Phn 1:

1.1

TNG QUAN...................................................................................................8
GII THIU DIPTEROCARPOL........................................................................8

1.1.1

Ngun gc......................................................................................................8

1.1.2

Cu trc ha hc..........................................................................................11

1.1.3

Danh php....................................................................................................11

1.1.4

Tnh cht vt l:...........................................................................................11

1.1.5

Cc sn phm c tng hp t dipteroarpol..............................................12

1.2

MT S PHN NG TRN MCH NHNH CA DIPTEROCARPOL.....14

1.2.1

Phn ng oxi ha to lacton.........................................................................14

1.2.2

Phn ng trn nhm OH............................................................................18

1.2.3

S to thnh ester.........................................................................................19

1.2.3.1

Phn ng ester ha Fischer gia acid carboxylic v alcol di s hin

din ca acid v c................................................................................................19

1.2.3.2

Phn ng t clorur acid........................................................................20

1.2.3.3

Phn ng t anhydrid acid....................................................................21

1.2.3.4

Phn ng t nitril..................................................................................22

1.2.4

1.2.4.1

Tch nc ca alcol bng mt acid proton mnh.................................22

1.2.4.2

Tng hp Williamson...........................................................................22

1.2.5
Phn 2:
2.1

S to thnh eter..........................................................................................22

Phn ng tng hp epoxid...........................................................................23

THC NGHIM.............................................................................................25

HA CHT, THIT B V DNG C TH NGHIM....................................25

2.1.1

Ha cht:......................................................................................................25

2.1.2

Dng c:.......................................................................................................25

2.1.3

Thit b:........................................................................................................26
1

2.2

THC NGHIM.................................................................................................26

2.2.1

iu ch 20(s)-hydroxydammar-24-en-3-ol..............................................26

2.2.2

iu ch 20(s)-hydroxydammar-24,25-epoxyl-3 -ol.................................26

2.2.3

iu ch 20(s)-hydroxydammar-24,25-epoxy-3- p-toluenesulfonyl.........27

Phn 3:

KT QU V BIN LUN..........................................................................28

3.1

Kh nhm carbonyl vng A................................................................................29

3.2

Epoxid ha lin kt i C=C trn mch nhnh...................................................33

3.3

Tosyl ha nhm OH vng A...............................................................................38

Phn 4:

KT LUN.....................................................................................................47

Danh mc:
2

Hnh 1.1: Hnh dng cy l v qu ca cy du ri.............................................................9

Hnh 1.2: Dammarendiol...................................................................................................10
Hnh 1.3: Ocotillol.............................................................................................................10
Hnh 1.4: Dammardienon..................................................................................................10
Hnh 1.5: Dipterocarpol.....................................................................................................10
Hnh 1.6: Cu trc Dipterocarpol.......................................................................................11
Hnh 1.7: Mt s dn xut ca dipterocarpol....................................................................14
Hnh 1.8: Monomer...........................................................................................................16
Hnh 1.9: Dimer.................................................................................................................17
Hnh 1.10: Phn ng lacton...............................................................................................18
Hnh 1.11: Ester ha Fischer..............................................................................................20
Hnh 1.12: Phn ng acil ha to ester..............................................................................20
Hnh 1.13: Phn ng tng hp epoxid...............................................................................23
Hnh 3.1: Mt s dn xut ca dipterocarpol....................................................................28
Hnh 3.2: C ch phn ng to alcol dipterocarpol...........................................................31
Hnh 3.3: Hp cht alcol dipterocarpol.............................................................................32
Hnh 3.4: C ch phn ng to epoxid dipterocarpol........................................................35
Hnh 3.5: Hp cht epoxid dipterocarpol..........................................................................36
Hnh 3.6: Trang thi cng hng tosyl clorur....................................................................40
Hnh 3.7: C ch phn ng tosyl ha................................................................................42
Hnh 3.8: Hp cht 3-tosyl epoxy dipterocarpol...............................................................43

Danh mc:
3

Bng 1.1: Mt s phng php tng hp lacton................................................................15

Bng 1.2: T l sn phm thay i theo n.........................................................................16
Bng 1.3: to thnh benzanilid t anilin vi cc tc cht khc nhau.................................20
Bng 3.1: Mt s tc nhn cung cp hidrur.......................................................................29
Bng 3.2: D liu 1H ca 3-alcol dipterocarpol..............................................................32
Bng 3.3: D liu 1H ca vng epoxy dipterocarpol.......................................................37
Bng 3.4: D liu 13C ca vng epoxy dipterocarpol......................................................38
Bng 3.5: D liu 13C ca vng epoxyl dipterocarpol.....................................................44
Bng 3.6: D liu 1H ca vng epoxy dipterocarpol.......................................................45

Danh mc:
4

Ph lc 1: Ph 1H NMR ca dipterocarpol.......................................................................51
Ph lc 2: Ph dn 1H NMR ca dipterocarpol................................................................52
Ph lc 3: Ph dn 1H NMR ca dipterocarpol................................................................53
Ph lc 4: Ph 1H NMR ca 3-alcol dipterocarpol.........................................................54
Ph lc 5: Ph dn 1H NMR ca 3-alcol dipterocarpol..................................................55
Ph lc 6: Ph 1H NMR ca 3-alcol epoxy dipterocarpol..............................................56
Ph lc 7: Ph dn 1H NMR ca 3-alcol epoxy dipterocarpol.......................................57
Ph lc 8: Ph dn 1H NMR ca 3-alcol epoxy dipterocarpol.......................................57
Ph lc 9: Ph 1H NMR ca 3-tosyl epoxy dipterocarpol..............................................58
Ph lc 10: Ph dn 1H NMR ca 3-tosyl epoxy dipterocarpol.....................................59
Ph lc 11: Ph dn 1H NMR ca 3-tosyl epoxy dipterocarpol.....................................60
Ph lc 12: Ph 13C NMR ca 3-tosyl epoxy dipterocarpol..........................................61
Ph lc 13: Ph dn 13C NMR ca 3-tosyl epoxy dipterocarpol....................................62
Ph lc 14: Ph dn 13C NMR ca 3-tosyl epoxy dipterocarpol....................................63

LI CM N
5

Em xin t lng bit n su sc n thy L Vit Tin tn tnh hng dn

em trong thi gian qua.
Em xin cm n ch Phan Thanh Tho, cc anh ch v cc bn chung phng
lab gip em trong qu trnh lm thc nghim.
Em xin gi li cm n n cc thy c khoa ha tn tnh ch dy trong
nhng nm thng ngi trn ging ng gip em trao di kin thc c th hon
thnh tt bi tiu lun ny.
Mt ln na em xin gi li cm n n tt c v xin chc qu thy c li chc
sc khe v thnh cng trn s nghip ca mnh. Chc cc anh ch v cc bn sc
khe v thnh cng trong cng vic.

Trn trng cm n
TP.HCM ngy 22 thng 07 nm 2015
SV: V Thnh Lun

M U
6

Trong tng hp hu c, nghin cu v m rng kh nng ng dng ca mt

hp cht bt k, ngi ta to ra nhiu dn xut khc nhau bng s bin i a dng
trn cht . Bin i c th l s oxid ha, s kh, ester ha v thng
c tin hnh trn cc nhm chc nh carbonyl, hydroxyl, amin, aldehyd hay
bin i t nhm chc ny sang nhm chc khc hot ng hn.
Dipterocarpol l mt tritepen chim hm lng cao trong nha cy thuc h
Sao du (Dipterocarpaceae). Vi cu trc mch nhnh l alkenol, dipterocarpol c
th cho nhiu phn ng nh ng vng alkenol to thnh lacton, phn ng trn
alken v alcol. Trn vng A ca lacton cn nhm carbonyl c th chuyn ha
thnh vng epoxid.
Trong ti ny, chng ti tm hiu phn ng bin i nhm carbonyl trn
vng A ca dipterocarpol thnh dn xut hydroxyl v tosylat, ngoi ra lin kt i
trn mch nhnh c chuyn ha thnh dn xut epoxyl.

Phn 1: TNG QUAN

1.1 GII THIU DIPTEROCARPOL
1.1.1

Ngun gc[1]

Dipterocarpol l mt hp cht c tm thy trong nha du ca cc cy h

Du (qu hai cnh) (Dipterocarpaceae). c bit, trong cc cy thuc ging du ri
(Dipterocarpus), dipterocarpol chim hm lng rt cao (gn 50%)[1].

Hnh 1.1: Hnh dng cy l v qu ca cy du ri

Vit Nam, cy h Du phn b t Bc n Nam nhng ph bin nht l cy

du ri hay cn gi l du con ri trng hay du nc (l loi Dipterocarrpus

alatus)[2]. V th Vit Nam, dipterocarpol ch yu c c lp t nha du

(oleresin) tch t cy du ri[1].
Cc loi cy thuc h Sao du c cng dng trong cng nghip: lm sn bo
v tu, lm mc in y hc: tr au nhc, l lot...
Nm 1966, G. Ourisson v Biset nghin cu phn cn ca nha cy thuc
h Sao du, kt qu trong nha chai c 4 thnh phn ha hc chnh:
dammadienon, ocotillol, dammarendiol v dipterocarpol. Trong , hp cht
chim hm lng cao nht l dipterocarpol.

Hnh 1.2: Dammarendiol

Hnh 1.3: Ocotillol

Hnh 1.4: Dammardienon

Hnh 1.5: Dipterocarpol

1.1.2

Cu trc ha hc.

Dipterocarpol l mt tetracyclic triterpen (dammaran) gm 4 vng A, B, C, D,

vi vng A cha nhm C=O ti C 3 v mt dy nhnh cha mt nhm OH gn trn
C20 v mt ni i C=C u mch.
Cng thc phn t: C30H50O2

Hnh 1.6: Cu trc Dipterocarpol

1.1.3

Danh php.

[2]

Tn thng thng: Dipterocarpol, Hydroxydammarenon II.

Tn IUPAC:(5R,8R,9R,10R,14R)-17-((S)-1-hydroxy-1,5-dimetyl-hex-4-enyl)4,4,8,10,14-pentametyl

hexadecahydrocyclopenta[A]phenanthren-3-on,

20

hydroxy-3-oxodammar.
1.1.4

Tnh cht vt l[3]:

Dipterocarpol l mt cht rn mu trng, tinh th hnh kim.

10

Dipterocarpol khng tan trong nc v alcol lnh. N tan tt trong alcol nng,
benzen, cloroform, dietyl eter.
Cng thc phn t: C30H50O2
Trng lng phn t: 442.70 g/mol
Nhit nng chy: 135 1360C
1.1.5

Cc sn phm c tng hp t dipteroarpol[5]

[9]

Cc sn phm tng hp t dipterocarpol rt a dng v dipterocarpol mang

nhng nhm linh hot d dng bin i nh nhm ceton, alcol, alken.
Cc sn phm bin tnh t dipterocarpol ch yu c hot tnh sinh hc vi kh
nng chng vim ng dng trong y hc.
T dipterocarpol c th cho ra nhiu dn xut khc nhau nh:
- To dn xut epoxyd bng cch cho phn ng vi m-CPBA sau thy phn
trong acid cho ra sn phm l diol.
- To dn xut lacton bng tc nhn O3, CH2Cl2.
- Bin tnh vng A bng cc tc nhn nh NaBH4 hoc phenylhydrazyn.
Dipterocarpol v mt s dn xut ca n cng mang nhng hot tnh ca cc
hp cht triterprnoid c khung dammaran nh hot tnh khng vim, khng virus
typ A v typ B. Trong hp cht 24-metyl-20(S),24(R)-epoxydammaran-3-one
c coi l hp cht c tnh khng virus mnh nht. Tuy nhin, hp cht ny
chim hm lng rt t trong thc vt. Trong khi , dipterocarpol chim hm
lng cao hn v t n chng ta c th tng hp cht 24-metyl-20(S),24(R)epoxydammaran-3-one mang li tim nng c th tng hp ra nhiu hp cht c
tnh khng vim vi lng ln.
Mt s kho st hot tnh ca dipterocarpol v dn xut ca n c thc
hin:
11

- Kho st tc dng khng vim cp tnh trn chut nht trng.

Ngi ta tim vo gan bn chn chut nht hp cht gy vim, sau chn
nhng con c th tch chn b sng ph 50-100% tin hnh th nghim. Tip
theo cho chut ung cc dung dch c pha dipterocarpol v cc dn xut khc ri
theo di mc sng ph chn chut. Kt qu cho thy dipterocarpol v cc dn
xut u c hot tnh khng vim nht nh.
- Kho st hot tnh khng u trn t bo[5]
Ngi ta nui ly t bo ca cc khi u, cc khi u ny c ly trn cc b
phn khc nhau ca c th nh gan, phi, thn... Sau cc t bo ny c nui
dng pht trin, trong qu trnh nui dng ny ngi ta thm vo mi
trng nui cc dn xut khc nhau ca dipterocarpol. Kt qu cho thy tc
tng trng ca cc mu t bo khi u c thm dn xut th b chm li rt nhiu.
T c th kt lun cc dn xut ca dipterocarpol trn c kh nng c ch s
pht trin ca t bo ung th.
V vy, chng ti hi vng c th tng hp thm nhiu dn xut khc ca
dipterocarpol vi nhng hot tnh khc, c th cho nhiu ng dng trong y
hc.
14-dimetyl-18-nortestosteron sau khi c Crabe nghin cu tng hp vo
nm 1958 tuy cha mang li nhiu ng dng to ln nh mong i nhng y c
xem l mt trong nhng nortestosteron c tng hp u tin m dng cho vic
nghin cu cc nortestosteron khc c nhiu ng dng hn trong y hc gip ci
thin cc tnh hnh sc khe ca con ngi.
Sn phm bin tnh amin mang li nhiu gi tr nghin cu cng nh thc tin
vi kh nng chng vim da. S tng hp bin tnh amin cho hiu sut cao ng
mong ch.
Phng php gn cc bin tnh ca dipterocarpol vo polymer mang li nhiu
ng dng a dng cho vic ko di cc tc dng ca thuc gip con ngi thun
12

tin hn trong vic dng thuc v trnh s khng thuc xy ra khi dng qu nhiu
thuc.
Chnh v nhng ng dng ca cc sn phm bin tnh t dipterocarpol mang li
m dipterocarpol tr thnh mt trong nhng cht c nghin cu nhiu nht.

Hnh 1.7: Mt s dn xut ca dipterocarpol

1.2 MT

PHN

NG

TRN

MCH

NHNH

CA

DIPTEROCARPOL.
T dipterocarpol, chng ta c th thc hin bin tnh trn vng v bin tnh
trn mch nhnh. Nhm carbonyl rt hot ng nn s tham gia vo cc phn ng
hon nguyn, cng thn hch, kh amin ha cho bin tnh vng. Trong ti
ny chng ti tm hiu mt s phn ng trn mch nhnh ca dipterocarpol.

13

1.2.1

Phn ng oxi ha to lacton.

Lacton l mt ester vng, thng gp l dng

(vng 5) v -lacton

(vng 6). S c mt ca nhm chc lacton lm cho cc hp cht c hot tnh sinh
hc ln tim, c gi tr y dc. C nhiu phng php khc nhau ng vng
lacton ty thuc vo c cu cht ban u cng nh cc loi tc cht phn ng.
Trong , iu ch lacton t cht nn hydroxyl carboxylic acid l phng php
c dung ph bin nht. Mt s phn ng lacton ha trong bng 1.1

STT

Cht nn

Tc cht

m-CPBA

NuH

Sn phm

H+,

Hiu
sut(%)

77-86

CO/H2
2

Pd(OAc)2
X= O, NH

>90

DPPB,1200C

OsO4
Oxone

1.Hg(OAc)2
4

MeOH

2.NaBH4
14

H+,
5

C6H5Cl

(CF3-Ph-CO)2O
TiCl2(OTf)2
6

Me3SiCl

CH2Cl2,

CrO3/AcOH

Bng 1.1: Mt s phng php tng hp lacton

Nm 2003, Isamu Shiina tng hp lacton bng phng php ng vng cht
nn hydroxyl carboxylic acid (phng php 6). Khi ng thay i cc iu kin
phn ng nh nhit , nng xc tc, t l gia nng cht xc tc v cht
nn th thu c nhiu t l sn phm monomer v dimer khc nhau. Phn ng
cho hiu sut c lp monomer cao nht ti 50C v 5 mol ca TiCl 2(OTf)2. Khi
thay i gi tr n cng lm thay i t l sn phm nh trong bng 1.2.

Hnh 1.8: Monomer

15

Hnh 1.9: Dimer

STT

% monomer

% dimer

10

83

C6H13

10

91

11

80

12

89

13

88

14

88

Bng 1.2: T l sn phm thay i theo n.

Do c cu cht nn dipterocarpol l alkenol nn chng ta c th p dng
phng php s 3 v phng php 7, s dng tc cht OsO 4, oxone
(2KHSO5.KHSO4.KSO4) hay CrO3/AcOH cho phn ng xy ra iu kin nh
nhng hiu sut cao. Nm 1958, G. Ourirron tin hnh oxi ha dipterocarpol
trong chui phn ng iu ch dn xut ca testosterone l 8,14-dimethyl-1,8nortestosteron, tc cht CrO3/AcOH(4)

16

Hnh 1.10: Phn ng lacton

1.2.2

Phn ng trn nhm OH.

Nhm hydroxyl cho hai loi phn ng chnh l s ct ni C-O v O-H.

C rt nhiu tc cht cho s ct ni C-O v ty vo tc cht c s dng m
chng ta c th thu c sn phm l cc halogenur alikil tng ng hoc cc
alken

Tc cht: SOCl2, HX, PX3.

Tc cht: H2SO4, Al2O3 (nhit cao), POCl3

Mt phn ng khc cng kh quan trng trn alcol l phn ng oxi ha. Cc
tc cht oxi ha thng dng l KMnO 4, K2Cr2O7, CrO3. Ty vo c cu alcol ban
u m chng ta c th thu c aldehid, acid carboxylic (t alcol bc nht), ceton
(t alcol bc nh), alcol tam cp khng cho phn ng oxi ha.
Ct ni O-H to eter, ester l phn ng quan trng v thng gp trong tng
hp hu c, mc ch to dn xut eter, ester hoc bo v alcol trong mt chui
bin i hu c.
17

S to thnh ester.

1.2.3

Ester l cht c tm thy rt nhiu trong thin nhin. Mt s ester n gin l

cht lng c mi thm d chu c dng nh hng liu trong ngnh thc phm
cng nh m phm. Ngoi ra, trong k ngh, ester thng dng lm dung mi nh
etyl acetate hay cht lm do cho polymer.
Ester c th c iu ch bng nhiu cch:
1.2.3.1 Phn ng ester ha Fischer gia acid carboxylic v alcol di s

hin din ca acid v c.

Di s hin din ca xc tc acid, alcol v acid carboxilic tc dng vi nhau

co ra ester v nc. Phn ng thng c xc tc bi H 2SO4 m c v un
hon lu trong thi gian di.
Phn ng xy ra theo c ch sau:
H

Cl

OH

R'

H
O
H
OH

OH2

OH

R'
R

R
H

O
HO

OR'
O

H3O

C
R

OR'

Hnh 1.11: Ester ha Fischer

18

1.2.3.2

Phn ng t clorur acid

RCOCl

R'OH

RCOOR'
N
H

Cl-

Hnh 1.12: Phn ng acil ha to ester

Alcol tc dng vi clorur acid theo c ch phn ng th thn hch acil cho ra
ester. Nhng phn ng loi ny thng xy ra di s hin din ca baz yu nh
pyridin. Phn ng cho hiu sut cao vi cc loi alcol nht, nh, tam
Theo nghin cu nm 2003, Satya Paul v cng s cho thy hiu sut ca
phn ng acyl ha bng clorur acid ph thuc vo cht xc tc c th hin
bng 1.3.
Tc cht

Thi gian (pht)

Nhit (oC)

Hiu sut (%)

PhCOCl/SiO2

62-64

89

PhCOCl/K10

59-61

71

PhCOCl/p-TsOH/SiO2

10

39-41

48

PhCOCl/Al2O3

52-54

64

PhCOCl/TFA/SiO2

10

51-53

45

PhCOCl/H2SO4/Si2

52-54

84

PhCOCl/DMSO/SiO2

50-52

77

PhCOCl-Py/Al2O3

92-94

100

Bng 1.3: to thnh benzanilid t anilin vi cc tc cht khc nhau

T bng 1.3, ta thy s acyl ha vi PhCOCl cho hiu sut cao, phn ng xy
ra vi thi gian ngn. Tuy nhin, s acyl ha bng acid clorur c s hin din ca
19

pyridin vi cht xc tc l Al2O3 cho hiu sut t n 100% vi thi gian rt ngn
1 pht.
iu cn chng t rng PhCOCl l mt tc nhn acyl ha rt tt (cho hiu
sut cao trong iu kin n gin khng c dung mi) c th c dng phn
ng to ester benzoat mt cch d dng hn cc tc nhn khc nh acid benzoic,
benzoic anhydrid, benzoyltetrazol
1.2.3.3

Phn ng t anhydrid acid

V d:

y l mt phng php tiu chun dng diu ch ester. Phn ng c xc

tc bng acid ( H2SO4) hay baz ( pyridin).
1.2.3.4 Phn ng t nitril.
RCN

R'-OH

H+, H2O

RCOO-R'

V d:

1.2.4

S to thnh eter.

C 2 phng php iu ch eter

1.2.4.1 Tch nc ca alcol bng mt acid proton mnh.

Hai phn t alcol tch mt phn t nc cho ra mt phn t eter i xng.

20

H2SO4

2ROH

1.2.4.2

ROR

H2O

Tng hp Williamson

c tm ra vo nm 1850, tng hp Williamson sm tr nn mt phng

php tt nht trong vic iu ch c eter i xng v bt i xng.
u tin chuyn ha alcol thnh alkoxid, sau cho alkoxid ny tc dng ci
halogenur alkil
R'X

RO-

ROH

ROR'

Vi eter bt i xng ROR cn phi bit chn phn no (R hay R) l

halogenur alkyl trnh phn ng tch nc to ra alken

ROH
RO-

1.2.5

RO-Na+

NaH

R'

ROR'

H2
X-

Phn ng tng hp epoxid.

Phn ng ng vng epoxid c pht hin vo nm 1961 bi A. William

Johnson v c nguyn cu su hn bi EJ Corey v Michale Chaykovsky.
Trimetylsulfoxonium iod l mui sulfoxonium. N c s dng to ra
dimetyloxosulfonium metyl bng phn ng vi natri hydride. Hp cht
dimetyloxosulfonium metyl c s dng ng vng epoxid.

21

Hnh 1.13: Phn ng tng hp epoxid

Ngoi phn ng ng vng epoxid Corey Chaykovsky cn ng dng cho
nhiu nhm chc khc.

X: O, CH2, NR2, S, CHCOR3, CHCO2R3, CHCONR2, CHCN.

Ngoi ra, ngi ta cn s dng m-CPBA tng hp epoxid t alken.

22

Phn 2: THC NGHIM

2.1

HA CHT, THIT B V DNG C TH NGHIM

2.1.1
-

Ha cht:
Dipterocarpol (Hydroxydammarenone II)
Ngun: Cc nhm thc nghim trc.
m-CPBA(Acid 3-chloroperoxybenzoic)
Hng sn xut: c
NaBH4(Natri bohidrur)
Hng sn xut: Trung Quc
Na2SO4(Natri sunfat)
Hng sn xut: Trung Quc
HCl (Acid chlohidric)
Hng sn xut: Trung Quc
CH3COONa (Natri acetat)
Hng sn xut: Trung Quc
Pyridin (Azine; Azabenzene)
Hng sn xut: Trung Quc
Tosyl clorur (4- methyl- benzenesulfonylchlorid)
Hng sn xut: Trung Quc
Silicagel
Hng sn xut: c
Eter du
Hng sn xut: Chemsol
Etanol
Hng sn xut: Chemsol
Metanol
Hng sn xut: Chemsol
Cloroform
Hng sn xut: Chemsol
23

2.1.2
2.1.3

Hexan
Hng sn xut: Chemsol
Etyl acetat
Hng sn xut: Chemsol
Dng c:
Bnh cu 100mL
Becher 100mL
Erlen 100mL
Bnh lng 150mL
ng hon lu
Bn mng silicagel Merk, Kielsegel 60F254, 250m
Silicagel - n
Thit b:

Bp un v khuy t hiu ARE-VELP

My c quay hiu EYELA
My o nhit nng chy - Wagner & munz- POLYTHERMA

Heiztisch Mikroskop
My o ph NMR hiu Brucker 500MHz, dung mi CDCl3.

2.2 THC NGHIM

2.2.1 iu ch 20(s)-hydroxydammar-24-en-3-ol.

20(s)-hydroxydammar-24-en-3-ol l sn phm ca phn ng hon nguyn vi

tc nhn hidrur thnh alcol. Phn ng c thc hin nh sau:
Ha tan 0.44g (1mmol) dipterocarpol trong 30ml dung mi EtOH trong erlen
250ml, sau cho thm vo hn hp phn ng 0.1g NaBH4 (2.6mmol), khuy t
trong 4h. Sau khi phn ng kt thc, cho vo hn hp phn ng 20ml dung dch
HCl 5%. Lc sn phm v ra sn phm nhiu ln vi H2O, kh, kt tinh li
nhiu ln sn phm trong MeOH, chng ti thu c 0.42g sn phm sch, tinh
th trng, hiu sut : 94%, Tnc=134-135C. Cu trc sn phm c xc nh bng
ph 1H-NMR v 13C-NMR.

24

2.2.2 iu ch 20(s)-hydroxydammar-24,25-epoxyl-3 -ol.

20(s)-hydroxydammar-24,25-epoxyl-3-ol

l sn phm ca phn ng to

epoxy ca dipterocarpol. Chng ti tin hnh phn ng nh sau:

Cho 1.76g (4mmol) 20(s)-hydroxydammar-24,25-epoxyl-3 -ol vo erlen nt
nhm 250ml, thm 80ml CHCl3, lc u cho tan ht. Dng bc nylon en bc kn
xung quanh erlen, thm 1.60g (10.40mmol) m-CPBA vo erlen, khuy t trong
24h.
Sau khi kt thc phn ng, ra hn hp phn ng vi dung dch mui
CH3COONa 10% (3x30ml), ra li vi H2O (2x30ml) v lm khan bng Na2SO4.
C quay thu hi dung mi v kt tinh li nhiu ln vi MeOH thu c 1.51g sn
phm sch, tinh th trng, hiu sut 82%, T nc=160-162C. Cu trc sn phm c
xc nh bng ph 1H-NMR v 13C-NMR.
2.2.3 iu ch 20(s)-hydroxydammar-24,25-epoxy-3- p-toluenesulfonyl.

Cho 0.46g cht s 8 vo bnh cu 100ml, ha tan vi 2ml pyridin. Sau , cn

0.28g p-toluenesulfonyl clorur cho vo hn hp trn, un hon lu hn hp trong
khong 8h. ngui hn hp phn ng, trung ha vi 40ml HCl 5%, c kt ta
trng c to thnh, lc ly kt ta, ra li vi nc nhiu ln vi H 2O. Kt tinh
hn hp sn phm vi methanol, thu c 0.12g sn phm sch hiu sut 38%.
Cu trc sn phm c xc nh bng ph 1H-NMR v 13C-NMR.

25

Phn 3: KT QU V BIN LUN

Trong bi tiu lun ny, chng ti tin hnh phn ng oxid ha ni i trn
nhnh thnh vng epoxyl, kh nhm carbonyl thuc vng A ca dipterocarpol
thnh alcol, v gn nhm tosyl v nhm alcol to thnh.

Hnh 3.14: Mt s dn xut ca dipterocarpol

26

3.1 Kh nhm carbonyl vng A.

Kh nhm carbonyl c th tin hnh bng nhiu phng php vi cc tc cht
phn ng khc nhau, ph bin nht l cng thm anion hydride vo nhm carbonyl
cho ra alkoxid anion, sau acid ha to thnh alcol.
Hai tc cht cung cp hydrur ph bin nht l: lithium aluminum hydride
(LiAlH4) v sodium borohydride (NaBH4).
Tc cht

Dung mi

Phn ng

Tinh ch

Sodium

Aldehyde 1

alcol.
Ketone 2

1. Trung ha
2. Chit sn

Borohydride

Ethanol;
ethanol +15%

NaBH4
-

NaOH
Trnh acid

phm

alcol.

mnh.
Lithium
Aluminum
Hydride
LiAlH4

Ether; THF
Trnh alcol,

Aldehyde 1-

amin, acid

alcol.
Ketone 2-

alcol.
Acid carboxylic

1-alcol.
Ester alcol.
Epoxid alcol
Nitril & amid

amin.
Halide & tosylate

mnh.

1. Cn thn
khi thm
nc.
2. Loi mui
nhm.
3. Chit sn
phm.

27

 alkan
Bng 3.4: Mt s tc nhn cung cp hidrur
Phn ng kh nhm carbonyl trn vng A, chng ti s dng tc cht NaBH 4
v tc cht bn trong iu kin thng, cho phn ng vi hiu sut cao v d dng
tinh ch sn phm.
Chng ti lm phn ng trn s sau:

0.44g Dip + 30ml EtOH

0.1g NaBH4
Khuy 24h
HH phn ng
Thm 20ml HCl, lc
Ra vi
CH3COONa v H2O
Sn phm th

Kt tinh vi MeOH
Sn phm sch

C ch phn ng c m t nh sau:
u tin, tc nhn thn hch l ion hidrur tn cng vo carbon ca nhm
carbonyl. i in t t do trn ion hydride hnh thnh lin kt vi carbon ca
nhm C=O, cc in t ca lin kt ca C=O dch chuyn n O, cho ra alkoxid.
28

Sau khi hnh thnh ion alkoxid, ion ny s ly mt ion hydrogen t phn t
nc to thnh alcol.

Hnh 3.15: C ch phn ng to alcol dipterocarpol

Chng ti kh 0.44g dip bng 0.1g NaBH4 trong dung mi EtOH ti nhit
phng trong 4 gi.
Kim tra vi sc k bn mng , h dung mi ED:EA=8:2, sn phm khng hin
mu UV, hin mu vi dung dch vaniline th ta thy sn phm l mt m trn,
duy nht.
Chng ti kt tinh sn phm nhiu ln trong MeOH, thu c 0.42g tinh th
trng.
Chng ti tin hnh em mu i xc minh cu trc vi my ph 1H-NMR v
13

C-NMR. Thu c kt qu nh sau:

29

Hnh 3.16: Hp cht alcol dipterocarpol

D liu 1H ca 3-alcol dipterocarpol:
H, ppm (s H)

V tr

Mi

C3

i i

3.20

C24

Ba

5.12

Bng 3.5: D liu 1H ca 3-alcol dipterocarpol

Ti v tr: =3.20ppm, H ca C3 trn vng A, gi tr ca c trng cho CHOH v H ghp spin vi hai H C2 khng tng ng nn c hin tng ch mi
4.
Ti v tr: =5.12ppm, gi tr ca c trng cho H trn ni i C=C, do hin
tng ghp spin vi hai H trn C23 tng ng nhau nn ph ch mi ba.
Vy c th kt lun c, phn ng thnh cng trong vic bin i nhm
C=O thnh nhm OH trn vng A v ni i C=C vn cn trn cu trc.
3.2 Epoxid ha lin kt i C=C trn mch nhnh.
Hin nay, c rt nhiu phng php vi cc tc cht a dng bin ni i
C=C thnh vng epoxyl nh: phn ng vi O 2 trong s c mt ca Ag nguyn t,
phn ng ca -halohydroxyl vi baz mnh, phn ng vi peroxy acid.
30

m-CPBA l mt tc nhn oxy ha mnh, thng c s dng cho cc phn

ng: aldehyde v keton thnh ester (Bayer-Villiger), olefin thnh epoxy, sulfide
thnh sulfoxide and sulfone, amin thnh nitroalkan, nitroxide hoc N-oxide.
V l do kinh t m ngy nay m-CPBA t c s dng, thay vo l
hydrogen peroxide vi xc tc thch hp v cc peracid n gin hn nh
peracetic acid hoc ozon.
Tuy nhin, trong nhiu phn ng m-CPBA vn c a chung bi tnh chn
lc cao hn so vi hydrogen peroxide v cc peracid khc.
Chng ti chn m-CPBA lm tc cht cho phn ng epoxid ha lin kt i
C=C. Quy trnh thc hin phn ng c m t nh s sau:

0.46g cht 4 + 2ml CHCl3

m-CPBA
Khuy t 24h
HH phn ng
Thm 20ml HCl, lc
Ra vi
CH3COONa v H2O
Sn phm th

Kt tinh vi MeOH
Sn phm sch

C ch phn ng c m t nh sau:
31

Phn t ca m-CPBA trong gn ging vi acid carboxylic nhng c thm mt

O. Lin kt O-O ny rt yu (khong 138kJ/mol), nn rt d t ni tham gia
hnh thnh lin kt mi.
Mt c im khc ca phn ng to epoxy t alken s dng m-CPBA l tnh
chn lc lp th, mt cis-alken s cho ra mt cis-epoxy v mt trans-alken s cho
ra mt trans-epoxy.
Phn ng xy ra thng qua mt trng thi chuyn tip, lin kt O v C=C hnh
thnh ng thi vi s t ni ca lin kt O-O, proton c dch chuyn t nhm
OH sang C ca nhm C=O.

Hnh 3.17: C ch phn ng to epoxid dipterocarpol

Chng ti tin hnh kho st phn ng oxid ha ni i C=C trn mch nhnh
ca dipterocarpol bng tc cht m-CPBA trong dung mi chloroform, phn ng
trong iu kin bng ti, khuy t trong 24h.

32

Kim tra vi sc k bn mng , h dung mi ED:EA=8:2, sn phm khng hin

mu UV, hin mu vi dung dch vaniline th ta thy sn phm l mt m trn,
duy nht.
Kt tinh li sn phm nhiu ln vi MeOH, chng ta thu c 1.51g sn phm
dng tinh th mu trng sng.
Chng ti tin hnh em mu i xc minh cu trc vi my ph 1H-NMR v
13

C-NMR. Thu c kt qu nh sau:

Hnh 3.18: Hp cht epoxid dipterocarpol

D liu 1H ca vng epoxy dipterocarpol:
V tr

Mi

H, ppm (s H)

C30

0.76

C18

0.83

C19

0.86

C28

0.94

C29

0.96

C26

1.10
33

C27

1.12

C21

1.20

C3

i i

3.27

C24

Ba

3.72

Bng 3.6: D liu 1H ca vng epoxy dipterocarpol

T d liu trn ph 1H-NMR, chng ti thy:
Ti v tr: =3.27ppm, J1=15Hz, J2=25Hz, mi bn, do H ti C3 ghp spin vi
2H ca C2, m 2H ny khng tng ng nhau v mt v tr xch o v mt
trc, nn ph cho ra bng mi vi tn s ghp khc nhau.
Ti v tr =3.72ppm, cho ra mt mi ba c trng ca s ghp spin vi 2H
tng ng, H ca C24 tc H duy nht ca vng epoxyl l ph hp vi gi tr
v hnh dng mi.
Ngoi ra, cc mi c th xc nh cn li u c dng mi n, nn c th nh
danh, y l cc H trn cc nhm CH3 ca sn phm:
Ti v tr =1.20ppm, mi n, v tr c trng ca H ca C-OH, C21.
Ti v tr =1.12 v 1.11ppm, mi n, H ca hai nhm CH3 trn vng epoxyl.
Ti v tr = 0.94 v 0.96ppm, mi n, H ca hai nhm CH3 trn C4.
Ti v tr =0.86 v 0.83ppm, mi n, ln lt l H ca hai nhm CH 3 trn C8
v C10.
Ti v tr =0.78ppm, mi n, H ca nhm CH3 trn C14.
D liu 13C ca vng epoxy dipterocarpol:
V tr C, ppm (loi C)
C25

71.45
34

C24

78.94

C20

83.32

C3

86.42

Bng 3.7: D liu 13C ca vng epoxy dipterocarpol

T d liu ph 13C-MNR, chng ti nhn thy:
Ti v tr =71.45 v 78.94ppm, mi n, C ca vng epoxyl ln lt l C25 v
C24, do C25 c hai nhm CH3 c kh nng cho in t gy hiu ng chn lm
C25 cng hng trng yu hn C24.
Ti v tr =83.32 v 86.42ppm, mi n, C gn trc tip vi cc nhm OH, do
C20 cha mt nhm C y in t, gy ra hiu ng chn mnh lm gim trng
cng hng nn C20 cng hng v tr thp hn C3.

3.3 Tosyl ha nhm OH vng A.

Alcol l mt hp cht kh ph bin, c to thnh d dng t nhm carbonyl,
hp cht ph bin hn, alcol l mt hp cht tng i bn, v chng cha nhm
xut km.
Nhm xut tt l bazo lin hp ca acid mnh, thng thng, mt nhm xut
tt nh alkyl halide th gi tr pKa acid hydrohalic phi thp hn -3.
Cc hp cht trung ha in v mnh nh acid hydrohalic c th k n nh:
phosphoric acid, nitric acid and sulfuric acid nhng chng kh tham gia cc phn
ng hu c.
Cc acid hu c ph bin nht c th k n l:
-

Methanesulfonic acid (mesylic acid)

35

MsOH pKa = 3
-

Trifluoromethanesulfonic acid (triflic acid)

TfOH pKa = 14
-

Para-toluenesulfonic acid (tosylic acid)

TsOH pKa = 6
Chuyn ha alcol thnh mt ester sunfonate l mt qu trnh n gin, alcol
c cho phn ng vi sunfonyl clorur, gi r v d tm, cho ra sn phm l mt
ester d dng.
Qu trnh phn ng ca chng ti c thc hin nh sau:

36

0.46g cht 8 + 2ml Pyridine

0.28g p-toluenesulfonyl
clorur
un hon lu 8h
HH Phn ng
Ra vi HCl 5% v
H2O
Sn Phm Th

Kt tinh vi MeOH
Sn Phm sch

Nguyn t lu hunh phn cc dng trng thi oxid ha cao. Cu trc cng
hng ca tosyl clorur c biu din nh sau:

Hnh 3.19: Trang thi cng hng tosyl clorur

V nguyn t sunfur c cha vn o 3d trng nn c kh nng nhn thm mt
nhm th th nm. Alcol phn cc m v pha nguyn t oxygen, nn i in t
t do trn oxygen tn cng thn hch mnh ln tm phn cc dng ca sunfur
37

hnh thnh lin kt mi. Clorur l mt nhm xut tt, nn n c th ra i phn

t tr v trng thi bn.
Nguyn t oxygen ca alcol c ba lin kt nn n mang in tch dng, H +
c tch ra mi trng v c trung ha bng pyridin c sn trong phn ng.
Tng qut, nguyn t Cl ca tosyl clorur c thay th bng -OR ca alcol, to
thnh mt ester lu hunh v c, HCl c hnh thnh trong phn ng c trung
ha bi pyridin.
C ch phn ng c th hin nh sau: tc nhn thn hch oxygen tn cng
vo tm sunfur thn in t trn tosyl clorur, nhm clorur tch ra di tc ng
ca nhm y O-, pyridin c thm vo trung ha H +, sn phm alkyl
sunfonate ch nhm xut tt OTs, alkyl sunfonate d dng chuyn ha thnh cc
nhm chc khc qua cc phn ng nh: SN2, SN1, E1, E2.

Hnh 3.20: C ch phn ng tosyl ha

38

Chng ti tin hnh kho st phn ng ca 20(s)-hydroxydammar-24,25epoxyl-3-ol v tosyl clorur trong dung mi pyridin ti nhit phng v trong
thi gian 4h.
Trch sn phm, kim tra bng sc k bn mng, gii ly bng ED:EA=8:2, hin
hnh vi vanilin, kt qu: c s hnh thnh sn phm mi di dng vt.
Phn ng tip n 24h, kim tra vi sc k bn mng, gii ly bng
ED:EA=8:2, hin hnh bng vanilin, kt qu: c s hnh thnh sn phm mi dng
vt, m m trn bn mng gn nh thay i khng ng k.
Nng nhit phn ng ln 40C, phn ng trong 8h, trch sn phm, kim tra
bng sc k bn mng, gii ly bng ED:EA=8:2, hin hnh vi vanilin, kt qu: c
s hnh thnh sn phm mi, hm lng khng ng k so vi tc cht ban u.
Cho hn hp phn ng vo h thng hon lu, un trong 4h, trch sn phm,
kim tra bng sc k bn mng, gii ly bng ED:EA=8:2, hin hnh vi vanilin,
kt qu: c s hnh thnh sn phm mi ng k so vi tc cht ban u, nhng
m tc cht vn cn rt m so vi sn phm nn chng ti quyt nh tin hnh
phn ng vi thi gian di hn, un qua m.
Kt qu: Kim tra bng sc k bn mng, gii ly bng ED:EA=8:2, hin hnh
vi vanilin, chng ti nhn thy, tc cht bn u by gi ch cn hin mt m rt
nh so vi cc sn phm c ti thnh, sn phm to thnh c nhiu m nhng
trong c mt m trn v m nht, nm tch kh xa vi cc tc cht v cc sn
phm khc, chng ti quyt nh c lp sn phm ny xc nh cu trc bng
phng php chy ct sc k v thu c sn phm sch.
Sn phm thu c sau khi tinh ch c tin hnh xc minh cu trc bng
ph 1H-NMR v 13C-NMR:

39

Hnh 3.21: Hp cht 3-tosyl epoxy dipterocarpol

D liu 13C ca vng epoxy dipterocarpol:

V tr C, ppm (loi C)
C3

78.95

C20

78.93

Ce

21.39

Cb

133.84

Cc

134.05

Ca

139.87

Cd

140.18

C24

215.10

C21

115.86
40

C20

117.50

Bng 3.8: D liu 13C ca vng epoxyl dipterocarpol

T d liu trn ph 13C-NMR, chng ti nhn thy:
Ti v tr =215.18ppm, v tr ny c trng cho C ca nhm C=O.
Ti v tr =140.18, 139.87, 134.05, 133.84ppm v =21.39ppm, cc v tr c
trng cho C trn vng tosyl, vy tosyl gn ln khung ca hp cht chng ta.
Ti v tr =115.86ppm, v tr c trung cho C ca nhm alken u mch.
Ti v tr =78.95 v 78.93ppm, cc v tr c trng cho C lin kt trc tip vi
O.
C th d on, vng epoxyl b t v c s hnh thnh ca nhm
carbonyl v ni i C=C.

D liu 1H ca vng epoxy dipterocarpol:

V tr

Mi

H, ppm (s H)

C22

5.31

C23

5.37

C17

5.94

C26

6.06 6.08

C26

6.08-6.11

C3

Ba

6.30

Vng tosyl

6.80

Bng 3.9: D liu 1H ca vng epoxy dipterocarpol

41

 T d liu trn ph 1H-NMR, chng ti nhn thy:

Ti v tr =6.80ppm, mi a, c trng H trn vng tosyl.
Ti v tr =6.30ppm, mi ba, H trn C lin kt vi nhm OTs, H tng tc
spin vi hai H ca C2 ch mi ba.
Ti v tr =6.06 6.08 v 6.08-6.1, mi i, l hai H u mch ca ni i C=C,
hai H ny ghp spin vi nhau nn ph c dng mi i.
Ti v tr = 5.31 v 5.37ppm, l H ca hai C22 v C23, do chng ghp spin
vi nhau nn c dng mi ba.
Ti v tr =5.94ppm, mi a, H ca C17, do H ghp spin vi 3H khng tng
ng nn c dng mi a.
Lin kt vi d liu ph 13C-NMR, c th kt lun rng nhm tosyl c
gn ln vng A v vng epoxyl b phn hy to thnh nhm C=O v
C=C lin k nhau.

42

Phn 4: KT LUN
1. tng hp c 20(s)-hydroxydammar-24-en-3-ol t dipterocarpol bng
phn ng kh vi NaBH4 trong ethanol. Hiu xut 94%, Tnc= 134-135C v
cu trc c xc minh bng ph 1H-NMR.
2. tng hp c 20(s)-hydroxydammar-24,25-epoxyl-3-ol t 20(s)hydroxydammar-24-en-3-ol bng phn ng oxid ha vi m-CPBA trong
chloroform. Hiu xut 82%, Tnc= 160-162C v cu trc c xc minh
bng ph 1H-NMR v 13C-NMR.
3. tng hp c 20(s)-hydroxydammar-24-en-3-ol

20(s)-

hydroxydammar-24,25-epoxyl-3-ol. Hiu xut 38% v cu trc c xc

minh bng ph 1H-NMR v 13C-NMR.

43

TI LIU THAM KHO

[1] Nguyn trng Giang (2012), Bin tnh vng A ca Dipterocarpol, lun vn
thc s, khoa ha, i Hc Khoa Hc T Nhin TPHCM, 2,3.
[2]Phm Thanh Thut (2013), Tm hiu phn ng bin i nhm carbonyl trn
vng A ca lacton dipterocarpol thnh epoxyd , tiu lun tt nghip, khoa Ha
Hc, trng i Hc Khoa Hc T Nhin TPHCM, 4- 6.
[3]Robert D. Bach, Carlo Canepa, Julia E. Winter, Paul E. Blanchette (1997),
Mechanism of acid- Catalyzed Epoxidation of Alkenes with peroxy Acids, J. Org.
Chem, 62, No. 15, 5191-5197.
[4]. L Ngc Thch, Ha Hc Hu C (Cc Nhm nh Chc Chnh), NXB i
Hc Quc Gia Tp. HCM, Thnh ph H Ch Minh, 283-301 (2002).
[5]o Thi Thu Huong, Tran Thi Thu Thuy, Tran Thi Hien, Nguyen Thanh Tra,
Nguyen Quyet Tien, E.Smirnova, O. B. Kazakova, E.M. Minnibaeva, G. A.
Tolstikov (2013), Synthesis and Cytotoxicity of Derivatives of Dipterocarpol,
Metabolite of Dipterocarpus Alatus, Chemistry of Natural Compounds, 49, No. 1,
58-64.
[6]HiDayat Hussain, Ahmed Al- Harrasi, Ivan R. Green, Ishtiaq Ahmed, Ghulam
Abbas, Najeeb Ur Rehman (2014), meta-Chloroperbenzoic acid (m-CPBA): A
Versatile Reagent in Organic Synthesis, RSC Advances, Accepted Manuscripts, 57.

44

[7] Wang, Zerong (2010), Comprehensive Organic Name Reactions and Reagent
Prilezhaev Reaction,

Journal of Medicinal Chemistry,

American Chemical

Society, 2270-2273.
[8]

Jacqueline,

Seyden-Penne (1991),

Reductions by the Alumino-and

Borohidrides in Organic Synthesis, 2nd edition, Wiley VCH, New York, 5-6.
[9] A. D. Zorina,

L. V. Balykina, O. V. Nazarova, A. A. Rebezov (2006),

polymeric Derivatives of Dipterocarpol, a Dammarane Triterpenoic, Russian

Journal of Applied Chemistry, 79, No.4, 654-659.
[10] http://www.organic-chemistry.org/synthesis/O1S/sulfonates.shtm (ngy truy

cp 09/06/2015)
[11] https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/aldket1.htm (ngy
truy cp 09/06/2015)
[12] http://www.organic-chemistry.org/synthesis/C1O/epoxids2.shtm (ngy truy
cp 09/06/2015)
[13] http://www.organic-chemistry.org/chemicals/oxidations/metachloroperbenzoicacid.shtm(ngy truy cp 10/06/2015)
[14] http://www.masterorganicchemistry.com/2011/06/17/reagent-friday-m-cpbameta-chloroperoxybenzoic-acid/(ngy truy cp 09/06/2015)
[15]https://pubchem.ncbi.nlm.nih.gov/compound/Dipterocarpol#section=Substanc
e-Categorization-Classification (ngy truy cp 01/06/2015).
[16]http://www.organic-chemistry.org/chemicals/oxidations/metachloroperbenzoicacid.shtm (ngy truy cp 09/06/2015).
[17] http://www.organic-chemistry.org/synthesis/C1O/epoxides2.shtm (ngy truy
cp 09/06/2015).
[18]Don Thi Tnh, C s Ha Hc Hu C, Tp 1, NXB Khoa Hc v K
Thut, H Ni, 142-176, 2001.

45

[19]B.D Mistry, A handbook of Spectroscopic Data Chemistry, Oxford book

company, Jaipur India, 2009.

PH LC:

Ph lc 1: Ph 1H NMR ca dipterocarpol

46

Ph lc 2: Ph dn 1H NMR ca dipterocarpol

47

Ph lc 3: Ph dn 1H NMR ca dipterocarpol

48

Ph lc 4: Ph 1H NMR ca 3-alcol dipterocarpol

49

Ph lc 5: Ph dn 1H NMR ca 3-alcol dipterocarpol

50

Ph lc 6: Ph 1H NMR ca 3-alcol epoxy dipterocarpol

51

Ph lc 7: Ph dn 1H NMR ca 3-alcol epoxy dipterocarpol

52

Ph lc 8: Ph dn 1H NMR ca 3-alcol epoxy dipterocarpol

53

Ph lc 9: Ph 13C NMR ca 3-alcol epoxy dipterocarpol

54

Ph lc 10: Ph 1H NMR ca 3-tosyl epoxy dipterocarpol

55

Ph lc 11: Ph dn 1H NMR ca 3-tosyl epoxy dipterocarpol

56

Ph lc 12: Ph dn 1H NMR ca 3-tosyl epoxy dipterocarpol

57

Ph lc 13: Ph 13C NMR ca 3-tosyl epoxy dipterocarpol

58

Ph lc 14: Ph dn 13C NMR ca 3-tosyl epoxy dipterocarpol

59

Ph lc 15: Ph dn 13C NMR ca 3-tosyl epoxy dipterocarpol

60