Carboxylic acids:

R-COOH, R-CO2H,

O R C OH

Common names:
HCO2H CH3CO2H formic acid acetic acid L. formica ant L. acetum vinegar

CH3CH2CO2H
CH3CH2CH2CO2H CH3CH2CH2CH2CO2H

propionic acid G. first salt

butyric acid valeric acid L. butyrum butter L. valerans

Carboxylic acids, common names:

CH3(CH2)4CO2H CH3(CH2)5CO2H caproic acid --L. caper goat

CH3(CH2)6CO2H
CH3(CH2)7CO2H CH3(CH2)8CO2H CH3(CH2)9CO2H CH3(CH2)10CO2H

caprylic acid
--capric acid --lauric acid oil of lauryl

5 4 3 2 1 CCCCC=O
B r C H C H C H C H C O O H 3 2 2

used in common names

C H 3 C H C H C H C O O H 3 2

b r o m o v a le r ica c id

m e th y lb u ty r ica c id
is o v a le r ica c id

C O O H

special names
be n zo ic acid

C O O H C H 3

C O O H

C O O H

C H 3 C H 3 o -to lu ic a cid m -to lu ic a cid p-to luic a cid

IUPAC nomenclature for carboxylic acids: parent chain = longest, continuous carbon chain that contains the carboxyl group alkane, drop e, add oic acid HCOOH methanoic acid

CH3CO2H
CH3CH2CO2H CH3 CH3CHCOOH

ethanoic acid
propanoic acid

2-methylpropanoic acid

Br CH3CH2CHCO2H

2-bromobutanoic acid

dicarboxylic acids:
HOOC-COOH HO2C-CH2-CO2H oxalic acid malonic acid

HO2C-CH2CH2-CO2H
HO2C-CH2CH2CH2-CO2H HOOC-(CH2)4-COOH HOOC-(CH2)5-COOH Oh, my! Such good apple pie!

succinic acid
glutaric acid adipic acid pimelic acid

C O H 2 C O H 2 p h th a lic a c id

C O H 2

C O H 2

C O H 2 C O H 2 is o p h th a lic a c id te re p h th a lic a c id

H H

C C

C O O H C O O H

H H O O C

C C

C O O H H

m a le ic a c id

fu m a ric a c id

salts of carboxylic acids:

name of cation + name of acid: drop ic acid, add ate

CH3CO2Na

sodium acetate or sodium ethanoate

CH3CH2CH2CO2NH4

ammonium butyrate

ammonium butanoate

(CH3CH2COO)2Mg

magnesium propionate

magnesium propanoate

O C H O O H c a r b o n ica c id

O C H O O N a s o d iu m b ic a r b o n a te s o d iu m h y d r o g e nc a r b o n a te N a H C O 3

O C N a O O N a s o d iu m c a r b o n a te N a C O 2 3

physical properties:

polar + hydrogen bond relatively high mp/bp

water insoluble exceptions: four carbons or less acidic turn blue litmus red

soluble in 5% NaOH

RCO2H + NaOH RCO2-Na+ + H2O

stronger acid stronger base weaker base weaker acid

RCO2H

RCO2-

covalent water insoluble

ionic water soluble

Carboxylic acids are insoluble in water, but soluble in 5% NaOH.

1. Identification.

2. Separation of carboxylic acids from basic/neutral organic compounds.

The carboxylic acid can be extracted with aq. NaOH and then regenerated by the addition of strong acid.

Carboxylic acids, syntheses:

1. oxidation of primary alcohols

RCH2OH + K2Cr2O7 RCOOH 2. oxidation of arenes ArR + KMnO4, heat ArCOOH 3. carbonation of Grignard reagents

RMgX + CO2 RCO2MgX + H+ RCOOH

4. hydrolysis of nitriles

RCN + H2O, H+, heat RCOOH

1. oxidation of 1o alcohols:

CH3CH2CH2CH2-OH
n-butyl alcohol 1-butanol

CrO3 CH3CH2CH2CO2H
butyric acid butanoic acid

CH3 CH3CHCH2-OH
isobutyl alcohol 2-methyl-1-propanol`

+ KMnO4

CH3 CH3CHCOOH
isobutyric acid 2-methylpropanoic acid

1. oxidation of arenes:
CH3 toluene KMnO4, heat COOH benzoic acid

CH3

KMnO4, heat

COOH

note: aromatic acids only!

H3C p-xylene

HOOC terephthalic acid

KMnO4, heat CH2CH3 ethylbenzene COOH + CO2 benzoic acid

1. carbonation of Grignard reagent: Mg R-X RMgX CO2 RCO2MgX H+ RCOOH

Increases the carbon chain by one carbon.

Mg CH3CH2CH2-Br n-propyl bromide
O R M g X+ C O

CO2 H+ CH3CH2CH2MgBr CH3CH2CH2COOH butyric acid

+ H

O R C O

++ M g X

O R C O H

CH3 Mg

CH3 CO2 H+

CH3

Br

MgBr

COOH p-toluic acid

Br2, hv CH3 CH2Br

Mg CH2MgBr CO2 H+

CH2 COOH phenylacetic acid

1. Hydrolysis of a nitrile: H2O, H+ R-CO2H heat R-CN H2O, OHheat R-X + NaCN R-CN + H+, H2O, heat RCOOH
1o alkyl halide

R-CN

R-CO2- + H+ R-CO2H

Adds one more carbon to the chain. R-X must be 1o or CH3!

C H 3 to lu e n e

B r2, h v

N a C N C H B r 2 C H N 2C H O ,H + ,h e a t 2

C H O O H 2C p h e n yla c e tic a c id K C N C H C H C H C H C H C H -B r 3 2 2 2 2 2 1 -b ro m o h e xa n e H O ,H + ,h e a t 2 C H C H C H C H C H C H -C N 3 2 2 2 2 2

C H C H C H C H C H C H -C O O H 3 2 2 2 2 2 h e p ta n o ic a cid

CH 2 OH KMnO 4

CH 3 KM nO 4 , heat CO 2 H

Br

Mg

MgBr CO 2 ; then H +

C N H 2 O, H+, heat

carboxylic acids, reactions: 1. as acids 2. conversion into functional derivatives a) acid chlorides b) esters c) amides

1. reduction
2. alpha-halogenation 3. EAS

as acids:

a) with active metals

RCO2H + Na RCO2-Na+ + H2(g) a) with bases

RCO2H + NaOH RCO2-Na+ + H2O

a) relative acid strength? CH4 < NH3 < HCCH < ROH < HOH < H2CO3 < RCO2H < HF a) quantitative HA + H2O H3O+ + Aionization in water

Ka = [H3O+] [A-] / [HA]

Ka for carboxylic acids 10-5

Why are carboxylic acids more acidic than alcohols?

ROH + H2O H3O+ + RORCOOH + H2O H3O+ + RCOOGo = -2.303 R T log Keq The position of the equilibrium is determined by the free energy change, Go. Go = H - TS Go H Ka is inversely related to H, the potential energy difference between the acid and its conjugate base. The smaller the H, the larger the Ka and the stronger the acid.

+ + A H O 3

potential energy

H A + H O 2

io n iz a tio n

The smaller the H, the more the equilibrium lies to the right, giving a larger Ka ( a stronger acid ).

O R C O-

OR C O

O R C O
Resonance stabilization of the carboxylate ion decreases the H, shifts the ionization in water to the right, increases the Ka, and results in carboxylic acids being stronger acids.

Effect of substituent groups on acid strength?

CH3COOH ClCH2COOH

1.75 x 10-5 136 x 10-5

Cl2CHCOOH
Cl3CCOOH

5,530 x 10-5
23,200 x 10-5

-Cl is electron withdrawing and delocalizes the negative charge on the carboxylate ion, lowering the PE, decreasing the H, shifting the ionization to the right and increasing acid strength.

Effect of substituent groups on acid strength of benzoic acids?

Electron withdrawing groups will stabilize the anion, decrease the H, shift the ionization to the right, increasing the Ka, increasing acid strength.
COOG

Electron donating groups will destabilize the anion, increase the H, shift the ionization in water to the left, decreasing the Ka, decreasing acid strength.

COOG

-NH2, -NHR, -NR2 -OH -OR -NHCOCH3 -C6H5 -R -H -X -CHO, -COR -SO3H -COOH, -COOR -CN -NR3+ -NO2

electron donating

electron withdrawing

Relative acid strength?

Ka
p-aminobenzoic acid p-hydroxybenzoic acid 1.4 x 10-5 2.6 x 10-5

p-methoxybenzoic acid
p-toluic acid benzoic acid p-chlorobenzoic acid p-nitrobenzoic acid

3.3 x 10-5
4.2 x 10-5 6.3 x 10-5 10.3 x 10-5 36 x 10-5

1. Conversion into functional derivatives: a) acid chlorides

O RC O H S O C l2 o rP C l3 o rP C l5 O RC C l

C O H + S O C l2 2

C O C l

O C H C H C H 3 2 2C O H

P C l3

O C H C H C H 3 2 2C C l

a) esters direct esterification: H+

RCOOH + ROH RCO2R + H2O -reversible and often does not favor the ester

-use an excess of the alcohol or acid to shift equilibrium

-or remove the products to shift equilibrium to completion

indirect esterification: RCOOH + PCl3 RCOCl + ROH RCO2R -convert the acid into the acid chloride first; not reversible

O C + C H O H 3 O H S O C l 2

+ H

O +H O C 2 OC H 3

O C C l

C H O H 3

a) amides

indirect only!
RCOOH + SOCl2 RCOCl + NH3 RCONH2 amide
O P C l 3 O C l N H 3 O N H 2 O H 3 M e t h y l b u t a n o i c a c i d

Directly reacting ammonia with a carboxylic acid results in an ammonium salt: RCOOH + NH3 RCOO-NH4+ acid base

O C O H

P C l 3

O C C l

N H 3

O C N H 2 a m i d e

N H 3

O C O N H 4

a m m o n i u m s a l t

1. Reduction:

RCO2H + LiAlH4; then H+ RCH2OH 1o alcohol

L i A l H 4 C H C H C H C H C H C H C H C O O H 3 2 2 2 2 2 2 O c t a n o i c a c i d ( C a p r y l i c a c i d ) 1 O c t a n o l
+ H

C H C H C H C H C H C H C H C H O H 3 2 2 2 2 2 2 2

Carboxylic acids resist catalytic reduction under normal conditions. RCOOH + H2, Ni NR

O CH2 C OH LiAlH4 H+

H2, Pt

NR

CH2CH2OH

1. Alpha-halogenation: (Hell-Volhard-Zelinsky reaction)

RCH2COOH + X2, P RCHCOOH + HX X -haloacid X2 = Cl2, Br2

C H C H C H C H C O O H+ B r , P 3 2 2 2 2 p e n t a n o i c a c i d

C H C H C H C H C O O H 3 2 2 B r 2 b r o m o p e n t a n o i c a c i d

C O O H B r , P 2 N R( n o a l p h a H )

R C H C O O H + B r2 ,P 2

R C H C O O H + H B r
+

H n e h t ; H O a N
R C H C O O H O H

B r N H 3 R C H C O O H N H 2

a m in o a c id

K O H (a lc ) R C H C H C O O H 2 B r
+ th e nH

R C H = C H C O O H

5. EAS: (-COOH is deactivating and meta- directing)

CO2H HNO3,H2SO4 NO2 CO2H CO2H H2SO4,SO3 SO3H CO2H benzoic acid Br2,Fe Br CH3Cl,AlCl3

NR

spectroscopy:

IR: -COOH

OH stretch 2500 3000 cm-1 (b) C=O stretch 1680 1725 (s)

nmr: -COOH

10.5 12 ppm

p-toluic acid

-COOH stretch

C=O

COOH c b CH3 a