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All posts Subject: Dimethoxyphenylalanine derivatives Please login to post

Rhodium
(Chief Bee)
04-03-03 00:40
No 423448
User Picture Dimethoxyphenylalanine derivatives
(Rated as: excellent)

Dimethoxyphenylalanine derivatives
Patent FR1496706

Abstract

Prepn. of I having a hypotensive activity and of their salts with nontoxic mineral acids is described. Thus, 122 g. 2,5dimethoxybenzaldehyde, 66.3 g. nitroethane (purity 90%), 147 ml. PhMe and 14.7 ml. BuNH2 were refluxed 6 hrs. with a watertrap to remove a slight excess of the theoretical amt. of H2O formed, then 75 ml. PhMe was distd., a part of the oil formed by cooling was triturated with MeOH and petroleum ether to give crystals, which served as seeds for crystn. of the remainder and to give 1-(2-nitropropyl)-2,5-dimethoxybenzene (II).

A soln. of 42.7 g. II in 364 ml. EtOH contg. 2% C6H6 was prepd. and 910 ml. H2O, 72.7 g. Fe powder and 2.91 g. FeCl3 were added. The mixt. was refluxed, and 131 ml. concd. HCl added during 2.5 hrs. with strong refluxing. The mixt. was stored 16 hrs. at room temp., the pH was adjusted to 6.4, the mixt. filtered and the residue washed with H2O and Et2O. The filtrate was acidified with HCl to pH 1 and extd. with 3 x 200 ml. Et2O and the ext. distd. to give 23.46 g. 1-(2,5-dimethoxyphenyl)-2-propanone, b1.25 95° (III).

A mixt. of 20 g. III and 215 ml. 95% EtOH was heated with stirring to dissoln.; a soln. of 72.5 g. (NH4)2CO3 and 15.75 g. KCN in 215 ml. H2O was added, and the mixt. stirred 84 hrs. at room temp., filtered, and the ppt. washed with cold water to give 21.3 g. 5-methyl-5-(2,5-dimethoxybenzyl) hydantoin (IV). A mixt. of 19 g. IV, 108 g. Ba(OH)2.8H2O and 537 ml. H2O was refluxed 60 hrs. with stirring under N; 1020 ml. H2O added, and the soln. adjusted to pH 7 with 2N H2SO4. BaSO4 was filtered off, the filtrate evapd. in vacuo, and the dry product dissolved in 500 ml. H2O, filtered with Supercel, and evapd. to dryness to give 20.8 g. a-methyl-b(2,5-dimethoxyphenyl)alanine (V), m. 176-207°, lMeOHmax. 240 mm (E% 87.5), 282 mm (E% 94.0).

The V obtained was refluxed 16 hrs. under N with 116 ml. 48% HBr; the dark red soln. was concd. in vacuo under N to crystn.; the crystals were washed with tert-BuOH and H2O, dissolved in H2O and mixed with 101.5 g. Amberlite IR-45 (in NH4 form). The mixt. was stirred, cooled in ice 15 min., filtered and washed with 4 ´ 300 ml. H2O. The aq. filtrate was concd. in vacuo to crystn., cooled and filtered; the filtrate was stored 64 hrs. in a freezer to give some more product. The 1st crystn. gave 5.6 g. a-methyl-b-(2,5- dihydroxyphenyl)alanine, m. 248-50° (decompn.), lMeOHmax. 296 mm (E% 182), 225 mm (E% 253), pink needles, giving pos. FeCl3test and neg. ninhydrin test.

Similarly prepd. were the following b-phenylalanines: a-methyl-2-4-dimethoxy, m. 239-41° (decompn.), (MeOH-iso-PrOH); a-methyl-2-4-dihydroxy, m. 284° (decompn.); aethyl-2-4-dimethoxy; a-ethyl-2-4-dihydroxy.

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		Rhodium (Chief Bee) 04-03-03 00:40 No 423448				Dimethoxyphenylalanine derivatives (Rated as: excellent)
						Dimethoxyphenylalanine derivatives Patent FR1496706 Abstract Prepn. of I having a hypotensive activity and of their salts with nontoxic mineral acids is described. Thus, 122 g. 2,5dimethoxybenzaldehyde, 66.3 g. nitroethane (purity 90%), 147 ml. PhMe and 14.7 ml. BuNH2 were refluxed 6 hrs. with a watertrap to remove a slight excess of the theoretical amt. of H2O formed, then 75 ml. PhMe was distd., a part of the oil formed by cooling was triturated with MeOH and petroleum ether to give crystals, which served as seeds for crystn. of the remainder and to give 1-(2-nitropropyl)-2,5-dimethoxybenzene (II). A soln. of 42.7 g. II in 364 ml. EtOH contg. 2% C6H6 was prepd. and 910 ml. H2O, 72.7 g. Fe powder and 2.91 g. FeCl3 were added. The mixt. was refluxed, and 131 ml. concd. HCl added during 2.5 hrs. with strong refluxing. The mixt. was stored 16 hrs. at room temp., the pH was adjusted to 6.4, the mixt. filtered and the residue washed with H2O and Et2O. The filtrate was acidified with HCl to pH 1 and extd. with 3 x 200 ml. Et2O and the ext. distd. to give 23.46 g. 1-(2,5-dimethoxyphenyl)-2-propanone, b1.25 95° (III). A mixt. of 20 g. III and 215 ml. 95% EtOH was heated with stirring to dissoln.; a soln. of 72.5 g. (NH4)2CO3 and 15.75 g. KCN in 215 ml. H2O was added, and the mixt. stirred 84 hrs. at room temp., filtered, and the ppt. washed with cold water to give 21.3 g. 5-methyl-5-(2,5-dimethoxybenzyl) hydantoin (IV). A mixt. of 19 g. IV, 108 g. Ba(OH)2.8H2O and 537 ml. H2O was refluxed 60 hrs. with stirring under N; 1020 ml. H2O added, and the soln. adjusted to pH 7 with 2N H2SO4. BaSO4 was filtered off, the filtrate evapd. in vacuo, and the dry product dissolved in 500 ml. H2O, filtered with Supercel, and evapd. to dryness to give 20.8 g. a-methyl-b(2,5-dimethoxyphenyl)alanine (V), m. 176-207°, lMeOHmax. 240 mm (E% 87.5), 282 mm (E% 94.0). The V obtained was refluxed 16 hrs. under N with 116 ml. 48% HBr; the dark red soln. was concd. in vacuo under N to crystn.; the crystals were washed with tert-BuOH and H2O, dissolved in H2O and mixed with 101.5 g. Amberlite IR-45 (in NH4 form). The mixt. was stirred, cooled in ice 15 min., filtered and washed with 4 ´ 300 ml. H2O. The aq. filtrate was concd. in vacuo to crystn., cooled and filtered; the filtrate was stored 64 hrs. in a freezer to give some more product. The 1st crystn. gave 5.6 g. a-methyl-b-(2,5- dihydroxyphenyl)alanine, m. 248-50° (decompn.), lMeOHmax. 296 mm (E% 182), 225 mm (E% 253), pink needles, giving pos. FeCl3test and neg. ninhydrin test. Similarly prepd. were the following b-phenylalanines: a-methyl-2-4-dimethoxy, m. 239-41° (decompn.), (MeOH-iso-PrOH); a-methyl-2-4-dihydroxy, m. 284° (decompn.); aethyl-2-4-dimethoxy; a-ethyl-2-4-dihydroxy.

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