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zjzh945 发表于 2007-7-28 10:47

Condensation of aminoalcohols with salicylic acids; Salicyloxazolines

[url=http://www.33ge.com/bbs/][b][color=black][font=Verdana][size=13.5pt]Condensation of aminoalcohols with salicylic acids; Salicyloxazolines[/size][/font][/color][/b][/url]
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X,B/F [color=black][font=Verdana][size=12pt]SyntheticPage 230 (2005)
1\z6~ p(x!DN-n Submitted [/size][/font][/color][color=black][font=Verdana][size=12pt]30th Sep 2005[/size][/font][/color][color=black][font=Verdana][size=12pt], published [/size][/font][/color][color=black][font=Verdana][size=12pt]30th Sep 2005[/size][/font][/color][color=black][font=Verdana][size=12pt][/size][/font][/color]~,v3kG4hvz6R
[color=black][font=Verdana][size=12pt]Max Hammond ([/size][/font][/color][i][color=black][font=Verdana][size=12pt][email=m.l.hammond@warwick.ac.uk]m.l.hammond@warwick.ac.uk[/email][/size][/font][/color][/i][color=black][font=Verdana][size=12pt]),
%`LA7R*]"h7pbd A contribution from the Scott Group, Warwick[/size][/font][/color]
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M MW u%SY-@;BB [b][color=black][font=Verdana][size=12pt]Chemicals Used[/size][/font][/color][/b][color=black][font=Verdana][size=12pt]
vES]!~S 3,5-di-tert-butylsalicylic acid (TCI) 2-amino-2-methyl propan-1-ol (Aldrich) Triphenylphosphine (Aldrich, recrystallized from hot hexane) CCl4 (Aldrich, distilled from CaH2) Triethylamine (Aldrich, distilled over CaH2) Acetonitrile (Aldrich, distilled over CaH2)[/size][/font][/color]
1FJ/T#[YU [b][color=black][font=Verdana][size=12pt]Procedure[/size][/font][/color][/b][color=black][font=Verdana][size=12pt]
'{K|8G\V)B To 3,5-di-tert-butyl salicylic acid (2.5 g, 10 mmol) in a Schlenk vessel was added PPh3 (10.38 g, 4 eq), and the atmosphere in the vessel replaced with argon. Acetonitrile (25 ml), and then triethylamine (6 ml, 4 eq) were added, with stirring. 2 amino-2-methyl-1-propanol (0.89 g, 1 eq) was injected in a small volume of acetonitrile. CCl4 (10 ml, 10 eq) was added dropwise over 3 hours. The mixture was stirred for 48 hours, after which time the solution was filtered, washed through with Et2O, which caused a further precipitation, this precipitate was also removed by filtration. The solvents were removed in vacuo, and the product extracted with hexane (3 x 100 ml). The combined extracts were dried in vacuo, and the pale yellow powder was purified by flash chromatography on a silica column, eluted with hexane-ethyl acetate (50:1), affording the product as a pale yellow powder (1.4 g, 46%) after removal of solvent.[/size][/font][/color]
%Z0hc~.Ka [b][color=black][font=Verdana][size=12pt]Author's Comments[/size][/font][/color][/b][color=black][font=Verdana][size=12pt]\.h!gg9b Zo/K
We have synthesized a wide range of salicyloxazolines using this procedure, yields are variable between 70% and 10% depending on the species. It is easier to add the Et2O gradually, with stirring; otherwise the precipitate formed is very sticky and hard to extract from.[/size][/font][/color]Zk*@x6i-X
[b][color=black][font=Verdana][size=12pt]Data[/size][/font][/color][/b][color=black][font=Verdana][size=12pt]
R @W${G.t1r _ 1H NMR 400 MHz (CDCl3): ppm 12.60 (s, [/size][/font][/color][color=black][font=Verdana][size=12pt]1[/size][/font][/color][color=black][font=Verdana][size=12pt]H[/size][/font][/color][color=black][font=Verdana][size=12pt], [/size][/font][/color][color=black][font=Verdana][size=12pt]OH[/size][/font][/color][color=black][font=Verdana][size=12pt]), 7.54 (d, 4JHH = 2 Hz, 1H, ArH), 7.44 (d, 4JHH = 2 Hz, 1H, ArH), 4.09 (s, 2H, CH2), 1.46 (s, 9H, C(CH3)3), 1.40 (s, 6H, CH3) 1.32 (s, 9H, C(CH3)3)[/size][/font][/color]
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6wI,V&?$r%pH [b][color=black][font=Verdana][size=12pt]Lead Reference[/size][/font][/color][/b][color=black][font=Verdana][size=12pt]+Q5F Cq1H,E
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H. Vorbrüggen and K. Krolikiewicz, Tetrahedron Lett., 1981, 22, 4471-74. [/size][/font][/color]
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Z\zgtMd [b][color=black][font=Verdana][size=12pt]Other References[/size][/font][/color][/b][color=black][font=Verdana][size=12pt]
W"O{0B]I@p H. Vorbrüggen and K. Krolikiewicz, Tetrahedron, 1993, 49, 9353-72. [/size][/font][/color]
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