351893-47-5|Diethyl 2-(((3-bromophenyl)amino)methylene)malonate| Ambeed

Yield	Reaction Conditions	Operation in experiment
88%	In diphenylether; at 235℃; for 1h;Inert atmosphere;	General procedure: The malonate derivates 11a-d were dispersed in diphenylether(1.7 mL/mmol), flushed with argon and heated to 235 C for 1 h with aheating jacket. The reaction mixture was poured into petroleum ether,the formed precipitate was collected by filtration and washed with amixture of LP/EtOAc 1/1 to yield the desired product.5.1.3.1. Ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylate (12a).12a (colorless solid, 5 g, 88%) was obtained from 11a (5.03 g,29 mmol) according to general procedure B; m.p. > 300 C; 1H NMR(600 MHz, DMSO-d6) delta 1.27 (t, J=7.1 Hz, 3H), 4.21 (q, J=7.1 Hz,2H), 7.57 (dd, J=8.6, 1.9 Hz, 1H), 7.82 (d, J=1.9 Hz, 1H), 8.06 (d,J=8.6 Hz, 1H), 8.58 (s, 1H), 12.31 (s, 1H); 13C NMR (151 MHz,DMSO-d6) delta 14.8, 60.2, 110.9, 121.5, 126.2, 126.6, 128.2, 128.4, 140.5,146.0, 165.0, 173.3.
69.3%	With diphenyl ether-biphenyl eutectic; at 250℃;	Dowtherm (50 niL) was taken in double neck round bottom flask (100 rnL) and heated to 2500C in sand bath. At this temperature diethyl [(3- bromophenyl)amino]methylidene}propanedioate (Intermediate 32, 10.0 g, 29.2 mmol) was added and the reaction temperature was maintained for another 1 h at 250 0C. After completion of the reaction, the reaction mixture was cooled to room temperature, a white solid was collected by filtration and dried to yield 6.0 g (69.3%) ethyl 7-bromo-4-oxo-l,4- dihydroquinoline-3-carboxylate.1H NMR (400 MHz. DMSO-d): 1.07 (t, 3H), 1.22 (s, 12H), 3.16 (q, 2H), 7.29 (m, IH), 7.31 (d, 2H), 7.61 (s, IH), 7.88 (s, IH), 8.31 (s, IH), 8.65 (s, IH), 9.44 (s, IH).
42%	In diphenylether; for 0.5h;Inert atmosphere; Reflux;	3 mL of diphenyl ether was vigorously stirred in a test tube and heated to reflux with a sand bath, and to which, 800 mg (2.35 mmol) of starting material (22) was added. The resulting solution was refluxed for another 30 min, cooled to rt, and triturated with diethyl ether to give the product as a precipitation, which was collected by filtration. The solid was washed with diethyl ether for several times to give 497 mg of white powder as the crude product, which is sufficiently pure for the further coupling reactions. For analytical purpose, the crude product was washed with 20% MeOH in DCM for three times by means of centrifuge. The resulting solid was dissolved in a minimum amount of boiling DMSO, and then cooled to rt to give the pure product as a white powder 24 (291 mg, 0.99 mmol, 42%). 1H NMR (400 MHz, DMSO-d6, measured at 100 C due to solubility issue) delta 11.88 (s, 1H, NH), 8.45 (s, 1H, H-2), 8.07 (d, J = 8.6 Hz, 1H, Haryl), 7.80 (d, J = 1.7 Hz, 1H, Haryl), 7.51 (dd, J = 8.6, 1.7 Hz, 1H, Haryl), 4.24 (q, J = 7.1 Hz, 2H, Et), 1.29 (t, J = 7.1 Hz, 3H, Et). 13C NMR (100 MHz, DMSO-d6, measured at 100 C due to solubility issue) delta 173.17(CO), 164.99(CO), 145.27(C-2), 140.86(Cq,aryl), 128.36(CHaryl), 127.94(CHaryl), 126.76(Cq,aryl), 126.00(Cq,aryl), 121.55(CHaryl), 112.01(Cq,aryl), 60.03(Et), 14.62(Et); HRMS (ESI-) calcd for C12H9BrNO3-(M-H+) 293.9771, found 293.9772; HPLC: Solubility is too poor to make an HPLC analysis; Mp: 334-335 C (decomp., recrystallized from DMSO).

	With Dowtherm A; for 0.5h;Reflux;	General procedure: A solution of the appropriate meta or para-substituted anilines (100 mmol), 20.4 mL (100 mmol) of diethyl ethoxymethylenemalonate and 20 mL of ethanol was heated under reflux for 2 hours. The mixture was allowed to cool and then was poured into ice-cold water. The precipitate was collected by filtration and the corresponding enamine-type derivatives (3.0 g) were refluxed for 30 minutes in 30 mL of Dowtherm A, leading to crude oxoquinolines 4 that were recrystallized from dimethylformamide.
	In diphenylether; at 210℃;Microwave irradiation;	General procedure: A solution of theappropriate aniline derivative (1 eq) in toluene (20-50 mL) was treated withdiethyl 2-(ethoxymethylene)malonate (1.2 eq) and was refluxed for 15-20 h. Thesolvent was removed under reduced pressure and the crude product wasrecrystallized from n-hexane at -20 C.After that, the resulting diethyl (2-(amino)methylene)malonate was dissolved in5-10 mL diphenyl ether and was reacted for 20-60 min at 210 C undermicrowave irradiation.
	at 250℃; for 1h;	Intermediate 55Ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylateDowtherm (50 mL) was taken in double neck round bottom flask (100 mL) and heated to 250 C. in sand bath. At this temperature diethyl [(3-bromophenyl)amino]methylidene}propanedioate (Intermediate 54, 10.0 g, 29.2 mmol) was added and the mixture was maintained at 250 C. for another 1 h. After completion of the reaction, the reaction mixture was cooled to room temperature, and the solid was collected by filtration and dried to yield 6.0 g (69.3%) ethyl 7-bromo-4-oxo-1,4-dihydroquinoline-3-carboxylate as the predominant isomer.1H NMR (400 MHz, DMSO-d6): delta 1.07 (t, 3H), 1.22 (s, 12H), 3.16 (q, 2H), 7.29 (m, 1H), 7.31 (d, 2H), 7.61 (s, 1H), 7.88 (s, 1H), 8.31 (s, 1H), 8.65 (s, 1H), 9.44 (s, 1H).LC-MS: m/z 294 (M+H).

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Diethyl 2-(((3-bromophenyl)amino)methylene)malonate

CAS No.: 351893-47-5

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[ 351893-47-5 ] Synthesis Path-Downstream 1~1

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