Ethyl formate → HCID 178503475、化合物

HRID 518366ノート

反応式

HRID 518366 の反応式
[H-].[Na+].C(OCC)=O.[CH:8]1([CH2:11][O:12][CH2:13][C:14]([O:16]CC)=O)[CH2:10][CH2:9]1.S(O)(O)(=O)=O.[CH3:24][S:25][C:26](=[NH:28])[NH2:27].[CH3:29]SC(=N)N.[O-]CC.[Na+]>C1COCC1.CCO.C(O)(=O)C>[CH:8]1([CH2:11][O:12][C:13]2[C:14]([OH:16])=[N:28][C:26]([S:25][CH3:24])=[N:27][CH:29]=2)[CH2:10][CH2:9]1

参加物

9

反応物 5

HCID 8025Ethyl formateHCID 13347Bis(S-methylisothiouronium) sulfateHCID 24758Sodium hydrideHCID 2723922Sodium ethoxideHCID 43119684Ethyl 2-(cyclopropylmethoxy)acetate

生成物 1

HCID 178503475HCID 178503475、化合物収率 17.7%

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 702Ethanol溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a stirred suspension of NaH (35.20 g, 0.88 mol, 60% in mineral oil) in anhydrous THF (1000 mL) was added ethyl formate (88.80 g, 0.90 mol) and the title compound of step 1 (126.0 g, 0.80 mol) in anhydrous THF (100 mL). The mixture was stirred at r.t. for 0.5 hour and refluxed for 3 h. In a separate flask, S-methylthiopseudourea hemisulfate (133.44 g, 0.96 mol) and sodium ethoxide (65.28 g, 0.96 mol) in EtOH (200 mL) were stirred at r.t. for 1 h, whereupon this mixture was added to the above mixture. There combined mixture was refluxed for 15 h, cooled, and the pH was adjusted to 5 with acetic acid. After concentration under vacuum, silica gel chromatography (DCM: MeOH=50/110/1) gave the title compound (30.00 g, 17.7% yield) as a yellow solid. 1H NMR (CDCl3, 400 MHz) δ 12.08 (s, 1H), 7.49 (s, 1H), 3.83-3.80 (m, 2H), 2.55 (s, 3H), 1.37-1.28 (m, 1H), 0.65-0.62 (m, 2H), 0.37-0.34 (m, 2H).

後処理

  1. temperaturerefluxed for 3 h
  2. additionwhereupon this mixture was added to the above mixture
  3. temperaturewas refluxed for 15 h
  4. temperaturecooled
  5. concentrationAfter concentration under vacuum, silica gel chromatography (DCM: MeOH=50/110/1)

出典と根拠

ORDレコード
ord-45ecc728b5804535844362162dcee953
出典データセット
uspto-grants-2015_08
特許番号
US09115114B2

反応ノート

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