Download - Ch14 Deriv. of Carb. Acids
-
7/24/2019 Ch14 Deriv. of Carb. Acids
1/45
14-1
WILLIAM H. BROWN
THOMAS POON
www.wiley.com/college/brown
C H A P T E R F O U R T E E N
Functional Derivative
o! Car"o#$lic Aci%
Copyright2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
2/45
14-2
Carboxyl Derivatives
& In t'i c'a(ter) *e tu%$ !our clae o!
or+anic co,(oun% %erive% !ro, car"o#$licaci%.- Un%er t'e +eneral !or,ula o! eac' i a %ra*in+ to
'o* 'o* it i relate% to t'e car"o#$l +rou(.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
3/45
14-3
Acid Chlorides
& T'e !unctional +rou( o! an aci% 'ali%e i an ac$l
+rou( "on%e% to a 'alo+en.- T'e ,ot *i%el$ ue% are t'e aci% c'lori%e.
- To na,e) c'an+e t'e u!!i# -ic acidto -yl chloride.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
4/45
14-4
Acid Anhydrides
& T'e !unctional +rou( o! an aci% an'$%ri%e i
t*o ac$l +rou( "on%e% to an o#$+en ato,.-An'$%ri%e ,a$ "e $,,etrical t*o i%entical
ac$l +rou(/ or ,i#e% t*o %i!!erent ac$l +rou(/.
- To na,e) re(lace acido! t'e (arent aci% "$anhydride.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
5/45
14-5
Acid Anhydrides
& A ('o('oric aci% an'$%ri%e contain t*o
('o('or$l +rou( "on%e% to an o#$+en ato,.- S'o*n 'ere are t*o ('o('oric an'$%ri%e. Eac' 'o*n
a it *oul% "e ioni0e% at (H 1.2) t'e (H o! "loo%.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
6/45
14-6
Esters
& T'e !unctional +rou( o! an eter i an ac$l
+rou( "on%e% to 3OR or 3OAr.- Na,e t'e al4$l or ar$l +rou( "on%e% to o#$+en
!ollo*e% "$ t'e na,e o! t'e aci%.
- C'an+e t'e u!!i# -ic acidto -ate.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
7/4514-7
Lactones
& Lactone5 a c$clic eter- IUPAC5 na,e t'e (arent car"o#$lic aci%) %ro( t'e
u!!i# 3icaci%) an% a%% 3olactone.
- T'e location o! t'e o#$+en ato, on t'e car"on
c'ain i co,,onl$ in%icate% "$ a 6ree4 letter.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
8/4514-8
Phosphoric esters
& P'o('oric aci% !or, ,ono3) %i3) an% trieter.
- Na,e "$ +ivin+ t'e na,e o! t'e al4$l or ar$l +rou(/"on%e% to o#$+en/ !ollo*e% "$ t'e *or% phosphate.
- In ,ore co,(le# ('o('ate eter) it i co,,on to na,e
t'e or+anic ,olecule !ollo*e% "$ phosphate.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
9/4514-9
Amides
& T'e !unctional +rou( o! an a,i%e i an ac$l +rou(
"on%e% to a trivalent nitro+en.- IUPAC5 %ro( 3ic acid!ro, t'e na,e o! t'e (arent aci%
an% a%% 3amide.
- I! t'e a,i%e nitro+en i "on%e% to an al4$l or ar$l +rou()
na,e t'e +rou( an% 'o* it location on nitro+en "$ N3.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
10/4514-10
Lactam
& Lactam5 a c$clic a,i%e.- Na,e t'e (arent car"o#$lic aci%) %ro( t'e u!!i#
ic aci% an% a%% 3 lactam.
- T'e location o! t'e nitro+en ato, in t'e rin+ i
co,,onl$ in%icate% "$ a 6ree4 letter) ) ) etc.
- 73'e#anolacta, i an inter,e%iate in t'e
$nt'ei o! n$lon 7 Section 81.9A/.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
11/4514-11
The Penicillins
& T'e (enicillin are a !a,il$ o! 3lacta, anti"iotic.
- T'e tructural !eature co,,on to all (enicillin i a lacta, rin+ !ue% to a !ive3,e,"ere% rin+ containin+one S ato, an% one N ato,.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
12/4514-12
Cephalosporins
& T'e ce('alo(orin are alo 3lacta,
anti"iotic.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
13/4514-13
Characteristic Reactions
& Nucleophilic acyl substitution5 an a%%ition3
eli,ination e:uence reultin+ in u"titutiono! one nucleo('ile !or anot'er.- T'e reaction %e(en% on 'avin+ a uita"le
leavin+ +rou( ;/ "on%e% to t'e ac$l car"on.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
14/4514-14
Characteristic Reactions
- In t'e +eneral reaction on t'e (reviou creen) t'e
nucleo('ile a an anion< t'i nee% not "e t'e cae.- Neutral ,olecule uc' a *ater) alco'ol) a,,onia) an%
a,ine can alo erve a nucleo('ile.
- In t'e +eneral reaction) *e 'o*e% t'e leavin+ +rou( a
an anion to illutrate an i,(ortant (oint a"out t'e,5 t'e*ea4er t'e "ae) t'e "etter t'e leavin+ +rou(.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
15/4514-15
Characteristic Reactions
- Hali%e ion i t'e *ea4et "ae an% t'e "et
leavin+ +rou(. Aci% 'ali%e are) t'ere!ore) t'e,ot reactive to*ar% nucleo('ilic ac$l
u"titution.
-A,i%e ion i t'e tron+et "ae an% t'e (ooret
leavin+ +rou(< a,i%e) t'ere!ore) are t'e leat
reactive to*ar% nucleo('ilic ac$l u"titution.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
16/4514-16
Hydrolysis - Acid Chlorides
- Lo*3,olecular3*ei+'t aci% c'lori%e react ra(i%l$
*it' *ater to !or, a car"o#$lic aci% an% HCl.- Hi+'er ,olecular3*ei+'t aci% c'lori%e react le
rea%il$.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
17/4514-17
Hydrolysis - Acid Anhydrides
- Lo*3,olecular3*ei+'t aci% an'$%ri%e react
rea%il$ *it' *ater to +ive t*o ,olecule o!car"o#$lic aci%.
- Hi+'er3,olecular3*ei+'t aci% an'$%ri%e alo
react *it' *ater) "ut le rea%il$.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
18/4514-18
Hydrolysis - Esters
& Eter are '$%rol$0e% onl$ lo*l$) even in "oilin+ *ater.
& H$%rol$i "eco,e ,ore ra(i% i! t'e$ are 'eate% *it' eit'era:ueou aci% or a:ueou "ae.
& H$%rol$i in a:ueou aci% i t'e revere o! Fic'er
eteri!ication.
& T'e 4e$ te( in t'e ,ec'ani, o! '$%rol$i i !or,ation o!a tetra'e%ral car"on$l a%%ition inter,e%iate !ollo*e% "$ it
colla(e ee t'e ne#t creen !or %etail/.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
19/4514-19
Hydrolysis - Esters
- 8/ A%%ition o! a
(roton increae t'eelectro('ilic
c'aracter o! t'e
car"on$l car"on.
T'en !ollo*
- =/ Reaction o! a
nucleo('ile *it' an
electro('ile to !or, a
ne* covalent "on%
!ollo*e% "$ >/ (rotontran!er an% 2/
colla(e o! t'e TCAI
to e?ect a leavin+
+rou(.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
20/4514-20
Hydrolysis - Esters
& H$%rol$i o! an eter in a:ueou "ae i
o!ten calle% saponiication.- Eac' ,ole o! eter '$%rol$0e% re:uire 8 ,ole o!
"ae< !or t'i reaon) eter '$%rol$i in a:ueou
"ae i ai% to "e "ae (ro,ote%.
- Bae3(ro,ote% eter '$%rol$i involve
!or,ation o! a tetra'e%ral car"on$l a%%ition
inter,e%iate !ollo*e% "$ it colla(e.Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
21/45
14-21
Hydrolysis - Esters
- !tep "5 Reaction o! a nucleo('ile an% an electro('ile to
!or, a ne* covalent "on%.
- !tep #5 Colla(e o! t'e car"on$l a%%ition inter,e%iate to
e?ect a leavin+ +rou(.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
22/45
14-22
Hydrolysis - Esters
- !tep $5 Proton tran!er co,(lete t'e reaction.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
23/45
14-23
Hydrolysis - Esters
& T'ere are t*o ,a?or %i!!erence "et*een
aci%3catal$0e% an% "ae3(ro,ote% eter'$%rol$i.
8. For aci%3catal$0e% '$%rol$i) aci% i re:uire% in
onl$ catal$tic a,ount< !or "ae3(ro,ote%'$%rol$i) e:ui,olar a,ount o! eter an%
"ae are re:uire%.
=. H$%rol$i o! an eter in a:ueou aci% i
reveri"le< "ae3(ro,ote% '$%rol$i iirreveri"le "ecaue a car"o#$late anion i not
uce(ti"le to nucleo('ilic attac4.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
24/45
14-24
Hydrolysis - Amides
& H$%rol$i o! an a,i%e re:uire ,uc' ,ore
vi+orou con%ition t'an '$%rol$i o! an eter.- H$%rol$i in a:ueou aci% re:uire 8 ,ole o! aci% !or
eac' ,ole o! a,i%e.
- T'e (ro%uct are a car"o#$lic aci% an% an a,,oniu,
alt.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
25/45
14-25
Hydrolysis - Amides
- H$%rol$i o! an a,i%e in a:ueou "ae re:uire
8 ,ole o! "ae (er ,ole o! a,i%e.- T'e (ro%uct are a car"o#$late alt an% an
a,ine.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
26/45
14-26
Hydrolysis
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
27/45
14-27
Reaction %ith Alcohols
& Aci% c'lori%e react *it' alco'ol an%
('enol to +ive an eter an% HCl.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
28/45
14-28
Reaction %ith Alcohols
& Aci% an'$%ri%e react *it' alco'ol to +ive
one ,ole o! eter an% one ,ole o! car"o#$licaci%.
-A(irin i (re(are% "$ t'e !ollo*in+ reaction5
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
29/45
14-29
Reaction %ith Alcohols
& Eter un%er+o an e#c'an+e reaction calle%
transesteriication.- T'e e#c'an+e i aci% catal$0e%.
- T'e ori+inal 3OR +rou( i e#c'an+e% !or a ne*
3OR +rou(.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
HOOH
1,2-Ethandiol(Ethylene glycol)
OCH3
O
Methylbenzoate
+2
H2SO4O
O
O
O
(A diete! o" ethylene glycol)
+ 2CH3OH
-
7/24/2019 Ch14 Deriv. of Carb. Acids
30/45
14-30
Reaction %ith Alcohols
& A,i%e %o not react *it' alco'ol un%er an$
con%ition.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
31/45
14-31
Reaction %ith NH$and Amines
& Aci% 'ali%e react *it' a,,onia) 8@ an% =@
a,ine to !or, a,i%e.- t*o ,ole o! t'e a,ine are re:uire% (er ,ole o!
aci% c'lori%e< one to !or, t'e a,i%e an% one to
neutrali0e t'e HCl "$(ro%uct.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
-
7/24/2019 Ch14 Deriv. of Carb. Acids
32/45
14-32
Reaction %ith NH$and Amines
& Aci% an'$%ri%e react *it' a,,onia) 8@ an%
=@ a,ine to !or, a,i%e.- t*o ,ole o! a,,onia or a,ine are re:uire%