Carboxylic Acid Derivatives

Front 1

Carboxylic Acid Derivatives

4 types

Back 1

- acyl halides

- anhydrides

- amides

- esters

Front 2

Acyl Halides: Nomenclature

also known as?
whats good about them in reactions?

Back 2

- acid or alkanoyl halides

- most reactive derivative

-

Front 3

Acyl Halides: Synthesis

reagents? alternative nucleophiles?

Back 3

- C.A. + thionyl chloride (SOCl2) >>> Acyl Chloride + HCl + SO2

- also can use PBr3, PCl3, PCl5

Front 4

Acyl Halides: Reactions - Nucleophilic Acyl Substitution

3 types

Back 4

- Hydrolysis
> remakes Carboxylic Acid

- Conversion to Esters
> react with alcohols, makes ester

- Conversion into Amides
> react with nucleophilic amines

Front 5

Acyl Halides: Other Reactions

2 types
nucleophile in type 1?

Back 5

- Friedel-Crafts Acylation
> aromatic ring is the nucleophile.

- Reduction
> product can be alcohol or intermediate aldehydes
> reagents are H2/Pd BaSO4 (quinoline) (catalytic hydrogenation)

Front 6

Anhydrides: Nomenclature

how to cyclic anhydrides form?

Back 6

- general formula RCOOCOR.

- from intramolecular condensation or dehydration of diacids

Front 7

Anhydrides: Synthesis

regular Anhydride formation
> reagents? nucleophile?
cyclic Anhydride formation
> reagents? nucleophile?

Back 7

- acid chloride + carboxylate salt

- heat + 2 carboxylic acids
> hydroxyl of one of the C.A.'s acts as nucleophile, attacks other C.A.

Front 8

Anhydrides: Reactions

4 types

Back 8

- Hydrolysis

- Conversion into Amides

- Conversion into Esters

- Acylation

Front 9

Reactions: Anhydride Hydrolysis

reagents? whats the leaving group?

Back 9

- water + anhydride >>> C.A.'s

- the leaving group is actually a C.A.!

Front 10

Reactions: Anhydride conversion to amide

reagents? first product? second product?

Back 10

- ammonia + anhydrides

- first product is amide + second product is ammonium salt of a carboxylate anion

Front 11

Reactions: Anhydride conversion into Esters and C.A.'s

reagents?

Back 11

- alcohol + anhydride >>> C.A. + Ester

Front 12

Reactions: Anhydride Acylation

reagents? products?

reaction mechanism?

Back 12

- Anhydride + Benzene + AlCl3 >>> ketone + carboxylate anion.

- Electrophilic Aromatic substitution.

Front 13

Amides: Nomenclature

Back 13

- general formula is RCONR2

- alkyl substituents on nitrogen are labeled as prefixes with an N to specify location.

Front 14

Amides: Synthesis

2 types
> 1. reagents? restrictions?
> 2. reagents?

Back 14

- Acyl chlorides + amines
> only primary and secondary amines will work

- acid anhydrides + ammonia

Front 15

Amides: Reactions

3 types

type 2 reagents? mechanism?

type 3 reagents?

Back 15

- Hydrolysis

- Hofmann rearrangement
> converts amides to primary amines with loss of carbonyl carbon.
> amide + BrOH >>> nitrene >(rearranges)> isocyanate >(hydrolyzed)> primary amine

- Reduction
> LAH + amide >>> amine

- Reduction

Front 16

Esters: Nomenclature

Back 16

- dehydration products of C.A.'s and alcohols.
> IUPAC naming: alkyl or aryl alkanoates

Front 17

Esters: Synthesis

2 types of reagents

Back 17

- C.A. + alcohol will condense into esters + H20

- Acid Chlorides or Anhydrides + Alcohol

Front 18

Esters: Reactions

6 types

Back 18

- Hydrolysis

- Conversion into Amides

- Transesterification

- Grignard Addition

- Condensation

- Reduction

Front 19

Reactions: Hydrolysis of Esters

reagents? nucleophile?

realworld/biological application?

Back 19

- water + ester >>> C.A. + alcohol

- triacylglycerols (fatty acids/glycerol). Process of Saponification; hydrolyzation of fats under basic conditions to make soaps.

Front 20

Reactions: Esters converted to Amides

reagents? nucleophile?

Back 20

- Ammonia (nitrogen bases) + ester >> amide + alcohol side product

- nucleophile is ammonia

Front 21

Reactions: Transesterification

Back 21

- alcohols act as nucleophile, displace alkoxy group

- creation of new ester

Front 22

Reactions: Grignard Addition to Esters

1 equivalent of Grignard makes?

2 equivalents of Grignard makes?

reaction mechanism?

Back 22

- grignard reagent equivalent to R- nucleophiles

- 1 grignard + ester >>> ketone

- 1 grignard + ester >>> ketone + 1 grignard >>> Tertiary alcohols

- first, nucleophilic substitution, then, nucleophilic addition.

Front 23

Reactions: Ester Condensation

nickname?

reagents (simplest case)? products?

mechanism

biological application

Back 23

- Claisen Condensation (acetoacetic ester condensation)

> 2 moles ethyl acetate >>(basic conditions)>> B-keto ester/ethyl 3-oxobutanoate/ acetoacetic ester

- enolate of another ester acts as nucleophile, attacks carbonyl of target ester. this then causes the alkoxy group to leave, creating this keto/ester product and alkoxy ion.

- claisen condensation is mechanism by which lipids are created.

Front 24

Reactions: Ester Reduction

reducing reagent? product?

which reducing reagent that is similar cannot be used.

Back 24

- Esters + LAH >>> primary Alcohol
> allows for selective reduction in molecules with multiple functional groups.

- NaBH4

Front 25

Esters: Phosphate Esters

mechanism? reagents? products?

biological application?

Back 25

- phosphate esters (phosphoric ester) get cleaved under acidic conditions

- phosphate esters >>(acidic conditions)>> parent acid (H3PO4) + alcohols.

- found in living systems as PHOSPHOLIPIDS(phosphoglycerides)
> main component of cell membranes, also part of backbone (phosphodiester bonds) of nucleic acids.
- found in ATP!