CA DERIVATIVES ACYL HALIDE RXNS Chemistry Specialist: Alicia Hart

UC Davis - SASC
a) Hydrolysis
O O

H2O
R Cl R OH
- pyridine is often used to prevent the formation of HCl when reacting with acyl chlorides

b) Alcoholysis

O O

R'OH, pyridine
or NaOR', R'OH
R Cl R OR'

c) Ammonolysis/Aminolysis
O O

NH3
R Cl R NH2
- can use 1 and 2 amine, but NR with 3 amine

d) Alkylation
i) Organometallic Reagents
OH
O

1. R'Li or R'MgX, Ether

R R'
R Cl 2. H3O+ R'
- given 2 eq. of the organometallic reagent, does alkylation twice by kicking off the Cl and reforming the carbonyl.

ii) Organocuprate
O
O

1. R'2CuLi
R R'
R Cl 2. H3O+

- unlike the grignard above, organocuprate adds only one R' stopping at the ketone
- Mcmurry 7 edition states, "diorganocuprate only reacts with acyl halides; does not with carbox. acid, anhydrides, ester and amides."
e) Reduction OH
O
NaBH4, EtOH
or 1. LiAlH 4, ether R H
R Cl 2. H3O+ H
O

To stop at aldehyde, 1. LiAlOC(CH 3)3H, THF

use less reactive red. agent...
2. H3O+ R H
- Note: DIBAL is still too reactive to stop at aldehyde with acy halide.