TONG HdP MOT SO a-AMINOPHOTPHONAT M0I<br />
Tir2-AMIN0-5-ETYL-1,3,4-THIADIAZ0L<br />
DANG NHl/ TAr, NGUYEN THI Hl/ONG\<br />
PHAM DUY NAM^ VUdNG VAN TRl/ClNG^<br />
'/C/?oa Hda hpc - Trudng D?i hpc Khoa hpc tu nhien<br />
Dai hpc Qudc gia Hi NCI<br />
^Trung tim Nhi^t ddi Viet - Nga - Bp Qudc phdng<br />
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SUMMARY<br />
A series of new diethyl l-(5-ethyl-l,3,4-thiadiazol-2-yl)aminoaryl methylphosphonates was synthe-<br />
sized by the three-component condensation reactions of 2-amino-5-ethyl-l,3,4-thiadiazoles with di-<br />
ethylphosphite (DEP) and aromatic aldehydes by Kabachnik-Fields reaction with Ti02 catalyst. The<br />
structure of products were confirned by 'H, '^C, ^'P- NMR and MS.<br />
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L M 6 DAU<br />
Axit a-aminophotphonic vg cgc din xulft (trong dd ed Trong cgc phUdng phgp tdng hpp a-aminophot-<br />
cgc a-aminophotphonat) lg mflt ldp cgc hpp cha't ed phonat, phin Qng Kabachnik-Fields lg phuong phap<br />
photpho quan trpng va dang tigp tgc thu hut nhigu sg thugn tign nhlt [3, 4, 5], day la phin Qng ngong tg<br />
quan tam nghign cQu do chung cd nhQng tfnh chit hoa glQa ba hpp phin (phin Qng one-pot) cacbonyl, amin va<br />
sinh quy bgu. diankyi hoge triankyi photphit, phin Qng thodng dope<br />
tign hanh trong nhQng digu kign gm dju, vdi cgc thao<br />
^ Da cd mflt sd lopng Idn cgc cflng trinh nghign cQu tac don giln.<br />
tdng hpp va hogt tfnh sinh hpc cua ldp chit nay dupc<br />
Trong cflng trinh nay, chung tOi nghign cQu tdng<br />
cOng bd trong khoing hai thgp ky gin day [1, 2]. Mgt<br />
hpp mflt sd a-aminophotphonat di tQ amin ban dIu lg<br />
khac, 1,3,4-thiadiazd va cgc din xult ciia nd cd khi<br />
2-amino-5-etyl-1,3,4-thiadiazd cflng hpp vdi cac andehit<br />
nang khang khuin, khgng u, giup digu hoa dudng huyg't<br />
thdm va dietyl photphit trong digu kign khflng cd dung<br />
[6], Chung cung dupc sQ dgng Igm hog ehg't diing trong mOi vg sQ dgng Ti02 Igm xuc tgc. Phin Qng dope dun<br />
nOng nghigp vl cd khi nang trQ sau, digt cd va trQ nim each thuy d nhigt dfl 80 - 90°C. Phin Qng dign ra theo<br />
rlt tdt [7]. phoong trinh sau:<br />
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<br />
N-N OEt TIO, N-N<br />
+ 0=HC ^'j'^OEt H20<br />
0=P-OEt<br />
C2H5<br />
H<br />
<br />
<br />
<br />
<br />
n. KET QUA VA THAO LU^N<br />
Cgc a-aminophdphonat cua day 2-amin-5-etyl-1,3 4- trong digu kign khflng dung mfli va sQ dgngxuc tgc<br />
thiadiazd dii?c tdng hpp blng phin fug Kabachnik-Fields TiOj. PhOdng phgp ngy ddn giln, phin Qng dign ra<br />
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<br />
Hda hpc & Lfng dung<br />
S^21 (i05)/2oog<br />
(Cd<br />
gm dju, nhg nhgng, khOng sQ dgng dung mOi. Phin chg cgc sin phlm nay la phUdng phap sic kf cOt vdi<br />
Qng dope dun hdi luii, each thuy d nhigt dO 80 - gO^C, ehg't nhdi silicagel.<br />
trong khoing thdi gian 6 - 8h. Phin Qng dupc theo doi<br />
TQ ch^t dIu lg 2-amino-5-etyl-1,3,4-thiadiazd, cgc<br />
binp sic kf bin mdng hign mau blng den tQ ngogi vg<br />
thuoc thQ Dragendorft. TI Ig md cac chSft phin Qng lg andehit thdm khac nhau va dietyl photphit blng phin<br />
amin : andehit : dietylphotphit = 1,0 : 1,0 : 2,5. Hdn Qng Kabachniek-Fields, chung tfli thu dope 8 a-amino<br />
hpp phin Qng thodng d dgnp dIu, rg't khd ket tinh. photphonat vdi cae sd ligu dupc trinh bay trong blng<br />
PhOdng phgp cd higu qui nhgt theo chung tOi dg tinh dudi day:<br />
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Dgng Digm Higu suit<br />
stt Andehit tpu(h)<br />
bg ngoai ndng chay (°C) (%)<br />
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1 p-isopropylbenzandehit 6 mau trIng 90-91 25,5<br />
2 p-(N,N-dimetylamino)benzandehit 7 mau trIng 147-147 18,1<br />
3 m-Nitrobenzandehit 8 mgu trIng 129-133 16,9<br />
4 o-Nitrobenzandehit 6,5 mgu trIng 145-145,5 16,2<br />
5 Naphtandehit 8 mgu trIng 141-142 35,7<br />
6 p-Clorobenzandehit 6,5 mgu trIng 129-131,5 22,4<br />
7 Benzandehit 7 mgu trIng 116-117 28,6<br />
8 p-Florobenzandehit 7 mau trIng 127-127,5 32,5<br />
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Cac cha't tdng hpp da dupe ghi phd 'H-NMR, '^c-NMR, phd ^'P-NMR va phd MS. Hlnh 1 dodi day la phd 'H-<br />
NMR cua dietyl (phenyl) (5-etyl-1,3,4-thiadiazcl-2- ylamino) metylphotphonat.<br />
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