CHEM 232 EXAM 3

Ch.18- Wittig & Baeyer Villager

100

ketones/aldehydes substrates

mCPBA or peracids

BAEYER-VILLAGER OXIDATION

ketones/aldehydes ---> ester (can be cyclic)

200

PPh₃=R₁R₂ + ketone or aldehyde

CIS ALKENE -- (PPh₃-CH₃), (PPh₃-ketal), (PPh₃-OCH3) - EDG

TRANS ALKENE -- (PPh₃-CO₂Me), (PPH₃-NO₂)

Ch.19-Carboxylic Acids

100

Ester + H₂O + cat. ACID

ESTER HYDROLYSIS 

R-COOH, R-OH

200

Aldehyde substrate

1) NaCN

2) aq. acid (HCl)

aldehydes--> OH where carbonyl oxygen was, CN (nitriles) where hydrogen was

300

R-COOH + R-OH, cat. ACID

FISCHER ESTERIFICATION

Product- ESTER

400

H₂O, HCl/heat

OR 

1) NaOH, H₂O, heat

2) H₃O⁺ workup

NITRILES ---> COOH

500

1^o alkyl/benzylic halide 

NaCN/DMF

HYDROLYSIS OF NITRILES

Sn2 Br ---> CN (Nitriles)

Ch.20-Acyl Transfer Reactions

100

Acyl Chloride subst. 

Pyridine

Acyl Chloride--> Ester

(Base or Nucleophilic Catalysis)

200

Acyl chloride OR anhydride

1) NaOH/H₂O

2) H₃O⁺ workup

Acyl Chloride ---> Carboxylic Acid

Anhyride ---> 2 carboxylic acids

300

Acyl Chloride substrate

NaOCOCH₃/DMF

_{(carboxylate)}

Acid chloride ---> Anhydrides

400

Acyl Chloride substrate

2 equiv. NH₃, R-NH₂, R-NH

Acyl Chloride ---> 1^o, 2^o, 3^o Amide

500

 Anhydride

HO-R/pyridine

Anhydride ---> ester

Ch.20- Acyl Transfer Reactions

100

Anhydrides

H₂N-R/Et₃N

Anhydrides ---> Amides

200

carboxylic acid substrate

DCC/R-NH₂, R-NH

R-COOH --> Amides

300

Esters OR R-CN (Nitriles)

1) excess R-MgBr /// R-MgBr

2) H₃O⁺ workup

Esters ---> 3^o OH

R-CN (Nitriles) ---> Ketone

400

Ester substrates

H₂SO₄, H₂O/heat

Esters ---> COOH

500

Ester substrates

NaOH, H₂O/heat

SAPONIFICATION

ESTERS --> Carboxylates (RCOO^-)

Ch.20 & Ch.21 Acyl Transfer and Enols/Enolates

100

Amides

6M HCl / H₂O, heat

or 

1) NaOH, H₂O

2) H3O+ workup

Amides ---> COOH

200

1) LDA, THF, -78^oC OR NaH, Et₂O

2) Aldehyde

3) H₃O⁺ workup

DIRECTED ALDOL

Aldehyde/ketone ---> ALDOL

1) LDA - kinetic (less subst)

2) NaH- thermodynamic (more subst)

300

CO-OR 

NaOH/Br2

ACIDIC HALOGENATION

Ketone or aldehyde ---> 1x Bromination where alpha proton was

'' ---> 2x bromination

400

1) Br₂, NaOH, H₂O

2) H₃O⁺ workup

methyl ketone ---> R-COOH (OH where CH₃ was)

500

NaOH/H₂O

vs

NaOH/H2O/heat

ALDOL ADDITION

2x aldehyde ---> aldehyde + alcohol

'' ---> aldehyde + alkene (E1cb)