Iodine → Ethyl 2-amino-2-cyanoacetate

HRID 131359

반응식

HRID 131359 반응식
[C:1]([C:3](=[N:9]O)[C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2].CCCCCCC.II>C(O)(=O)C.CCOC(C)=O.[Pt]>[CH2:7]([O:6][C:4](=[O:5])[CH:3]([NH2:9])[C:1]#[N:2])[CH3:8]

참가 물질

7

반응물 3

HCID 807IodineHCID 8900HeptaneHCID 6399078Ethyl 2-cyano-2-(hydroxyimino)acetate

생성물 1

HCID 288716Ethyl 2-amino-2-cyanoacetate수율 141.1%

시약·촉매·용매 3

HCID 23939Platinum촉매HCID 176Acetic Acid용매HCID 8857Ethyl Acetate용매2회

실험 절차

Combine ethyl cyanoglyoxylate-2-oxime (20.0 g, 141 mmol) and 5% Pt/C (2.0 g, 10% wt. load) in acetic acid (120 mL) and EtOAc (60 mL) and hydrogenate under 40 psi H2 overnight until the reaction is complete by TLC (5:1/heptane:EtOAc, I2 stain). Carefully filtered the spent catalyst using partial vacuum through glass fiber paper, and rinse with HOAc/EtOAc without allowing the cake to dry out. Concentrate the filtrate in vacuo on a rotovapor to an oil, leaving 25.5 g (96%) of crude amino-cyano-acetic acid ethyl ester as the HOAc salt. Partition a portion (13.0 g) of the HOAc salt between EtOAc (70 mL) and water (35 mL). Stir the biphasic solution and add dropwise aqueous 5N NaOH (16.5 mL) to adjust the pH to 8.0-8.2. Separate the layers, and extract the aqueous layer with more EtOAc (3×25 mL). Combine the organic layer, dry (MgSO4), filter, and concentrate the filtrate to dryness in vacuo on a rotovapor at low bath temperature (30-35° C.) to afford 5.68 g (65%) crude amino-cyano-acetic acid ethyl ester which was used immediately in the next reaction.

후처리

  1. customhydrogenate under 40 psi H2 overnight
  2. filtrationCarefully filtered the spent catalyst
  3. washrinse with HOAc/EtOAc
  4. customto dry out
  5. concentrationConcentrate the filtrate in vacuo on a rotovapor to an oil

출처 및 근거

ORD 기록
ord-57b89e166bb64269b2551ecb9cef03d9
출처 데이터셋
uspto-grants-2008_06
특허 번호
US07384934B2

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