Tổng hợp và ngưng tụ 2 metoxy 5 (3 metylfuroxan 4 yl) phenylhyd9razin với một số andehit thơm

TONG
HQfP
VA
NGlTNG
TU
2-MET0XY-5-(3-METYLFUR0XAN-
4-YL)-PHENYLHYDRAZIN
VQfl MOT SO ANDEHIT
THOfM
NGUYIN
QUANG
TRUNG, NGUYEN
WQU
DTNH
Khoa Hda hpc, Trudng
Dai
hpc
Su pham
Hi
NCI
SUMMARY
Anethole was isolated from
Illiciumverum
Hookf essential
oil is
transformed into 2-methoxy-5-(3-
methylfuroxan-4-yl)phenylamine. The amine
is
converted to diazonium salt, which
is
reduced to form

2-methoxy-5-(3-methylfuroxan-4-yl)phenylhydrazine. The condensation of the later product with aro-
matic aldehydes gives a series of 16 arylhydrazones containing furoxan ring. The structure of reported
compound was determined by IR, NMR and MS methods.
I. MO DAU
Cac
din
xult
cua
hydrazin
cd vai trd
quan trpng
trong
hoa hpc
hQu
cd.
Phenylhydrazin,
dinitrophenyl-
hydrazin tQ lau
da
dupe diing
pho
bien trong nghign cQu
hpp
chit
cacbonyl
die
bigt
la cac
gluxit. Mflt
sd

din
xuat
ciJa
hydrazin
da
dupc diing trong
y
dupe
nhu:
phenelzin (antidepressant), hydralazine (vasodilator)
[1,
2].
Ndi
bat la
cac
arylhydrazin
va
arylhydrazon, chung dupe
diing
phd
bien trong tdng
hpp
nhieu loai
dj
vdng
nhU:
indoi,
pyrazol, pyridazin
[3, 4, 5],
trong sd dd

cd
nhieu
chat dupc diing
lam
thufle chQa bgnh
[6, 7].
Hign
nay
cac
arylhydrazin
gin
kg't vdi
cac
dj
vdng
dang
thu hut sp chu y cua
nhidu
nha hda hpc [2, 8],
tuy nhign
cac
arylhydrazin
va
arylhydrazon dfnh
vdi
vdng furoxan
hlu
nhu cdn
chua dupc nghign
cQu.

fl
cflng trinh [9], chung tfli
da
trinh
bay kdt
qui
tdng
hpp
arylhydrazin chQa vong furoxan tQ safrole trong tinh
dIu
xa
xi^
Trong cflng trinh
nay
chung tfli thpe hign
sp
chuyen
hda
anetole
cd
trong tinh
dIu
hdi
thanh
2-
metoxi-5-(3-metylfuroxan-4-yl)phenylhydrazin
rdi
ngung
tp
vdi

mflt
sd
andehit thdm.
n,
THl^C
NGHIEM
2-Metoxi-5-(3-metylfuroxan-4-yl)phenylhydrazin
(Hy) va
cae
hydrazon chQa vong furoxan
(1 - 16, Ar
xem
6
bing 1) dupc tong
hpp
theo
so
dd
sau:
H3CO^^CH=CH-CH3 NaNO,^H,COOH
(I)
NH-N =CH-Ar
(Al
-
A16)
O O
NO,
O
H,CO-f\^^
O'

"O
CHj
-CH3
|. NaNOj+HO
'^^^^'^O
2-SnCU/HCl
Na,S204+NaOH
(IV)
H3CO
/~\
,-^CH3
(Am)
NH,
O
0-1
Cae
giai
doan
I, II va III
dupe thpe hign dpa theo
tai hpp
mudi diazoni ddn
-5°C
rdi
thgm tQ tQ hOn hpp
SnClj
'^" ^ '' cJQpe
hda tan
trong
HCI

dam
dac,
ddng thdi
khuly
Hydrazin
Hy
dupe didu
chd
blng each diazoni
hda
manh
6
nhigt
dfl
thlp trong
2,5 gid Lpc lly
kit tiJa
amin Am
0
nhigt
dfl 0 -
2°C,
sau
dd
lam
lanh
sau
hOn Hy.HCI,
gp
khfl,

rdi chd
hda
vdi
dung dich NaOH
2M
O))
Hoa
hpc &
Lfng dung
5^23
(i07)/2oog
dg'n mfli trudng trung
tfnh,
thu dupc
chit
rln
mau
trIng.
Kdt tinh lai nhidu lln trong etanol ; clorofom
(3:1).
Cac hydrazon deu thu dupc blng each dun hdi luu Hy
vdi andehit thdm trong dung mfli etanol khan vdi thdi
gian tQ 1 - 4 gid, sau dd tach
chit
rln, ket tinh lai
trong dung mfli thfch hpp ddn nhigt dfl ndng chly en
djnh {bing 1).
Nhigt dfl ndng chly eua cac
chit
dupe do trgn

may
Gallemkamp tai Bfl mfln Hda HQu ed - Dai hpc Su pham
Ha
Nfli.
Phd IR (ep vign vdi KBr, may IMPACT 410
Nicoiet), phd NMR (trong
de-DMSO,
may Brucker
Avance 500 MHz), phd El MS (may HP 5989B) cua
cac
hpp
chit
nghign cQu dupe do tai Vign Khoa hpc
va
Cflng nghg Vigt Nam.
HL
KET QUA VA THAO
LU^N
Nhigt dfl ndng chly cua Am triing vdi tai ligu
[XO].
Hydrazin Hy
va
cac hydrazon tdng hpp dQpc ddu d
dang tinh the, ndng chly d nhigt dfl eao hon so vdi Am
{Bing 1).
Bing 1:
KS't
qui
tdng h(fp cac
cha't

Ki
hi^u
Am
Hy
A1
A2
A3
A4
AS
A6
A7
A8
A9
AID
All
A12
A13
A14
A15
A16
Ar
-
-
CeHs
4-CH3C6H4
2-CH3C6H4
4-CH3OC6H4
3-CH3OC6H4
2-HOC6H4
4-(CH3)2NC6H4

4-HO-3-CH3OC6H3
4-NO2-C6H4
3-NO2C6H4
2-N02C6H4
C6H5CH=CH
4-FC6H4
4-CIC6H4
2-CIC6H4
4-BrC6H4
Hlnh dang
bi ngoil
Hlnh kim,
mJu trIng
Hlnh kim,
miu trlng
Hlnh
viy,
mau trdng
Hinh kim,
miu trIng
Hlnh
vSy,
miu
trIng
Hlnh
khO'i,
miu da cam
Hlnh kim,
mku trSng
Hlnh kim,

miu trJng
Hlnh
khCfi,
mSu
da cam
Hlnh kim,
miu trIng
Hlnh
vJy,
mJu
do
Hlnh kim,
mJu
dfl
Hlnh kim,
miu
dfl
Hlnh
l<im,
miu
ving
Hlnh
viy,
mau
trSng
Hlnh
vJy,
mau
trSng
Hlnh kim, miu ving

Hlnh
khfli,
miu
nSu
Dung mCi
kg't tinh
Etanol :
node
(3;1)
Etanol : clorofom (3:1)
Etanol
Etanol
Etanol
Etanol
Etanol : dioxan (1:1)
Etanol : dioxan (1:1)
Etanol : dioxan
(1:1)
Etanol
Etanol : dioxan (1:2)
Etanol:
dioxan (1:1)
Etanol : dioxan (1:1)
Etanol
Etanol
Etanol
Etanol
Etanol:
dioxan (1:1)
Diem

chiy,
(»C)
119-120
126
138
168-170
175
184
140
212
199
209
> 250, phan huy
232
225
185
166-168
179
196
207
H/S
(%)
40
85
65
57
77
55
68
78

51
88
93
90
91
64
62
50
66
79
Khi khQ mudi diazoni thanh Hy (phln Qng 2 b giai
doan IV) Chung tfli da
sQ
dpng
chit
khQ
la Na2S03
trong
dung djch HCI
ya SnClz
trong axit clohydric
djc.
Thpe
nghigm cho thly
chit
khQ sau cho higu
suit
cao hdn.
Trong khi phln Qng ngung tp amin Am vdi
cac

andehit
thom cln phli dung xuc tac axit
hoac
bazd
va
thdi gian
dun hdi luu tdi 8 gid
[10]
thl phln Qng ngQng tp Hy vdi
cac andehit thdm khflng cln dung xuc tac, thdi gian
phln Qng rut
ngIn
efln 1 - 4 gid. Nguygn nhan
la
do
cap
electron d nguygn tQ nitd trong nhdm
-NH2
cua Hy
khflng tham lign hpp vdi vdng benzen
lam
cho phln
Qng cflng nucleophin xly ra dg dang hdn.
Trgn phd IR cua Am
va
eua Hy, d vung tQ 3.200 -
3.500em"'
ddu ed ba
van hip
thp manh, vdi cudng dfl

trung
blnh.
Trong viing phd dd cua
cac
hydrazon A, -
A„
(trQ A8)
ehl
cd mflt
van hip
thp trung
binh.
Didu
dd
la
do sau phln Qng ngung tp vfli andehit, nhdm
-NH2
cua Hy da chuyen thanh nhdm -N=CH
Trgn phd cua
cac
hydrazon A1 - A16 deu cd van
hip
thp cudng dfl manh d 1488 - 1603. Chung tfli cho
ring vln
nay khflng nhQng dupc tao bdi dao dflng
hfla
trj eua nhdm -N=CH- hydrazon ma cdn bdi dao dflng
khung cua vong benzen
va
vdng furoxan (dao dflng

khung cua nhan thdm thudng the hign
bt^i
hai ba
van
Hoa hpc & Lfng dung
Si
23
(i07)/20og
m
hap thp
5
1,500-1.600cm'').
Vl vay trong bang 2 cac dao dflng dd dupc xdp chung
vao cflt
vc^,
vc.c-
van hip
thp
5
1,639cm''
trgn phd cua Am la
dac
trung cho dao dflng bidn dang cua nhdm
NHj.
Van hap thp cua nhdm
0-N
->
0 dupe quy ke't theo tai ligu
[11].
Bing 2: Mpt sd

vSn hS'p
thg chfnh trgn
ph^
IR
cua
cac hfp chi't nghifin
cii'u,
cm'^
Cha't
Am
Hy
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
All
A12
A13
A14
A1S
A16
VNH
,
(VQH)

3483,
3397,
3203
3447,
3318, 3230
3307
3313
3321
3341
3277
3291
3359
3337,
(3380)
3312
3319
3293
3335
3317
3301
3293
3353
\'C-H
(IMm)
3080,
3050
3096,
3030
3060,
3030

3050,
3026
3050,
3020
3078,
3015
3080,
3040
3078,
3008
3000
3060,
3031
3100,3062
3098,
3050
3086,
3050
3060,
3020
3064,
3040
3060,
3024
3095,
3060
3076,
3000
Vc-H
(no)

2981,
2916, 2850
2960,
2931, 2852
2970,
2932,
2855
2970,2919,2855
2979,
2940,
2843
2970.
2944,
2852
2958.
2930,
2840
2960, 2930,
2939.
2900,
2818
2974,
2920,
2845
2980,
2933,
2830
2970,
2933.
2854

2950,
2872.
2850
2989,
2940,
2890
2980,
2945,
2853
2960,
2924,
2853
2968,
2930,
2840
2970,
2941, 2842
vcHi.
V(M:
(1639),
1591,1535
1591,
1531,
1590,
1539,
1500
1582, 1538,
1511
1582, 1540,
1511

1603, 1536,
1497
1587,
1560,
1503
1590, 1536,
1495
1596, 1531,
1499
1586,
1520.
1494
1588, 1560,
1505
1592, 1529,
1505
1598, 1540.
1509
1587,
1538,
1497
1599, 1540,
1488
1582, 1541,
1500
1599,
1538,1500
1599, 1538,
1500
VMO

1477
1459
1457
1456
1456
1463
1450
1429
1460
1435
1460
1477
1471
1464
1470
1454
1467
1469
v^^i
1282
1267
1267
1265
1265
1242
1260
1276
1266
1270
1269

1272
1263
1268
1267
1271
1264
1265
Sp bien dfli clu tao tQ hydrazin Hy den cae hydrazon A1 - A16 dupe thd hign rlt ro trgn phd
'H
NMR cua
Chung.
Bing 3 la sp so sanh cac tin higu
'H
NMR cua Hy va hydrazon A1. Cae vj trf trong phan tQ dung cho
phan tich phd NMR dupe chung tfli ghi nhu trong
cae
cflng thQc sau;
16)
(5)
(7)
H3CO
(^2
(5)
(10)
'''
i>/
V)
|g)
(9)^CH3
H3CO

'
|g)
(91^^
^0-^0
Bing 3: Dfl'i chig'u tfn higu
'H
NMR cua Hy vfli hydrazon
Al,
5(ppm),
J{Hz).
Hy
A1
H3
7,39
d,
J2
7,77 d,
J2
H5
7,00
dd,
J
8.5;
2
7,16
dd,
J
8;
2
H6

6,96
d,
J
8,5
7,13
d,
J
8
H7
3,84
s
3,84
s
H10
2,31
s
2,33
s
HN
6,28
s
9,95
s
H2N
4,05
s
-
Hi
-
8,23

H12-H16
-
7,64 d,
J
8; 7,41 d, J
8;
7,32
t.
J
8
Trgn phfl
'H
NMR eua Hy chi cd cac
van
cflng hudng
cua cac proton thupc hpp phan hydrazin (H3,
H5,
Hg,
H?
H,o,
NH va
NH2),
tren phfl cua
Al
- A16 khflng cdn tiri
higu
cua nhdm
NHj
ma xuat hign tin higu cua proton
nhdm -N=CH (Hi)

6
8,1- 8,6ppm ddng thdi cd thgm
cac van cflng hudng
ciJa
cac proton khac
thufle
hpp
phan andehit
(HI2
-
HI6).
Cae van cflng hudng cua
cae
proton d 2 vdng benzen thudng dan xen vao nhau.
Tren phd
'^C
NMR eua cac hydrazon
Al
- A16 cd du
14 - 18 tfn higu cflng hudng tUdng Qng vdi sd nguygn
tQ C trong phan tQ. Trong dd cd tdi 12
-14
tfn
hi§u
cua
cacbon thufle 3 nhan thdm.
V)
thd vigc quy kdt chi tidt
tQng tfn higu proton
va

tQng tfn higu cacbon phli diing
phd 2D NMR ngn khflng dupe trlnh bay trong
khuOn
khd
ciJa bai
bao nay.
Cac pic chfnh trgn phd khfl'i lupng cua Hy, A2
vi
A11 dupe
ligt
kg 6 bing 4.
O))
Hoa hpc
Ajifng dung
Si
23
(l07)/20og
Bing 4:
cac
pic chfnh trgn
phl^
khO'l li/clng cija
Hy, A2
va
A11, m/z, (%)
HOP
chj't
" 0 OCHj
""O^
OCH,

o,N
M
(tfnh)
236
338
369
M"
236
(100)
338
(100)
369
(16)
MOt
SO
ion
mJnh (m/z)
220(8), 206(2), 176(75), 161(83), 132(32),
116(46), 89(58), 77(31), 63(35)
322(14), 308(1), 278(59), 263(34), 220(14),
163(32), 132(17), 117(53), 91(62), 77(38), 63(23)
339(2), 309(4), 233(29), 205(15), 148(52),
130(30), 115(100), 103(38), 92(35). 77(60), 65(47)
Gia tri
nfi/z ciJa pfe
ion phan tQ
phii
hpp vdi gia tri
khfl'i lupng
phan

tQ tfnh theo cflng thQc dp
kidn.
Dieu
do ChQng to
ring
khi diing natri dithionit khQ nhdm
nitro thanh nhdm amino (phan Qng ill) va
diinq SnClj
khQ mufl'i diazoni thanh dan xult hydrazin (phan Qng
IV),
nhdm N
-> 0
cua vong furoxan
vIn dupe
bao
toan.
Vigc phan tich phd cho thly sp phan manh dau tien
ddu xay ra
b
vdng furoxan, sau dd la b cac nhdm the
cua vong benzen nhu b sd dd sau:
N=CH-R
(M-16)
HjCO-f \—C=C—CH3
1^
NO
^N=CH-R
(M-30)
NO
OH'

V-C-C-C
NH—N=CH—R
(M-75)
N=CH-R
(M-60)
IV. KET LUAN
TQ anetol trong tinh
dIu
hdi, qua 4 giai doan phln
Qng da tdng hpp dupc arylhydrazin cd chQa vdng
furoxan la 2-metoxi-5-(3-metyifuroxan-4-yl) phenylhydrazin.
NgQng tp hydrazin dd vdi andehit thom da thu dQpc
16
hydrazon,
Clu true
cija
hydrazin va cac hydrazon da dupe
xac djnh blng cae phuong phap phd IR, NMR va MS,
(Xem tiep trang 37)
XAY
DI/NG
PHlTflfNG
AN
(Tiep theo trang 48)
TAI
Lieu
THAM KHAO
X.
Dang
Nguygn Thoai, "Nghien cdu khi ning tiet

ki?m nSng
iupng trong cdng ngh$ sin xuit
dudng,
dng
dpng
cho
Nhi
miy
dudng
Tuy Hda,
tinh
Phu
Yen",
Luan
van Thac sT, Trudng Dai hpc Bach khoa Ha Npi, 2009.
2.
Nguygn
Ngfl,
Lg Bach Tuyg't, Phan
Van
Higp, Trln
Manh Hung, Pham
Vinh
Vign, "Cdng
ngh^
sin xuit
dudng
mla",
Nxb, Khoa hpc va Ky thuat, 1984.
3.

L8
van Lai, Nguygn Ngpc Khanh,
"Niu
mit",
Nxb,
Nflng nghigp, 1996.
4.
Tgp
thd tac gil,
"SStay
qui trinh vi thiet bi cdng
ngh?
hda
chit",
tap
1, Nxb. Khoa hpc va ky
thu|t,'2006.
5.
Nguygn Bin,
"Tinh
toin qui trlnh vi thiet bj trong
cdng nghe hda chit
vk
thtfc phim", tap 1, Nxb, Khoa
hpc va ky
thugt,
1999.
6,
Nha may dudng Tuy Hda, "Luan chdng Kinh te -
Ky thuat", 2008.

7, Chen and Chou,
"Cane
Sugar
Handbook",
12"^
edi-
tion,
John Wiley and Sons,
Inc,
1993,
8, E. Hugot,
"Handbook
of
Cane
Sugar
Engineering",
Elsevier Science Publishers B.V, 1986,
9, J. Eisner, "Basic Calculation for the
Cane
Sugar
Factory", The International Sugar Journal,
1978.
v
NgUttiphdn
bifn: TS LE
NGQC THyV
H6a hpc & Lfng dung
Si
23
(i07)/20og

(CO
dat
cac
ygu clu ky thu|t trgn ky thuat hang khflng. So
sanh vdi ifl'p mlu ciing loai do Nga chd tao, dfl gilm
ap
suit
bdm hdi dupc Hfli ddng bay thQ Ifl'p cua Quan
chijng
Phdng khflng - Khflng quan danh gia
dat
tQdng
dUdng;
3. Lfl'p may bay bdm hdi khflng cd sam do Cflng ty
Co phln Cao su Sao vang va Vign Ky
thuSt
Phdng
khflng - Khflng
q^uan
hpp tac chd tao da md ra mflt
cflng nghg mdi ve che tao lfl'p may bay khflng
sSm
tai
Vigt nam,
dac
bigt la gdp phan vao vigc
chii
dflng cung
dp Ifl'p phpc vp an ninh
qufl'e

phong.
TAI
LIPU
THAM KHAO
[1]
Kleflmann,
Jens
(Continental
aktiengesellschatf).
Rubber mixture tor inner liner of pneumatic vehicle
tires.
United states patent and trademark office pre-grant
publication.
May 2008,
PaLno;US20080125537.
[2]
Krueger,
Joern (Continental Aktiengesellschaft),
Rubber blend for the inner liner of vehicle
tires.
United
states patent and trademark office pre-grant publication,
Feb 2009,
PaLno:US7491765
& Apr 2008,
PaLno:
US20080097021.
[3] Marsh W/Coddington D (Exxon research +engi-
neering
Co.) halogenated butyl tubeless tire

innerliner.
United states patent and trademark office granted
patent, Oct 1973,
Pat.no;US3769122.
[4]
Lin, Kuang
F.
/
Klosiewicz,
Daniel W. (Hercules
incorporated) Tire
innerliner.
United states patent and
trademark office granted patent, Aug 1991,
Pat.no;
US5040583.
[5]
Sandstrom, Paul Harry (The Goodyear Tire &
Rubber
Company),
Pneumatic tyre having an innerliner
comprised or butyl rubber and dispersion of pre-eured
diene-based rubber, European patent, Jan 2006, Pat.no;
EP1612242.
V
NgiMphdn
bifn: PGS, TS PHAM THE TRINH
TONG HQ[P
VA
NGITNG

TU
(Tiep theo trang 41)
TAI
LIEU
THAM KHAO
1.
Fiedorowicz,
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