Triethylamine → di-tert-butyl N-(4-nitro-2-fluorobenzoyl)-(L)-glutamate

HRID 2051556

反応式

HRID 2051556 の反応式
[F:1][C:2]1[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=O.Cl.[C:15]([O:19][C:20](=[O:32])[C@H:21]([CH2:23][CH2:24][C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[NH2:22])([CH3:18])([CH3:17])[CH3:16].ON1C2C=CC=CC=2N=N1.C(N(CC)CC)C.C1(N=C=NC2CCCCC2)CCCCC1>CN(C)C=O.CO>[N+:11]([C:9]1[CH:8]=[CH:7][C:3]([C:4]([NH:22][C@H:21]([C:20]([O:19][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:32])[CH2:23][CH2:24][C:25]([O:27][C:28]([CH3:31])([CH3:29])[CH3:30])=[O:26])=[O:6])=[C:2]([F:1])[CH:10]=1)([O-:13])=[O:12]

参加物

8

反応物 5

HCID 8471TriethylamineHCID 10868DicyclohexylcarbodiimideHCID 757711-HydroxybenzotriazoleHCID 208636Di-tert-butyl glutamate hydrochlorideHCID 3026792-Fluoro-4-nitrobenzoic acid

生成物 1

HCID 10071104di-tert-butyl N-(4-nitro-2-fluorobenzoyl)-(L)-glutamate

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 6228Dimethylformamide溶媒

実験手順

A solution of 2-fluoro-4-nitrobenzoic acid (6.26 g, 33.8 mmoles), (L)-glutamate di-tert-butyl ester hydrochloride (10.0 g, 33.8 mmoles), and 1-hydroxybenzotriazole (4.57 g, 33.8 mmoles) in dry dimethylformamide (150 mL) was stirred under nitrogen while triethylamine (3.42 g, 4.71 mL, 33.8 mmoles) was added in one portion. After 15 minutes, 1.3-dicyclohexylcarbodiimide (7.67 g, 37.2 mmoles) was added in portions during 1 minute. The reaction mixture was filtered after 20 hours and the solids rinsed with dichloromethane (1×50 mL). The filtrate was spin evaporated to an amber residue that was partitioned between dichloromethane and saturated bicarbonate solution (200 mL each). The organic phase was washed successively with saturated bicarbonate, 5% citric acid, and brine (1×200 mL each). The organic phase was then dried (MgSO4), filtered, spin evaporated, and dried (high vacuum) to an oily yellow solid (11.9 g, 83%) that showed a major spot on tlc (silica, 2:1 hexane/ethyl acetate, Rf =0.5). The product was purified by the flash chromatography technique to give a light green gum; yield, 9.7 g (67%); 1H-NMR (CDCl3) δ 1.42 (s, 9H), 1.50 (s, 9H), 2.02-2.41 (m, 4H), 4.72 (m, 1H), 7.44 (br t, 1H), 8.0-8.3 (m, 3H); uv (MeOH) 260 nm max (11000), 225 min (4710), 215 sh (7680); mass spec (CI) m/e 427 (24%), 371 (20), 315 (100).

後処理

  1. additionwas added in one portion
  2. filtrationThe reaction mixture was filtered after 20 hours
  3. washthe solids rinsed with dichloromethane (1×50 mL)
  4. customevaporated to an amber residue that
  5. customwas partitioned between dichloromethane and saturated bicarbonate solution (200 mL each)
  6. washThe organic phase was washed successively with saturated bicarbonate, 5% citric acid, and brine (1×200 mL each)
  7. dry with materialThe organic phase was then dried (MgSO4)
  8. filtrationfiltered
  9. customspin evaporated
  10. dry with materialdried (high vacuum) to an oily yellow solid (11.9 g, 83%) that
  11. customThe product was purified by the flash chromatography technique
  12. customto give a light green gum
  13. customyield

出典と根拠

ORDレコード
ord-814f335b1faf48bf9ce10d50f93957d0
出典データセット
uspto-grants-1991_05
特許番号
US05019577

関連ノート

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