Ch14 Deriv. of Carb. Acids

7/24/2019 Ch14 Deriv. of Carb. Acids

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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.


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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.


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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.



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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.



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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%.



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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.



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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.



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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.



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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.



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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/.



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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,.



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Cephalosporins

& T'e ce('alo(orin are alo 3lacta,

anti"iotic.



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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.



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- 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(.



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- 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.



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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$.



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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$.



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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/.



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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(.



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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.


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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(.



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Hydrolysis - Esters

- !tep $5 Proton tran!er co,(lete t'e reaction.



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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.



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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.



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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.



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14-26

Hydrolysis



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14-27

Reaction %ith Alcohols

& Aci% c'lori%e react *it' alco'ol an%

('enol to +ive an eter an% HCl.



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14-28


& 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



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& 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(.


HOOH

1,2-Ethandiol(Ethylene glycol)

OCH3

O

Methylbenzoate

+2

H2SO4O

O

O

O

(A diete! o" ethylene glycol)

+ 2CH3OH


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14-30


& A,i%e %o not react *it' alco'ol un%er an$

con%ition.



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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.



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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%

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Ch14 Deriv. of Carb. Acids

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