CHM143L Organic Chemistry 2 Laboratory

3rd Quarter SY 2013-2014 rou! "o# $% &he '(coho(ics

Amines
Martin, Marilen
1
, Taeda, John Paul, D., CHM143L/B31

1
)ro*essor+ Schoo( o* Chemica( ,ngineering+ Chemistry and -iotechno(ogy+ Ma!ua .nstitute o* &echno(ogy/
2
Student 0s1+ Sub2ect3Section+ Schoo( o* Chemica( ,ngineering+ Chemistry and
-iotechno(ogy+ Ma!ua .nstitute o* &echno(ogy
ABSTRACT
This experiment introduced amines, its properties such as solubility and basicity, and the different tests that can be used to
classify amines. Amines are organic compounds which usually contain one or more atoms of nitrogen and they can either be
primary, secondary, or tertiary depending on the number of carbon substituents attached to the nitrogen atom. Amines are
also classified as aliphatic or aromatic in terms of the presence of either alkyl or aryl groups. Amines are usually basic
because of the weak hydrogen bonding happening that can easily be protonated een by weak acids and soluble because the
nitrogen atom can easily perform hydrogen bonding. They can be classified by means of using different test that
distinguishes them form the result of the reaction and the obseration during performance of the test. The tests used were
Acetyl Chloride Test, !insberg Test, and "itrous Acid Test. #sing methylamine, ethylamine, ben$yl amine, aniline,
ethanolamine, diethanolamine, triethanolamine, "%butylaniline, and ","%dimethylaniline as the test compounds and the
necessary reagents to perform the tests mentioned, with interpretation and analysis of the data and obseration obtained, the
group was able to identify the basicity and solubility of amines with different substituents attached to it and the chemical
basis for each test depending on the structure of the amine reacting. Acetyl Chloride Test is used to distinguish primary and
secondary amines from their tertiary counterparts. !insberg test is the best way to differentiate primary, secondary and
tertiary amine from each other wherein Ben$ensulfonyl chloride reacts differently to each type amine to gie clearly
distinguishable results. &astly, "itrous Acid Test has the ability not only to classify the different degrees of amines but also to
differentiate aromatic from aliphatic amines. Then, using the tests performed, the unknown gien to the group was identified.
'espite different sources of error, the group was able to perform the experiment well and achiee the ob(ecties.
)"TR*'#CT)*"
'mines are organic com!ounds 4hich usua((y contain
one or more atoms o* nitrogen# &hese can ha5e additiona(
!ro!erties based on carbon connecti5ity# 6rom this statement+
the nitrogen can ha5e+ besides hydrogen+ di**erent organic
substituents (i7e a(7y( and aromatic grou!s# &his is to be
di**erentiated *rom amides and ha5e !ro!erties 4hich are distinct
to it#
'mines can either be !rimary+ secondary+ or tertiary+
de!ending on the number o* carbon-containing grou!s that are
attached to them# .* there is on(y one carbon-containing grou!
then that amine is considered !rimary# &4o carbon-containing
grou!s ma7es an amine secondary+ and three grou!s ma7es it
tertiary#
'mines ha5e (o4er boi(ing !oints as com!ared to other
organic com!ounds such as a(coho(s due to a 4ea7er hydrogen
bonding 0"-H1 un(i7e O-H hydrogen bonding *orming a !o4er*u(
intermo(ecu(ar attraction# )rimary amines ha5e the highest
boi(ing !oints as *o((o4ed by secondary and tertiary amines# &his
is because !rimary amines ha5e t4o hydrogen atom a5ai(ab(e *or
hydrogen bonding !ur!oses+ 4hereas *or tertiary amines+ there
are no hydrogen atoms bonded direct(y to the nitrogen atom#
'nother im!ortant !ro!erty o* amines are their basicity#
'mines usua((y ha5e a !H range o* 10 to 11+ re*erring that they
are stronger bases than com!ounds such as a(coho( and ethers+
4hich they can be !rotonated e5en by 4ea7 acids# &his is in the
case o* a(7y( amines# .n terms o* ary( amines+ they are much
more acidic because o* the de(oca(i8ed nature o* the (one !air o*
the nitrogen atom+ ma7ing the com!ound resonance-stabi(i8ed#
'mines can be !re!ared in di**erent 4ays such as
substitution reactions (i7e a(7y(ation+ '8ide Synthesis+ and
abrie( Synthesis and reducti5e amination 4ith the use o* a
reducing agent such as sodium cyanoborohydride#
9hi(e amines ha5e a(so many reactions !ossib(e+ there
are certain reactions that can be used+ 4hich gi5e resu(ts
de!ending on the structure o* the amine that reacted# ,:am!(es
o* these tests are 'cety( Ch(oride &est+ -en8enesu(*ony( Ch(oride
&est or much ca((ed the Hinsberg &est+ and "itrous 'cid &est#
Experiment 06 Group No. 8 March 11. 2014 1 of
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CHM143L Organic Chemistry 2 Laboratory
3rd Quarter SY 2013-2014 rou! "o# $% &he '(coho(ics
&he *irst test mentioned is ca((ed the 'cety( Ch(oride
&est# &his is used to distinguish !rimary and secondary amines
*rom their tertiary counter!arts#
&he second test mentioned is the -en8enesu(*ony(
Ch(oride or Hinsberg test# &his is the best 4ay to di**erentiate
!rimary+ secondary and tertiary amine *rom each other#
-en8ensu(*ony( ch(oride reacts di**erent(y to each ty!e amine to
gi5e c(ear(y distinguishab(e resu(ts#
&he (ast test is ca((ed the "itrous 'cid &est# &his test has
the abi(ity not on(y to c(assi*y the di**erent degrees o* amines but
a(so to di**erentiate aromatic *rom a(i!hatic amines#
+AT,R)A&S A"' +,T!*'S

&his e:!eriment consisted o* three !arts% )ro!erties o*
'mines+ &est *or 'mines+ and ;etermination o* <n7no4n# &4o
!ro!erties 4ere obser5ed in this e:!eriment% So(ubi(ity and
-acisity 4hi(e three tests 4ere !er*ormed in this e:!eriment *or
reacti5ity o* amines% 'cety( Ch(oride &est+ Hinsberg &est+ and
"itrous 'cid &est# &he *o((o4ing a!!aratuses3materia(s 4ere
used% 2 and = m( !i!ets+ test tube rac7+ micro test tubes 4ith cor7
sto!!ers+ !H !a!er+ ho4 !(ate+ and dro!!ers# &hen the *o((o4ing
reagents 4ere used% methy(amine+ ethy(amine+ ben8y( amine+
ani(ine+ ethano(amine+ diethano(amine+ triethano(amine ani(ine+
"-buty( amine+ "+"-dimethy(ani(ine+ 3#0M "aOH+ =#= !H acetate-
acetic acid bu**er so(ution+ => HC(+ 0#2 g ninhydrin in =0-m( 4ater
so(ution+ and ben8enesu(*ony( ch(oride#
&he *irst !art dea(t 4ith the so(ubi(ity and basicity o*
amines# &he test com!ounds 4ere methy(amine+ ethy(amine+
ben8y( amine+ and ani(ine# 6or their so(ubi(ity+ t4o dro!s o* each
o* the test com!ounds to 1-m( disti((ed 4ater in se!arate micro
test tube# &hen *or their basicity+ 0#20-m( o* the 4ater-so(ub(e test
com!ounds 4ere disso(5ed in 3-m( o* 4ater and the same
amount 4ere disso(5ed *or 4ater-inso(ub(e test com!ounds but
4ith the addition o* =#= !H acetate-acetic acid bu**er so(ution#
&heir !H 4ere measured 4ith the use o* a !H !a!er#
Obser5ations 4ere then recorded a*ter !er*orming#
&he second !art dea(t 4ith the di**erent tests *or
c(assi*ication o* amines# &he test com!ounds 4ere ethano(amine+
diethano(amine+ triethano(amine+ ani(ine+ "-buty(ani(ine+ and "+"-
dimethy(ani(ine# &he *irst test is ca((ed the 'cety( Ch(oride &est#
Here+ 0#30-m( o* the test com!ounds 4ere !(aced in se!arate
micro test tubes *o((o4ed by dro!-by-dro! addition o* $ dro!s o*
acety( ch(oride# &he mi:tures 4ere stand out *or about t4o
minutes then !oured 4ith 1-m( o* disti((ed 4ater# &he second test
is ca((ed the Hinsberg &est# 0#20 m( o* the test com!ounds 4ere
mi:ed 4ith ?#0 m( o* 3#0M "aOH and 0#= m( o* ben8enesu(*ony(
ch(oride in micro test tubes# &he &est tubes 4ere
co5ered 4ith a cor7 sto!!er and 5igorous(y sha7en *or about *i5e
minutes# &he so(ution 4ere tested 4ith (itmus !a!er *or basicity
assurance# .t 4as then coo(ed and se!arated *rom the residue
that may be *ormed# &he residues *ormed 4as added 4ith =>
HC(# Other4ise+ => HC( 4as added to the so(ution and obser5ed
i* a !reci!itate *ormed# &hen+ the (ast test is ca((ed the "itrous
'cid &est# .n se!arate micro test tubes+ 0#20-m( o* each test
com!ound 4as added to 1-m( o* 0#20 g ninhydrin in =0-m( 4ater
so(ution# &he so(utions 4ere boi(ed *or about 1= minutes and
obser5ation 4ere recorded therea*ter#
6or the third !art+ an un7no4n 4as gi5en and using the
!rocedures and test !ro5ided+ it 4as to be identi*ied by means o*
the resu(ts and inter!retations dra4n there#
R,S#&TS A"' ')SC#SS)*"
). -roperties of Amines
Table .. Solubility and Basicity of Test Compounds
Test Compounds Solubility Basicity
Methy( amine So(ub(e 11
,thy( amine So(ub(e 11
-en8y( amine So(ub(e @
'ni(ine .nso(ub(e =
.n terms o* so(ubi(ity in 4ater+ it is obser5ed that ani(ine
is inso(ub(e 4hi(e the rest o* the test com!ounds are so(ub(e#
Methy( amine+ ethy( amine+ and ben8y( amine are so(ub(e in
4ater because the nitrogen atom can *orm hydrogen bonds
easi(y 4ith 4ater# Ho4e5er+ in the case o* ani(ine+ 4hich the
nitrogen atom is direct(y attached to an aromatic ring+ it great(y
decreases the basicity o* the amine grou! due to e(ectron-
4ithdra4ing !ro!erties 4ith the addition that no other
substituents are attached to the aromatic ring#
&hen *or their basicity+ ani(ine is considered to be acidic
o* !H = 4hi(e the others are considered to be basic com!ounds
0!H o* 11 and @1# 'ni(ine is considered to be acidic because o*
the de(oca(i8ed nature o* the (one !air o* the nitrogen atom by the
aromatic system+ rendering it resonance-stabi(i8ed and this
!articu(ar stabi(i8ation 4i(( be (ost i* the (one !air is !rotonated+
ma7ing the nitrogen here (ess basic#
)). Test for Amines
Table /. *bserations of Test Compounds #sing Acetyl
Chloride Test
Test Compounds *bserations
Experiment 06 Group No. 8 March 11. 2014 2 of
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CHM143L Organic Chemistry 2 Laboratory
3rd Quarter SY 2013-2014 rou! "o# $% &he '(coho(ics
,thano(amine 011 Aeacted 5io(ent(y 4ith acety( ch(oride+
!roducing a c(ear ye((o4 so(ution a*ter
addition o* disti((ed 4ater
;iethano(amine 021 )a(e ye((o4 so(ution 4as !roduced
4ith 4hite !reci!itate 4here it disso(5ed
u!on 5igorous sha7ing
&riethano(amine 031 C(ear so(ution !roduced 4ith no heat
or gas e5o(5ed u!on acety( ch(oride
addition
'ni(ine 041 Heat and gas e5o(5ed u!on acety(
ch(oride addition# ' c(oudy so(ution 4ith
*ormation o* !reci!itate a*ter adding
disti((ed 4ater
"-buty(ani(ine 0=1 Heat and gas e5o(5ed u!on addition
o* acety( ch(oride# .t *ormed a go(den
bro4n so(ution u!on addition o* 4ater
"+"-dimethy(ani(ine 0?1 C(ear so(ution 4as !roduced 4ith a
2e((y-(i7e (ayer residing at the to!/
immiscib(e mi:ture
Table 0. *bserations of Test Compounds #sing !insberg
Test and "itrous Acid Test
Test Compounds *bserations
!insberg Test "itrous Acid Test
,thano(amine 0B1 So(ub(e in
"aOH/ no
*ormation o*
!reci!itate
0131 6ormation o*
bubb(es 4ere
obser5ed a*ter
boi(ing *or a 5ery
short time
;iethano(amine 0$1 .nso(ub(e in
"aOH and HC(/
*ormation o* 4hite
!reci!itate
0141 ' ye((o4-
orange so(ution 4as
!roduced
&riethano(amine 0@1 .nso(ub(e in
"aOH and HC(/ t4o
(ayers o* immiscib(e
(iCuids 4ere *ormed
01=1 ' c(ear orange
so(ution 4as
!roduced
'ni(ine 0101 So(ub(e in
"aOH( no *ormation
o* !reci!itate
01?1 6ormation o*
bubb(es 4ere
obser5ed a*ter
boi(ing the mi:ture
*or some time
"-buty(ani(ine 0111 .nso(ub(e in
"aOH and HC((
*ormation o* 2e((y-
(i7e !reci!itate
01B1 ' ye((o4-oi( (i7e
so(ution 4as *ormed
"+"-dimethy(ani(ine 0121 .nsoub(e in
"aOH and HC(/ t4o
(ayers o* immiscib(e
(iCuids *ormed
01$1 '*ter boi(ing *or
some time+ it
resu(ted to an
orange so(ution
Table 1. Reactions )noled in -art ))
Reactions )noled
2.3
OH
N H
2
+
CH
3
O
Cl
O H
NH CH
3
O
+
HCl(g)
2/3
OH
NH
O H
+
CH
3
O
Cl
O H
N CH
3
O
O H
+
HCl(g)
203
+
CH
3
O
Cl
N
OH
O H
O H
n o r e a c t i o n
213
+
CH
3
O
Cl NH CH
3
O
+
HCl(g)
NH
2
243
+
CH
3
O
Cl N CH
3
O
C H
3
+
HCl(g)
NH
C H
3
253
+
CH
3
O
Cl
N
C H
3
CH
3
n o r e a c t i o n
263
NH
2
O H
+ S
O
O
Cl
2 N a O H
S
O
O
N
-
OH
Na
+
+ NaCl + O H
2
2
S
O
O
N
-
OH
Na
+
H
+
S
O
O
NH
OH
+
NaCl
273
NH
O H
OH
+ S
O
O
Cl
2 N a O H
S
O
O
N
OH
OH
+ NaCl +
O H
2
H
+
S
O
O
N
OH
OH
n o r e a c t i o n
283
Experiment 06 Group No. 8 March 11. 2014 3 of
6
CHM143L Organic Chemistry 2 Laboratory
3rd Quarter SY 2013-2014 rou! "o# $% &he '(coho(ics
+ S
O
O
Cl
2 N a O H
+ NaCl +
O H
2
H
+
S
O
O
Na +
N
OH
O H
O H
N
OH
O H
O H
N
OH
O H
O H
NH
+
O H
O H
O H
Cl
-
2.93
+ S
O
O
Cl
2 N a O H
S
O
O
N
-
+ NaCl +
O H
2
H
+
NH
2
Na
+
Na
+
S
O
O
N
-
S
O
O
NH
NaCl
+
2..3
+ S
O
O
Cl
2 N a O H
S
O
O
N
CH
3
+ NaCl +
O H
2
H
+
n o r e a c t i o n
NH
C H
3
S
O
O
N
CH
3
2./3
+ S
O
O
Cl
2 N a O H
+ NaCl +
O H
2
H
+
N
CH
3
C H
3
S
O
O
Na
N
CH
3
C H
3
+
N
CH
3
C H
3
NH
+
C H
3
C H
3
Cl
-
2.03
H O N O
Cl H 2
N N
+
OH
Cl
- O H
2
N
2
(g)
+ + N H
2
OH
O H
OH
O H
Cl
+
O H
OH
+
O H
+
a l k e n e
2.13
NH
OH
O H H O N O
N
O H
O H
N O
+
O H
2
2.43
N
OH
O H
O H
H O N O
NH
+
OH
O H
O H
2.53
H O N O
NH
2
Cl H 2
N N
+
Cl
-
O H
2
N
2
(g)
+
OH
+
Cl H
2.63
H O N O
N
O H
N O
+
O H
2
NH C H
3
2.73
H O N O
N
C H
3 CH
3
N H
+
ON
CH
3
CH
3
Cl
-
+
O H
2
Cl
-
N H
+
ON
CH
3
CH
3
NaOH
N ON
CH
3
CH
3
+
NaCl
+
O H
2
.n 'cety( Ch(oride &est+ a nuc(eo!hi(ic acy( substitution
occurs in this test# &he nitrogen atom *rom the amine com!onent
attac7s the carbony( carbon+ brea7ing the carbony( bond due to
the carbon atom ha5ing a (imit o* *our bonds and the o:ygen
atom ha5ing the additiona( (one !air because it is more
e(ectronegati5e than the carbon# &hen+ o:ygen atom rebui(ds the
carbony( bond+ !ushing the ch(oride atom *rom the com!ound
since it is a 5ery good (ea5ing grou!# 6ina((y+ a !roton trans*er 4i((
occure 4here the ch(oride atom 4i(( get the hydrogen *rom the
amine com!onent+ (iberating hydrogen ch(oride gas#
.n the case o* tertiary amines such as triethano(amine
and "+"-dimethy(ani(ine+ they do not react 4ith acety( ch(oride
because o* steric e**ect around the nitrogen atom and the
absence o* a re!(aceab(e hydrogen atom since a neutra( nitrogen
atom can *orm u! to three bonds on(y#
&he ne:t test !er*ormed 4as ca((ed the Hinsberg &est#
6rom the obser5ations recorded in &ab(e 3+ it is sa*e to say that
!ositi5e resu(ts 4ere obtained *rom the !er*ormance o* the test
using di**erent structures o* amines#
)rimary amines disso(5e in the basic so(ution and yie(d
a !reci!itate# 6irst is that the amine+ under basic conditions+ 4i((
attac7 the ben8enesu(*ony( ch(oride+ 4hich ser5es as an
e(ectro!hi(ic reagent+ then by means o* substitution+ it 4i(( yie(d a
sa(t+ 4hich is a su(*onamide deri5ati5e that is acidic and disso(5ed
in aCueous base# <!on !rotonation o* it using an acid+ it 4i((
Experiment 06 Group No. 8 March 11. 2014 4 of
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CHM143L Organic Chemistry 2 Laboratory
3rd Quarter SY 2013-2014 rou! "o# $% &he '(coho(ics
come out as a !reci!itate because it 4i(( become inso(ub(e in
4ater#
Secondary amines undergo the same reaction as that o*
!rimary amines+ but resu(ting in an inso(ub(e sa(t e5en be*ore
acidi*ication# Since the nitrogen atom a(ready contains three
bonds+ 4hich ma7es it neutra(+ it cannot be *urther !rotonated+
resu(ting to no reaction occurring#
Last(y in tertiary amines+ they 4i(( be inso(ub(e in the
basic reaction mi:ture+ but 4i(( disso(5e u!on addition o* HC(#
&ertiary amines are considered to be inso(ub(e in the reaction
mi:ture because the attac7 o* it to the ben8enesu(*ony( ch(oride is
not iso(ated+ meaning that it ra!id(y brea7s do4n in basic
condition to *ormed a 4ater-so(ub(e com!ound+ (iberating the
origina( amine# .nstead+ ben8enesu(*ony( ch(oride 4i(( react 4ith
the base !resent and the inso(ub(e amine 4i(( readi(y disso(5e
u!on the addition o* acid such as HC(#
'm!hoteric com!ounds+ ho4e5er+ may gi5e erroneous
resu(ts using the Hinsberg &est# .n terms o* secondary amines+
the *ormation o* a !reci!itate *rom a base and no reaction *rom
addition o* acid indicates a !ositi5e resu(t# -ut i* the com!ound is
am!hoteric be*ore the reaction occurred 0ha5ing the
characteristics o* an acid and a base and ca!ab(e o* reacting
chemica((y either as an acid or a base1+ then the
ben8enesu(*onamide 4i(( be so(ub(e in the acid a(so 4hich can
(ead to 4rong conc(usions+ ma7ing it seem as though it is a
tertiary amine#
&hen+ simi(ar to the other tests+ "itrous 'cid &est a(so
ga5e out !ositi5e resu(ts *rom each o* the test com!ounds
uti(i8ed#
&he reactions o* nitrous acid 4ith !rimary and
secondary a(i!hatic amines may be e:!(ained by considering
their beha5ior 4ith the nitrosonium cation 0"O1 *rom nitrous acid+
4hich acts as an e(ectro!hi(e# 6or !rimary a(i!hatic amines+ the
amine attac7 the said cations and under acidic conditions+ a
dia8onium cation 0"-" tri!(e bond1 is *ormed and by (iberation o*
nitrogen gas and treatment o* the a(7y( com!ound 4ith 4ater+
a(coho(s and a(7enes are then *ormed# &hen *or secondary
a(i!hatic amines+ the amine com!ound attac7s the nitrosonium
cation *rom nitrous acid much simi(ar *rom !rimary a(i!hatic
amines+ and by !roton trans*er brought about by the hydro:ide
ion+ an o:ime is readi(y *ormed in the *orm o* a ye((o4 oi( or so(id#
.n the case o* tertiary a(i!hatic amines+ 4hich are di**erent *rom
!rimary and secondary+ they undergo sa(t *ormation under acidic
conditions+ !roducing a so(ub(e sa(t#
"itrous acid reactions o* !rimary aromatic amines *orm
ary( dia8onium ion intermediates+ simi(ar to !rimary a(i!hatic
amines+ then nitrogen gas is then (iberated+ (ea5ing
behind an ary( carbocation+ 4hich is unstab(e# -y treatment o*
4ater+ 4hich ser5es as a nuc(eo!hi(e+ attac7s the said
carbocation+ yie(ding !heno(#
Secondary aromatic amines gi5e o:ime deri5ati5es
simi(ar to their a(i!hatic counter!arts#
Last(y+ *or tertiary aromatic com!ounds+ they react 4ith
the e(ectro!hi(ic nitrosonium cation in the para- !osition# &his is
!ossib(e because the aromatic ring is high(y acti5ated by the nitro
grou! un(i7e ben8ene#
Table 4. Tests -erformed and )dentity of #nknown
#nknown "umber 7
Test -erformed Results Conclusion
Odor 6ou(+ stingy sme((
Co(or -ric7 red
So(ubi(ity .nso(ub(e in 4ater
'cety( ch(oride test ,5o(ution o* gas
and heat
,ither !rimary or
secondary amine
Hinsberg &est .nso(ub(e in ?M
"aOH 4ith
ben8enesu(*ony(
ch(oride/ so(ub(e in
HC(
Secondary amine
"itrous 'cid &est <!on addition o*
ninhydrin+ a ye((o4
oi(-(i7e so(ution
*ormed
Secondary aromatic
amine
Conclusion &he un7no4n com!ound is "+"-
dimethy(ani(ine+ a secondary aromatic
amine
9ith the tests !er*ormed in order to identi*y the
com!ound+ it is 5ery im!ortant to determine *irst the !hysica(
!ro!erties such as the odor+ co(or+ and so(ubi(ity o* the
com!ound+ as tested here# 'mines usua((y ha5e a *ou( sme((+
o*ten associated 4ith *ishy odor# .t is so(ub(e in 4ater+ meaning
that it can !ossib(y contain an aromatic grou! that is direct(y
attached to the amine grou! as !er discussed in )art .# 6orm the
'cet(y Ch(oride &est+ it can be said that the e5o(ution o* gas and
heat 4as obser5ed that indicates a !ositi5e resu(t using the said
test+ in*erring that it is either a !rimary or secondary amine#
6o((o4ed by the Hinsberg &est+ in the !resence o* a basic
mi:ture+ the resu(ting !roduct is an inso(ub(e sa(t# &his is to say
that the un7no4n is a secondary amine# 6ina((y+ to determine i*
the un7no4n is an a(i!hatic or aromatic com!ound+ "itrous 'cid
&est 4as used# 6rom here+ it is determined that the un7no4n is
Experiment 06 Group No. 8 March 11. 2014 5 of
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CHM143L Organic Chemistry 2 Laboratory
3rd Quarter SY 2013-2014 rou! "o# $% &he '(coho(ics
an aromatic amine# .n conc(usion+ *rom the test com!ounds used+
the un7no4n is readi(y identi*ied#
)ossib(e sources o* errors can be determined in this
e:!eriment such as the im!urities !resent in the reagents that
may !ossib(y gi5e de5iated resu(ts+ im!recise amount o* reagents
during !er*ormance o* e:!eriment+ and other errors such as
!ro(ong boi(ing o* so(utions in "itrous 'cid &est#
C*"C&#S)*"
&he ob2ecti5es o* the e:!eriment 4ere achie5ed since
the grou! 4as ab(e to identi*y the chemica( tests necessary to
c(assi*y amines and the chemica( basis *or 4hich di**erent
structura( ty!es o* amines 4i(( react using the di**erent tests and
identi*y the un7no4n com!ound using the identi*ication tests
!er*ormed#
# 'mines are usua((y basic because o* the 4ea7
hydrogen bonding ha!!ening that can easi(y be !rotonated e5en
by 4ea7 acids and so(ub(e because the nitrogen atom can easi(y
!er*orm hydrogen bonding# 'romatic amines are acidic rather
than basic because it is resonance-stabi(i8ed caused by the
de(oca(i8ed nature o* the (one !air o* the nitrogen atom+ and
inso(ub(e because o* e(ectron-4ithdra4ing !ro!erties#
&he *irst reaction used in this e:!eriment that can be
used to distinguish !rimary and secondary amines *rom their
tertiary counter!arts is the reaction to acety( ch(oride# &ertiary
amines o*ten *ai( to react due to steric e**ects encountered
around the nitrogen atom o* the amine#
&he second test used 4as the Hinsberg test# &his is the
best 4ay to di**erentiate !rimary+ secondary and tertiary amine
*rom each other# -en8ensu(*ony( ch(oride reacts di**erent(y to
each ty!e amine to gi5e c(ear(y distinguishab(e resu(ts# ' !rimary
amine 4i(( disso(5e in the basic so(ution and yie(d a !reci!itate#
Secondary amines 4i(( be inso(ub(e in the basic so(ution and the
addition o* HC( to the mi:ture 4i(( resu(t to no reaction# &ertiary
amines+ on the other hand+ 4i(( be inso(ub(e in the basic reaction
mi:ture+ but 4i(( disso(5e readi(y u!on addition o* HC(#
&he (ast test 4as ca((ed the "itrous acid test# &his test
has the abi(ity not on(y to c(assi*y the di**erent degrees o* amines
but a(so to di**erentiate aromatic *rom a(i!hatic amines# &he
addition o* nitrous acid to a !rimary a(i!hatic amine resu(ts in the
immediate *ormation o* nitrogen gas 4hich is c(ear(y seen in the
*ormation o* bubb(es# -ut !rimary aromatic amines a(so !roduce
the nitrogen gas but on(y a*ter some heat is a!!(ied#
Secondary amines react to nitrous acid to yie(d o:imes
4hich are indicated by the !roduction o* a ye((o4 so(id or oi(#
&ertiary a(i!hatic amine disso(5es readi(y in nitrous
acid so(ution# On the other hand+ tertiary aromatic amines react
to nitrous acid to yie(d an orange so(ution or so(id# .t turns green
u!on addition o* a base#
R,:,R,"C,S
. Baluyut, ;ohn <srael =. > 'e Castro, ?athlia, A. *rganic
Chemistry &aboratory +anual for Chemical
,ngineering Students -art /.
/ ?lein, 'aid R. *rganic Chemistry, Baltimore, +aryland@ ;ohn
Ailey > Sons, )nc, /9...
0 -arsons, Andrew :. ?eynotes in *rganic Chemistry, /
nd
edition.
,lon, "C@ ;ohn Ailey B Sons, )nc., /991.
1 +c+urry, ;ohn. :undamentals of *rganic Chemistry :ifth
,dition. )thaca, "<@ Cornell #niersity.

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