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OH
COOHNH(CH3CO)2O
A
AlCl3B
Br2 (CHCl3)
C D
E
LiAlH4
H2/Pd-C
Salbutamol
TRNG I HC S PHM H NI
THPT CHUYN CHUYN : HON THNH S BIN HO- THHC
DNH CHO HC SINH I TUYN CHNH THC
Cu 1: Hon thnh s :
NO
NO
Toluen
Cl2
FeCl3
F
SO2Cl2, AIBN
10 h, heatG
C7H7Cl
+ H
J
Butan-2-on
+ HCHO + K
J +
a salt, can not be isolated
MHCl
Clobutinol-hydrochlorid
HCl
N
(L)
(L)
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Cu 2: Hon thnh s sau:
Cu 3:Hon thnh s :
O
COOH
+ ZnBrCH2COOC2H51.
2. H+, H2O
A
(C14H22O3 )
H+, H2O,
- C2H5OH, -H2O
B
(C12
H16
O2
)
isomerisation
C
(C12H16O2)
a derivate of benzene
C2H5OH/H++
D
(C14H20O2)
LiAlH4E
(C12H18O)
HBrF
(C12H17Br)
+ CH3CH(COOC2H5)2
-
Na+
G
(C20H30O4)
1. ester cleavage
2. decarboxilation
SOCl2
H
(C15H21OCl)
AlCl3
I
(C15H20O)
NaBH4
(C15H22O)
J+S, heat
cadaline
carvone
OH
A1. O3
2. H2O2/H+
BI2, OH
-
CHI3
CKMnO4
hotE
H2
D
H2SO4H2
GH2
H
HBr
F
limonene
cat
cat
cat
+
m t d n xu t c a benzen
ng phn ho
1. thu phn este
2. cacboyxyl ho
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1.
cat: ngha l xc tc.
2. Tm cc cation sau y.
Cu 4: Hon thnh s :
OH OH
H+
K+-H2O
L+cyclisation
M+?
?
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OH
COOEt
COOEt
PBr3A (C10H21Br)
NaOEt
in EtOH
+ A
2. H+,
B (C12H24O2)
B + SOCl2 C
+ C2H5OH
D (C14H28O2)
D
LiAlH4E
PBr3F (C12H25Br)
F + Mg G
EtOOC-(CH2)5CHOH
Zn/HCl
I J
dann H+, H2O
CrO3I
K
Ether
1. OH-, H2O
1. OH-, H2O
2. H+
dann: sau vi
Cu 5: Hon thnh s :
COOC2H
5
COOC2H
5
Cl
OO
+
?
A B
KOH/H2O1.
2. HAc, in EtOH (C6H10O2)- CO2
LiAlH4
1. TsCl/Pyridin
2. NaCN/DMSO
+ CH3MgI1.
2. H+/H2O (C6H12O)(C8H14O)
MCPBA
(C7H11N)
(C8H14O2)H+
unstable intermediate(C8H16O3)
via cyclisation
CDE
F
O
COOEt COOEt
OH
COOEt
OH
O
OH
OO
yeast, sugar
H2O 1
2
LDA
CH3I
CrO3
MCPBA
Baeyer-Villinger
oxidation
G(C9H14O4)
LiAlH4
H(C7H16O3)
a triol
+
PC
J
+H+,
(-)-frontalin
PC
KL M N
ng vngthng qua m t ch t trung gian
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yeast: ln men.
Frontalin:
Cu 6: Hon thnh s :
O
O 12
3
45
6
7
8
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Cu 7: Hon thnh:
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Cu 8: Hon thnh:
Cu 9: Hon thnh:
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Cu 10: Hon thnh:
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LI GII CHUYN Hon thnh s . THHC
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Cu 1:
A: 2 bp
B: 4 bp C: 3 bp
D: 3 bp
E: 2 bp
7.2. Mechanism: SN2 1 bp
7.3.Allocation 5 bp
7.4. R-salbutamol: 2 bp
7.5. Structures F to N
CH
CH
CH
OH
C
H2
OHCH
OH
CH
2
NH
CH3
CH3
CH3
OOH
O
O
OOH
OH
O
OOH
OH
O
Br
OOH
OH
O
N
OH
OH
OH
N
4.40
4.60
4.60
4.60
6.8-7.3
6.8-7.3
6.8-7.3
4.40
4.601.05
1.05
1.052.5
NH
OH
OH
OH H
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F: 2 bp
G: 2 bp H: 2 bp
Mg
J: 2 bp K: 2 bp
M: 4 bp
N: 2 bp
7.6. Name of the reaction: Mannich 1bp
7.7. Mechanism: SE1bp
7.8. Mechanism: SR 1bp
7.9. chiral centres 2 bp
7.10. Stereoisomers:4 1bp Relationship: enantiomers/diastereomers 2 bp
Cu 2:
ClOH
N
**
Cl
Cl
Cl
Cl
MgCl
NH
ClO
N
MgCl+
ClOH
NH+
Cl-
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A: 1, 5 bp B: 2 bp C: 1 bp D: 1 bp
E: 1 bp F: 1 bp G: 2 bp H: 1 bp
I: 2 bp J: 1 bp
Cu 3:
7.1. Strucutres A to H
A: 1 bp B: 1.5 bp C: 2 bp D: 2 bp
E: 1 bp F: 1.5 bp G: 1bp H: 1bp
7.2. stereo descriptors geraniol: E- 1 bp nerol: Z-
OH
CH2COOC
2H
5
CHCOOH CH2COOH COOC
2H
5
OH Br
COOC2H5
COOC2H5
ClOC
O OH
O
OH
O
O
OH
O
OH
OH
OHBr
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OH
1 bp
7.3. structur of K +
1.5 bp
7.3. structur of L+
1.5 bp
7.3. structur of M+
2 bp
7.3. formulae + H2O -H+
1 bp
7.4. centre
1 bp
7.5. N 1
bp
7.5. O 1
bp
OH2+
+
+
*
OH
OH
O
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7.6. mechanism 3 bp
Cu 4:
7.1. Name: 10-Methyloctadecansure 1 bp
7.2. configuration formula: 1 bp
7.3. A
1 bp
7.3. B
3 bp
OH
+
++ H2O
- H+
O
OH
Br
O
OH
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7.3. C
1 bp
7.3. D
1 bp
7.3. E
2 bp
7.3. F
1 bp
7.3. G
1 bp
7.3. H
2 bp
O
Cl
O
O
OH
Br
MgBr
O
OOH
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7.3. I
1 bp
7.3. J
2 bp
Cu 5:
Frontalin a pheromone of the bark beetle
6.1. Which substance is referred to in the case of the question mark above the arrow in the first step o
the synthesis?
strong base, e.g. NaOEt 1bp
6.2. Find the structures of the compoundsA, B, C, D, E, F and the unstable intermediate.
6.3. Determine the number of stereogenic centres in frontalin and mark them with * in the formula in thbox. How many stereoisomers has frontalin?
A 2bp B 2bp C 2bp
O
OO
O
O
COOEt
COOEtCOOH OH
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D 3bp E 3bp F 1.5bp
Unstable intermediate 1.5bp frontalin: 1bp
stereoisomeres: 2 1bp
6.4. Attach the signals which are marked with a, b and c to the respective protons in frontalin. Thereb
combine the letters with the numbers of the C-atoms where the hydrogen-atoms which create th
signal, are bound to.
a: 2 H at C7 1bp b: 6 H at C2. C3. C4 1bp c: 6 H at C1. C5 1bp
6.6. Give the IUPAC-name of (-)-frontalin.
(1S. 5R)-1.5-Dimethyl-6.8-dioxa-bicyclo[3.2.1]octan 3bp
6.7. Determine the absolute configuration at C1 and C2 in the -hydroxyester.
(1R. 2S) 2bp
6.8. Find the structures of the compounds G, H,J, L, M and N.
G 1bp H 3bp
CN
OO
O
O
OH
OH
OO
* *
O
COOEt
O
O
COOEt
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J 2bp L 2bp
M 2bp N 1bp
Cu 6:
OHOH
OH
OOHC
O
OH
O
O O
OO
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Cu 7:
Cu 8:
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Cu 9:
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Cu 10:
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