carboxylic acid derivatives and their...

31
Carboxylic Acid Derivatives and Their Reactions.

Upload: nguyentram

Post on 28-Aug-2018

242 views

Category:

Documents


0 download

TRANSCRIPT

Page 1: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Carboxylic Acid Derivatives and Their Reactions.

Page 2: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Carboxylic Acid Esters

R C

O

OH R’HO R C

O

R’O+ + H2OH+

Synthesized from a carboxylic acid and an alcohol:

carboxylic acid alcohol or

phenol

ester

Nomenclature base on parent alcohol and carboxylic acid:

CH3 C

O

OH CH3HO CH3 C

O

CH3OCH2CH2 + + H2O

methanolpropanoic acid methyl propanoate

hydrolysis

condensation

Page 3: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

C

O

OHC

O

HO CH3HO + excess

terephthalic acidH+

methyl alcohol

C

O

OCH3

dimethyl terephthalate

C

O

CH3O + 2 H2O

A Diester Synthesis

Page 4: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

C

O

OHC

O

HO CH2CH2HO + excess

terephthalic acidH+

ethylene glycolethanediol

OH

C

O

OC

O

CH2CH2 O

n

A polyester

A Polyester Synthesis

Page 5: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Hydrolysis Reaction of Esters

Hydrolysis of Esters Under Acidic Conditions

R C

O

OH R’HOR C

O

R’O ++ H2O H+

ester carboxylic acid alcohol or

phenol

Notice that this is the reverse of the condensation reaction used to synthesize an ester !!

Page 6: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Hydrolysis Reaction of Esters

Hydrolysis of Esters Under Basic Conditions

R C

O

O-Na+ R’HOR C

O

R’O ++ NaOHH2O

esteralcohol

or phenol

carboxylate salt

H2O

R C

O

OH + NaOH[ ] The carboxylic acid is an intermediate but reacts with the

basic NaOH !!

Page 7: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Hydrolysis Worksheet

Page 8: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

HCl, H2O

CO

O CH2F

F

CH3

CO

O CH2F

F

CH3H

OH

ethyl-2,4-difluoro benzoate

2,4-difluoro benzoic acid ethyl alcohol

NaOH, H2O

OC

O

CH2 CHCH3

CH3

OC

O

CH2 CHCH3

CH3

H

HO

phenyl-3-methyl butanoate

phenol

3-methyl butanoic acid

C

OO

CH2 CHCH3

CH3Na+

sodium 3-methylbutanoate

Page 9: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

COCH2 CH

CH3

CH3

ONaOH, H2O

COCH2 CH

CH3

CH3

O

HHO

isobutyl benzoate

benzoic acid

2-methyl-1-propanol2-methylpropyl benzoate

“isobutyl alcohol”

CO

O

Na+

Page 10: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Soaps

Soaps are produced by a process called “saponification” (technically, “basic hydrolysis of fats”)

H2C

C

H2C

OH

O

O

C

C

O

O

C

O

C

C

O

O

C

O

-O

-O

-O

Na+

Na+

Na+

Hot aq NaOH

H2C

C

H2C

OHH

OH

OH

Page 11: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

C

O

CH2CH2

CH2CH2

CH2CH2

CH2CH2

CH2CH2

CH2CH2

CH2CH2

CH3-ONa+

Soaps

Soaps are the sodium or potassium salts of long-chain fatty acids.

hydrophilic region

hydrophobic region

Page 12: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

How Do Soaps Work?

micelle micelle+grease

Page 13: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Synthetic Detergents

S

O

O-ONa+

O

S

O

-ONa+

O

S

O

-ONa+

O

Sodium Dodecyl Sulfate (SDS)

Sodium Alkyl Benzene Sulfonate (ABS)

Sodium Dodecyl Benzene Sulfonate (LAS)

Page 14: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

N+CH2

N+

Synthetic Detergents

Na+

O

O

O

O

OS

O

O

-O

O

O

O

HO

Page 15: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Amides - Synthesis and Nomenclature

CH3 C

O

OH CH3H N+H

CH3 C

O

CH3 N

H>100o C+ H2O

acetic acid methylamine N-methylacetamide

condensation

Page 16: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Amides - Basic Hydrolysis

O

R C R’ N

HH2O, NaOH R C

O

O Na+ R’ N

H

H

O

R C R’ N

H

Two Products

Page 17: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Amides - Basic Hydrolysis

Example

CN

CH2CH3

CH2CH3

O

+ Na + OH-H2O

H-NCH2CH3

CH2CH3Na+

C

O

O +

N,N-diethylbenzamide

sodium benzoate diethylamine

Page 18: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Amides - Acid Hydrolysis

O

R C R’ N

HH2O, H3O+

O

R C R’ N

H

R C

O

OH R’ N

H

HH2O

H3O+ ??

[ ]

R C

O

OH R’ N

H

H

H

+

Page 19: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Hydrolysis Worksheet

Page 20: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Amides - Acid Hydrolysis

Example

CN

CH2CH3

CH2CH3

O

+ H 2SO4H2O

C

O

OH

N,N-diethylbenzamide

benzoic aciddiethylammoniumhydrogen sulfate

+ NCH2CH3

CH2CH3+

H HSO4

H

Page 21: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

H CH2CH3CO

NCH2CH2CH3

HCl, H2O

H CH2CH3CO

NCH2CH2CH3

OH

H

HN

HCH2CH3

CH2CH2CH3Cl-

HCl

formic acid

ethylpropylammonium chloride

Page 22: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

NO2

CH2CH3CO

NH

NaOH, H2O

NO2

CH2CH3CO

NH

OH

H

NaOH

Na+

CO

O

NO2

ethylamine

sodium 2-nitro-benzoate

Page 23: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

C

O

OHC

O

HO CH2CH2HO + excess

terephthalic acidH+

ethylene glycolethanediol

OH

C

O

OC

O

CH2CH2 O

n

A polyester

A Polyester Synthesis

Page 24: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Amides - Condensation Polymers

H2N CH2CH2CH2CH2CH2CH2 NH2CH2CH2CH2CH2C

O

C

O

OHHO +adipic acid hexamethylene diamine

mix at room temperature

CH2CH2CH2CH2C

O

C

O

OO CH2CH2CH2CH2CH2CH2NH3H3N-- + +

H2Oheat

CH2CH2CH2CH2C

O

C

O

CH2CH2CH2CH2CH2CH2NH

NH

C

O

NH )( n

polyhexamethylenediamine adipate

Nylon 6,6

hexamethylene diammonium adipate

Page 25: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Carboxylic Acids and Their Derivatives

Page 26: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Carboxylic Acid Anhydrides and Halides

R C

O

OH RC

O

HO R C

O

ORC

O

+ H2O+H+

Synthesis from a carboxylic acid:

R C

O

OH Cl”“H+ R C

O

Cl + H2O

Very unstable; very “reactive” Low boiling points and melting points

“Lachrymators” Generate the starting acids upon hydrolysis

carboxylic acid carboxylic acid carboxylic acid anhydride

carboxylic acid carboxylic acid chloride

Page 27: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Carboxylic Acid Anhydrides and Halides

Used to Synthesize Esters

CH3 C

O

OCH3C

O

+C

O

OH

O CH3C

O

C

O

OH

OH

ethyl alcohol acetyl chloride ethyl acetate

salicylic acid acetic anhydridesalicyl acetate

acetyl salicylic acid aspirin

CH3C

O

Cl

CH3CH2OH CH3C

O

CH3CH2O+

Cl H+

C

O

CH3HO+

Page 28: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

CH3C

O

Cl

CH3CH2OH CH3C

O

CH3CH2O+

CH3 C

O

OCH3C

O

+C

O

OH

O CH3C

O

C

O

OH

OH

These highly reactive compounds are use to transfer the acetyl group to an alcohol group.

CH3C

O

Carboxylic Acid Anhydrides and Halides

Summary of reactivity of carboxylic acid related functional groups:

Acid Anhydrides

Acid HalidesCarboxylic Acid

EstersCarboxylic Acid

Amides Carboxylic Acids

Page 29: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Similar Derivatives of Inorganic Acids

CH3 C

O

OH HO S

O

OH

O

HO P

O

OH

OH

S

O

OCH3CH3O

O

P

O

OCH3CH3O

OCH3

C

O

OCH3CH3

C

O

OCH3C

O

CH3 OHS

O

O S

O

HO

O O

P

O

O OHP

O

HO

OH OH

acetic acid sulfuric acid phosphoric acid

methyl acetate dimethyl sulfate trimethyl phosphate

acetic anhydride pyrosulfuric acid pyrophosphoric acid

Page 30: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

Similar Derivatives of Inorganic Acids

C

O

OCH3C

O

CH3 OHS

O

O S

O

HO

O O

P

O

O OHP

O

HO

OH OH

acetic anhydride pyrosulfuric acid pyrophosphoric acid

ANHYDRIDE LINKAGES

“REACTIVE LINKAGES”

“HIGH ENERGY BONDS”

Page 31: Carboxylic Acid Derivatives and Their Reactions.profkatz.com/.../uploads/...12-Carboxylic-Acid-Derivatives-29-copy.pdf · Carboxylic Acid Derivatives and Their Reactions. ... Generate

What is ATP??