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O
OH
+ CH3OH
+ CH3O
A)
O OH
+ CH3OH + CH3O
B)
OH
OH2
+ + CH3OH
CH3O
C)
• SN1
• SN2
90 % 10 %
P
HMPA – hexanamethylphosphoric triamide (H3C)2N N(CH3)2
(H3C)2N
Sec. 6: Alcohols, Ethers 3
Oxidation States of Carbon
A reaction of an organic molecule usually corresponds to increasing its hydrogen
content or decreasing its oxygen content.
O [O] O
[O] [O]
RCH3 RCH2OH R C H R C OH
[H] [H] [H] Highest
Lowest Oxidation
Oxidation State
State OH [O] O
R CH R R C R
[H]
Oxidation → broad definition → a reaction that increases its content of any element
more electronegative than carbon
[O]
CH3 CH2Cl
[H]
Nucleophile Electrophile
(base) (acid)
These reductions are achieved by the addition
of a H¯ ion (nucleophile) to the electropositive
carbon and a proton to the electronegative
oxygen
R R
H2O
H C OH + NaB(OH)3 4 H C OH + (CH3CH2O)4B
R + CH3CH2OH R
H
Electrophile
O R C R
(acid)
Oδ R 3 C
R O R
R
- + R R H C O Al O C H +
C δ+ H C OAlH3 Li R
H C OAl Li
R R
O R or
R Solvent: Et2O R C R R 4
+ H
Li H3Al- H a tetra-alkyl aluminate
R H3O+
Nucleophile
(base) LiOH + Al(OH)3 + H C work-up
OH
OS = -1 OS = +1
O very hard to OS = +3 O
KMnO4 / OH¯ / heat stop oxidation
CH3CH2CH2OH CH CH CH
3 2 CH3CH2COH
or
propanol NaCr2O7 / H2SO4 propanal propanoic acid
or
H2CrO4 or CrO3 Jones reagent
OH O OH
H2CrO4 No Reaction
H2CrO4
acetone
acetone
OS = 0 OS = +2 can’t break C-C σ bond
O
CH2Cl2
CH3CH2CH2OH + PCC CH3CH2CH
Cl
stops at aldehyde C
H Cl
H
aprotic solvent
The Cr(IV) species disproportionates into Cr(III) and Cr(V) (redox reaction).
The Cr(V) may also function as an oxidizing agent. Eventually all is reduced to
Cr(III).
Sec. 6: Alcohols, Ethers 11
Examples O
OH O OS = +3
1) LiAlH4/Et2O OS = -1
O 2) H3O+
OH
A) B) C)
H
OS = +1
CH3
(H3C)2HCO OH (H3C)2HCO OH
NaBH4/H2O
A) B)
CH3 CH3
O O
O O O OH
A) D)
OH O OH O O O
B) E)
NaCr2O7 / H2SO4
H OH
OH
OS = 0 OH OS = +3
OS = +3 OH OS = +2
C) already
oxidized
Sec. 6: Alcohols, Ethers 12
Organometallic Compounds
+
δ δ+
C M - C M C M
CH3Li
CH3MgCl
ether Li + LiBr
Br + 2 Li
Grignard Reagents
Br ether MgBr
+ Mg
ether
Br + Mg MgBr
General Reactions
The actual structure of the Grignard reagents are more complex than the formula
2 RMgX R2Mg + MgX2
It also forms a complex with the solvent, ether
δ δ+ δ δ+ δ δ+
CH
- 3 MgBr
- + CH3CH2-
O-H CH4 + CH3CH2O Mg2+ + X
weaker base
carbon with a negative charge is a stronger base than an oxygen with a negative charge
δ δ+ δ δ+ δ
C C H + CH
- 3MgBr C -C MgBr- + CH4
sp sp3
sp2 weaker base
OH SN2 δ
O-
δ+ δ+
C6H5 C C CH2 C CH3
CH3 OMgBr
+ MgBrCl
steric interaction
dilute HCl C6H5 C C CH2 C CH3
CH3
Step One
Mechanism
R
nucleophilic attack R
δ δ+ δ δ+ δ on carbonyl carbon
-R MgX- + C -O R C O Mg2+ X
nucleophile ether
R R
(base)
electrophile halomagnesium alkoxide
Step Two (acid)
R H R
+
R C O H O X R C OH + H2O + MgX2
Mg2+ X
H R
R
alcohol
δ δ+ δ H H HBr H
δ+ δ ether
-R1MgBr- + (dilute)
C -O R1 C OMgBr R1 C OH + MgBr2
H H H
formaldehyde 1° alcohol
R2 R2 R2
δ δ+ δ HCl
δ+ δ ether
-R1MgBr- + (dilute)
C -O R1 C OMgBr R1 C OH + MgBrCl
H H H
an aldehyde 2° alcohol
R2 R2 R2
δ δ+ δ HCl
δ+ δ ether
-R1MgBr- + (dilute)
C -O R1 C OMgBr R1 C OH + MgBrCl
R3
R3 R3
a ketone
3° alcohol
Sec. 6: Alcohols, Ethers 18
General Reactions
R2 R2
δ δ+ δ R2
δ+ δ ether
-R1MgBr- + C -O R1 C O + R3OMgBr
C OMgBr
R3O R1
R3O
leaving δ δ+
a ester
group -R1MgBr
R2
R2
HCl
R1 C OH (dilute)
R3OH + MgBrCl +
R1 C OMgBr
R1
R1
3° alcohol
Grignard Reagent add twice because a ketone is created as an intermediate that can
react with the second equivalence of the Grignard Reagent
Although we can make acetylenic Grignards through an acid base reaction and
use it to our advantage. δ O
δ δ+ OH
CH MgBr δ δ+ 1) -δ+
CH3CH2C CH - 3 CH3CH2C -CMgBr H
ether
+ CH4(g) 2) H3O+
H3C δ δ+
O 1) CH - 2Li
CH
δ+ δ H3 C
-
2) H3O+ OH
O δ O δ δ+ OH
δ δ+ ether - CH- 3MgBr
CH
- 3MgBr + HOCH2CH2CCH3 BrMgOCH2CH2CCH3 HOCH2CH2C CH3
δ+ 2) H3O+
+ CH4(g) CH3
Oδ
- +
C δ+ Na O
+
δ δ+ 1) H3C CH3
CH3CH2C CH Na NH2 CH3CH2C C C CH3
CH3CH2C C- Na
2) NH4Cl, H2O CH3
H
+
H N H
OH
H Cl
CH3CH2C C C CH3 acid
+ NH3 + NaCl CH3
Cl O
A) B) C) D)
react with itself
C) CH2 O
A)
D) CH2
B) CH2
HO
Na2Cr2O7/H2SO4
Mg/ether 1) H
1 2 3
+
2) H3O
Br
O HO H O
O
HO
H
C) D) E)
A) B)
OH
1) CH3MgI 1) NaH
H2CrO4 1 2 3
2) NH4Cl
2) CH3I
O O O
A B C D
2) H3O+
O
OH
H
Cl
OH
A) OH B) C) D)
Which of the reagents would not produce the ethoxide ion from ethanol?
• NaNH2 ?
• LiN(CH(CH3)2)2 CH 3 CH 2 OH CH3CH2O
• KH
• NaSCH3 ¯NR2 Stronger base the alkoxide ion
• Na(s) H¯ Stronger base the alkoxide ion
Na or any alkaline metals Li, Na, K, Cs (2H2O + 2M 2M+ ¯ OH + H2(g)
Which would react faster with water Li or Cs - why
Order the following carbocations from most stable to least stable?
A) 1>2>3>4
H
B) 4>3>2>1
C) 1>2>4>3 C H
D) 3>4>2>1 H
E) 2>3>1>4 1) 2) 3) 4)
Free Energy
∆G‡ =
100°C
A) B) C) D) E)
Explanation:
The conjugate bases of acids such as HBr or HI are also good
nucleophiles, Br, I , whereas the conjugate bases of H2SO4 and H3PO4
are not good nucleophiles HSO4 and H2PO4 .
Explanation:
The chloride ion is a much poorer nucleophile and reacts very slowly. This
is a very poor method to make 1o chloroalkanes but a good way to make
simple primary iodo- and bromoalkanes
Sec. 6: Alcohols, Ethers 28