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-<br /> 4-YL)-PHENYLHYDRAZIN VQfl MOT SO ANDEHIT THOfM<br /> N G U Y I N QUANG TRUNG, NGUYEN WQU DTNH<br /> Khoa Hda hpc, Trudng Dai hpc Su pham Hi NCI<br /> <br /> <br /> <br /> <br /> SUMMARY<br /> Anethole was isolated from Illiciumverum Hookf essential oil is transformed into 2-methoxy-5-(3-<br /> methylfuroxan-4-yl)phenylamine. The amine is converted to diazonium salt, which is reduced to form<br /> 2-methoxy-5-(3-methylfuroxan-4-yl)phenylhydrazine. The condensation of the later product with aro-<br /> matic aldehydes gives a series of 16 arylhydrazones containing furoxan ring. The structure of reported<br /> compound was determined by IR, NMR and MS methods.<br /> <br /> <br /> I. MO DAU<br /> <br /> Cac din xult cua hydrazin cd vai trd quan trpng Hign nay cac arylhydrazin g i n kg't vdi cac dj vdng<br /> trong hoa hpc hQu cd. Phenylhydrazin, dinitrophenyl- dang thu hut sp chu y cua nhidu nha hda hpc [2, 8],<br /> hydrazin tQ lau da dupe diing pho bien trong nghign cQu tuy nhign cac arylhydrazin va arylhydrazon dfnh vdi<br /> hpp chit cacbonyl die bigt la cac gluxit. Mflt sd din vdng furoxan hlu nhu cdn chua dupc nghign cQu. fl<br /> xuat ciJa hydrazin da dupc diing trong y dupe nhu: cflng trinh [9], chung tfli da trinh bay kdt qui tdng hpp<br /> phenelzin (antidepressant), hydralazine (vasodilator) [1, 2]. arylhydrazin chQa vong furoxan tQ safrole trong tinh dIu<br /> Ndi bat la cac arylhydrazin va arylhydrazon, chung dupe xa xi^ Trong cflng trinh nay chung tfli thpe hign sp<br /> diing phd bien trong tdng hpp nhieu loai dj vdng nhU: chuyen hda anetole cd trong tinh dIu hdi thanh 2-<br /> indoi, pyrazol, pyridazin [3, 4, 5], trong sd dd cd nhieu metoxi-5-(3-metylfuroxan-4-yl)phenylhydrazin rdi ngung<br /> chat dupc diing lam thufle chQa bgnh [6, 7]. tp vdi mflt sd andehit thdm.<br /> <br /> <br /> <br /> n, THl^C NGHIEM<br /> <br /> 2-Metoxi-5-(3-metylfuroxan-4-yl)phenylhydrazin (Hy) va cae hydrazon chQa vong furoxan (1 - 16, Ar xem 6<br /> bing 1) dupc tong hpp theo so dd sau:<br /> <br /> H 3 C O ^ ^ C H = C H - C H 3 NaNO,^H,COOH -CH3<br /> (I)<br /> <br /> O'<br /> O "O<br /> O NO, O<br /> <br /> CHj Na,S204+NaOH<br /> H , C O - f \ ^ ^<br /> |. NaNOj+HO<br /> '^^^^'^O 2-SnCU/HCl<br /> NH-N = C H - A r (IV) H3CO /~\ ,-^CH3<br /> <br /> <br /> (Al - A16) (Am) NH, O 0 - 1<br /> <br /> <br /> <br /> 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<br /> '^" ^ '' cJQpe hda tan trong HCI dam dac, ddng thdi khuly<br /> Hydrazin Hy dupe didu chd blng each diazoni hda manh 6 nhigt dfl thlp trong 2,5 gid Lpc lly kit tiJa<br /> 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<br /> <br /> <br /> <br /> Hoa hpc & Lfng dung<br /> O)) 5 ^ 2 3 (i07)/2oog<br /> dg'n mfli trudng trung tfnh, thu dupc chit rln mau trIng. Nhigt dfl ndng chly eua cac chit dupe do trgn may<br /> Kdt tinh lai nhidu lln trong etanol ; clorofom (3:1). Gallemkamp tai Bfl mfln Hda HQu ed - Dai hpc Su pham<br /> Ha Nfli. Phd IR (ep vign vdi KBr, may IMPACT 410<br /> Cac hydrazon deu thu dupc blng each dun hdi luu Hy<br /> Nicoiet), phd NMR (trong de-DMSO, may Brucker<br /> vdi andehit thdm trong dung mfli etanol khan vdi thdi<br /> gian tQ 1 - 4 gid, sau dd tach chit rln, ket tinh lai Avance 500 MHz), phd El MS (may HP 5989B) cua<br /> trong dung mfli thfch hpp ddn nhigt dfl ndng chly en cac hpp chit nghign cQu dupe do tai Vign Khoa hpc va<br /> djnh {bing 1). Cflng nghg Vigt Nam.<br /> <br /> <br /> <br /> HL KET QUA VA THAO LU^N<br /> Nhigt dfl ndng chly cua Am triing vdi tai ligu [XO]. dang tinh the, ndng chly d nhigt dfl eao hon so vdi Am<br /> Hydrazin Hy va cac hydrazon tdng hpp dQpc ddu d {Bing 1).<br /> <br /> Bing 1: KS't qui tdng h(fp cac cha't<br /> <br /> Ki Hlnh dang Dung mCi Diem chiy, H/S<br /> Ar<br /> hi^u bi ngoil kg't tinh (»C) (%)<br /> <br /> Am - Hlnh kim, mJu trIng Etanol : node (3;1) 119-120 40<br /> Hy - Hlnh kim, miu trlng Etanol : clorofom (3:1) 126 85<br /> A1 CeHs Hlnh viy, mau trdng Etanol 138 65<br /> A2 4-CH3C6H4 Hinh kim, miu trIng Etanol 168-170 57<br /> A3 2-CH3C6H4 Hlnh vSy, miu trIng Etanol 175 77<br /> A4 4-CH3OC6H4 Hlnh khO'i, miu da cam Etanol 184 55<br /> AS 3-CH3OC6H4 Hlnh kim, mku trSng Etanol : dioxan (1:1) 140 68<br /> A6 2-HOC6H4 Hlnh kim, miu trJng Etanol : dioxan (1:1) 212 78<br /> A7 4-(CH3)2NC6H4 Hlnh khCfi, mSu da cam Etanol : dioxan (1:1) 199 51<br /> A8 4-HO-3-CH3OC6H3 Hlnh kim, miu trIng Etanol 209 88<br /> A9 4-NO2-C6H4 Hlnh vJy, mJu do Etanol : dioxan (1:2) > 250, phan huy 93<br /> AID 3-NO2C6H4 Hlnh kim, mJu dfl Etanol: dioxan (1:1) 232 90<br /> All 2-N02C6H4 Hlnh kim, miu dfl Etanol : dioxan (1:1) 225 91<br /> A12 C6H5CH=CH Hlnh l