Methyl cyanoacetate → Methyl 2-amino-4-(hydroxymethyl)thiophene-3-carboxylate

HRID 601167

Reaction equation

HRID 601167 reaction equation
[C:1]([CH2:3][C:4]([O:6][CH3:7])=[O:5])#[N:2].O.O.O.O.O.O.O.O.O.[S-2:17].[Na+].[Na+].C([O:23][CH2:24][C:25]([CH2:27]Cl)=O)(=O)C.C(N(CC)CC)C>CO.O>[NH2:2][C:1]1[S:17][CH:27]=[C:25]([CH2:24][OH:23])[C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

7

Reactant 4

HCID 7747Methyl cyanoacetateHCID 8471TriethylamineHCID 384132-Propanone, 1-(acetyloxy)-3-chloro-HCID 73972Sodium sulfide nonahydrate

Product 1

HCID 15889790Methyl 2-amino-4-(hydroxymethyl)thiophene-3-carboxylateYield 51%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

A solution of methyl cyanoacetate (1.18 mL, 13.28 mmol) and sodium sulfide nonahydrate (3.20 g, 13.28 mmol) in methanol (25 mL) at 0° C. was treated with 1-acetoxy-3-chloroacetone (2.0 g, 13.28 mmol). The cold bath was removed and triethylamine (1.86 mL, 13.28 mmol) was added dropwise. The solution was stirred at room temperature for 20 hours then diluted with water and extracted into ethyl acetate. The organic layer was dried over sodium sulfate, filtered, and the solvent removed under vacuum to provide the titled compound (1.25 g, 51%). MS (DCI/NH3) M/Z 188 (M+H)+; 1H NMR (300 MHz, DMSO-d6) δ 3.68 (s, 3 H) 4.45 (dd, J=5.52, 1.47 Hz, 2 H) 4.88 (t, J=5.70 Hz, 1 H) 6.12 (s, 1 H) 7.28 (s, 2 H)

Workup

  1. customThe cold bath was removed
  2. extractionextracted into ethyl acetate
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. filtrationfiltered
  5. customthe solvent removed under vacuum

Sources & evidence

ORD record
ord-34d3693602e0460bb323e90f52a7b8b0
Source dataset
uspto-grants-2011_03
Patent number
US07902203B2

Linked notes

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