Hiện nay các arylhyđrazin gắn kết với các dị vòng đang thu hút sự chú ý của nhiều nhà hóa học. Tuy nhiên các arylhyđrazin và arylhyd9razon đính với vòng furoxan hầu như còn chưa được nghiên cứu. Ở công trình, tác giả đả trình bày kết quả tổng hợp arylhyd9razin chứa vòng furoxan từ safroxan từ safrole trong tinh dầu xá xị. Trong công trình này tác giả thực hiện sự chuyển hóa anetole trong tinh dầu hổi thành 2metoxi5(3metylfuroxan4yl) phenylhyđrazin rồ ngưng tụ với một số anđehit thơm.
Trang 1TONG HQfP VA NGlTNG TU 2-MET0XY-5-(3-METYLFUR0XAN-4-YL)-PHENYLHYDRAZIN VQfl MOT SO ANDEHIT THOfM
N G U Y I N 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 d i n 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 d i n
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 g i n 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:
H 3 C O ^ ^ C H = C H - C H 3 NaNO,^H,COOH
(I)
NH-N = C H - A r
(Al - A16)
O O NO, O
H , C O - f \ ^ ^
O' "O CHj
-CH3
| NaNOj+HO ' ^ ^ ^ ^ ' ^ O 2-SnCU/HCl
Na,S204+NaOH
(IV) H3CO / ~ \ ,-^CH3
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 l l y 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
Trang 2dg'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 r l n , 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
Trang 3hap 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 r l t 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 A l , 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
H 1 2 - H 1 6
-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 A l - A16 cd du
14 - 18 tfn higu cflng hudng tUdng Qng vdi sd nguygn
tQ C trong phan tQ Trong dd cd tdi 12 - 1 4 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
Trang 4Bing 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 = C H - R (M-16)
H j C O - f \ — C = C — C H 3
1 ^ NO
^ N = C H - R (M-30)
NO
OH' V-C-C-C
NH—N=CH—R (M-75) N = C H - 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)
X A Y D I / N G PHlTflfNG AN
(Tiep theo trang 48)
TAI L i e u 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
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dudng mla", Nxb, Khoa hpc va Ky thuat, 1984
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ngh? hda chit", tap 1, Nxb Khoa hpc va ky thu|t,'2006
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cdng nghe hda chit vk thtfc phim", tap 1, Nxb, Khoa
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6, Nha may dudng Tuy Hda, "Luan chdng Kinh te
-Ky thuat", 2008
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edi-tion, John Wiley and Sons, Inc, 1993,
8, E Hugot, "Handbook of Cane Sugar Engineering",
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NgUttiphdn bifn: TS LE NGQC THyV
H6a hpc & Lfng dung
Trang 5dat 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
d p 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 N G I T N G T U
(Tiep theo trang 41)
TAI LIEU THAM KHAO
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Pages 665 - 675
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Thiiy Linh Tap chl Hda hpc T,47 (4A), Tr 63-767
(2009),
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Journal of Chemistry T 41 (1), , p, 115 - 119, (2003),
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New York - London, (1981) v
NgMphan bi}n: PGS, TS NGUYEN TH} THANH PHONG
H6a hpc & Lfng dung