matriculation chemistry carboxylic acid.pdf

8/12/2019 Matriculation Chemistry Carboxylic Acid.pdf

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2

C OHR

O

RCOOH or RCO 2H

(R alkyl, aryl or H)

Structure


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3

NOMENCLATURE


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4

HCOOHMethanoic acid

Formic acid

CH 3COOHEthanoic acid

Acetic acid

CH 3CH 2COOHro!anoic acid

ro!ionic acid

CH 3CH 2CH 2COOH

"#tanoic acid"#tyric acid

CH 3CH 2CH 2CH 2COOH

entanoic acid$aleric acid

IUPAC Nomenclature Common Name


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%

&'he lon e t chain m# t contain the car*o+yl ro#!

&'he car!o"#l $rou% i at the terminal, there-ore the car*ono- the car*o+yl ro#! i not n#m*ered

One COOH . car*o+yl ro#! i at one end '/o COOH . car*o+yl ro#! are at *oth end

&0ame the com!o#nd a alkane, &ro% 'e( )n al*ane an&

a&& 'o)c ac)&( (e methan o)c ac)& )

IUPAC Nomenclature


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4 *romo 3 methyl!entanoic acid

% hydro+yhe+anoic acid

CH CHCH 2 CH CH +COH

O CH+

% methyl 3 he+enoic acid

CH CH2

CH C OH

O

CH+

Br CH +

CH2 CH2CH2 C OH

O

CHOH

CH+


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6

C C

H

CH 2 H

CH 2 COOH

HOOC

tran 3 he+enedioic acid

CH 2 CH 2CH C OH

O

CH 2COH

O CH +

3 methylhe+anedioic acid


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7

& 8hen R i an ar#l $rou% , the !arent name i !en,o)cac)&

COOHCl

4 chloro*en9oic acid


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1:

CH

CH +

CH +

HOOC

COOH

HOOC

COOH

1,3 *en9enedicar*o+ylic acid

2 i o!ro!yl 1,4 *en9enedicar*o+ylic acid

& An aromat)c &)car!o"#l)c ac)& )- name& a-1,x-benzenedicarboxylic acid


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& A cyclic car*o+ylic acid i named a cycloalkanecarboxylicacid

& 'he C atom /hich i attached to ;COOH i n#m*ered aC1

COOH

cyclo!entanecar*o+ylic acid

.


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12

COOH

CH +

Br

4 *romo 2 methylcyclohe+anecar*o+ylic acid

.

COOH

cyclohe+anecar*o+ylic acid

.


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13

COOH

COOH

COOH

COOHCl

1,2 cyclohe+anedicar*o+ylic acid

4 chloro 1,2 cyclohe+anedicar*o+ylic acid

A c#cl)c &)car!o"#l)c ac)& )- name& a-1,x-cycloalkanedicarboxylic acid


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14

COOH

CH +

3 methyl 2 cyclohe+enecar*o+ylic acid

&8hen a com!o#nd contain a car*o+yl ro#! and other-#nctional ro#!( ), the !riority i i


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1%

PHYSICAL PROPERTIES O/

CARBOXYLIC ACIDS


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1

Bo)l)n$ Po)nt'he *oilin !oint o- car*o+ylic acid i hi her than an alcohol, aketone or an aldehyde (/ith M r that almo t the ame) *eca# e

i it e+i t a ta*le &)mer- that -orm hydro en *ondii molec#le in dimer are arran ed clo-el# %ac*e& ,

there-ore the hydro en *ond are relati


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1

C

O

O

R

H

C

O

O

R

H

H#&ro$en !on&

H#&ro$en !on&


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16

C

O

O

R

H

O

H

H

C

O

O

R

H

O H

H

Solu!)l)t#a0 Solu!)l)t# )n 1ater

& Car*o+ylic acid are ol#*le in /ater d#e to the-ormation o- #&ro$en !on& !et1een t e 1ater

molecule- an& car!o"#l)c ac)& molecule-3H#&ro $en Bon&-


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& T e -olu!)l)t# o4 car!o"#l)c ac)& )n 1ater )- almo-t t e -ame a- alco ol3

& Al)% at)c car!o"#l)c ac)&- 1)t C 5 6 are )n-olu!le )n 1ater3 S),e o4 R 78#&ro% o!)c area 73

R C OH

O

hydrophilic

hydrophobic


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2:

& Aromat)c car!o"#l)c ac)&- are -l)$ tl# -olu!le )n1ater &ue to t e u$e aromat)c r)n$3

& D)car!o"#l)c ac)&- are relat)9el# more -olu!le -)ncemore #&ro$en !on&- are 4orme&3


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E+am!le =e cendin order o- ol#*ility

CH CH 2 CH 2CH +

COOH COOH

CH 2 CH 2 CH 2CH +

COOH

CH + CH2 CH2

COOH

COOH

5 5

5


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22

* Solu!)l)t# )n non %olar -ol9ent

& Car*o+ylic acid are ol#*le in non !olar ol


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23

Ac)&)t# o4 Car!o"#l)c Ac)&

& T e ac)&)t# o4 car!o"#l)c ac)& )- )n4luence& !#; )3 Re-onance e44ect ))3In&uct)9e e44ect


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Car*o+ylate ion

heno+ide ion

R C O3

O

O3

Re-onance E44ect


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2%

& Car*o+ylic acid are more acidic d#e to the re-onance-ta!)l)-at)on o4 t e car!o"#late )on

& 'he electron )n car!o"#late )on are delocali ed!et1een t1o o"#$en atom-8 /herea )n % eno")&e)on , the electron are delocali9ed )n t e !en,ene r)n$3

& 'he C


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2

& Car*o+ylic acid i relat)9el# a 1ea* ac)&8 ho/e

OH

> OH 2 > R OH


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2

OH O=

>H+O >

phenoxide ion(resonance structure)

> H 2O

phenol

CR

O

OH

> H 2O > H +O >

carboxylate ion(resonance structure)

CR

O

O =

CR

O=

Ocarboxylic acid

R?O?H > H 2O R?O @ > H +O > alkoxide ionalcohol


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In&uct)9e E44ect

An electron /ithdra/inro#! (deacti


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i. The inductive effectelectron-withdrawing group in the

co pound & electron /ithdra/in ro#!

e3$ @NO2 8=/8=Cl8=Br8 =I 0 red#ce the electronden ity o-

.O H

&'h# the O=H !on& *ecome 1ea*er and H> can*e ea-)l# relea-e&

&'he com!o#nd i aid to *e more acidic Electron= /ithdra/in ro#! )ncrea-e- theac)&)t#


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3:

& E"am%le;CH +CHCl=COOH an& CH +CH 2COOH

& Cl i an electron= /ithdra/in $rou%-8 there-ore re&uce t eelectron &en-)t# o4 @OH3

& 'h# the O=H !on& *ecome 1ea*er and H>

can *e ea-)l#relea-e&

& Ac)&)t# ;

. CH +CHCl=COOH > CH +CH 2COOH

& Electron= /ithdra/in ro#! )ncrea-e the ac)&)t#


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& E"am%le;CH +CH/=COOH an& CH +CHCl=COOH

& Bot / an& Cl are electron=attract)n$ $rou%3

& 'he electrone$at)9)t# o- / 5 Cl

& 'he electron &en-)t# o4 @OH in CH +CH/=COOH )- le-- ,

th# the @OH !on& )- 1ea*er than inCH +CHCl=COOH 'here-ore, H> )- ea-)l# &onate&3

& Ac)&)t# ; CH +CH/=COOH 5 CH +CHCl=COOH

ii) The electronegativity of electron- withdrawing group in the co pound


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& E"am%le;CH +C Cl02=COOH an& CH +CHCl=COOH

& CH +C Cl02=COOH conta)n- 2 Cl atom- that make the*ond o- @OH 1ea*er than CH 3CHCl COOH (/ith onl#one Cl atom ) T u-8 H > )- ea-)l# &onate&3

& Ac)&)t# ; CH +C Cl02=COOH 5 CH +CHCl=COOH

iii) !u ber of electron-attracting group inthe co pound.


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& E"am%le;CH +COOH an& CH +CH 2COOH

& =R i an electron @relea-)n$ $rou%3

& 'he -),e o- .R ro#! in CH 3CH 2COOH i lar er than inCH 3COOH, o CH 3CH 2 i a -tron$er relea in ro#!than CH 3

& 'he electron den ity o- .OH in CH +CH 2COOH)ncrea-e- and H> )- &)44)cult to !e &onate&3

Electron=relea-)n$ $rou%- re&uce t e ac)&)t# o4 acar!o"#l)c ac)&3

(v ) The inductive effect of electron- releasing(electron-donating) group in the co pound


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3%

SYNTHESIS O/

CARBOXYLIC ACIDS


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3

C OHR

H

H

C O

R

H

C O

R

OH

oxidizingagent

oxidizingagent

1 o alcohol aldehyde carboxylic acid

Common o+idi9in a ent are ;& MnO H2SO

!ota i#m !erman anate

& 2Cr 2O F G Na 2Cr 2O F H2SO

!ota i#m ? odi#m dichromat ($@)

.3 O")&at)on o4 %r)mar# alco ol an& al&e #&e


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3

23 O")&at)on o4 Al*#l Ben,ene

Roxidizing

agent COOH

MnO 8 H>

> CO 2 > H 2O

COOH

Cl

CH

CH +

CH +

Cl


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+3 /ormat)on an& H#&rol#-)- o4 n)tr)le

R CH 2 X NaCN R CH 2 CN H2O8H> R CH 2 COOH

NaCN H2O8H>

CH 2 CNCH 2 Br CH 2 COOH


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3 Car!onat)on o4 r)$nar& Rea$ent-

R?M$X O C O

CO 2H2O8 H>

R?COOH > M$ OH0X

CH 2 M$Br

H2O8 H>

CH 2 COOH

> M$ OH0Br


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& Main reaction o- car*o+ylic acid,

a 'he reaction that in


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a3 T e react)on t at )n9ol9e- t e &onat)on o4H> 4rom @OH $rou%

.3 Neutral)-at)on& Car*o+ylic acid are acidic, it can react /ith *a e #ch a

0aOH (aB) to i Na OH CR

O

O=

Na>

> H 2O


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> Na OH > H 2O

COOH COO @Na >

So&)um !en,oate


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23 React)on 1)t electro%o-)t)9e metal- -uc a- Na88 Ca8 M$ an& /e3

R C OH

O

R C O

O

M H 2M

E"erc)-e;

C

OH

OCl

D


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4%

!3 T e react)on t at )n9ol9e- t e -u!-t)tut)ono4 @OH $rou% to 4orm )t- &er)9at)9e-0

.3 Ac)& c lor)&e 4ormat)on Acid chloride can *e !re!ared -rom the reaction o-

car*o+ylic acid /ith thionyl chloride, SOCl 2 !ho !horo#!entachloride, PCl 6 !ho !horo# trichloride, PCl +

R C OH

O

R C Cl

O

R C Cl

O

R C Cl

O

> SO 2 > HCl

> POCl + > HCl

> H +PO +

SOCl 2

PCl 6

PCl +


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4

> H? OR(C OHR

O

C OR RI

O

> H 2OH>

23 E-ter)4)cat)onCar*o+ylic acid react /ith alcohol in the !re ence o- miner

acid cataly t to !rod#ce e-ter-3

> H OCH2CH

+

H> CH 2 CCH + OCH 2

O

CH +CH2

CCH+

OH

O

> H 2O

carboxylic acid alcohol ester

propanoic acid ethanol ethyl propanoate


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46

+3 Ac)& an #&r)&e 4ormat)on Acid anhydride can *e !re!ared -rom car*o+ylic acid *y

the lo o- /ater thro# h heatin

R C OH

O

RCOH

O

> heat

CH + C O C CH +

O O

R C O C R

O O

> H 2O

CH + C OH

O

CH + C OH

O

> heat

> H 2O

ethanoic anhydride

acid anhydride


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47

3 Am)&e- 4ormat)on Reaction o- car*o+ylic acid /ith an

ammonia or amine i H 2O

> H 2O

> H 2O

1 o a ide

" o a ide(1 o a ine)

(" o a ine) (# o a ide)


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%:

CH C Cl

OCH +

CH +

CH + NH 2

CH + NHCH +

NH+E+erci e


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%1

c3 T e react)on t at )n9ol9e- t e re&uct)on 1)tL)AlH to %r)mar# alco ol

Car*o+ylic acid are red#ced to !rimary alcohol *yreaction /ith lithi#m al#mini#m hydride, iAlH 4

C OR RI

O

L)AlHet er CH 2 OHR

1 o alcohol > R(OH

C O CH 2CH CH +CH +

O

CH +

L)AlHet er CH 2 OHCHCH +

CH +

> HO?CH 2CH +

$ $


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%2

Met ano)c ac)&8 HCOOH a- a re&uc)n$ a$ent

& Methanoic acid molec#le, ha *othC OHH

O

C OH

O

and

& @t ho/ the !ro!ertie o- *oth car*o+ylic acid and aldehyde

& @t al o ho/ red#cin !ro!ertie in reaction /ith acidi-iedDMnO 4 or D 2Cr 2O and 'ollen 5 rea ent

C

O

H

car!o"#l)ccar!on#l


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%3

C OHH

OMnO H>

CO 2 > H 2O > MnO 2

A$ NH+02>

A$ > CO 2 > H 2O

( $rown )


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%4

DERIVATIVES O/CARBOXYLIC ACIDS

R C Cl

O

acid chloride

O CC RR

O O

acidanhydride

R C NH2

O

a ide C OR RI

O

ester


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%%

React)on- o4 car!o"#l)c ac)& &er)9at)9e-

)3 H#&rol#-)- o4 ac)& c lor)&e-

R C Cl

O

H2O R C OH

O

> HClacid chloride carboxylic acid

))3 H#&rol#-)- o4 ac)& an #&r)&e-

O CC RR

O OH2O

carboxylic acid

2 C OHR

O

acidanhydride


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%


)))3 H#&rol#-)- o4 e-ter-

H2OH>

carboxylic acid

> RO H

H2ONaOH > RO H

alcohol

alcohol Na >C O

=R

OC ORR

O

ester

R C OH

O


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%


)))3 H#&rol#-)- o4 am)&e ac)&)c #&rol#-)-0

R C NH2

OH2OH>

R C OH

ONH >

a ide %arboxylicacid

& oniu ion


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%6


)))3 H#&rol#-)- o4 am)&e al*al)ne #&rol#-)-0

R C NH2

OH2OOH = NH+

a idea onia

R C O3

O

%arboxylate ion


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%7


)))3 H#&rol#-)- o4 am)&e al*al)ne #&rol#-)-0

= )4 &)lute ac)& )- a&&e& to t e car!o"#late -alt8 t e car!o"#l)c ac)& are 4orme&3

%arboxylic acid

R C O3

O

%arboxylate ion

H> R C OHO


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1

ethyl ethanoate

H2OH>

E+am!le

C O CH +CH +

O


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2

& 'he reacti


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3

Cl @ J RCOO @ J RO @ J HO @ J NH 2 @

Relat)9e !a-)c)t)e- o4 t e lea9)n$ $rou% -u!-t)tuent0

acid chloride

acid anhydride

ester carboxylic acid

a ide

react)9)t# )ncrea-e-

R C Cl

O

C O CR

O

R

O

C ORR

O

R C NH 2

O

R C OH

O

8 8 8 8


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4

ACYL CHLORIDE

& Ac#l c lor)&e )- t e mo-t react)9e *eca# e o- it

electro%o-)t)9e car!on#l $rou% i attac to the

electrone$at)9e Cl atom (/hich i a relea in ro#!)


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%

ANHYDRIDE ACID

& An #&r)&e ac)& )- more react)9e t an e-ter an&am)&e *eca# e the car*o+yl ro#! o- anhydride iattached to the car*onyl car*on

& 'hi make the car*onyl car*on *ecome moreelectro!o iti


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ESTER

& E-ter )- le-- react)9e to/ard n#cleo!hile *eca# e the&elocal),at)on o- electron make the !o iti


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AMIDE

& Am)&e )- t e lea-t react)9e *eca# e, NH2 ro#! i anelectron=&onat)n$ ro#! that make the car*onyl le--electro%o-)t)9e

& 'he re-onance -tructure o- amide ho/ that thecar!on#l car!on )- not electro%o-)t)9e3

0

R

O H

H

0

R

O H

H


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'he G e o- Car*o+ylic Acid

Car*o+ylic acid ? deri

matriculation chemistry carboxylic acid.pdf

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