Ethyl (chloroformyl)acetate → HCID 57906588, compound

HRID 420516Notes

Reaction equation

HRID 420516 reaction equation
[C:1]([O:5][C:6](=[O:17])[NH:7][CH2:8][C:9]1[C:14]([Br:15])=[CH:13][N:12]=[C:11]([NH2:16])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].[CH2:18]([O:20][C:21](=[O:26])[CH:22](Cl)[CH:23]=O)[CH3:19]>O1CCOCC1.CCOC(C)=O>[CH2:18]([O:20][C:21]([C:22]1[N:12]2[CH:13]=[C:14]([Br:15])[C:9]([CH2:8][NH:7][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:17])=[CH:10][C:11]2=[N:16][CH:23]=1)=[O:26])[CH3:19]

Participants

5

Reactant 2

HCID 118030Ethyl (chloroformyl)acetateHCID 57906440HCID 57906440, compound

Product 1

HCID 57906588HCID 57906588, compoundYield 41%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

A solution of (2-amino-5-bromo-pyridin-4-ylmethyl)-carbamic acid tert-butyl ester (3.5 g, 11.6 mmol, prepared according to Example 1, Step 1.3) and freshly prepared 2-chloro-3-oxo-propionic acid ethyl ester (8.97 g, 59.6 mmol, prepared according to a patented procedure U.S. Pat. No. 5,559,158-A1) in dioxane (60 mL) was stirred at RT for 14 h. The reaction mixture was diluted in AcOEt (400 mL) and washed with a 2.0 M aqueous Na2CO3 solution (2×200 mL). The organic layer was dried over Na2SO4, filtered, and evaporated. The residue was purified by Combi-Flash Companion™ (Isco Inc.) column chromatography (SiO2; gradient elution, [hexane/DCM 1:1]/TBME 95:5→2:8) to yield the title compound (1.31 g, 4.83 mmol, 41%) as a light yellow solid. MS: 398 [M+1]+; HPLC: AtRet=1.85; TLC: RF 0.47 (hexane/DCM/TBME 1:1:2).

Workup

  1. washwashed with a 2.0 M aqueous Na2CO3 solution (2×200 mL)
  2. dry with materialThe organic layer was dried over Na2SO4
  3. filtrationfiltered
  4. customevaporated
  5. customThe residue was purified by Combi-Flash Companion™ (Isco Inc.) column chromatography (SiO2; gradient elution, [hexane/DCM 1:1]/TBME 95:5→2:8)

Sources & evidence

ORD record
ord-94f6458b9eeb45cbae5e6a31123451a5
Source dataset
uspto-grants-2012_01
Patent number
US08097617B2

Reaction notes

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