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Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

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Page 1: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Carboxylic acidand carboxylic acid

derivatives

Dr. Nabila Al Jaber

Page 2: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Carboxylic acid R-COOH Ar-COOH Aliphatic (carboxylic cid) aromatic (benzoic acid)

1) replace ane by -ic acid

Nomenclature :

Common IUPAC Formula No. C

Formic acidAcetic acidPrpionic acidButyric acidvaleric acid

Salicylic acid

Benzoic acid

Methanoic acidEthanoic acidPrpanoic acidButanoic acidPentanoic acid

2-hydroxy ben. a

HCOOHCH3COOH

CH3CH2COOH

CH3(CH2)2COOH

CH3(CH2)3COOH

12345

OH

COOH

COOH

Page 3: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

2) Longest continuous chain

CH3CH2CHCH2CH2COOH 4-Methyl hexanoic acid CH3

C-C-C-C-C-COOH

CH3CH2CHCH2CH2COOH γ-Methyl hexenoic acid CH3

Page 4: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

CH3-CH-CH-COOHCH3CH3

commmone: -- Dimethyl butyric acidIUPAC: 2,3-Dimethyl butanoic a

CH3-CHBr-CHCl-CO2H

3-Bromo-2-chlorobutnoic acid

Page 5: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

3) In cyclic ring ------ cycloalkane carb. a'

COOHCOOH

COOH

cyclopropanecarb.ac.

cyclobutanecarb.ac.

cyclopentanecarb.ac.

cyclohexanecarb.ac.

COOH

COOH 2-Cyclohexene carboxylic acid3

Page 6: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

5) Aromatic acid by common name

CO2H CO2H

(comm.) Phthalic a'

(comm.) Terephthalic a'

CO2H

CO2H

CO2H

benzoic acid

OH

CO2H

Salycilic acidO- hydroxy benzoic acid

Page 7: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

CH2CH2COOH

3-Phenyl-propionic acid

OH

HOOC

Hydroxy-phenyl-acetic acid

Page 8: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Physical properties

1] They form hydrogen 2] comp. 1-7 soli in H2O . 3] mor than 7 carbon less soli. (bec. R

increased)4] Aromatic acids insoluble. In H2O5] BP. Acid > Alcohol

Page 9: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Deac. gps inc. acidity Acti gps dec. acidity

COOH

NO2NO2

COOH

NO2

COOH COOH

CH3

> > >

inc. acidity

OHCOOH COOH OH

inc acidity

Page 10: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

HCOOH > CH3COOH > CH3CH2COOH > CH3 CH2 CH2COOH

More acidity

Substitution with halogen :

CH3CH2COOH < CH2Cl-CH2COOH (more acidic)

CH3CH2COOH < CH2ClCOOH < CHCl2COOH < CCl3COOH

More acidity

Page 11: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Preparation of carboxylic acid

1] Oxidation

a) 1 alcohols & Aldehydes

CH3CH2OH KMnO4 / H+ CH3CHO CH3COOHheat

CH2OH CHO COOH

KMnO4 / H+

or K2Cr2O7 /H+

heat

Page 12: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Preparation of carboxylic acid

RCH2OH

Cu / Heat

or KMnO4 / H+

or CrO3 / pyridineR-CHO

K2Cr2O7 / H+RCOOH

Page 13: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

b) of alkyl benzene

CH3 COOH

KMnO4 / H+

or K2Cr2O7 /H+OCH3 OCH3

COOHKMnO4 / H+

or K2Cr2O7 /H+

CH3

NO2 NO2

COOH

KMnO4 / H+

or K2Cr2O7 /H+

CH2CH2CH3

Page 14: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

2)Hydrolysis of nitriles

RCN +H2O

R-COOH

RCOO

R-X + NaCNheat

OH

H+

(K,Na,..)

RCH2NH21)Li AL H4, ether

2)H3O or H2 / Pt amine

(K<Na..)

CH3CH2Cl1)NaCN

CH3CH2CN + H2O 2) Hheat

CH3CH2CO2H

CH2Cl

1)NaCN

CH2CN

2) H

heat

CH2CO2H

+ H2O

Page 15: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

3] Carbonation of Grignard reagent:

R-Mg X R-COOMgX H3O RCOOHCO21) 2)

CH3-Mg Br CH3-COOMgBr2) H3O

CH3COOH+ Mg(OH)Br

1)CO2

Mg Br COOH

1)CO22) H3O+

Page 16: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Preparation of carboxylic acid

• Hofmann Reaction

• Collb’s Reaction

O

+ NaOHI2

OH

O

+ CHCl3

Page 17: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Reactions of acids

1)Salt formation:

it react with strong base & we can use CaOH, NaOH or KOH

RCOOH + KOH RCOOK + H2O

RCOOH + NaOH RCOONa + H2Osodi. acetate

Page 18: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

reaction with weak base

RCOOH + NaHCO3 RCOONa + CO2 + H2O

Sodium bicarb. Can be used to distinguish between carboxylic acid and phenols

OH

+ NaHCO3NO reaction

Reactions of acids

Page 19: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

2) Formation of Easter:

RCOOH R'-OH / H+heat R-COO-R' + H2O

OH

COOH

CH3CH2OH OHCOOC2H5H+ / heat

3) Formation of amide:

RCOOH NH3 or R-NH2 ,heat R-CONH2

CH3COOH heatCH3-CONH2

NH3 ,

Reactions of acids

Page 20: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

4) Formation of acid anhydride:

2 RCOOH R-C-O-C-RO O

2 CH3CH2COOH CH3CH2-C-O-C-CH2CH3O OH2SO4

H2SO4

5) Formation of acid chloride:

2 RCOOH SOCl3 PCl3 R-C-ClO

2 CH3COOHO

or PCl5

SOCl3 PCl3or PCl5

CH3-C-Cl

,

,

2

2

Reactions of acids

Page 21: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Reactions of acids

Addition anti marco.

OH

O

HBrH2OOH

O

OH

O Br

HH

OH

H+

Page 22: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Nomenclature of carboxylic acid derivatives

When Oxygen of Carboxylic acid is replaced with Nu.------ Carb. a' deriv

OH

O

R

Nu

O

R Nu

O

Ar

Page 23: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

R Cl

O

R OR'

O

R N

O OO

R-C-O-C-R

Acid chl. Ester AmideAcid anhydride

R O-(K or Na)

O

Salts

When Oxygen of Carboxylic acid is replaced with Nu.------ Carb. a' deriv

Page 24: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

1] Salt:

H3C O- Na

O

Com. Sodium acetate

IU. Sodium etanoate

from Acet.a'.

from Ethan.a'.h

, K

Page 25: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

2] Acid chloride

Cl

O

CH3CH2

(Com.) Proanyl chloride from propanoic a'(I) Propionyl chloride from propionic a'

I

Com.

Cl

O

Benzoyl chloride

Page 26: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

3] Ester:The alkyl gp. Named 1st then the name of parent acid with ending –ate in place of -ic acid

OCH2CH3

O

CH3(Com.) Ethyl ethanoate from ethanoic a'

(I) Ethyl acetate from acetic a'

I

Com.

OCH3

O

H (Com.) Methyl formate from formic a'(I) Methyl methanoate from mthanoic 'a

Page 27: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

O-CH3

O

Methyl benzoate Methyl salisylate

OCH3

O

OH

O-C-CH3

O

CH2-O-C-CH3

O

(I) Phenyl ethanoate(Com.) Phenyl acetate

(I) Benzyl ethanoate(Com.) Benzyl acetate

O-CH=CH2

O

CH3Vinyl acetate

Page 28: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

4]Amides:

-oic acid or -ice a' by –amide .f 1 or 2 subst. on nitrogen we say N-subs. or N,N-disubs. (sub. Name 1st )

NH2

O

R NH2

O

ArOr

O

C-NH2Benzamide

Page 29: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

NH2

O

CH3CH2Propanamide

C-NCH3

O

CH3C-N

CH3

C2H5

O

(I) N,N-Dimethyl benzamide(I) N,Ethyl-N-methyl benzamide

Page 30: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

4] Acid anhydride:

replacing -acid with anhydride

O

C-O-C-R

O

R

O

C-O-C-R

O

Ar

O

C-O-C-CH3

O

CH3 Ethanoic anhydride

O

C-O-C-CH2CH3

O

CH3CH2(I) Propanoic anhydride (C) Propionc anhydride

Page 31: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

R-CO-Cl > R-(CO)2O-R > RCO2R > RCO2H > RCONH2

Acid chloride Acid anhydride Ester Acid Amide

Order of reaction:

O

OO

Benzoic acid anhydride

O

O

O

Dihydro-furan-2,5-dione

Succinic anhydride

Page 32: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

AMIDES

Page 33: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

ESTERS

Page 34: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

ANHYDRIDES

Page 35: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Overview Reaction

Page 36: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

Reactions of acid derivatives

a) Acid chlorides:

R-C-ClO

R-C-OH + HClO

R-C-OR'O

R-C-NH2

O

R-C-NHR'O

R-C-NO

H2O/ H+

R'OH

NH3

R'NH2

R'2NH

+ HCl

+ HCl

+ HCl

R'

R' + HCl

Reduction:

Cl

O

R

1) Li Al H4 / ether

2) H3OR-CH2OH

Page 37: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

B] Acid anhydride:

R-C-O-C-RO

R-C-OHO

R-C-OR'O

R-C-NH2

O

R-C-NHR'O

R-C-NO

H2O/ H+

R'OH

NH3

R'NH2

R'2NH

+ RCOOH

+ RCOOH

+ RCOOH

R'

R' + RCOOH

O

acid

Ester

Amid

2

O

O

R

O

ROH

COOH

O CH3

O

+CH3-COOHCOOH

acetyl salisilic acid + acetc acidCH3CH3

Reduction:

1) Li Al H4 / ether

2) H3O2 R-CH2OHO

O

R

O

R

Page 38: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

C] Esters:

RCOOR' + H2O RCOOH + R'OHH+

RCOOR' + R''OH RCOOR'' + R'OHH+

RCOOR' + NH3 RCONH2+ R'OHH+

Reduction:

RCOOR' RCH2OH+ R'OH1)Li Al H4 / ether

2) H3O

CH3CH2CH2OH+ CH3OH1)Li Al H4 / ether

2) H3OCH3-CH2COOCH3

R-C-OO-R' 1) 2 R'' Mg X

2 ) H3O / H+R-C-R''

OH

R''

+ R' OH

Page 39: Carboxylic acid and carboxylic acid derivatives Carboxylic acid and carboxylic acid derivatives Dr. Nabila Al Jaber

d] Amide:R-C-NH2

OR-C-OH + NH3

O

R-C-NH2

OR-C-ONa + NH3

O

+ H2OH+

NaOH / heat

Reduction:

R-C-NH2

O

R-C-NHR'O

1) Li Al H4 / Ether2) H3O

1) Li Al H4 / Ether

2) H3OR-CH2NHR'

R-CH2NH2

R-C-NO 1) Li Al H4 / Ether

2) H3OR-CH2NR'2

R'

R'

Dehydration:O

P2O5

- H2OR-CN nitrileR-C-NH2

Hoffman degradation:

RCH2-C-NH2

O Br2/ NaOH

or NaOBrR-CH2NH2

OBr2/ NaOH

CH3NH2CH3-C-NH2