Tổng hợp một số a-aminphotphonat mới từ 2-amino-5-etyl-1,3,4-thiadiazol

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 /> <br /> <br /> <br /> <br /> 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 /> <br /> <br /> 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 /> <br /> <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 /> <br /> <br /> <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 /> <br /> <br /> Dgng Digm Higu suit<br /> stt Andehit tpu(h)<br /> bg ngoai ndng chay (°C) (%)<br /> <br /> 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 /> <br /> <br /> 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 /> <br /> \oa>^^o^CTllnv•H^0r^von^oWvtpl£r^l