Functional Groups

• An alcohol contains a carbon bonded to an –OH (hydroxyl)

group

• A phenol is a benzene ring bonded to an –OH group

2
 Naming Alcohols
• Examples

5
 Phenol & Other Naming
• Phenols – named as a phenol
– Can use ortho, meta or para if two groups on aromatic ring

• Enols & Ynols

– Alcohol takes priority over an alkene or alkyne

6
 Properties of Alcohols & Phenols
• Acidities of some alcohols and phenols
Relative Acidity:
H2O > ROH > RC≡CH > H2 >NH3 > RH
Strong Weak

Relative Basicity:
−OH < RO − < RC≡C − < H − < NH − < R −
2
Weak Strong

Phenols are more acidic than

alcohols because the phenoxide
anion is resonance stabilized

10
 Reaction Review
• Acid catalyzed hydration
Markovnikov
Product

• Oxymercuration-demercuration
Markovnikov
Product

• Hydroboration-oxidation
Anti- Markovnikov
Product
12
 Reaction Review
• Osmium tetroxide – forms cis 1,2-diol

• Ring opening epoxides – forms trans 1,2-diol

13
 Carbonyl-Containing Compounds
• These compounds don’t have leaving groups

• These compounds have leaving groups

15
 Reduction/Oxidation
• Reduction – adding hydrogen or removing oxygen
• Oxidation – removing hydrogen or adding oxygen

• Oxidation may also be defined as a compound that

increases its content of any element more
electronegative than carbon

16
 Reductions to Form Alcohols
• Lithium aluminum hydride (LiAlH4) is stronger
than NaBH4
• Mechanism for reduction of an ester

21
 Reductions to Form Alcohols
• NaBH4 → reduces only aldehydes and ketones
to alcohols
• LiAlH4 → reduces aldehydes, ketones,
carboxylic acids, and ester to alcohols

22
 Notes on Reductions
• LiAlH4 reacts violently with water and alcohols so
reductions most be carried out in anhydrous aprotic
solvent (like Et2O or THF)
– LiAlH4 reactions are usually two-step reactions

• NaBH4 can be carried out in water or alcohol solvents

– NaBH4 reactions are usually one-step reactions

23
 Reduction Summary
• Summary

24
 Oxidation of Alcohols
• Alcohols can undergo oxidation reactions

25
 Oxidation Summary
• Summary

Note: 3° alcohols cannot be oxidized 33

 Grignard Reagents
• Grignard reagents are organomagnesium reagents
• They are easily prepared from any alkyl, vinyl or aryl
halide

• Examples

34
 Organometallic Compounds
• Grignards & organolithium reagents are very
strong bases & will react with any compound
that has a hydrogen attached to an
electronegative atom like O, N or S
• Protic solvents cannot be used with these
reagents

35
 Organometallic Compounds
• Grignard & organolithium reagents also react
with terminal alkynes

• Grignard reagents react with epoxides

36
 Grignard Reagents
• More Grignard reactions

38
 Grignard Reagents
• Grignard reagents react with esters
– It takes 2 equiv. of Grignard reagent to fully reduce
the ester
– With 1 equiv. reaction stops at the ketone

39
 Grignard Reagents
• Grignard + ester example

• With any Grignard reaction, an acidic workup

is needed → typically H3O+ is used but NH4Cl
& H2O can be used as well

40
 Grignard Reagents
• Restrictions
– They cannot be prepared from an organic
compound that contains an acidic hydrogen (like
−OH, −NH, −SH, −COOH, etc.)
– They cannot be prepared from an organic
compound that contain a group that they can
react with (like −CHO, −CN, −CO2R, etc.)
– They can be prepared in the presence of alkenes,
internal alkynes, ethers, aromatics, and −NR2

42
 Preparing Alkyl Halides
• Phosphorus tribromide (PBr3) & thionyl chloride (SOCl2)
– Used to convert 1° and 2° alcohols into their corresponding halides

• Binary Acids (H-X)

– Used to convert 3° alcohols into their corresponding halides

44
 PBr3 Mechanism
• Mechanism

• Note: PBr3 reacts via SN2 → inversion of

configuration

46
 SOCl2 Mechanism
• Mechanism

• Note: SOCl2 reacts via SN2 → inversion of

configuration

47
 Good Leaving Groups
• An alcohol’s leaving group is hydroxide (−OH) which is
a bad leaving group (because it is a strong base)

• However the alcohol can easily be converted into a

compound that has a good leaving group like −OMs,
−OTs or −OTf

48
 Good Leaving Groups
• Preparing sulfonate leaving groups

• Note: Look at stereochemistry

Stereochemistry retained

Stereochemistry inverted
49
 Protecting Groups
• Silyl ethers as protecting groups for alcohols

• Silyl protecting groups can be removed with

fluoride (like Bu4NF or HF)

50
 Dehydration of Alcohols
• Catalytic acid and heat is a good way to
dehydrate 3° alcohols

• Follows E1 elimination mechanism

(carbocation)
• Follows Zaitsev’s rule

51
 Dehydration of Alcohols
• An alternative is POCl3 & pyridine
• Works with 2° and 3° alcohols
• Follows E2 elimination mechanism
• Watch out: H- & HO- need to be antiperiplanar

52
 Oxidation of Amines
• Reaction of amines with nitrous acid
– Nitrous acid (HONO)

– HONO can be generated in situ & react with a 1°

amine to form a diazonium salt

– 1° aryl amines react with nitrous acid

53
 Sandmeyer Reactions & Other
Diazonium Replacement Reactions
• Replaces diazonium group with other groups
like –Cl, –Br or –CN

55