Transcript Document

2010/10/11
1
2010/10/11
2
Functional group
Reagent conditions
Result of positive test
-C=C-
bromine inert solvent
decolourisation
-Cl
warm with NaOH(aq)
add HNO3 then AgNO3 then NH3 (aq)
white ppt.
soluble in dil. NH3 (aq)
-Br
warm with NaOH(aq)
add HNO3 then AgNO3 then NH3 (aq)
cream ppt.
soluble in conc NH3 (aq)
-I
warm with NaOH(aq)
add HNO3 then AgNO3 then NH3 (aq)
yellow ppt.
insoluble in conc NH3 (aq)
-OH
add solid PCl5/SOCl2
acrid steamy fumes
-C=O
add 2,4-dinitrophenylhydrazine
warm with Fehling's solution
yellow ppt.
no change in blue colour
-CHO
add 2,4-dinitrophenylhydrazine
warm with Fehling's solution
yellow ppt.
red/brown ppt forms
-COOH
add NaHCO3
effervescence CO2 formed
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4
2010/10/11
5
Conc H2SO4/HNO3
Br2 FeBr3
NaOH/CH3Br
NaOH/CH3COCl
Br2(aq)
C=benzaldehyde
D=Benzoate
NaNO2
HCl, 0oC
A=cyclohexanol
B=cyclohexanone
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6
O
H
H3C
CH3O-
propene
H
H
CH2
C6H5OC2H5
Q
Br
H
R +
Br
CH3
H
CH3
OMe
H3C
CH2Br
Light, Br2
route 1
CH3
CH3
route 2
Br
Alc. KOH; HBr
CH3
2010/10/11
Br
Br
CH2 CH2Br
CH3
CH3 +
H
(1)
MnO4-
OH-
,
(2)
H+
FeBr3/Br2
-H2O
M
7
H3 C
H
heat
N (C8H4O3)
C6H4(CO2H)2 C6H4COOCO
MnO4-
Fe/Br2
OH-
Br
conc H2SO4
HNO3
Br
+ClC
H
NH
6
5
3
OHSn
B
NH2
nitrobenzene
40oC
A
conc. HCl
excess
H 2-3-dibromobutane
OHH3 C C
P
C2 H5OH
CH3
H3 C
H
CH3
H
H
H
CH3
Br
CH3O-
CH3
OHC2H5OH
C
but-2-yne
trans-but-2-ene
propene
C (C4H8)
CO2-
H3C
H
+
S (C9H12O)
1-methoxy-1-phenylethane
CNA
Br S 1
N
CH3
B (C5H10O2)
CH3I
NaOH
O
OH
A=2-cyano-2-methylpropane
B=2,2-dimethylpropanoic acid
Q
Methoxybenzene
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8
H
H
(1)
COCH3
CH3 CH2 C
(2)
LiAlH4, dry ether
H2O
LiAlH4
Dry ether
O
NHCH3
P2O5
O
2,2-dibromobutane
ex c es s HBr
CH
P
NH2
CH2NHCH3
C6H5CN
A
OHS-
H+
Q
+
HR
2010/10/11
B
Benzoic acid
Br2 NaOH
CH3 CH2
CH2NH2
LiALH4
T
O
C6H5CH=CHCH2OH
NH2
2,4-dinitrophenylhydrazine
CH3
9
Phenyl ethanoate
K
CH3COCl
-OH
-OH
OH
CH3COCl
NH2
O
CH3
HCl
+NH
3
O
solid I
2,4,6-tribromophenol
NO2
H
N
CH3Br methoxybenzene
Br2(aq)
OH
H
N
J
+N
HNO2
0oC
CuCl
Br
H3PO2
Naphthal-2-en-ol
N
N
N
H2O
OH
Cl
OHA + B
Benzoic acid + cyclopentylamine
C6H11NHCH3
C
NH2
little
CH3Br
Cl
excess
D
O
H
CH3
O
2010/10/11
CH 3Br
10
C6H11N(CH3)3
Alc. KOH
Methylcyclohexene
O3 Zn/H2O
OH
H
O
H
H
H
CH3
H2O
Cr2O72-
OH
H+
H+
Conc. H2SO4
HO
N
NH2
NO2
+
NaOH, 300oC
SO3H
O
O
NaBH4
????
C
H3 C
H
MnO4-/OH-;H+
CH3
Sn/conc.
???HCl
C2H5OH, H2SO4
CO2 C2H5
Benzocaine
H2N
Cl
P H3C
H3C
CH3
H2SO4
O3 Zn/H2O
MnO4- H+
NaBH4
(CH2)4 CO2H
O2N
CO2H
Cl2
CH3
CO2H
CH2OH
O
OH
OH
CH3
CO2H
LiAlH4
I2
NaOH
H
OH
N
NH2
H3C
NH3
CH3
CO2H
I2 NaOH; H+
PCl5
AlCl3
Benzene
HSO3-
H2SO4
NaBH4
O3;Zn/H2O
NaBH4
H2SO4
H2SO4
HNO3
AlCl3
H2SO4
Cr2O72H+
2010/10/11
I2 NaOH;
12
H+
H2SO4
ethanol
I2 NaOH
CH3Br
PCl5
KCN/ethanol
H+
KCN/ethanol
LiALH4
SOCl2 NH3
Br2 NaOH
Alc. KOH
O3;Zn/H2O
KCN/ethanol
LiAlH4
O
??
CH3
O
OH
CH2 NH2
CH3
NaBH4
NH3
C6H??
5COCl
HNO2 0oC
Phenol
CH2NH
NH2
CH2Br
??
N
N
HO
CH2OH
O
Cr2O72-/H+
???
NH3 heat
CH3Br
CH3
O
O
NHCH 3
CH3
OH
????
CH3
OH
NH
Cl
MnO4-/H+
C6H5NH2
CO2H
(CH2)4--CO2H
H
Rosenmund
(1) MnO4- / OH-
CH3
NO2
Fe/Br2
+
(2) H
Sn/conc.HCl Br
H
3-bromonitrobenzene
2010/10/11
B
B=Benzoic acid
C=Benzoyl chloride
D=benzaldehyde
NH2
Br
HNO2 0oC
14
H2
PCl5
C
D
Pt
+N2
Br
H2O
OH
OH
H
Cl
HCl
CH3
CH3
H
CN
KCN
CH3
ethanol
CH3
H
H
CO2H
+
CH3
H2O H
CH3
CH3
CH3
CH2OH
LiAlH4
CH3
CH3
dry ether H
H
A
CH 3
H2
O
C
Cr2 O72- H+
CO2H
OH
H+
KCN/ethanol
O
Benzaldehyde 2,4-dinitrophenylhydrazone
D
2,4-dinitrophenylhydrzaine
H
NaBH4 /ethanol
:NH2CH3
E
B C6H5CH=NCH3
I2 NaOH
OH
???
OH
COOH
Benzyl alcohol
???HCl
KCN
CH 3
CH3
O
??
O
OC2H5
MnO4-/H+
Ethanol/H2SO4
NO2
?
Cl
NH
CH3
CH3COCl
O
CH2OH
I2 NaOH
LiAlH4
Cl
KI
NO2
A
Sn/HCl
CH3
???
CH 3
A
Sn/HCl
H+
CO2H
B
NaNO2/HCl
I
NH3 ??
C6H5COCl
Cl
NH
O
O
OH
Br
NaBH4 C6H11OH
H3PO4 cyclohexene
OH
OH
CH3-C-(CH2)4-CO2H
H
CH3
I2 NaOH
CH3 LiAlH4
H
???
PCl5
CH2 NH2
???
??
Br(aq)
HCN H3PO4
LiAlH4
CH2 NH2
NaBH4 PCl5
KCN LiAlH4
????
toluene  benzaldehyde
NO2
Br2/FeBr3
OH
H
P
H
CH3
excess
OH-
CH3
C2H5OH
CH3
H
2010/10/11
C
-HCl
PCl5
Cl
CH3
H
KCN
NH2
CH3
NH3
H
L
H2O
I???
2 NaOH
CH3CH2-C-NH 2
PCl5
NH3
OH
o
0C
HNO2
Primary amine
16
N
O
CH3CH2-C-CH 3
-HCl
H+
C2H5OH
O
CH3
but-2-yne
trans-but-2-ene
OH
Br
H3C C
M
3-bromonitrobenzene
CH3O
CH3O
H3C
CH2Cl
CH3
H
+ N2
3-bromonitrobenzene
3-bromoaniline
Aniline
2,4-dibromoaniline
CH3COCl/AlCl3
FeCl3 Cl2
Zn/Hg HCl
Br2 Alc. Excess KOH
a = SOCl2 b = benzoyl chloride
E=H2N(CH2)3CH3
D=C6H11CH2CONH2
E=Benzyl alcohol
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OH
O
O
CNCF3
H
CF3
CN
ethanol
OH2
O
OH
CH 2
CH2
LiAlH 4
CH 2
H
dry ether
CH2
MnO4-
CO2H
+
H
G
OH
H2??
SO4
+
H H2O
O
1-Phenylethanol
KCN
H+
G
PCl3
OH
CH3NH2
H
N
H
CO2H
CO H
H 2 and
HCN
????
PCl
5
KCN
H+
OH
OH
O
O
OH LiALH4
H
CH3
2-Phenylethanol
CH 2CO2H
+
H
heat
F
E
H
H
conc. HCl
O
O
H
Zn
COCl
H
CF3
CH2OH
CF3
CO2H
dry ether
AlCl 3
H
CH2OH
OH
LiAlH4
+
phenylethanoic acid
CH3
OHJ + K
O
CH3
H
NH3
CO2H
I
N CH3 Br
+
CH3
NaBH4
KCN
H+
H2SO4
PCl5
KCN
NaBH4
H+
PCl5
KCN
I2
NaOH
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NaBH4
20
H+
C
conc.H2SO4
1
+
C2
+
C3
heat
HO
CH3CH2COCl
NHNH2
NO2
D
H
K2Cr2O7
H3O+
NH2
H3C
F
CH2NH2
CONH2
CH=CH2
D
C
B
A
NO2
E
Br
NH2
HBr
CH 2NH 2
and
CH3
OH
step 1 CH CH CH
N(CH3)2
3
2
CH3CH2CO
N(CH3)2
step 2
CH3CH=CH
N(CH3)2
A
conc.HNO3/conc.H2SO4
NO2
Sn in HCl, heat under reflux
NaNO2/HCl
>10oC
55oc
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NH2
21
OH
O
O
HO
CH2OH
CO2H
O
H
O
H+
LiAlH4
NH2
I
N
Hea
t
O
O
CH3
H3C
H
CH3
CH3
CH2OH
H3C
NH2
H
CH3
OH
H3C
CHO
H
H
H3C
CN
Br2 NaOH
NH2
H
H
Cl
CN
CH3
CH3
H3C
NH2
H
H
CN
H3C
NH2
H CO2H
H
NH2
LiAlH4
H
O
H
CH2CH2OCOCH3
CH2Br
CH2OH
KCN
ethanol
HBr
O
HO
2010/10/11
O
LiAlH4
CH2CN
H+
CH2CH2OH
B
CH3CO2H
H2SO4
O
+
HOCH2CH2OH
OCH2CH2O
OH
22
O
O
-H2O
N
???
O
Br
OH
N
CH2CO2H
CO2H
CH3
CH 2NH 2
CN
CONH2
CO2 CH3
????
CN
alc.
CH2 NH2
LiAlH4
I2 NaOH
LiAlH4
PCl5
KCN/ethanol
H+
dry ether, H+
CN-
H+
heat
CO2H
CH2 OH
LiAlH4
dry ether
PCl5
dry ether
Br
C2H5OH
C(CH3)3
CH2Cl
CH2OH
CO2H LiAlH
4
CN
CH2CN LiAlH
-
4
ethanol
C(CH3)3 (1) O3
KOH
dry ether
C(CH3)3CO(CH2)3CHO
(2) Zn dust
O
CH3CHCH2
HO
OCH2CH3
CH3CHCH2CO2H
????
CH2CH2NH2
CO2H
CO2 H
CH3OH
conc.
OH
W INTERGREEN OIL
(ACIDIC)
H2SO4
Good for ethanoylation
SALICYLIC
ACID
CH3 CO-O-COCH3
OH
ASPIRIN
CO2 H
cyanohydrin
G
NaBH4
C2H5OH
CN-
Benzoate
CH2OH
O
Ag(NH3)2+
H
F
NH2OH
E
Benzaldehyde oxime
Remove –SO3H
conc H2SO4
H3C
L
Br2
M
FeBr3
O
LiAlH4 dry ether
CH2=CH
OC2H5
H
CH2OH
??H2SO
4
HCl
H2O
H
Cl
OH2
N
2-bromotoluene
P
+
H
O
2-bromobenzoate
H
CH2=CH
Q
KOH
Cr2O72-/H+
??2,4 DNP
MnO4-/OH-
R
H
HBr
O2N
N
N
H
NO2
KCN, LiAlH4
NH3 Br2 NaOH
CH3COCl MnO4- H+
Benzyl chloride
HCl KCN H+ LiALH4
I2 NAOH LiALH4 PCl5
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25
propanone
Hex-3-ene
Light Br2
2010/10/11
O3 Zn/H2O
Alc. KOH
26
H
LiAlH4
OH
O
O
drastic
OH
oxidation
G C7H6O2
C15H14O (ketone)
C15H16O (2o alkanol)
F
F contains two separate benzene rings and drastic oxidation reduces the compound to benzoic
G (C7H6O2 ) which has a pKa of 4.2
E
CH3
OH
-CO2(CH2)2
CO2NH3+
pH = 9
-CO2(CH2)2
OH
H
CO2H
NH3+
Cl2
O3
+
H
H2
O
heat
OH
O
OH
N2
OH
N
+2
HNO2 <5oC
O
Br2 NaOH
ethanol
+
NH2
NH2
KOH
CH2OH
H2
O
O
Cl
light
CH2N2
LiAlH4 ether
CO2NH2
pH = 13
+
<0oC
CH2NH2
O
-CO2(CH2)2
pH = 5
HNO2
NH2
H
CO2NH3+
HCO2(CH2)2
pH = 2
Br2 NaOH
OH
O
H
H
O
H3C H
OH
Zn , acid
H3PO4
O
H3C
CH3 O
3
+ N2
O
O
O
NO2
O2 N
NO2
N- NH
+
O
H2 N- NH
OH
OH
Br
Br
3Br2
NO2
+
+
3HBr
Br
CO2 CH3
NaBH4 in methanol
H3C
H
N (CH3)2
No reaction
N(CH3)2
I2 NaOH
O
PCl5
CH3CH2-C-CH 3
CH3CH2-C-NH 2
NH3
O
H2 with Pd
CN-
H
LiALH4
Dry ether
O
LiAlH4 in dry ether
CH3
H3C
O
C2H5
C2H5
CN-
O
CN
C2H5
-O
cyanide attacks from both sides of the planar ketone,
resulting in a racemic mixture of two optical isomers.
CH3
H3C
Cl
CH3
2010/10/11
H
H
O3
NaOH
C2H5OH
H3C
Zn/CH3CO2H
CH3
28
H3C
H3C
H
O
+
O
H
OH
????
CHCH3
CH3O
CH3O
N
H2 NCH(CH3)2
(1)
P
CH2 NH2
CH3OCH(CH2)2 CONHCH(CH3)2
CH3
NaBH4
OH
(2) H2O
CH3
O
OH
CH3
H
+
O
OCOCH3
O
CH3
H3C
CH3CO2H
H
CH3
OH
O
C(CH3)3
(H3C)3C
+
C(CH3)3
(H3C)3C
+ ROO.
ROOH
+
hydroperoxide
CH3
CH3
O
H
OH
CH3
NaCN, NH4Cl
NH2
CH3
CH3
H3O+
CN
heat
OH
CO2H
CH3
H
H
MnO4-/H+
NH2
CH3COCl
CO2H
OCOCH3
Aspirin
CO2H
Distinguish between Isomers
Cl
CH3
CH2Cl
Cl
and
and
Cl
OH
NH2
CH2OH
CH3 and
H
an d
O
O
H
OH
and
O
O
CH3CH2CCH2CH3
and
O
NH 2
and
CH 2NH 2
O
O
and
C 2H 5
C 3H 7
H2N
O
NH2
NH
CH 2NH 2
and
CH3
CH2OH
and
OH
CH3
O
OH
OH
CH2CH3
and
O
CH3 and
CHCH3
CH3
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30
anhydride
H+/ MnO4-
2010/10/11
32
Synthesize compound B, commonly known as methamphetamine by the following route.
O
?
N
A
LiAlH4, H2O
(i)
what class of organic compound is A?
B
(ii)
what reagents are needed to convert the starting material into A?
(iii)
draw the structure of compound B.
(iv)
what other reagent(s) could accomplish the transformation A to B?
(v)
into A.
Draw the mechanism for the transformation of the starting material
2010/10/11
33
O
Distinguish between these two compounds
CH(OH)CH3
and
CH3
CH2NH2
CN
COOCH3
O
CH3
O
CO2H
Cl
NH2
O
CHO
CH2OH
H3C
A
G
O
HSO3-
Ag(NH3)2+
NaOH
NO2
O
NaBH4
O2N
H
CH2
2010/10/11
NHNH2
D
E
H
C
CN-
H
I2
O
B
K2 Cr2O7 /H+
F
O
O
O
O
CH3
CH3
OH
34
H3C
CH3
H
CN-
H
SN2
H
CH3
+
Br
CH3
Br
+
Br
CH3
OH
H
+
H
ethanol
CH3
H3C
CH3
CN-
+
Cl
CH3
H3C
CH3
CN
CH3
in ethanol is a good nucleophile but a weak base and only substitution prodcut is formed
Alc. NaOH
Cl
H
H
+
CH3
H3C
CH3
OH-
CH3
CN-
H3C
H
H
H3C
Br
CH3
+
H3 C
SN1
H
+
CN
H
HBr
H
OH
CH3
H3 C
NC
C3H7
Br
O
CH3
(major disubstitution product)
H
H
+
H
SN1
H
H
O(CH3)3
Electrophilic substitution
NO2+
electrophilic
addition
H3C
Br
O2N
H
H3C +
O
O
Br
-H+
OH
+
OH
H
and
CN
CN-
H3C
Br
O
C2H5
O2N
restore
aromaticity
C2H5
CN
and
CN
C2H5
CN
C2H5
Nucleophilic addition on carbonyl group
OH
O
OH
O
oxygen in air / enzyme
brown polymer
Diquinone
R
R
CO2-
OH-
NH
NH2
+
O
O2N
CONH2
COCl
CO2H
PCl5
O2N
O2N
2010/10/11
NaOH
T
O2 N
Hoffmann degradation
HBr
Br
NH2
Br2
37
U
C 2H 5
CH=CH 2
CO2H
X, optically active
H
H
C 2H 5
H2
CH 2CH 3
CO2H
optically inactive
Ni
H
+
OH
-H2O
CH 3
H
H
+
H 3C
CH 3
H
CH 3
H
+
CH 3
H
tri-substituted alkene
is the major product
H
CH(CH 3)2
H
mono-substituted
alkene is minor
+
H
H
H
CH3
H
H
OH
H
H
+
-H2O
+
H
CH3
1-methylcyclopentene
H
H
H
CH2
I
H
H
+
CH3
OH
H
-H2O
(major)
CH3
3-methylcyclopentene
2-methylcyclopentanol
H
H
+
CH2
H
H
I
H
H
H
CH2
H
H
Di-substituted alkene
is the major product
H3C
Br
CH3
CH3
SN1
H3C
substitution product
is another major product
CH2
H
CH3
H
+
CH3
mono-substituted
alkene is the minor
CH3
O
H3C
O
CH3
As phenolate is a strong nucleophile but a weak base, substitution product predominates.
2010/10/11
38
2010/10/11
39
HO
CO2H
CH3CHOHCO2H
KMnO4
+
Zn/Ch3CO2H
C10H12O
CO2-
H 3C
OH
CH 3
H 3C
H3C
CH 3
+
H 3C
CH 3
NH2
Cl
CH 3
+N
H3C
LiAlH4
dry ether
T
H 3C
CH 3
Cl
V
C10H14O
O
CH 3
OH 2+
CH 3
H 3C
Pd
CH3
CH 3
+
H
CH3
U
I 2/NaOH
iodoform test
H
H2
H
H CH3
O3
O
CH 3
HO
H
planar tertiary carbocation
+
is a stable intermediate,
CH 3
CH 3
favoring the SN1 mechanism
CH 3
H 3C
Cl
Same product is formed
whether Cl- attacks from
above or below the plane
HO
N
N
H3C
Azo dye coupling
Br2
FeBr3
N
red
precipitate
MnO4
CO2-
-
Br
OH-
Nitrobenzene
HNO3
40oC
Sn
Zn/Hg
conc H2SO4
A
conc. HCl
B
Br
OH-
NH2
H
H
H
Cl
H3C
H
cis-1-chloropropene
does not give Cl
H
H
H
CH2Cl
H
H
+
H
H
CH2 +
3-chloropropene gives a primary carbocation
which is stabilized by resonance. The carbocation
H
forms H
and AgCl with AgNO3
H
CH 2OH
CH3
alkaline
C
CH3
heat
C=1,2-benzenedicarboxylic acid
D=Benzoic anhydride
D
MnO4-
NH2 HNO
N
2
+
N
N
OH
N
N
+
N Cl
+
H
Br2 NaOH
NH2
OH
H2O
O
C (C4H8)
2010/10/11
C2H5OH
H3C
P
heat
CH3
OH-
N2
+
Azo dye
HCl
H
P2O5
NH2
H
+
OH
NH2
H
P=Butanenitrile
LiALH4
CN-
Br S 1
N
CH3
41
A
B (C5H10O2)
H
OH
OH 2
Cr2O7
+
+
O
I2/NaOH
NOH
NH 2OH
H
H
O
O
2-
NH3
then H+
O
-H2O
OH
NH2
HO
O
CH3
OH
+
H
excess
CO2H
Similar to phenolmethanal reaction
O
CH3
B
D
OH
CO2H
E
O
O
phenolphthalein
O
CH3I
Na
C
OH
C
O
C
SN2
OMe
Q
triphenylmethanol
CH3I
triphenylmethoxymethane
is a primary halide which will not underdo SN1 reaction because the carbocation is unstable
The nucleophile, Q therefore attacks
CH3I
via SN2 reaction. As the electron-rich site of Q is
sterically hindered, its nucleophilic substitution with CH3I is difficult and extremely slow.
CO2H
CO2H
CH3(CH2)3OH
acid catalyst
CO2(CH2)3CH3
F
CO2(CH2)3CH3
= C16H22O4