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Ethyl Acetate → N-(2-Amino-6-methylpyridin-3-ylmethyl)-N-(4-hydroxy-1-methyl-2-propyldisulfanylbut-1-enyl)formamide

HRID 1360833
ノート
印刷プレビュー

反応式

HRID 1360833 の反応式
[NH2:1][C:2]1[C:7]([CH2:8][N:9]([C:12]([CH3:37])=[C:13](SSC(CCO)=C(NC(CC2C(N)=NC(C)=CC=2)=O)C)[CH2:14][CH2:15][OH:16])[CH:10]=[O:11])=[CH:6][CH:5]=[C:4]([CH3:38])[N:3]=1.[CH2:39]([S:42][S:43]CCC)[CH2:40][CH3:41].[OH-].[Na+].C(OCC)(=O)C>CO.O.C(Cl)(Cl)Cl>[NH2:1][C:2]1[C:7]([CH2:8][N:9]([C:12]([CH3:37])=[CH:13][CH2:14][CH:15]([S:43][S:42][CH2:39][CH2:40][CH3:41])[OH:16])[CH:10]=[O:11])=[CH:6][CH:5]=[C:4]([CH3:38])[N:3]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 4

HCID 8857Ethyl AcetateHCID 12377Dipropyl disulfideHCID 14798Sodium HydroxideHCID 86616941N-(2-amino-6-methylpyridin-3-ylmethyl)-N-{2-[2-[(2-amino-6-methyl-pyridin-3-ylmethyl)formylamino]-1-(2-hydroxyethyl)-propenyldisulfanyl]-4-hydroxy-1-methylbut-1-enyl}formamide

生成物 1

HCID 86616940N-(2-Amino-6-methylpyridin-3-ylmethyl)-N-(4-hydroxy-1-methyl-2-propyldisulfanylbut-1-enyl)formamide
収率 81.3%

試薬・触媒・溶媒 3

HCID 887Methanol溶媒2 回HCID 962Water溶媒HCID 6212Chloroform溶媒

反応条件

温度
40 °C

実験手順

To a solution of N-(2-amino-6-methylpyridin-3-ylmethyl)-N-{2-[2-[(2-amino-6-methyl-pyridin-3-ylmethyl)formylamino]-1-(2-hydroxyethyl)-propenyldisulfanyl]-4-hydroxy-1-methylbut-1-enyl}formamide (250 mg, 0.45 mmol) and propyl disulfide (0.21 mL, 1.34 mmol) in methanol (3 ml) was added 1 molar aqueous sodium hydroxide (0.089 mL, 0.089 mmol). The resulting solution was stirred at 35-45° C. for 18 hr. The solution was diluted with water (10 mL) and chloroform (10 mL), but the product remained as a milky insoluble layer. Addition of ethyl acetate (10 mL) and methanol (2 mL) resulted in the formation of two clear layers. The product was contained in the lower layer. This layer was washed with brine (10 mL) dried over sodium sulfate, and evaporated. The residual oil was dissolved in chloroform (1 mL) and chromatographed on silica gel (Waters Sep-Pak 5 g column, using 97.5/2.5 chloroform/methanol as eluent, Fraction size 9 mL). Fractions 4-9 were pooled and evaporated to give 130 mg (41%) of the title compound as nearly colorless oil. MS (LCMS): 356.0 (M+H)+. 1H NMR (CDCl3) δ 0.95 (t, 3H), 1.55 (m, 3H), 1.97 (s, 3H), 2.35 (s, 3H), 2.42 (t, 2H), 2.84 (t, 2H) 3.76 (t, 2H), 5.36 (br. s, 1H), 6.35 (d, 1H), 7.02 (d, 1H), 7.96 (s, 1H).

後処理

  1. customresulted in the formation of two clear layers
  2. washThis layer was washed with brine (10 mL)
  3. dry with materialdried over sodium sulfate
  4. customevaporated
  5. dissolutionThe residual oil was dissolved in chloroform (1 mL)
  6. customchromatographed on silica gel (Waters Sep-Pak 5 g column, using 97.5/2.5 chloroform/methanol as eluent, Fraction size 9 mL)
  7. customevaporated

出典と根拠

ORDレコード
ord-d24d588c57824ce5a9a788ce8ddbb71f
出典データセット
uspto-grants-2011_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07879885B2

反応ノート

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