1. Alcohols Condensation Reaction CH3 – OH + HO – CH3 CH3 – O – CH3 + H2O
H2SO4
CH3 – OH +
HO – CH3
CH3 – O – CH3
+ H2O
two molecules combine to form
larger molecule + water
ether
H2O
alcohol +
alcohol +

2. Ethers O- - R water alcohol ether H-bond acceptor no H-bond donor
dipole-dipole interactions
low b.p.
soluble in polar solvents

3. Ethers “ether” bunny Common nomenclature : name both R groups + ether
propyl 2 1 3 1
methyl propyl
ether
methyl
methyl
dimethyl ether O ..
methyl
“ether” bunny
propyl
people
ether

4. Ethers Reactions Formation: Peroxide formation: condensation reaction
H2SO4
condensation reaction
Peroxide formation:
peroxide

5. Aldehydes and Ketones 120o aldehyde ketone C=O carbonyl group
C and O are sp2 hybridized
polar
higher b.p. than alkanes
H-bond acceptor
soluble in polar solvents
no H-bond donor
lower b.p. than alcohols

6. Aldehydes and Ketones Nomenclature 1. Longest chain with C=O is parent
2. Suffix is “-al” or “-one”
3. C1 is always C=O in aldehydes
In ketones, C=O is given lowest number
4. C=O has precedence over -OH
(called “hydroxy”)

7. 2-bromo-3-methyl butan al 3- pentan one trans- 3-hydroxy- 2-methyl4 2 1 3-
pentan
one 1 4 2 5 3
trans- 1 2
3-hydroxy-
2-methyl
cyclobutanone 3

8. Reactions Reduction [R] = reducing agent LiAlH4 NaBH4 H2/Pt butan al3 1 2
CH3-
CH2-
CH2-
CHO
CH3-
CH2-
CH2-
CH2- OH
butan al
[R] 1 3 4 2 2-
butan
one

9. Nucleophilic addition
ketone
aldehyde O C : O C : + -
C=O
very polar
Nucleophilic addition - O C : +
H-Nu H Nu O C H Nu +
H-OH
H-OR
H-NH2 + -

10. Nucleophilic addition
C O-H R
O-H
C O R .. H
C = O R .. H+
C = O R ..
+ H+ H H+
hydrate or diol
C O R .. H C R
O-H
O-R
+ H+ +
H-OH O .. H R .. O H N H ..
C = O R .. +
H-OR
hemi-ketal C R
O - H
N - H2
+ H+ C R N H
+ H2O +
H-NH2
Schiffs base

11. Addition of alcohol H C O CH3 H3C H C O H3C H+ + CH3OH H OCH3 ketone
hemi-
ketal
unstable
aldehyde
+ alcohol =
hemi-
acetal
unstable

12. _ more stable = -D-glucose b.p. = 150o -D-glucose b.p. = 146o CH2OH3 OH 1 2 4 5 6 O
CH2OH H
more stable OH HO 1 2 3 4 5 6
CH2OH O = C _ H HO 1 2 OH 3 HO
-D-glucose 4
b.p. = 150o OH 5 OH 3 OH 1 2 4 5 6 O
CH2OH H 6 OH HO
CH2OH
CH2OH
-D-glucose
b.p. = 146o

13. Nucleophilic substitution .. .. hemi - acetal condensation reaction
H3C H OH
O - CH2 - CH3
O - CH2 - CH3 H .. .. H+ C
H3C H OH
O - CH2 - CH3 H+ ..
OH - CH3 - CH2 .. .. +
H2O
hemi -
acetal C
H3C H
O - CH2 - CH3
+ H+
aldehyde
alcohol +
alcohol
acetal +
condensation reaction
hemi-acetal + alcohol
acetal + H2O

14. acetal
propanal +
2 equivalents ethanol
stable
hemi-
ketal
2-butanone +
1 equivalent methanol
unstable

15. Carboxylic acids [O] [O] 1o alcohol aldehyde carboxylic acid methanol
methanal
methanoic acid
H-bond acceptor -
very high b.p.
H-bond donor - +
2 H-bonds / molecule

16. Carboxylic acids Nomenclature 1. Carboxyl group (COOH) always C1
2. Family name is longest C chain with COOH
3. Suffix is “-oic acid”
4. Carbonyl groups (C=O) called “oxo”
Hydroxy groups (OH) called “hydroxy”

17. Carboxylic acids 2-ethyl butan oic acid 2-ethyl 4-hydroxy 2-ethyl-
CH3 – CH2 – CH – C
CH2 – CH3 O OH 4 3 2 1
2-ethyl
butan
oic acid O
CH3 – CH2 – CH – CH2 – CH – CO2H OH
CH2 – CH3
2-ethyl
4-hydroxy 6 5 4 3 2 1
2-ethyl-
4-hydroxy
hexan
oic acid
2-ethyl-
4-oxo
hexan
oic acid
add [O]

18. Carboxylic Acids Chemical properties = = OH C=O + Bronsted acid
H+ donor HA
H+ + A- H+ +
weak acids, small dissociation
Ka = [A-] [H+]
Ka  1 x 10-5
pH  2.5 for 1M
[HA]

19. Carboxylic Acids H+ + H+ + -
resonance structure
anion stabilized

20. Carboxylic Acids - acidity also affects solubility soluble
short chain acids
H-bonding
long chain acids
insoluble
benzoic acid
LDF -
add a strong base (OH-)
soluble
ion-dipole

21. Reactions Acid-base reactions: + NaOH octanoic acid insoluble
sodium octanoate + water
soluble

22. Reactions Reduction: 5-oxo hexanoic acid 1,5- hexanediol 5-hydroxy
LiAlH4 6 5 4 3 2 1
5-oxo
hexanoic acid
1,5-
hexanediol
H2/ Pt
NaBH4
5-hydroxy
hexanoic acid