Triethylamine → HCID 6455298、化合物

HRID 2050175ノート

反応式

HRID 2050175 の反応式
P(Cl)(OCC)(OCC)=O.[CH3:10][C@@H:11]([CH:31]([OH:33])[CH3:32])[CH:12]1[O:14][CH:13]1[CH2:15][C@H:16]1[C@H:21]([OH:22])[C@H:20]([OH:23])[C@H:19]([CH2:24]/[C:25](/[CH3:30])=[CH:26]/[C:27]([OH:29])=[O:28])[O:18][CH2:17]1.C(N(CC)CC)C.[Cl-].[CH3:42][O:43][C:44]([CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][NH3+:54])=[O:45]>O1CCCC1>[CH3:42][O:43][C:44]([CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][NH-:54])=[O:45].[CH3:10][C@@H:11]([CH:31]([OH:33])[CH3:32])[CH:12]1[O:14][CH:13]1[CH2:15][C@H:16]1[C@H:21]([OH:22])[C@H:20]([OH:23])[C@H:19]([CH2:24]/[C:25](/[CH3:30])=[CH:26]/[C:27]([OH:29])=[O:28])[O:18][CH2:17]1

参加物

7

反応物 4

HCID 8471Triethylamine2 回HCID 13139Diethyl chlorophosphateHCID 6455298HCID 6455298、化合物HCID 10656735HCID 10656735、化合物

生成物 2

HCID 6455298HCID 6455298、化合物HCID 131711747HCID 131711747、化合物

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

Diethyl chlorophosphate (0.507 g; 2.94 mM) was added to a solution of monic acid A (0.982 g; 2.94 mM) and triethylamine (0.412 ml; 2.94 mM) in dry tetrahydrofuran (50 ml). This solution was stirred at room temperature for three hours, under a nitrogen atmosphere. A solution of 8-methoxycarbonyloctylammonium chloride (0.65 g; 2.94 mM) and triethylamine (0.412 ml; 2.94 mM) in aqueous tetrahydrofuran (10 ml) was then added and the reaction mixture stirred for a further sixteen hours at room temperature. The solvent was then removed at reduced pressure and the residue partitioned between ethyl acetate and saturated sodium bicarbonate solution. The organic layer was washed with brine, dried over anhydrous magnesium sulphate and the solvent removed to yield the crude amide as a yellow oil. The product was purified by preparative thin layer chromatography on four 20×20×20×0.2 cm silica plates, eluting with 12% methanol/chloroform. The major band afforded the pure 8-methoxycarbonyloctylamide of monic acid A as a colourless oil. (0.610 g; 40%), [α]D20 -0.74° (c, 1.0 CHCl3), λmax (EtOH) 223 nm (εm 14,130); νmax (CHBr3) 3350, 1780, 1660 and 1630 cm-1 ; δH (CDCl3) 5.93 (1H, broad t, (NH), 5.62 (1H, s, CH=C), 3.65 (3H, s, CO2CH3), 2.13 (3H, s, CH3 -15), 1.30 (s, methylene envelope), 1.20 (3H, d, J 6.0 Hz, CH3 -14), 0.92 (3H, d, J 7.0 Hz, CH3 -17); δC (CDCl3) 174.4, 167.6, 150.3, 120.4, 75.1, 70.8, 70.5, 68.9, 65.5, 61.0, 55.7, 51.5, 42.7, 39.8, 39.4, 34.1, 31.8, 29.6, 29.1, 27.0, 24.9, 20.8, 18.7, 12.6, m/e 513 (M+) 482, 366, 269, 227, 188, 172, 156, 11, 83.

後処理

  1. stirringthe reaction mixture stirred for a further sixteen hours at room temperature
  2. customThe solvent was then removed at reduced pressure
  3. customthe residue partitioned between ethyl acetate and saturated sodium bicarbonate solution
  4. washThe organic layer was washed with brine
  5. dry with materialdried over anhydrous magnesium sulphate
  6. customthe solvent removed
  7. customto yield the crude amide as a yellow oil
  8. customThe product was purified by preparative thin layer chromatography on four 20×20×20×0.2 cm silica plates
  9. washeluting with 12% methanol/chloroform

出典と根拠

ORDレコード
ord-47221a716cce4a6088841783df08c898
出典データセット
uspto-grants-1980_04
特許番号
US04200635

反応ノート

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