Acetic Acid → Ethyl 2-Formyl-2-(2-formylamino-4-thiazolyl)acetate

HRID 4935

反応式

HRID 4935 の反応式
[H-].[Na+].[NH2:3][C:4]1[S:5][CH:6]=[C:7]([CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])[N:8]=1.[CH:15](OCC)=[O:16].[C:20](O)(=[O:22])C>CCCCCC.O1CCCC1>[CH:15]([CH:9]([C:7]1[N:8]=[C:4]([NH:3][CH:20]=[O:22])[S:5][CH:6]=1)[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[O:16]

参加物

7

反応物 4

HCID 176Acetic AcidHCID 8025Ethyl formateHCID 24758Sodium hydrideHCID 1044544-Thiazoleacetic acid, 2-amino-, ethyl ester

生成物 1

HCID 13309500Ethyl 2-Formyl-2-(2-formylamino-4-thiazolyl)acetate

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒

実験手順

Under nitrogen, 14 g (0.29 mmol) of 50% NaH in oil was washed with 2×40 ml of hexane and then suspended in 90 ml of anhydrous tetrahydrofuran (THF). To this slurry at 0° C. was added dropwise a solution of ethyl 2-(2-amino-4-thiazolyl)acetate (27 g, 0.145 mmol) in 290 ml of anhydrous THF, followed by ethyl formate (21.5 g, 0.29 mmol), and the mixture stirred at room temperature for 18 hours. The pH of reaction mixture was adjusted to 7 by the addition of 50% aqueous acetic acid and the mixture extracted with 250 ml ethyl acetate. The aqueous layer was further extracted with 2×50 ml of 1:1 THF:ethyl acetate. The extracts were combined, dried over Na2SO4 and evaporated to a solid, which was recrystallized from ethyl acetate to yield purified title product, 17.8 g (50.7%); m.p. 179°-180° C.; 1H-nmr (CDCl3 -d6 -DMSO) 1.33 (t, 3H), 4.16 (q, 2H), 7.50 (s, 1H), 8.00 (s, 1H), 8.53 (s, 1H).

後処理

  1. customThe pH of reaction mixture
  2. extractionthe mixture extracted with 250 ml ethyl acetate
  3. extractionThe aqueous layer was further extracted with 2×50 ml of 1:1 THF
  4. dry with materialdried over Na2SO4
  5. customevaporated to a solid, which
  6. customwas recrystallized from ethyl acetate
  7. customto yield
  8. custompurified title product, 17.8 g (50.7%)

出典と根拠

ORDレコード
ord-d6f8a145407c4859b6e938637fa82e5b
出典データセット
uspto-grants-1993_09
特許番号
US05242913

関連ノート

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