Potassium Carbonate → methyl N-(2-chloro-5-nitropyrimidin-4-yl)-N-1,4-d ioxaspiro[4.5]dec-8-yl-D-alaninate

HRID 530116Notes

Reaction equation

HRID 530116 reaction equation
[Cl:1][C:2]1[N:7]=[C:6](Cl)[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][N:3]=1.C(=O)([O-])[O-].[K+].[K+].[O:18]1[C:22]2([CH2:27][CH2:26][CH:25]([NH:28][C@@H:29]([C:31]([O:33][CH3:34])=[O:32])[CH3:30])[CH2:24][CH2:23]2)[O:21][CH2:20][CH2:19]1>CC(C)=O.C(OCC)(=O)C>[Cl:1][C:2]1[N:7]=[C:6]([N:28]([CH:25]2[CH2:26][CH2:27][C:22]3([O:18][CH2:19][CH2:20][O:21]3)[CH2:23][CH2:24]2)[C@@H:29]([C:31]([O:33][CH3:34])=[O:32])[CH3:30])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][N:3]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 5212662,4-Dichloro-5-nitropyrimidineHCID 89561568methyl N-1,4-dioxaspiro[4.5]dec-8-yl-D-alaninate

Product 1

HCID 89570510methyl N-(2-chloro-5-nitropyrimidin-4-yl)-N-1,4-d ioxaspiro[4.5]dec-8-yl-D-alaninateYield 40.6%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred mixture of 2,4-dichloro-5-nitropyrimidine (4, 12 g, 62.1 mmol), potassium carbonate (11.7 g, 84.78 mmol) in acetone (100 mL) was added methyl N-1,4-dioxaspiro[4.5]dec-8-yl-D-alaninate (13.8 g, 62.1 mmol) at rt. The reaction mixture was stirred for 16 h at rt. The bulk of solvent was removed under reduced pressure to give a residue, which was diluted with ethyl acetate (100 mL), washed with water, dried over sodium sulfate. The solvent was evaporated to give a crude material, which was then purified by silica gel flash chromatography (eluent: ethyl acetate-hexane mixture (v:v=5:95)) to afforded the desired product (10.1 g). 1HNMR (300 MHz, CDCl3): δ 1.55-1.64 (m, 3H), 1.70-1.99 (m, 6H), 2.05-2.20 (m, 3H), 3.06-3.15 (m, 1H), 3.75 (s, 3H), 3.99 (t, 4H), 8.61 (s, 1H).

Workup

  1. customThe bulk of solvent was removed under reduced pressure
  2. customto give a residue, which
  3. washwashed with water
  4. dry with materialdried over sodium sulfate
  5. customThe solvent was evaporated
  6. customto give a crude material, which
  7. customwas then purified by silica gel flash chromatography (eluent: ethyl acetate-hexane mixture (v:v=5:95))

Sources & evidence

ORD record
ord-af6edf119f314c06b0ff131f747da936
Source dataset
uspto-grants-2016_05
Patent number
US09351974B2

Reaction notes

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