Hydrochloric Acid → 2-[[(4-Methylphenyl)sulfonyl]amino]-6-[[(phenylmethoxy)carbonyl]amino]hexanoic acid

HRID 6369

反応式

HRID 6369 の反応式
[C:1]([NH:11][CH2:12][CH2:13][CH2:14][CH2:15][C@@H:16]([C:18]([OH:20])=[O:19])[NH2:17])([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2].[C:21]1([CH3:31])[CH:26]=[CH:25][C:24]([S:27](Cl)(=[O:29])=[O:28])=[CH:23][CH:22]=1.Cl>[OH-].[Na+].O1CCOCC1.C(OCC)(=O)C>[CH3:31][C:21]1[CH:26]=[CH:25][C:24]([S:27]([NH:17][CH:16]([CH2:15][CH2:14][CH2:13][CH2:12][NH:11][C:1]([O:3][CH2:4][C:5]2[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=2)=[O:2])[C:18]([OH:20])=[O:19])(=[O:29])=[O:28])=[CH:23][CH:22]=1

参加物

7

反応物 3

HCID 313Hydrochloric AcidHCID 73974-Toluenesulfonyl chlorideHCID 1715626epsilon-(Benzyloxycarbonyl)-L-lysine

生成物 1

HCID 140824522-[[(4-Methylphenyl)sulfonyl]amino]-6-[[(phenylmethoxy)carbonyl]amino]hexanoic acid収率 81,024.5%

試薬・触媒・溶媒 3

HCID 8857Ethyl Acetate溶媒HCID 14798Sodium Hydroxide溶媒2 回HCID 312751,4-Dioxane溶媒

反応条件

温度
0 °C

実験手順

Nε -Carbobenzyloxy-L-lysine (30.0 g, 0.107 mmol) was dissolved in a solution of 2N NaOH (60 mL) and dioxane (150 mL) under nitrogen. After about 15 minutes at room temperature, the mixture was cooled to about 0° C. and subsequently treated with additional 2N NaOH (60 mL) and p-toluenesulfonyl chloride (20.4 g, 0.107 mmol) in 5 g portions over about 15 minutes. The mixture was stirred at about 0° C. for about 1 hour and at room temperature for about 18 hours before it was neutralized to pH 6 with 1N HCl. The mixture was then diluted with ethyl acetate and the organic phase was separated and washed with brine. The aqueous phase was extracted twice more with ethyl acetate and the combined organic phases were treated further as mentioned above. Following drying and solvent evaporation of the combined organic phases, the residue was first pre-columned on silica gel (elution with 10% methanol in dichloromethane) and subsequently recrystallized from ethyl acetate/hexanes (2:1) to give 37.67 g (81%) of the title compound as a white solid, m.p. 120°-121° C.; 1H NMR (CDCl3) δ 8.37 (v br s, 0.5H), 7.71 (d, J=8.0 Hz, 2H), 7.32 (s, 5H), 7.23 (d, J=7.6 Hz, 2H), 6.49 and 4.89 (2m, 1H), 5.73 (d, J=8.4 Hz, 1H), 5.10 and 5.04 (2s, 2H), 3.91 (m, 1H), 3.17-3.02 (m, 2H), 2.35 (s, 3H), 1.73-1.66 (m, 2H), 1.40-1.24 (m, 4H); 13C NMR (CDCl3) ppm 199.88, 175.06, 174.57, 158.37, 156.89, 143.66, 136.86, 136.32, 129.66, 128.54, 128.10, 127.19, 67.47, 66.89, 55.28, 40.95, 40.44, 32.25, 29.10, 28.75, 21.77, 21.46; IR (KBr, cm-1) 3382, 3264, 2950, 1738, 1656 1550, 1334, 1286, 1160, 1092, 818, 678, 568; MS m/z (MH+) 435.1590, obsd 435.1595.

後処理

  1. customthe organic phase was separated
  2. washwashed with brine
  3. extractionThe aqueous phase was extracted twice more with ethyl acetate
  4. additionthe combined organic phases were treated further
  5. customFollowing drying
  6. customsolvent evaporation of the combined organic phases
  7. customsubsequently recrystallized from ethyl acetate/hexanes (2:1)

出典と根拠

ORDレコード
ord-379118b96b384749848f4c9aace367b8
出典データセット
uspto-grants-1993_09
特許番号
US05248673

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