AN INTRODUCTION TO

SYNTHETIC ORGANIC CHEMISTRY

KNOCKHARDY PUBLISHING

KNOCKHARDY PUBLISHING

ORGANIC REACTION SEQUENCES

INTRODUCTION This Powerpoint show is one of several produced to help students understand selected topics at AS and A2 level Chemistry. It is based on the requirements of the AQA and OC specifications but is suitable for other e!amination boards. Individual students may use the material at home for revision purposes or it may be used for classroom teachin" if an interactive white board is available. Accompanyin" notes on this# and the full ran"e of AS and A2 topics# are available from the $%OC$&A '( SCI)%C) *)+SIT) at...

www.argonet.co.uk/users/hoptonj/sci.htm
%avi"ation is achieved by... either or clic,in" on the "rey arrows at the foot of each pa"e usin" the left and ri"ht arrow ,eys on the ,eyboard

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REACTIONS OF ORGANIC COMPOUNDS

POLYMERS

DIBROMOALKANES

KETONES

ALKANES

ALKENES

ALCOHOLS

ALDEHYDES HALOGENOALKANES ESTERS

AMINES

NITRILES

CARBOXYLIC ACIDS

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REACTIONS OF ORGANIC COMPOUNDS

POLYMERS

DIBROMOALKANES
P F C S

KETONES

ALKANES

ALKENES

D
M G V

ALCOHOLS
N T U R

ALDEHYDES ESTERS
U T O Q

HALOGENOALKANES
H I

AMINES

NITRILES

CARBOXYLIC ACIDS

CHLORINATION OF METHANE
Cl Cl# + CH, Cl + CH-# Cl# + Cl# Cl# + CH-# CH-# + CH-# !!" Cl# $a%i&al' &$(at(% $a%i&al' .'(% an% t/(n $(0*(n($at(% $a%i&al' $(1o2(%

Initiation P$o)a*ation

!!" CH-# + HCl !!" CH-Cl + Cl# !!" !!" !!" Cl CH-Cl C H3

T($1ination

S.11a$4
D.( to t/( la&5 o6 $(a&ti2it4 o6 al5an(' 4o. n((% a 2($4 $(a&ti2( ')(&i(' to )($'.a%( t/(1 to $(a&t F$(( $a%i&al' n((% to 7( 6o$1(% 74 /o1ol4ti& 6i''ion o6 &o2al(nt 7on%' T/i' i' %on( 74 '/inin* UV li*/t on t/( 1i8t.$( 9/(at &o.l% 7( .'(%: C/lo$in( $a%i&al' a$( )$o%.&(% 7(&a.'( t/( Cl0Cl 7on% i' t/( ;(a5('t Yo. onl4 n((% on( &/lo$in( $a%i&al to 'ta$t t/in*' o66 <it/ (8&('' &/lo$in( 4o. ;ill *(t 6.$t/($ '.7'tit.tion an% a 1i8t.$( o6 &/lo$inat(% )$o%.&t'

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ELECTROPHILIC ADDITION OF HB$

H4%$o*(n 7$o1i%(=== it i' (l(&t$o)/ili& a' t/( H i' 'li*/tl4 )o'iti2( Roo1 t(1)($at.$(= C H,9*: + HB$9*: !!!" C H?B$9l: bromoethane

R(a*(nt Con%ition E>.ation M(&/ani'1

St() @

A' t/( HB$ n(a$' t/( al5(n(A on( o6 t/( &a$7on0&a$7on 7on%' 7$(a5' T/( )ai$ o6 (l(&t$on' atta&/(' to t/( 'li*/tl4 )o'iti2( H (n% o6 H0B$= T/( HB$ 7on% 7$(a5' to 6o$1 a 7$o1i%( ion= A &a$7o&ation 9)o'iti2(l4 &/a$*(% &a$7on ')(&i(': i' 6o$1(%= T/( 7$o1i%( ion 7(/a2(' a' a n.&l(o)/il( an% atta&5' t/( &a$7o&ation= O2($all t/($( /a' 7((n a%%ition o6 HB$ a&$o'' t/( %o.7l( 7on%=
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Step 2

ELECTROPHILIC ADDITION OF BROMINE

B$o1in(= 9N(at li>.i% o$ %i''ol2(% in t(t$a&/lo$o1(t/an(A CCl, : Roo1 t(1)($at.$(= No &atal4't o$ UV li*/t $(>.i$(%B

R(a*(nt Con%ition'

E>.ation M(&/ani'1

C H,9*: + B$ 9l:

!!"

CH B$CH B$9l:

-#2 . dibromoethane

It i' '.$)$i'in* t/at 7$o1in( '/o.l% a&t a' an (l(&t$o)/il( a' it i' non0)ola$=

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DIRECT HYDRATION OF ALKENES

't(a1

R(a*(nt

Con%ition' /i*/ )$(''.$( Catal4't P$o%.&t )/o')/o$i& a&i% al&o/ol

E>.ation U'(

C H,9*: +

H O9*:

C H?OH9*:

ethanol

(t/anol 1an.6a&t.$(

Co11(nt'

It 1a4 7( '.$)$i'in* t/at ;at($ n((%' '.&/ 2i*o$o.' &on%ition' to $(a&t ;it/ (t/(n(= It i' a /i*/l4 )ola$ 1ol(&.l( an% 4o. ;o.l% (8)(&t it to 7( a *oo% (l(&t$o)/il(= Ho;(2($A t/( O0H 7on%' a$( 2($4 't$on* 'o $(>.i$( a *$(at %(al o6 (n($*4 to 7( 7$o5(n= T/i' n(&(''itat(' t/( n((% 6o$ a &atal4't=

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HYDROGENATION
/4%$o*(n ni&5(l &atal4't 0 6in(l4 %i2i%(% al5an(' C H,9*: + H 9*: !!!" C H39*: ethane

R(a*(nt Con%ition' P$o%.&t E>.ation U'(

1a$*a$in( 1an.6a&t.$(

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POLYMERISATION OF ALKENES
EXAMPLES OF ADDITION POLYMERISATION
ETHENE POLY9ETHENE:

PROPENE

POLY9PROPENE:

CHLOROETHENE

POLY9CHLOROETHENE:
/O0(1I%(0C&0O I') /1C

TETRAFLUOROETHENE

POLY9TETRAFLUOROETHENE: /T2) 3Teflon4

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NUCLEOPHILIC SUBSTITUTION
AQUEOUS SODIUM HYDROXIDE

R(a*(nt Con%ition' P$o%.&t N.&l(o)/il( E>.ation M(&/ani'1

A>.(o.'C 'o%i.1 9o$ )ota''i.1: /4%$o8i%( R(6l.8 in a>.(o.' 'ol.tion 9SOLVENT IS IMPORTANT: Al&o/ol /4%$o8i%( ion 9OHD: e.". C H?B$9l: + NaOH9a>: !!!" C H?OH9l: + NaB$9a>:

C <ARNING

It i' i1)o$tant to >.ot( t/( 'ol2(nt ;/(n an';($in* >.('tion'= Eli1ination ta5(' )la&( ;/(n (t/anol i' t/( 'ol2(nt T/( $(a&tion 9an% t/( on( ;it/ ;at($: i' 5no;n a' HYDROLYSIS

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NUCLEOPHILIC SUBSTITUTION
AMMONIA

R(a*(nt Con%ition' P$o%.&t N.&l(o)/il( E>.ation

A>.(o.'A al&o/oli& a11onia 9in EXCESS: R(6l.8 in a>.(o.'A al&o/oli& 'ol.tion .n%($ )$(''.$( A1in( A11onia 9NH-: e.". C H?B$ + 5i6 5ii6 NH- 9a> E al&: !!" C H?NH NH- 9a> E al&: + NH,B$ + HB$

C H?B$ + HB$

!!" C H?NH NH,B$

+ NH- 9a> E al&:

!!"

M(&/ani'1

Not('

T/( (>.ation '/o;' t;o a11onia 1ol(&.l('= T/( '(&on% on( (n'.$(' t/at a 'alt i' not 6o$1(%= E8&('' a11onia i' .'(% to )$(2(nt 6.$t/($ '.7'tit.tion 9SEE NEXT SLIDE:
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NUCLEOPHILIC SUBSTITUTION
AMMONIA

</4 (8&('' a11oniaF T/( '(&on% a11onia 1ol(&.l( (n'.$(' t/( $(1o2al o6 HB$ ;/i&/ ;o.l% l(a% to t/( 6o$1ation o6 a 'alt= A la$*( (8&('' a11onia (n'.$(' t/at 6.$t/($ '.7'tit.tion %o('nGt ta5( )la&( . see below P$o7l(1 T/( a1in( )$o%.&(% i' al'o a n.&l(o)/il( 9lon( )ai$ on N: an% &an atta&5 anot/($ 1ol(&.l( o6 /alo*(noal5an( to )$o%.&( a H a1in(= T/i' in t.$n i' a n.&l(o)/il( an% $(a&t' 6.$t/($ )$o%.&in* a -H a1in( an%A (2(nt.all4 a >.a$t($na$4 a11oni.1 'alt= C H?NH + C H?B$ !!" HB$ + 9C H?: NH diethylamine# a 27 amine

9C H?: NH + C H?B$

!!"

HB$

9C H?:-N

triethylamine# a 87 amine

9C H?:-N

C H?B$

!!"

9C H?:,N+ B$D

tetraethylammonium bromide# a 97 salt

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NUCLEOPHILIC SUBSTITUTION
POTASSIUM CYANIDE

R(a*(nt Con%ition' P$o%.&t N.&l(o)/il( E>.ation M(&/ani'1

A>.(o.'A al&o/oli& )ota''i.1 9o$ 'o%i.1: &4ani%( R(6l.8 in a>.(o.' A al&o/oli& 'ol.tion Nit$il( 9&4ani%(: &4ani%( ion 9CND: e.". C H?B$ + KCN 9a>Eal&: !!!" C H?CN + KB$9a>:

I1)o$tan&(

it (8t(n%' t/( &a$7on &/ain 74 on( &a$7on ato1 t/( CN *$o.) &an t/(n 7( &on2($t(% to &a$7o84li& a&i%' o$ a1in('=
J K

R(%.&tion H4%$ol4'i'

C H?CN + ,IHJ C H?CN + HO

!!" C H?CH NH !!" C H?COOH + NH-

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ELIMINATION
Al&o/oli& 'o%i.1 9o$ )ota''i.1: /4%$o8i%( R(6l.8 in al&o/oli& 'ol.tion Al5(n( Eli1ination C-HKB$ + NaOH9al&: !!!" C-H3 + HO + NaB$

R(a*(nt Con%ition' P$o%.&t M(&/ani'1 E>.ation M(&/ani'1

t/( OHD ion a&t' a' a 7a'( an% )i&5' .) a )$oton t/( )$oton &o1(' 6$o1 a C ato1 n(8t to t/( on( 7on%(% to t/( /alo*(n t/( (l(&t$on )ai$ 1o2(' to 6o$1 a '(&on% 7on% 7(t;((n t/( &a$7on ato1' t/( /alo*(n i' %i')la&(%L o2($all t/($( i' ELIMINATION o6 HB$= <it/ .n'411(t$i&al /alo*(noal5an('A a 1i8t.$( o6 )$o%.&t' 1a4 7( 6o$1(%=
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ELIMINATION OF <ATER 9DEHYDRATION:

&on&= '.l)/.$i& a&i% 9H SO,: o$ &on&= )/o')/o$i& a&i% 9H-PO,: $(6l.8 at @MNHC al5(n( e.". C H?OH9l: !!!!" CH O CH 9*: + H O9l:

R(a*(ntE&atal4't Con%ition' P$o%.&t E>.ation M(&/ani'1

St() @ St() St() Not(

)$otonation o6 t/( al&o/ol .'in* a lon( )ai$ on o84*(n lo'' o6 a ;at($ 1ol(&.l( to *(n($at( a &a$7o&ation lo'' o6 a )$oton 9H+: to *i2( t/( al5(n(

Alcohols with the O& in the middle of a chain can have two ways of losin" water. In Step 8 of the mechanism# a proton can be lost from either side of the carbocation. This "ives a mi!ture of al,enes from unsymmetrical alcohols...
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OXIDATION OF PRIMARY ALCOHOLS

P$i1a$4 al&o/ol' a$( (a'il4 o8i%i'(% to al%(/4%(' e.". CH-CH OH9l: + IOJ !!!" CH-CHO9l: + H O9l:

it i' (''(ntial to %i'til o66 t/( al%(/4%( 7(6o$( it *(t' o8i%i'(% to t/( a&i% CH-CHO9l: + IOJ !!!" CH-COOH9l:

OXIDATION TO ALDEHYDES DISTILLATION

OXIDATION TO CARBOXYLIC ACIDS REFLUX

Al%(/4%( /a' a lo;($ 7oilin* )oint 'o %i'til' o66 7(6o$( 7(in* o8i%i'(% 6.$t/($
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Al%(/4%( &on%(n'(' 7a&5 into t/( 1i8t.$( an% *(t' o8i%i'(% to t/( a&i%

OXIDATION OF ALDEHYDES
Al%(/4%(' a$( (a'il4 o8i%i'(% to &a$7o84li& a&i%' e.". CH-CHO9l: + IOJ !!!" CH-COOH9l:

: : : :

one way to tell an aldehyde from a ,etone is to see how it reacts to mild o!idation ALDEHYES are EASILY OXIDISED KETONES are RESISTANT TO MILD OXIDATION rea"ents include TOLLENSG REAGENT and FEHLINGGS SOLUTION

TOLLENSG REAGENT R(a*(nt a11onia&al 'il2($ nit$at( 'ol.tion O7'($2ation a 'il2($ 1i$$o$ i' 6o$1(% on t/( in'i%( o6 t/( t('t t.7( P$o%.&t' 'il2($ + &a$7o84li& a&i% E>.ation A*+ + (0 !!" A* FEHLINGGS SOLUTION R(a*(nt a 'ol.tion o6 a &o))($9II: &o1)l(8 O7'($2ation a $(% )$(&i)itat( 6o$1' in t/( 7l.( 'ol.tion P$o%.&t' &o))($9I: o8i%( + &a$7o84li& a&i% E>.ation C. + + (0 !!" C.+
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OXIDATION OF SECONDARY ALCOHOLS

S(&on%a$4 al&o/ol' a$( (a'il4 o8i%i'(% to 5(ton(' e.". CH-CHOHCH-9l: + IOJ !!!" CH-COCH-9l: + H O9l:

T/( al&o/ol i' $(6l.8(% ;it/ a&i%i6i(% K C$ OK= Ho;(2($A on )$olon*(% t$(at1(nt ;it/ a )o;($6.l o8i%i'in* a*(nt t/(4 &an 7( 6.$t/($ o8i%i'(% to a 1i8t.$( o6 a&i%' ;it/ 6(;($ &a$7on ato1' t/an t/( o$i*inal al&o/ol=

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REDUCTION OF CARBOXYLIC ACIDS

lit/i.1 t(t$a/4%$i%oal.1inat(9III: LiAlH, $(6l.8 in (t/o84(t/an( al%(/4%( e.". CH-COOH9l: + IHJ !!!" CH-CHO9l: + H O9l:

R(a*(ntE&atal4't Con%ition' P$o%.&t E>.ation

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REDUCTION OF ALDEHYDES
'o%i.1 t(t$a/4%$i%o7o$at(9III: NaBH, ;a$1 in ;at($ o$ (t/anol )$i1a$4 al&o/ol e.". C H?CHO9l: + IHJ !!!" C-HKOH9l:

R(a*(nt Con%ition' P$o%.&t E>.ation

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REDUCTION OF KETONES
'o%i.1 t(t$a/4%$i%o7o$at(9III: NaBH, ;a$1 in ;at($ o$ (t/anol '(&on%a$4 al&o/ol e.". CH-COCH-9l: + IHJ !!!" CH-CH9OH:CH-9l:

R(a*(nt Con%ition' P$o%.&t E>.ation

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ESTERIFICATION
&a$7o84li& a&i% + 't$on* a&i% &atal4't 9(=* &on&= H SO, : $(6l.8 ('t($ e.". CH-CH OH9l: + CH-COOH9l: CH-COOC H?9l: + H O9l:

R(a*(nt9': Con%ition' P$o%.&t E>.ation Not('

Con&(nt$at(% H SO, i' al'o a %(/4%$atin* a*(ntA it $(1o2(' ;at($ a' it i' 6o$1(% &a.'in* t/( (>.ili7$i.1 to 1o2( to t/( $i*/t an% t/.' in&$(a'in* t/( 4i(l% o6 ('t($= E't($' a$( 6ai$l4 .n$(a&ti2( 7.t t/at %o('nGt 1a5( t/(1 .'(l('' U'(% a' 6la2o.$in*' Na1(% 6$o1 t/( al&o/ol an% &a$7o84li& a&i% ;/i&/ 1a%( t/(1=== CH-OH + CH-COOH
from (t/anoi& a&i%

U'(' o6 ('t($'

Na1in* ('t($'

CH-COOCH- + H O
from 1(t/anol

CH-COOCH;)T&(0 )T&A%OAT)
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HYDROLYSIS OF ESTERS
%il.t( a&i% o$ %il.t( al5ali $(6l.8 &a$7o84li& a&i% an% an al&o/ol e.". CH-COOC H?9l: + H O9l: CH-CH OH9l: + CH-COOH9l:

R(a*(nt9': Con%ition' P$o%.&t E>.ation

Not('

If al5ali is used for the hydrolysis the 'alt o6 t/( a&i% i' 6o$1(% CH-COOC H?9l: + NaOH9a>: !!!" CH-CH OH9l: + CH-COO0Na+9a>:

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BROMINATION OF ALCOHOLS
&on&= /4%$o7$o1i& a&i% HB$9a>: o$ 'o%i.1 9o$ )ota''i.1: 7$o1i%( an% &on&(nt$at(% '.l)/.$i& a&i% $(6l.8 /aloal5an( C H?OH9l: + &on&= HB$9a>: !!!" C H?B$9l: + H O9l:

R(a*(nt9': Con%ition' P$o%.&t E>.ation M(&/ani'1 -=

T/( 1(&/ani'1 'ta$t' o66 in a 'i1ila$ ;a4 to %(/4%$ation 9)$otonation o6 t/( al&o/ol an% lo'' o6 ;at($: 7.t t/( &a$7o&ation 9&a$7oni.1 ion: i' atta&5(% 74 a n.&l(o)/ili& 7$o1i%( ion in 't()

St() @ St() St() -

)$otonation o6 t/( al&o/ol .'in* a lon( )ai$ on o84*(n lo'' o6 a ;at($ 1ol(&.l( to *(n($at( a &a$7o&ation 9&a$7oni.1 ion: a 7$o1i%( ion 7(/a2(' a' a n.&l(o)/il( an% atta&5' t/( &a$7o&ation

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AN INTRODUCTION TO

SYNTHETIC ORGANIC CHEMISTRY

THE END

2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING