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Carboxylic acids:

O R-COOH, R-CO2H, R C OH

Common names: HCO2H CH3CO2H CH3CH2CO2H CH3CH2CH2CO2H CH3CH2CH2CH2CO2H formic acid acetic acid L. formica ant L. acetum vinegar

propionic acid G. first salt butyric acid valeric acid L. butyrum butter L. valerans

Carboxylic acids, common names: CH3(CH2)4CO2H CH3(CH2)5CO2H CH3(CH2)6CO2H CH3(CH2)7CO2H CH3(CH2)8CO2H CH3(CH2)9CO2H CH3(CH2)10CO2H caproic acid --caprylic acid --capric acid --lauric acid oil of lauryl L. caper goat

5 4 3 2 1 CCCCC=O used in common names


Br CH3CH2CH2CHCOOH CH3 CH3CHCH2COOH

E bromovaleric acid

F -methylbutyric acid
isovaleric acid

COOH benzoi i

special names

COOH CH3

COOH

COOH

CH3 CH3
o ol i

m ol i

p ol i

IUPAC nomenclature for carboxylic acids: parent chain = longest, continuous carbon chain that contains the carboxyl group alkane, drop e, add oic acid HCOOH CH3CO2H CH3CH2CO2H CH3 CH3CHCOOH Br CH3CH2CHCO2H methanoic acid ethanoic acid propanoic acid

2-methylpropanoic acid

2-bromobutanoic acid

dicarboxylic acids: HOOC-COOH HO2C-CH2-CO2H HO2C-CH2CH2-CO2H HO2C-CH2CH2CH2-CO2H HOOC-(CH2)4-COOH HOOC-(CH2)5-COOH Oh, my! Such good apple pie! oxalic acid malonic acid succinic acid glutaric acid adipic acid pimelic acid

CO2H CO2H phthali aci

CO2H

CO2H

CO2H CO2H i ophthalic aci terephthalic aci

H H

C C

COOH COOH

H HOOC

C C

COOH H

maleic aci

f maric aci

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

HO

O C

OH

HO

O C

ONa

carbonic aci

odi m bicarbonate sodi m hydrogen carbonate NaHCO3

NaO

O C

ONa

sodi m carbonate Na2CO3

physical properties: polar + hydrogen bond water insoluble exceptions: four carbons or less acidic turn blue litmus red relatively high mp/bp

soluble in 5% NaOH

RCO2H + NaOH
stronger acid stronger base

RCO2-Na+ + H2O
weaker base weaker acid

RCO2H covalent water insoluble

RCO2ionic 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 2. oxidation of arenes ArR + KMnO4, heat ArCOOH RCOOH

3. carbonation of Grignard reagents RMgX + CO2 4. hydrolysis of nitriles RCN + H2O, H+, heat RCOOH RCO2MgX + H+ RCOOH

1. oxidation of 1o alcohols:

CH3CH2CH2CH2-OH + CrO3
n-butyl alcohol 1-butanol

CH3CH2CH2CO2H
butyric acid butanoic acid

CH3 CH3CHCH2-OH + KMnO4


isobutyl alcohol 2-methyl-1-propanol`

CH3 CH3CHCOOH
isobutyric acid 2-methylpropanoic acid

2. oxidation of arenes:
CH3 tol ene 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

3. 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 CH3CH2CH2MgBr CO2 H+ CH3CH2CH2COOH butyric acid
H+ +
+

RMgX +

O C O

O R C O-

MgX

O R C OH

CH3

CH3 C
2

CH3 H+

Br

MgBr

p-toluic acid Br2, hv CH3 CH2Br C H+ Mg CH2MgBr

CH2 C phenylacetic acid

4. Hydrolysis of a nitrile: H2O, H+ R-C|N heat H2O, OHR-C|N heat R-X + NaCN
1o alkyl halide

R-CO2H

R-CO2- + H+

R-CO2H

R-CN + H+, H2O, heat

RCOOH

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

CH3 toluene

Br2, hv

aCN CH2Br CH2 CN H2 , H+, heat

CH2 C

phenylacetic acid CN CH3CH2CH2CH2CH2CH2-Br 1-bro ohexane H2 , H+, heat CH3CH2CH2CH2CH2CH2-CN

CH3CH2CH2CH2CH2CH2-C heptanoic acid

CH2 H Mn
4

CH3 Mn
4,

heat C
2H

Br

Mg

MgBr C
2;

then H+

C N H2 , H+, heat

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

3. reduction 4. alpha-halogenation 5. EAS

as acids: a) with active metals RCO2H + Na b) with bases RCO2H + NaOH c) relative acid strength? CH4 < NH3 < HC|CH < ROH < HOH < H2CO3 < RCO2H < HF d) quantitative HA + H2O ' H3O+ + AKa = [H3O+] [A-] / [HA] ionization in water RCO2-Na+ + H2O RCO2-Na+ + H2(g)

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-T S

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.

H3

+ A-

potential energy

HA + H2

ionization

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 Cl2CHCOOH Cl3CCOOH

1.75 x 10-5 136 x 10-5 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 p-methoxybenzoic acid p-toluic acid benzoic acid p-chlorobenzoic acid p-nitrobenzoic acid 1.4 x 10-5 2.6 x 10-5 3.3 x 10-5 4.2 x 10-5 6.3 x 10-5 10.3 x 10-5 36 x 10-5

2. Conversion into functional derivatives: a) acid chlorides


O R C OH SOCl2 or PCl3 orPCl5 O R C Cl

CO2H + SOCl2

COCl

O CH3CH2CH2 C OH

PCl3 CH3CH2CH2 C

O Cl

b)

esters H+

direct esterification:

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 + R OH RCO2R

-convert the acid into the acid chloride first; not reversible

O C OH SOCl2

H+ + CH3OH

O + H2O C O CH3

O C Cl

CH3OH

c)

amides

indirect only! RCOOH + SOCl2


O PCl3 OH 3-Methylbutanoic acid

RCOCl + NH3
O Cl NH3

RCONH2 amide
O NH2

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

O C OH

PCl3

O C Cl

NH3

O C NH2 amide

NH3

O C O

NH4

ammoni m salt

3. Reduction: RCO2H + LiAlH4; then H+ RCH2OH 1o alcohol


H+

CH3CH2CH2CH2CH2CH2CH2COOH Octanoic acid (Caprylic acid)

Li lH4

CH3CH2CH2CH2CH2CH2CH2CH2OH 1-Octanol

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

O CH2 C OH LiAlH4 H+

H2, Pt

NR

CH2CH2OH

4. Alpha-halogenation: (Hell-Volhard-Zelinsky reaction) RCH2COOH + X2, P RCHCOOH + HX X -haloacid

X2 = Cl2, Br2

CH3CH2CH2CH2COOH pentanoic acid

Br2,P

CH3CH2CH2CHCOOH Br 2-bromopentanoic acid

COOH Br2,P NR (no alpha H)

RCH2COOH + Br2,P

RCHCOOH + HBr
+

nH e ;th OH Na
RCHCOOH OH

Br NH3 RCHCOOH NH2

aminoacid

KOH(alc) RCH2CHCOOH Br then H+ RCH=CHCOOH

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

Carboxylic acids, syntheses: 1. oxidation of primary alcohols RCH2OH + K2Cr2O7 2. oxidation of arenes ArR + KMnO4, heat ArCOOH RCOOH

3. carbonation of Grignard reagents RMgX + CO2 4. hydrolysis of nitriles RCN + H2O, H+, heat RCOOH RCO2MgX + H+ RCOOH

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

3. reduction 4. alpha-halogenation 5. EAS