DAI HOC ou6c
(;f
A
HA
NAI
BAO CAO
KfiT
QUA THUC
HI$N
Dfi
TAI
DAc
BlfiT
CA'P
DHQG:
2001
- 200.1
T«n
dt
Ml
•
"NGHIEN CtJtJ
T6NG
HOP,
CAU
TRUC VA HOAT
TfNH
SINH
HOC
COA
CAC

nhChig ngUiVi
tham gia
dC
tai
3
Danh muc cac bang s6
li6u ^
Danh
miic
c^c
hinh ^
TOM TAT NHUNG KET QUA CHINH
^
L
Ke't
qua
v6
mat khoa hoc 4
2.
K6t
qua phuc vu thuc
te 5
3.
K6x
qua dao tao 5
4.
K6'l
qua niing cao
tiOm
luc khoa hoc 6

11
IIL Phuang phap nghien cuu va
Ihuc
nghiem 12
3.1
Pliuotig
phap xac djnh cau tao do tinh
khiet yh
hoat tfnh sinh hgc
ciia
12
cac hgp
cliiit
tdng hop dugc
3.2 Tdng hgp cac este
ciia
phenol va thuc hien phan ung
chuyen
vi Fries 12
cua chiing
'5-3 HiU(/ng
phap chung tdng hgp cac xeton
a,
\\-
khAng no: 14
3.4
Pliuang
phap chung tdng hgp cac hgp chat tuong tu flavon 19
.^.5 Hurtrng
phap chung (dng hgp cac

Kie'n nghj 30
TAI
LifiU
THAM KHAO 31
IHCNG
NGUOI
THAM
(ilA
DE TAI
1.
Nguyen Minh Thao - GS. TSKH - Truong Dai hoc Khoa hoc Tu nhicn- DHQG HN.
2.
Pham
Van
Phong - ThS. - Trucmg Dai hgc Khoa hgc Tu nhien- DHQG HN.
3.
M6t
s6' hgc vien cao hgc va sinh vien.
DANH MUC CAC BANC; SO
LI$U
Bang
I:
Cac san phiim phan
ihig
chuyen vi
Irics
Bang 2: Cdc xeton a.
p-
khAng no day agienol va iso(rgicnol
(E,.;)

khdng no di
tir
7- hidroxi- 4- metylcumarin
(C|.g)
Bang 8: Cdc hgp
ch^t
tucmg tu flavon di
tir
agienol va
iso(tgicnol
{FEU.)
Bang 9: Cdc hgp chat tuong tu flavon di tu resoxinol
(F,i,.s
va
F„K6 >)
Bang
10:
Cdc hop chat tuong lu flavon di lu
hidrcxjuinon
(F,,,
0
Bang
11:
Cac hgp chat luang tu
llavon
di lu
hidroxiquinolin (F,^,^)
Bang
12:
Cac

hgp phdn axil
deiiidroaxclic
(PDHA,
,,)
Bang 17: Cac
pinizolin clura
vong
tiuinolin (P^i i)
Bang
18:
Cac pirazolin chua hgp phan cumarin
(Pf,.,)
Haiij^
10;
Kli;i
iiAiij;
kh;uig
khuan
\
a
1.
liOnji
nam
cim
c:\c
xclon
(X,
p-
khAng no day
hidroquinon va resoxinol

P-
khong no CL
Hinh
4: Phd kho'i lugng cua xeton a,
P-
khong no
Cl.
Hinh
5: Phd cong huong
tir
proton cua hgp chat loai pirazolin
P^.
ffinh 6: Phd khA'i lugng cua hgp chat loai pirazolin
IVi-
AT
NHUNG
KEI
QUA CHINH
D6
tai: "Nghien ciiru tdng hgp,
caiu true
va
lioiit
tinh sinh hoc
ciia
cac
ligp chai
tuong lu
Flavon, co
chiira nlian

cdc hidroxi
ciia
cumarin va quinolon- 2. San
phdm cua phan
ihig
nay la cdc chdt ddu cho cac chuyen hod licp theo.
Da thuc hien phan
ung
ngung tu giua cac san pham
chuyen
vi Fries
a
tren
v6i
cac
indol - 3 - andehit
hodc v6i
cdc
andehit
day Furan lrong dieu
kiCn ciia
phan
ihig
Claisen-
Smith
d^
nhan dugc cac day xeton
rx,
p - khAng no luong ung co chira cdc nhan di vong
(khoang 50 hgp chat mdi).

phdp ti'nh Hod lugng lir ti'nh gan dung dc xdc djnh mat dd
dien tfch
Iren
cac vi
Iri
lrong phan tir. xac dinh do dai va nang lugng
lien
ke't trong phan tir.
Tren CO sd do da xdc dinh cau
h'mh
uu tien
ciia
phAn
tif,
ddng thdi gdp phdn lam sang ro
them ve chieu hudng va co che phan
i'mg.
Da tham dd hoat tfnh smh
IIDL
ciia
mgl
.so
Ja\
chat tdng hgp dugc va xdc djnh dugc
khoang 30 hgp chat cd hoat tinh khang khuan
vii
chdng nam d muc do khac nhau. trong dd
cd mot sd chat rat dang
chii
y va cdn dugc nghien

2.
Nguyen Minh Ihao,
Fhani
Van Phong,
'Tong
hap vd chuyen hod cdc hap chdt tuang tu khan con cd
chda
vong
indndTi.
T6t^
hap vd chuyen hod cdc hap chat xeton
a,
p-
khdny,
no
tif
cdc
3-fom\lin£n
w
J^
tuai
agienol \
Tuyen
tap cdc cong trinh Hoi nghi khoa hoc Idn thu hai
Tntang
Dai
htx KJtau
hpc Tu nhien
• DHQGHN, Hd Noi - 2000. Nhd .\udt bdn
"DHQCHN",

phdp tinh Hod luang
tu\
Tap
chi
Hod hpc, T.40,
so
J, tr. 9 (2002)
5. Nguyen Minh Thao, Pham
Vdn
Phong,
*Xdc
dinh cdu hinh cua xeton a,
/?-
khdng no (td o
-axetylagienol
vd
3-fomylindol)
vd mot
vdi sdn phdm chuyin hod cua nd hdng phuang phdp tinh todn Hod luang
td\
Tap
chi
Hod hpc, T.40,
so
2, tr.
I-10
(2002)
6. Nguyen Minh
I
hao, Nguyen Van

T.41.
so
I.
tr.
6/
(200.^
H.
Nguyen Minh Thao, Pham Van Phong,
'The
quantum calculating application in Fries rearrangement of resorcinol diacetate
\
Bdo cdo lai Hdi nghi Khoa hoc Chdu A lan
tht'r 10
hop tai
lid
noi vdo ngdy
21-
24 thdng
10
ndm 2003.
9.
Nguyen Minh Thao, Pham Van Phong, Nguyen Xuan Tu,
\Synthesis
and transformation of some
ac,
fi unsaturated ketones from coumarine
derivatives and
indole-
3- aldehydes
\

duac:
Ig)
Ngoai ra
ci>n
I hgc
vien
cao hgc khac da hoan
th^h
chuong trinh hgc tap nhimg chua bao ve
luAn
van.
- Da hudng ddn 08 sinh vien bao
ve
thanh cAng khoa luan
lAt
nghiep: Trdn Van
Chie'n. Nguyen Manh Cudng, Nguyen Van
Nam.
Bui Manh Tung, Hoang
Hie
Thdng.
Duong Thi Hd.
Rii
Thi Minh Hai. Le Thanh Nghi.
- Da hudng
d^
mdt sd sinh vien lam nghien cuu khoa hgc lhu dugc ket qua tdt, Irong
66 cd sinh vien Nguyen XuAn
Tir
dat ket qua rat tot, dat giai

de lai
Fliam
V.ln
Phong
sau khi bao
ve
xua't siic luan vdn thac sT cung
dii heu
chuan de dugc xet chuye'n tie'p nghien
cun
sinh.
Ve mat
thi6^t
bi, nhd viec thuc hien de tai vdi ngudn kinh phi dugc cdp ciing da tang
cudng mdt sd dung cu cdn thiet cho qua
trinh
thf nghiem nhu
lii
dd, bep dien, cac dung cu
ihuy
linh
di^c
biei.
va dac
biei
cd ngudn kinh phf dd mua cdc loai hod chdt dac biet phuc vu
qud trinh nghien
ci'm.
5.
Tmh

2003
XAC NHAN CUA
TRUONC;
OAI HOC
TUNHIEN.
DHQC.HN
OHO
MIEL
TRJONO
^^'
'
(
IIUNIIlftMDft IAI
.'C'^ffhi Jfrj/fU
GS.
TSKH.
Nguyin Minh
Tndo
XAC NHAN CUA DAI HOC OUOC GIA HA NOI
e and biological activity of the analogs
offlavone
compounds containing heterocyclic
nucleus'*
ABSTRACT
The Fries rearrangement reactions of aryl acetates from
derivatives
of
quinoline.
eugcnole,
isoeugenole,

unsaturated ketones also easily reacted with phenylhydrazine to form about 50 new
derivatives of pirazoline ring.
The constitutions of the producls have been determined by using IR-,
UV-,
MS- and
'H-
NMR- spectroscopies, and the their antibiotic abilities have
also
been tested. Some of them
have shown good results and wc have been proposed to
enlarge
the research in order to
dclerminc and developc the resulls.
Besides synthetic
reactions.
Chemical
Softwares,
such as
HypcrCiicm
7.0. have also been
used lo
help
determining charge
density,
binding
length,
and binding energy of
molecularly
optimal confonnations and studying mechanisms of
the

mdi d<}
dicn tfch, dA dai va nang luong lien
k^t.
cQng nhu cdc cdu
hinh
ben
ciia
phan tir. Tir dd cd
the
gdp phdn lam sang ro them chieu
hudng va co
ch^
phan ung.
-
Ti^n
hanh tham dd hoat tfnh khang
khudn,
chdng ndm va
xay
duu^
Inrdc
ddu mdi
quan he giGa cdu tnic phdn tir vdi hoat
linh
sinh hgc
ciia
hgp chat ldng
hgj)
dugc.
De thuc hien

BF^ ).
Phan ung xay ra vd ban chat gidng vdi su
the'electrophin
(Sg).
Thf du:
OCOR OH OH
AK.h
COR
Co
che'chung ciia
phan ung dugc
trinh
bay Irong so dd sau:
'OAlt'h
»
KC
-c>
-
COR
oil
O^
R
/?-axy^>hL'nr)l
Al(t,
li
(I
a.\ylplfc;ni)l
Thong
thirdng.
ti lc cstc:

hoa tan este.
2.2.
Vi
cdc xeton
a;
fi khdng no:
2.2.1.
Cdu
fuocac xolon
a,
\\-
khong no:
Cdc xeton a,
p-
khAng no
Id
cdc hgp chdl
hihi at
ma trong phan lir
ciia
chiing cd chira
nhdm vinyl xeton
(-CH=CH-CO-).
Chi'nh vl vdy ma cdc xeton a,
P-
khdng no cd kha ndng
tham gia
nhi^u
phan
ling

cue
dai ha'p lhu ndm d viing
tir
300«w
trd len vdi he sd tdt phdn tir khoang
lO'^
dac Irung cho budc chuyen electron
n->7r*.
240-
290nm
vdi he sd
Idt
phdn fir khoang
10^
dac
Irung
cho su chuyen budc
chuydn
electron
n->n*
va 200-
2?iOnm
dac
Inmg
cho su
chuyen
budc
chuyen electron
K—>7i*
cua

sliryloxazol'"',
bdng su phan
huy cdc
p-
aminoxeton''^-'"
'",
bdng
each
loai phan tir nudc
ciia
diaxetoancol''^'
va dac biet
bang phan ung ngung tu
Claisen-
Schmidt"^':
*^0-<N O OH O
^+'1^-'^
H"(HO")
M
I -
H7O II
AAC-CH3
+
R~CHO
5
U-Ar-C-CH2
CF*-R ^ • Ar-C-CH=:CH-R
I II
lluin
ung cd

;^ia
ra<;
pluin
\sv\)j.
a
i\-)i
doi
;ieng biet (cAng
bn>m
hay oxi hod bdi
KMnO,) hojc
phdn
(m,u tivit
nhdm CO
iihi du
lao ra 2,4-
10
di ca he xelon
a,
p- khAng no lien hgp de lao thanh cac
dJn
xuit cua vong pirazolin hoac
isoxazolin
Thfdu"^':
o
KCftll.,
C
CM
CM—t\.ii,ir
r,,HsNiiNn>M(

f.Ms
M.O
Cf^lh
Tif
o-
axelylphenol
va cdc
csli
COCMj
Cf.tlsCfX'l
»>
Pirklin
I4|.
((KM
KOII
OH
- " \/ OC(X
ftlls
Tit o-
axelylphenol
va andehit
Ihom"'*
'"^
o
COCHj
KOII
60%
+
CftHsCIIO
»-

48-
216
gid\di hieu
sudi
cao.
U VA
THUCNGHlfeM:
3.L
Phuang phdp xdc dinh cdu tao dp tinh khiet vd hoat tinh sinh hpc cua cdc hap
chdi tong hap duac:
- Sdc kl lop mdng dugc thuc hien tren ban mdng trdng silicagel. He dung mdi etyl
axetat: clorofom
=1:4.
Hien
hinh
bang hoi idt hoac
d\ia\
dnh sdng tir ngoai.
- Phd hdng ngoai
dvxoc
ghi dudi dang cp vien vdi KBr
tren
may
PI-
IK 1801
Shimadzu
tai vien Khoa hgc
Hinh
su- Bg cong an, Trung ldm Hod
inAi

tren
may 5989 BMS tai phdng hoa cdu tnic
Trung tam Khoa hgc Tu nhien va Cong nghe Qudc gia.
~ niir lu)al Ifnh
khang khuan
\l\
chdng
nam diroc Ihuc hicn
lhc(^
phuiyng
phdp ghi trong
dugc die'n Viet nam
(Idp kluiiig
sinh
dC))
tai Phdng
ihi nghiem
Hoa sinh
XMzuh
\
ien 19-8 B(>
cdng an va lai Medilalec Co. Ltd (38 Chau Long- Ha ngi).
3.2.
Tdng hap cdc este cda phenol vd thuc
hien
phdn
iaig
chuyen vi Fries cua chiing:
3.2.J.
Tdng

du. Tach lay
Idp
huu ca, rira bang
dung dich NaOH
loiing
rdi nra lai nhieu Idn bdng nuoc. lam khd rdi cat lay cstc d dp sudt
thdp (trong trudng hgp cd dung mdi de chicl
thi
trudc khi cat Idy este phai cdt loai dung
nidi
trudc).
Vdi cac dihidroxibcn/cn
thuinig chi
diing
axil
sunfuric
dixc
h\m
xiic lacva
chi cdn
khuay trdn hon hgp
plu'ui
iuv^^
d
nhiel
dd phdng
sO
(hu dugc cstc thudng d trang thai
rdn.
Dudi day la cdc este khdi ddu tdng hgp: duac:

Hieu sudt 84%.
12
Icumarin:
C,.,
150-
15r'(:
niico
lai
lieu ""'.
t",,
L50-
I51"C).
Hieu sudt
90%.
•
8-
Quinolinyl
axetat:
C,,
56- 57'C
(TIKM.
lai
lieu ''"'.
i".,.
56-
57C).
Hien sudt 60%.
3-2.2.
Thuc hien phan
utig

I.
Bdng
I:
Cdc sdn phdm phdn ifng chuyen vi
Fries
^
Phenol khdi
dSu
San pham
chuydn vi
urc)
Hieu
suat
(%)
Phd
hong ngoai
(cm ^)
'on
agienol
oil
II^CO^
J^
^((K
II,
100-102 50
CIU
H-Clh
3442 1603
Isoogienol
on

8-
hidroxiquinolin
COC
.<^^^^^^
(
111
^o-^o
^H^^^^COCU,
OH
162-163
'82-83
73
75
3370 1632
*: Hid 'IK
NMU,d/vw/:
'.53
{(\\d\
(^.?^(>i\\
<'
):
<>^^
(I I (\):
7,72
(IL
i\,)
*=*=:
I^d
'H-
NMR.

109
(M'
(II.CO).
****:
Phd 'H- NMR,
bppm:
2,40(CH,);
2,60(CH,C());
6,20
(H-C,):
6,90
(H-C,);
7.70 (H-
C,);
11.30
(HO-CJ.
MS:
218(M*);
203(UX)%)
(M'
- CH,);
190
(M*
- CO).
3.3.
Fhuang
phdp chung tdng hap cdc xeton
a,
/A
khdng no:

cd
the
ket tinh lai
tijrdung
dich etanol- nudc.
h.
D6i vdi cac hgp chat la axil
dehidio axclic
hay axctylcumarin
thi
thuc hien phan
i'rng bdng
each
dun ndng hdn
h(;p
ddng li lc mol
ciia
hai chdt phan ung lrong clorofom vdi
vai gigt piperidin lam
xiic
lac lrong sudt
3-
5 gid. San phdm o dang
ket tiia
dugc tach ra
bang lgc
hiit
va do khd ngoai khdng kin'.
Ke't qua dugc gidi thieu d cac hang 2. 3. 4, 5. 6. vd 7.
14

s
to
CO
CD
CO
CO
CO~
CO
CNT
CD
CO
c?
CO
a>
to
CM
t
CM
V
tO^
csT
o
lO
oi"
o
to
CM
3
*n
*n

>
*n
\o
r-
,.—V
NI
OC
t—,
*—'
re
•
o
X.
CO
Pi
s
:/'.
x: x:
a, a.
o
St
a
H
_
•
o
H
_,
.
o

H-
•KO
Z3
«>
:;;
-' ' '^
•<u
JZ
rr
o
CD
tz
-C
&
X
ton
Ol
2^
E
i«n
JCZ
X
t
to
o>
CO
94(
CM
CO
CO

x:
(D
•o
t;
'
O
c:
o
c:
.3
tJ"
£^
n?
^
CO
I
X
o
•u
x:
r—
O
,
to
"^
-«»^
o
CO
•
CD

tylindo
<D
S
CM
CI
o
c:
z»
ex
.£*
Ol
m
CO
•
X
g
'O
JZ
r~~
CM
O
. .
to
'—
'^
—
CO
•
CM
CD

anyli
Q_
CM
c
o
c:
:3
cr
x^
cu
if
tn
oo
•
X
p
'O
SZ.
r-
ro
O
, ,
oo
•^
'^
98(
•
—
to
-^

TD
c:
c:
<D
cn
:^i
cz
o
c:
J
cr
>^
<u
X
TO
CO
•
>:
P
•o
XT
r—
-J-
O
VO
^
6
Q-
^
cn

CM
CO
CD
CM
OJ
CD
to
CM
CO
cn
CD
-^
IO
CO CO
cn
to
CM
CO
to
CM
CM
CO
CD
CM
cn
IO
CM
CO
to
CM

o
o
u
cr»
fo
o.
•^
u
s:
"C
Q
5
:3
^
?s
met
•
'droxi-
4
'K.
r\
'^
*•*
"3
o
c
CMS
^
tf
dc

-^
X
c£
r^
J'
1
CO
cz
JZ.
o
&
X
tz
o
X
E
f.
ex
&
X
1-
•»^
CO
cn
CD
CM
CO
to
CM
•«-

r
.
o
•o
x:
CO
O
CM
C7>
cn
CD
to
to
rC
•-
C7>
CO
CO
CD
r
CD
to
CD
CM
r^
CM
<'»
1^
CM
. ^

to
CM
r-
CO
•^
•»—
CO
to
-*
<z>
r
CD
T-
CM
t.j
CM
:H
T3
CI
CD
to
T>
">.
CZ
(D
XI
Q-
CM
d
-cz

U>
UJ
CM
:c
CI
TO
"o
TJ
2:
tz
TZ
TO
E
u
CJ
r-
0
•0
JCZ
CD
h
CO
cn
cn
CD
CD
CD
^—
•^
CO

0
^
X
r-
0
JZ
c6
u*
0
to
00
cn
CO
CD
CO
CD
C»
•
cn
10
t—
CO
to
to
to
t^
CD
CO
r-
»M

cn
00
cn
CD
to
-b^
CM
-~
CD
-*
to
to
<o
-t*
(O
r
d)
r-
0
t'>
*o
C
J>
c«>
'
t_
CD
to
"0
TJ

CJ
to
,._
CO
CD
CD
r
CM
t)'>
to
<M
1
U)
•u
CI
TO
to
"0
TJ
«>
E
CM
>M
tz
(D
CD
IZ
d
TO
E

to
CO
0
c
tz
at
JZ
Ck.
CM
->%
N
d
CD
m
tz
"d
(O
E
u
CJ
OJ
X
CJ)
r-
X
0
•o
Icz
CO
0

:c
'•0
Of
vc
—
VO
>
r
'
11
:^
X
0
N
u
X
'O
ci:
S
y,
1
X
a-
X
00
3,4.
Phuang
phdp chung long hap
cdc
hap chdt tuang

kci linh
lui
lir
dtiiif;
ilii
h
rlaiiol:
tiuac
K6i
qua dugc gidi thieu trong cac bang 8, 9, 10, 11,
12.
/?a/ig
8:
Cdc hap chdt tuang
tu flavon
di tit
agienol
vd isoagienol
(Fp,^)
TT.
FEI
Fs2
Fn
F^
Fes
F^
xeton
a,
p-
khongno

48
40
%N
Tinh
4.23
4.06
3,44
3.33
-
-
Tim
4.38
4.34
3.72
3.57
-
'
Phd
h(V)g
ngoai
(cm')
Vc^
1632
1629
1624
1658
1645
1615
vcoc
1130;

xclon
Rl
R2
R3
R4
R5
l)1W
DR7
DR8
DR9
Bdng ^>
wrc)
193-194
203-204
255-256
150-151
105-106
20!>
?0(J
21S-216
161-162
242-243
';
Cdc
hap
elicit
tuang
tu
R,
1.54

-
Tim
5.25
4.78
3.83
4.95
3.54
Ei.)2
6.12
6,10
-
flavon
di tit resoxinol
(FRJ.S
vd
Fpufi.
9)
Phd
hong ngoai
(cm')
v«i
3169
3165
3137
3245
3136
-
-
-
-

210(3.71); 250(3.46); -; 407(3.60)
-;
256(3.90); 364(3.68)
204(3.94); 245(3.71); 266(3.59);
302(3.55)
2(Xi(3.64);
-,
258(3,37);
362(3.62)
?2:'H3.75).
253(3.39). 412(3.58)
210(3.83); 240(3,75); 263(3,56);
314(3.65)
209(3,65); 245(3.31); 300(3,34)
TT
F,„
F„2
F.n
F,M
F,.s
xeton
HI
H2
H3
H4
H5
bane
W:
L
UfC)

4.81
3,97
4.81
3.81
Tim
5.21
4.91
3.75
4.88
3.60
Phd
h6ng
ngoai
(on')
Va.
3167
3245
3200
3259
3248
Vco
1644
1634
1618
1635
1642
Vcoc
1132;
1217
1162;

Fo,
xeton
Ql
Q2
Q3
04
wrc)
191-192
180-181
251 252
102-103
R.
0,49
0.43
0.42
0.46
Hieu
su^
{%)
7a,
80
69
72
%N
hnt)
8.9
8.6
7.2
6.9
Tim

12:
Cdc hap chdt
titang tu
flavon di tir axit dehidroaxetic
(Ff),f^
,.12)
TT.
*lH4t
^BHA2
^0HA3
FoHA4
FBHAS
FBHAS
1 ^BNA7
'^OHAM
FBHAS
'DHA1$
'BHAIt
*BHAt2
_
1
Xeton
DHAl
DHA2
DHA3
\)\\M
DHA5
DHA6
DHA7
0HA8

0.35
0.65
HI6u
(%)
73
75
55
83
92
71
P^
C3
78
69
GO
47
%N
rmh
4.81
nm
5.03
4.M
j 4.31
3.81
4.59
3.67
-
3.a3
-
•

1640
1718;
1641
1719-154((
Vcoc
1244
1244
1224
1180
1242
1263
1249
1253
1233
1245
1252
1253
Phd
II;
ngoai
>_(«m)(tg,:)
221(4.?^).
263(4.64);
284(3.76); 432(4,33)
210(4.56);
244(4^:5);
302(4.21).
452{?,53)
-; 239(4.33):
30:

cac pirazolin chua nhdn di
vdng:
Dun sAi
h6i
luu hAn hgp theo
ti
le mol I: 1 ctia xclon
r/,
p-
khong no
v(5ri
phenylhidrazin trong etanol
vi
su c6 mat vai gigt axil axetic liim
xiic
tac
suAt
3- 5
gi5.
San
pliiim tach ra
(V
dang ke't tua dugc Igc hut va de khA
ngo^i
khAng
khi.
K^t
qua dugc
gidri
thieu 6 cdc bang 13,

138-140
114-116
177-179
107-109
R,
0.71
0.65
0.83
0,77
0.56
0,53
Ht^suat
(%)
74
61
55
75
78
72
%N
Tnh
9.93
9.61
8,42
8.22
-
-
Tim
9,64
9,33

305(vai); 340(394)
Ddng
14:
Cdc
pirazolin chda hgp phdn resoxinol
(Pjf,,^
vd
PoRf,.9)
TT.
PRI
P.«
Pm
Pw
PRS
PD«
•
t«7
Pt«l
PDTS
xeton
Rl
R2
R3
R4
R5
DR6
DR7
DR8
DR9
W(°C)

''
1
%N
TWi
11.38
10.97
9.44
10.97
9,15
13.38
12.80
-
12,80
Tim
11.10
10.85
9,30
11,17
9.33
13.12
12.50
-
1^50
Phd hdng
ngoai
V^Jon')
3432.
3381
3118,3380
3150.3138

long
nap cac pirazolin chua nhdn di
vong:
Dun sAi h6i luu hAn hgp theo
(i le
mol 1: 1
ciia
xeton a,
^~
khong no
voi
phenylhidrazin trong etanol
\h.
su co mat vai gigt axil axetic
lim xiic
lac suol 3- 5
gicr.
San
pliiim tdch ra
(V
dang ke't tua dugc Igc
hiit
va de khA
ngoii
khAng
khi.
K^t
qua dugc
gidri
thieu

114-116
177-179
107-109
R,
0.71
0.65
0.83
0.77
0.56
0.53
Hteusu^
(%)
74
61
55
75
78
72
%N
Tffih
9.93
9.61
8,42
8,22
-
-
Tim
9.64
9.33
8.25

14:
Cdc pirazolin chda
hgp
phdn
resoxinol
(Pf^,,^
vd
PDR^-V)
TT.
PR.
P.U
PR3
PR*
P«.
Ptw
"vm
PpB.
1 Pora
xelon
Rl
R2
R3
R4
R5
DR6
DR7
DR8
[)R9
tncTC)
173-174

%N
Vnt\
11.38
10.97
9,44
10.97
9.15
13.38
12.80
-
Tim
11.10
10.85
9.30
11.17
9.33
13.12
1Z50
-
12,80
12.50
Phd hdng
ngoai
V.„{rm')
3432.
3381
3418,3380
3150,3138
3311
4448.3312

P«
xeton
HI
H2
H3
H4
H5
Bane
UfC)
154-155
162-163
140-141
187-188
124-125
15:
Cdc pirazolin chiia hgp phdn hidroquinon
(Pfn-s)
Rr
0.61
0,66
0.46
0,53
0.44
HiOusuJt
(%)
66
47
42
72
64

-
Bang
16:
Cdc pirazolin chua hgp phdn axit dehidroaxetic
(PouAi-n)
TT.
PewM
PfHU
PoHU
' MM
Pavw
Pom;
PuM
POM
' DWMO
PflHAn
Pn«B
Pomu
xeton
DHAl
DHA2
0HA3
DHA4
DHA5
DHA6
DHA7
DHA8
DHA9
DHA10
DHA11

Hi&usuat
(%)
75
96
93
82
87
91
87
82
86
89
72
70
73
%N
Tinh
7,27
7.01
6,07
7,01
5.89
-
-
12,80
-
-
11,09
-
-

3443
Vcoc
1240
1244
1246
1245
1255
1253
1241
1265
1257
1213
1275
1253
1212
Phd tu ngoai:
^(nm)
(lgc)
218(4.48); -; 283(4,20); 424(4.17)
225(4.41): -; 344(4,36); 434(2,45)
-:
295(4.17)-;
392(3,85)
220(4.53); 285(4.13);
-;
392(3,99)
-; -; 287(4.02); 354(3,69)
-:
235:
-;

\.u%.
yuu4,olin
chita vdng quinolin
(PQI^)
TT.
Pu.
Paz
Po,
Po*
xeton
Ql
02
03
04
U^)
210-211
200-201
111-112
i7&-ieo
Rr
0,58
0.64
0.76
0.61
Hieu
suat
(%)
*
58
64

238(4.81): 303(3,92);
341(3,82)
236(4,43); 297(3.92); -
-: -:
341(4.45)
Bang
18:
Cdc pirazolin chUa hgp phdn cumarin
(Pci.9)
TT.
P*c.
Pc
Pa
PM
P«
Pes
Pa
Pes
P«
xeton
01
C2
C3
C4
05
06
07
08
09
U(^)

Phd
hdng
ngoai
(cm')
Vc.
3303
3277
3211
3411
3118
3510
3482
3273
3472
Vc01ac»on
1710
1710
1700
1721
1747
1726
1726
1722
1726
*: PhA
lil-NMK.
cS/7>//;:
2.4()(CI1,);
.>,7()
va 4.

ho^
nhom hidroxi bing anhidrit axetic trong su co mat cua mgl ft axil axit pholphoric
l^m
xiic
uic. DA'i
vdi c«ic
phenol dihidric
(hidrotiuinon
\a
rcs(>:\inol)
hoac hidroxicumarin cluing
t6i thuc hien phan
ling
tuong
lu nhinig thuiifng
dung axit
sunluric
lam
xiic
tac.
(Zac
este
nh$n
dugc co nhiet dA nong chay phu hgp voi du kicn trong tai lieu tham
khao.
tren phd hong ngoai cua chiing deu khong con pic dac trung cho dao dAng hoa tri cua
nh6m OH phenol, trong khi do xua't hien pic dac trung cho dao dAng hoa tri
cOa
nhom
cacbonyl este

180"C
trong dung mAi nitrobenzen hoac khAng co dung mAi.
San
ph^
ciia phan
iimg chuyen
vi Fries deu
la chat rdn
va co
di^m
chay ro rang, cung
nhu c6 gia tri
R,
tren
s;1c
ki
ban mong khac vcri
csle
ban ddu. Tren pho hong ngoai ciia
chiing deu
xua't
hien tra lai pic dac trung cho dao dong hoa tri cua nhom hidroxi phenol
trong khoang 3200-
3400c7/7''
va pic dac lrung cho nhom CO axetyl, thudng vdi sd sdng
nho hon cua nhdm CO este. PhA cong hudng
tir
proton cua cac san pham
chuyin
vj Fries

la
H-
axetyl-
7- hidroxicumarin cd su phan
manh nhu sau:
CM.
O^
"^Ctb
190
24

Trích đoạn IAIl ll d• M,A,M KIIAO

---