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

HRID 4935

반응식

HRID 4935 반응식
[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]

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매2회HCID 8058Hexane용매

실험 절차

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).

후처리

  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%)

출처 및 근거

ORD 기록
ord-d6f8a145407c4859b6e938637fa82e5b
출처 데이터셋
uspto-grants-1993_09
특허 번호
US05242913

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