons through the
Experiment 01 Group No. 8 January 21. 2014 1 of 6
CHM143L Organic Chemistry 2 Laboratory Group No. 8
3rd uarter !" 2#13$2#14 %he &'coho'ics
aromatic system 7ia inducti7e e))ect or through resonance
e))ect* ma6ing the ring more reacti7e 3hich speeds up the
reaction. %hese groups usua''y ha7e a 'one pair o) e'ectrons
in 3hich they can easi'y donate during substitution
reactions. -n terms o) regiose'ecti7ity* ortho- and para$
positions usua''y predominate* ha7ing high yie'd compared
to the meta$ position.
-igure 3" Ortho-, Para-, and Meta- 4ositions in a
Benzene Ring
1 /oogle *mages
Mean3hi'e* deacti7ating groups or deacti7ators
destabi'i:e the sigma comp'e4 by 3ithdra3ing e'ectron
density )rom the aromatic system* ma6ing it unstab'e and
s'o3ing do3n the rate o) reaction. %he 3ithdra3a' o)
e'ectron density )rom the aromatic ring a))ects the ortho-
and para- positions* thus 'ea7ing the meta- position as the
most reacti7e.
&cti7ating and deacti7ating groups can be
c'assi)ied as strong* moderate* or 3ea6 depending on the
e'ectronegati7ity o) the atom present* presence o) 'one pair*
and the presence o) a pi bond to an e'ectronegati7e atom
ad1acent to the aromatic ring.
Ha'ogens are an e4ception to this ru'e because
despite being deacti7ators* they are considered as ortho-
and para- directors. %his is because the resonance
structures dictate that ha'ogens donate e'ectron density to
the aromatic ring due to resonance being the dominant
)actor as compared to the inducti7e e))ects.
%he choice o) so'7ent can a'so a))ect the rate o) an
+&!. %he rate is readi'y a))ected by the po'arity o) the
so'7ent used because the re'ati7e rate o) +&! reactions are
a )unction o) the po'arity o) the so'7ent* ma6ing a di))erence
in the rate 3ith di))ering so'7ents.
%emperature can a'so be a )actor in a))ecting the
re'ati7e rate o) +&! reactions 1ust 'i6e most o) the other
reactions.
%he purpose o) this e4periment is to 7isua'i:e the
e))ect o) substituents and 6no3 the e))ect o) so'7ent and
temperature on the re'ati7e rates o) e'ectrophi'ic aromatic
substitution reactions.
0ATER*A5S A+( 0ET6&(S
%his e4periment had three parts8 substituent e))ect*
so'7ent e))ect* and temperature e))ect. %hese parts 3ere
per)ormed using the )o''o3ing apparatuses8 2$m' pipette*
micro test tubes 3ith cor6 stoppers* thermometer* hot p'ate*
hot 3ater bath* test tube rac6* test tube ho'der* 4## m'
bea6er* and stop3atch.
5or the )irst part 3hich is the e))ect o) the
substituents in the re'ati7e rates o) e'ectrophi'ic aromatic
substitution reactions* bromine so'ution 3as used as the
main reagent that ser7es as the e'ectrophi'e )or the said
reaction. %he reagents used as nuc'eophi'es 3ere #.2 M
so'utions in ethy' acetate o) the )o''o3ing8 ben:ene*
ch'oroben:ene* aspirin* acetani'ide* p$nitropheno'* aniso'e*
and pheno'. #.2# m' o) each o) the said reagents 3ere
trans)erred in separate test tubes and )or each* bromine
so'ution 3ith the same amount 3as trans)erred. 5or
ben:ene* ch'oroben:ene* and aspirin* any e7idence o)
reaction 3ere obser7ed. 5or pheno' and aniso'e*
deco'ori:ation or the presence o) a 7ery pa'e ye''o3 co'or
3as obser7ed. %hen )or acetani'ide and p$nitropheno'* the
'oss o) co'or 3as a'so obser7ed. %he time )or the reaction to
occur )or a'' so'utions 3ere recorded 7ia a stop3atch.
%he second part o) the e4periment is about ho3
the choice o) so'7ent a))ects the rate o) e'ectrophi'ic
aromatic substitution reactions. %he reagents used in this
part 3ere #.2M so'ution in ethy' acetate o) aniso'e* #.#;M
bromine in cyc'ohe4ane* and bromine in acetic acid. %3o
micro test tubes 3ere each added 3ith #.2#m' o) the
aniso'e so'ution. &t one test tube* #.2#m' o) #.#;M bromine
in cyc'ohe4ane and at the other test tube* #*2#m' o)
bromine in acetic acid 3as added. %he comp'etion o)
reaction )or the t3o so'utions 3ere indicated by the
appearance o) a 7ery pa'e ye''o3 co'or and the time )or it
3as a'so recorded.
%hen* the 'ast part o) the e4periment 3as about
ho3 temperature a))ects the rate o) e'ectrophi'ic aromatic
Experiment 01 Group No. 8 January 21. 2014 2 of 6
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substitution reactions. %he reagents used 3ere #.2M
acetani'ide in ethy' acetate and bromine in acetic acid.
#.2#m' o) #.2M acetani'ide in ethy' acetate 3as trans)erred
in a micro test tube )o''o3ed by the addition o) bromine in
acetic acid. &ppro4imate'y 3##m' o) 3ater 3as preheated in
a 4## m' bea6er then trans)erred in a 3ater bath. 5rom
there* the test tube 3as heated in there by the )o''o3ing
temperatures o) 3ater8 <#C* =#C* and ;#C. %hese 3ere
a'' per)ormed using on'y one 3##m' o) 3ater in order to
ha7e ease o) per)orming this particu'ar part o) the
e4periment. %he reaction 3as denoted by deco'ori:ation
and the time it too6 3as recorded by a stop3atch. &)ter
obtain the data* a graph 3as made 3ith 12t /sec0 as the
ordinate and the abso'ute temperature />0 as the abscissa.
RES,5TS A+( (*SC,SS*&+
Table ." Time of (ecolorization and Remar%s ,nder
Subtituent Effect"
Compound Time of
(ecolorization
Remar%s
,en:ene 4?; secs. Minima'
deco'ori:ation
Ch'oroben:ene 3;4 secs. Minima'
deco'ori:ation
&spirin 11= secs. Minima'
deco'ori:ation
&cetani'ide 1? secs. Co'or'ess
($nitropheno' ;? secs. Co'or'ess
&niso'e 1; secs. Light pin6 co'or
(heno' ? secs. (a'e ye''o3 co'or
Table 3" Reactions *nvolved on 4art *"
Reactions *nvolved
.!
Br
+ B r
2
3!
Cl
+
B r
2
Cl
Br
Cl
Br
+
7!
O
OH
COOCH
3
+
B r
2
O
OH
Br
COOCH
3
+
O
OH
COOCH
3
Br
8!
NHCOCH
3
+ B r
2
NHCOCH
3
Br
NHCOCH
3
Br
+
9!
N
+
O
-
O
O H
+
B r
2
N
+
O
-
O
OH
Br
:!
OCH
3
+ B r
2
OCH
3
Br
OCH
3
Br
+
;!
OH
+
B r
2
OH
Br
OH
Br
+
@eaction A2 on %ab'e 2 sho3s that despite
ch'orine being a deacti7ator* the bromine occupies the
ortho- and para- positions as separate products. %he time
o) deco'ori:ation )or this reaction shou'd be higher than
ben:ene because ch'orine is a 3ea6 deacti7ator. !ources
o) error regarding this 3ou'd be possib'y because o)
incorrect obser7ation )or e7idence o) reaction comp'etion.
@eaction A3 on %ab'e 2 sho3s t3o substituents
present in the ben:ene ring. Loo6ing at the time o)
Experiment 01 Group No. 8 January 21. 2014 3 of 6
CHM143L Organic Chemistry 2 Laboratory Group No. 8
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deco'ori:ation )or aspirin* it is re'ati7e'y 'o3 compared to
ben:ene despite the substituents present are both
deacti7ators due to the presence o) pi bonds on an
e'ectronegati7e atom ad1acent to the aromatic ring. &'so*
the reaction produced t3o products in 3hich one is ortho-
and the other one is para- in terms o) the COOCH3 group
because it is 3ea6er as a deacti7ator than the COOH
group.
@eaction A4 on %ab'e 2 sho3s that the bromine
occupies the ortho- and para- positions as separate
products 3ith the NHCOCH3 atom as the substituent
present* and because the time o) deco'ori:ation is 'o3
compared to ben:ene* the NHCOCH3 can be considered as
an acti7ator.
@eaction A; on %ab'e 2 sho3s that on'y one
product 3as produced* and that is the bromine at the ortho-
in terms o) the OH group. %ab'e 1 sho3s that the time o)
deco'ori:ation )or p$nitropheno' is re'ati7e'y 'o3 compared
to ben:ene* ma6ing the ortho- position in terms o) the OH
group being the most reacti7e )or as to 3hy the bromine
atom is substituted there. &'so* this a'so imp'ies that the OH
group is an acti7ator. %he NO2 is considered to be a
deacti7ator because a nitrogen 3ith a positi7e charge is
7ery e'ectronegati7e* there)ore capab'e o) 3ithdra3ing
e'ectron and 3i'' direct the e'ectrophi'e to the meta- position
in terms o) it. %his means that the NO2 a'so has contribution
to 3here the bromine atom 3i'' position itse') in the aromatic
ring.
@eaction A? on %ab'e 2 sho3s that the bromine
occupies the ortho- and para- positions as separate
products 3ith the OCH3 atom as the substituent present*
and because the time o) deco'ori:ation )or aniso'e is 'o3
compared to ben:ene* this denotes that the OCH3 atom can
be considered as an acti7ator.
@eaction A= on %ab'e 2 sho3s that the bromine
occupies the ortho- and para- positions as separate
products 3ith the OH atom as the substituent* and because
the time o) deco'ori:ation )or pheno' is 7ery 'o3 compared
to ben:ene* the OH atom can be considered as an
acti7ator.
Table 7" Time of (ecolorization and Remar%s ,nder
Solvent Effect
Compound Time of Remar%s
(ecolorization
&niso'e B bromine
in cyc'ohe4ane
=38 secs. %he reaction
produced a 'ight
ye''o3 co'or at
time o)
deco'ori:ation
&niso'e B bromine
in acetic acid
1;1 secs. %he reaction
produced a 'ight
ye''o3 co'or at
time o)
deco'ori:ation
Obser7ed )rom %ab'e 3* the compound 3ith acetic
acid as the so'7ent resu'ted in a )aster reaction rate by
means o) deco'ori:ation than 3ith cyc'ohe4ane as the
so'7ent. %his is due to the po'arity di))erences o) the t3o
so'7ents 3ith acetic acid being the more po'ar. %he more
po'ar the so'7ent* the )aster the rate o) the reaction 3ou'd
be.
Table 8" Time of (ecolorization and Remar%s ,nder
Temperature Effect
Temperature Time of
(ecolorization
Remar%s
<#C 128 secs. 5astest reaction
rate
=#C 228 secs. Moderate reaction
rate
;#C =3? secs. !'o3est reaction
rate
/raph ." .<t sec .=
'7
! >S" Absolute Temperature 2!
from Table 8"
Experiment 01 Group No. 8 January 21. 2014 4 of 6
CHM143L Organic Chemistry 2 Laboratory Group No. 8
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Obser7ing Graph 1* there is a trend that as the
temperature increases* the time it ta6es )or the reaction to
comp'ete decreases* in 3hich 12t increases. %his is
because by increasing the temperature* more energy is
being trans)erred to the reaction* 3hich is needed in order
to )orm the sigma comp'e4 that is necessary )or +&!
reactions. %he more the energy is being added to the
reaction* the )aster the reaction rate 3ou'd be. -n the case
o) this particu'ar part o) the e4periment* on'y one +&! is
considered. 5rom that* the temperature 3i'' be the )actor
a))ecting the speed o) the said reaction.
C&+C5,S*&+S A+( REC&00E+(AT*&+S
%his e4periment aims to 7isua'i:e the e))ect o)
substituents in the re'ati7e rates o) e'ectrophi'ic aromatic
substitution reaction. %he reactions 3ere c'ear'y 7isua'i:e
by means o) co'or change or deco'ori:ation and that re'ati7e
rates are a))ected by the substituents either acti7ating or
deacti7ating groups 3here it donates or 3ithdra3s e'ectron
density )rom the aromatic ring ma6ing more or 'ess reacti7e
3ith the e4ception o) ha'ogens. %hough there 3ere some
errors regarding the time o) deco'ori:ation* the theories
3ere consistent and thorough'y e4p'ained throughout.
%his e4periment a'so aims to 6no3 the e))ect o)
so'7ent on re'ati7e rates o) +&! reactions. %he more po'ar
the so'7ent* the )aster the re'ati7e rate o) reaction 3ou'd be.
Last'y* this e4periment aims to 6no3 the e))ect o)
temperature on the re'ati7e rates o) +&! reactions. &s the
temperature increases* the reaction rate o) the +&! a'so
increases. %his is because o) the presence o) the sigma
comp'e4 necessary to comp'ete the said reaction.
,ecause o) the committed error regarding the
e4periment* a p'ausib'e recommendation 3ou'd be to be
more obser7ant on the e7idences o) a comp'ete reaction
and to be more precise on getting the time it ta6es to
comp'ete such reaction.
Experiment 01 Group No. 8 January 21. 2014 5 of 6
CHM143L Organic Chemistry 2 Laboratory Group No. 8
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RE-ERE+CES
1 >'ein* C. Organic Chemistry. Dohn 9i'ey E !ons* -nc.* 2#12.
2 &buga* D.(. Organic Chemistry: Electrophilic Aromatic
Substitution Reactions. @etrie7ed Danuary 1=* 2#14 )rom
http822cutt'er.hubpages.com2hub2Organic$Chemistry$+'ectrophi'ic$
&romatic$!ubstitution$@eactions.
3 ,a'uyut* D. ". G. E Ce Castro* >. &. Organic Chemistry
Laboratory Manual for Chemical Engineering Students art !.
Experiment 01 Group No. 8 January 21. 2014 6 of 6