Topic 4.

10
ORGANIC SYNTHESIS AND ANALYSIS
Organic analysis
Organic synt!sis
DISTINGUISHING BETWEEN DIFFERENT ORGANIC COMPOUNDS
Many of the organic compounds prepared in AS Unit 2 and in A2 Unit 4 can be
distinguished by means of simple chemical tests. A number of these distinguishing tests
will be discussed in this chapter.
a) test for alkenes
Alkenes decolorize bromine water because they undergo an electrophilic addition
reaction with bromine
Add a few dros of !ro"#ne water to t$e sa"le and s$ake% If t$e !ro"#ne
de&olor#'es( an alkene #s resent% If not( no alkene #s resent%
b) test for $aloalkanes
!hen haloalkanes are heated with dilute sodium hydro"ide# a nucleophilic substitution
reaction occurs and halide ions are produced. $he halide ions can be identified using the
tests described in AS Unit 2
Add a)*eo*s sod#*" $+dro,#de to t$e sa"le and $eat% T$en allow to &ool( add
d#l*te n#tr#& a&#d and t$en a)*eo*s s#l-er n#trate% A w$#te re&##tate sol*!le #n
d#l*te a""on#a #nd#&ates t$at a &$loroalkane was resent( a &rea" re&##tate
sol*!le #n &on&entrated a""on#a #nd#&ates t$at a !ro"oalkane was resent( and a
+ellow re&##tate #nsol*!le #n a""on#a #nd#&ates t$at an #odoalkane was resent%
c) test for alde$+des
Aldehydes can be o"idized by mild o"idizing agents such as %ehling&s solution or
$ollen&s reagent.
Add Tollen.s rea/ent to t$e sa"le and $eat% A s#l-er "#rror #nd#&ates t$e resen&e
of an alde$+de%
'r
Add Fe$l#n/.s sol*t#on to t$e sa"le and $eat% A !r#&k0red re&##tate #nd#&ates t$e
resen&e of an alde$+de%
d) test for &ar!o,+l#& a&#ds
(arbo"ylic acids are acids and can liberate carbon dio"ide from carbonates
Add sod#*" &ar!onate sol*t#on to t$e sa"le% If effer-es&en&e #s seen( and t$e /as
rod*&ed t*rns l#"ewater "#lk+( a &ar!o,+l#& a&#d #s resent%
e) test for a&+l &$lor#des
Acyl chlorides release chloride ions )ery readily to gi)e hydrogen chloride gas.
Add water to t$e sa"le slowl+% If w$#te "#st+ f*"es are /#-en off( an a&+l &$lor#de
#s resent%
f) test for a"#nes
Amines are basic.
Add *n#-ersal #nd#&ator to t$e sa"le% If #t t*rns !l*e1*rle an a"#ne #s resent% It
w#ll also $a-e a f#s$+ s"ell%
g) test for al&o$ols
Alcohols react with carbo"ylic acids in the presence of sulphuric acid to make esters.
Add et$ano#& a&#d to t$e sa"le( followed !+ s*l$*r#& a&#d and $eat% If a t$e
"#,t*re starts s"ell#n/ sweet and fr*#t+ an al&o$ol was resent%
h) d#st#n/*#s$#n/ tests for r#"ar+( se&ondar+ and tert#ar+ al&o$ols
*rimary alcohols can be o"idized to form aldehydes. Secondary alcohols are o"idized to
form ketones. $ertiary alcohols cannot be o"idized.
Add otass#*" d#&$ro"ate and d#l*te s*l$*r#& a&#d to t$e "#,t*re and war"
/entl+%
If t$e "#,t*re /oes /reen a r#"ar+ or se&ondar+ al&o$ol #s resent% If #t does not /o
/reen a tert#ar+ al&o$ol #s resent% If t$e "#,t*re does /o /reen( add Fe$l#n/.s
sol*t#on to t$e "#,t*re and $eat% If a !r#&k0red re&##tate #f for"ed t$en a r#"ar+
al&o$ol was resent% If no !r#&k0red re&##tate #s for"ed t$en a se&ondar+ al&o$ol
was resent%
ORGANIC S2NTHESIS
+t is possible to make a large number of organic products from a few starting compounds
and the necessary reagents. $he following organic pathways are re,uired for Unit 4
-. alkane &$loroalkane
reagents chlorine
conditions U. light
e,uation (/4 0 (l2 (/1(l 0 /(l 2e"ample)
NB T$#s rea&t#on #ntrod*&es a new f*n&t#onal /ro* onto t$e "ole&*le
2. &$loroalkane al&o$ol
reagents a,ueous 3a'/
conditions warm# reflu"
e,uation 45(l 0 3a'/ 45'/ 0 3a(l
1. &$loroalkane alkene
reagents alcoholic 6'/
conditions heat# distillation
e,uation (/1(/2(l 0 6'/ (/27(/2 0 6(l 0 /2' 2e"ample)
4. &$loroalkane n#tr#le
reagents a,ueous 6(3
conditions heat# reflu"
e,uation 45(l 0 6(3 45(3 0 6(l
NB T$#s rea&t#on #ntrod*&es an e,tra &ar!on ato" onto t$e "ole&*le
8. &$loroalkane r#"ar+ a"#ne
reagents e"cess ammonia
conditions heat
e,uation 45(l 0 23/1 453/2 0 3/4(l
9. r#"ar+ a"#ne se&ondar+ a"#ne
reagents chloroalkane
conditions warm
e,uation 4-53/2 0 425(l 4-423/ 0 /(l
:. se&ondar+ a"#ne tert#ar+ a"#ne
reagents chloroalkane
conditions warm
e,uation 4-423/ 0 415(l 4-42413 0 /(l
;. tert#ar+ a"#ne )*artenar+ a""on#*" salt
reagents chloroalkane
conditions warm
e,uation 4-42413 0 445(l 4-4241443
0
(l
5
<. alkene alkane
reagents hydrogen# 3i catalyst
conditions -8=
o
(# 2 atm
e,uation (/27(/2 0 /2 (/1(/1 2e"ample)
-=. alkene d#!ro"oalkane
reagents bromine
conditions room temperature
e,uation (/27(/2 0 >r2 (/2>r(/2>r 2e"ample)
NB T$#s rea&t#on #ntrod*&es a new f*n&t#onal /ro* onto t$e "ole&*le
--. alkene !ro"oalkane
reagents hydrogen bromide
conditions room temperature
e,uation (/27(/2 0 />r (/1(/2>r 2e"ample)
-2. alkene alk+l$+dro/ens*l$ate
reagents concentrated sulphuric acid
conditions cold
e,uation (/27(/2 0 /2S'4 (/1(/2'S'1/ 2e"ample)
-1. alk+l$+dro/ens*l$ate al&o$ol
reagents water
conditions warm
e,uation (/1(/2'S'1/ 0 /2' (/1(/2'/ 0 /2S'4 2e"ample)
-4. alkene al&o$ol
reagents steam
conditions 1==
o
(# 9== k*a# phosphoric acid catalyst
e,uation (/27(/2 0/2' (/1(/2'/
-8. n#tr#le r#"ar+ a"#ne
reagents ?iAl/4
conditions dry ether
e,uation 45(3 0 4@/A 45(/23/2 2e"ample)
-9. n#tr#le &ar!o,+l#& a&#d 3not e"aminable)
reagents dilute /(l
conditions heat under reflu"
e,uation 45(3 0 2/2' 0 /(l 45(''/ 0 3/4(l
-:. al&o$ol alkene
reagents concentrated sulphuric acid
conditions heat# reflu"
e,uation (/1(/2'/ (/27(/2 0 /2' 2e"ample)
-;. r#"ar+ or se&ondar+ al&o$ol &ar!on+l
reagents potassium dichromate and dilute sulphuric acid
conditions warm# distillation
e,uation 4-42(/'/ 0 @'A 4-5('42 0 /2'
-<. r#"ar+ al&o$ol &ar!o,+l#& a&#d
reagents potassium dichromate and dilute sulphuric acid
conditions heat# reflu"
e,uation 45(/2'/ 0 2@'A 45(''/ 0 /2'
2=. alde$+de &ar!o,+l#& a&#d
reagents potassium dichromate and dilute sulphuric acid
conditions heat# reflu"
e,uation 45(/' 0 @'A 45(''/
2-. &ar!on+l al&o$ol
reagents 3a>/42a,)
conditions room temperature
e,uation 4-5('42 0 2@/A 4-42(/'/
22. &ar!o,+l#& a&#d &ar!o,+late salt
reagents 3a'/
conditions room temperature
e,uation 45(''/ 0 3a'/ 45(''3a 0 /'
21. a"#ne alk+la""on#*" salt
reagents /(l2a,)
conditions room temperature
e,uation 4-42413 0 /(l 4-42413/(l
24. &ar!on+l $+dro,+n#tr#le
reagents /(3
conditions room temperature
e,uation 4-('42 0 /(3 4-42('/(3
NB T$#s rea&t#on adds an e,tra &ar!on ato" and #ntrod*&es an e,tra f*n&t#onal
/ro* onto t$e "ole&*le
28. a&+l &$lor#de &ar!o,+l#& a&#d
reagents water
conditions room temperature
e,uation 45('(l 0 /2' 45(''/
29. a&+l &$lor#de a"#de
reagents ammonia
conditions room temperature
e,uation 45('(l 0 3/1 45('3/2
2:. a&#d an$+dr#de &ar!o,+l#& a&#d
reagents water
conditions warm
e,uation 24(')2' 0 /2' 245(''/
2;. a&#d an$+dr#de a"#de
reagents ammonia
conditions warm
e,uation 24(')2' 0 3/1 45('3/2 0 4(''/
2<. &ar!o,+l#& a&#d 4 al&o$ol ester
reagents concentrated sulphuric acid
conditions heat# reflu"
e,uation 4-(''/ 0 42'/ 4-(''42 0 /2'
1=. a&+l &$lor#de 4 al&o$ol ester
conditions room temperature
e,uation 4-('(l 0 42'/ 4-(''42 0 /(l
1-. a&#d an$+dr#de 4 al&o$ol ester
conditions warm
e,uation 24-(')2' 0 42'/ 4-(''42 0 4-(''/
12. ester &ar!o,+l#& a&#d 4 al&o$ol
reagents concentrated sulphuric acid
conditions heat under reflu"
e,uation 4-(''42 0 /2' 4-(''/ 0 42'/
11. ester &ar!o,+late salt 4 al&o$ol
reagents 3a'/2a,)
conditions heat under reflu"
e,uation 4-(''42 0 3a'/ 4-(''3a 0 42'/
14. a&+l &$lor#de 4 r#"ar+ a"#ne N0s*!st#t*ted a"#de
conditions room temperature
e,uation 4-5('(l 0 24253/2 4-5('3/42 0 4253/1(l
18. a&#d an$+dr#de 4 r#"ar+ a"#ne N0s*!st#t*ted a"#de
conditions warm
e,uation 24-(')2'0 4253/2 4-5('3/42 0 4-5(''/
19. !en'ene n#tro!en'ene
reagents concentrated sulphuric and nitric acids
conditions warm# reflu"
e,uation (9/9 0 /3'1 (9/83'2 0 /2'
1:. !en'ene alk+l!en'ene
reagents chloroalkane# Al(l1
conditions warm# reflu"
e,uation (9/9 0 4(l (9/84 0 /(l
1;. !en'ene $en+lalkanone
reagents acyl chloride# Al(l1
conditions room temperature
e,uation (9/9 0 4('(l (9/8('4 0 /(l
1<. n#tro!en'ene $en+la"#ne
reagents tin# concentrated /(l
conditions room temperature
e,uation (9/9 0 9@/A (9/83/2 0 2/2'
$he intercon)ersion of these compounds can be summarised in the following synthesis
maps
a) al#$at#& s+nt$es#s "a 5 s#"le &on-ers#ons
AMIDES
ALKYL
AMMONIUM SALTS
QUARTENARY
AMMONIUM SALTS
SECONDARY
AMINES
TERTIARY
AMINES
DIHALOALKANES
HALOALKANES
ALCOHOLS
ALKENES
CARBONYLS
CARBOXYLIC ACIDS
DIOLS
PRIMARY
AMINES
ALKANES
NITRILES
ACID
ANHYDRIDES ACYL CHLORIDES
CARBOXYLATE
SALTS
b) &ondensat#on rea&t#ons
N-substituted amides
estes
!ima" ami#es
a$%&'&$s
(
(
&
a%id a#'"dides
a%"$ %'$&ides
%ab&)"$i% a%ids
(
c) aro"at#& &on-ers#ons
R
C
O
R
NO
* NH
*