Nitromethane → Methyl 2-(8-(nitromethyl)-1,4-dioxaspiro[4.5]decan-8-yl)acetate

HRID 1694519Notes

Reaction equation

HRID 1694519 reaction equation
[CH3:1][O:2][C:3](=[O:15])[CH:4]=[C:5]1[CH2:14][CH2:13][C:8]2([O:12][CH2:11][CH2:10][O:9]2)[CH2:7][CH2:6]1.[N+:16]([CH3:19])([O-:18])=[O:17].[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1.O>[CH3:1][O:2][C:3](=[O:15])[CH2:4][C:5]1([CH2:19][N+:16]([O-:18])=[O:17])[CH2:6][CH2:7][C:8]2([O:9][CH2:10][CH2:11][O:12]2)[CH2:13][CH2:14]1

Participants

6

Reactant 3

HCID 6375NitromethaneHCID 2724141Tetrabutylammonium FluorideHCID 11063747Methyl 2-(1,4-dioxaspiro[4.5]decan-8-ylidene)acetate

Product 1

HCID 57795518Methyl 2-(8-(nitromethyl)-1,4-dioxaspiro[4.5]decan-8-yl)acetateYield 75.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of (1,4-dioxa-spiro[4.5]dec-8-ylidene)-acetic acid methyl ester (5.50 g, 25.9 mmol) in 14 mL of dry THF was treated by nitromethane (2.10 mL, 38.9 mmol) followed by a 1M solution of tetrabutylammonium fluoride in THF (26.5 mL, 26.5 mmol). The resulting mixture was stirred at reflux for 20 h under nitrogen. After cooling, the mixture was diluted with water and extracted with three portions of ether. The etheral portions were combined, washed with a 10% aqueous solution of potassium hydrogensulfate, dried over anhydrous Na2SO4 and concentrated. The crude was purified by silica gel column chromatography using a 20% EtOAc:hexanes mixture as eluent to afford (8-Nitromethyl-1,4-dioxa-spiro[4.5]dec-8-yl)-acetic acid methyl ester (5.34 g, 75%) as a colorless oil.

Workup

  1. temperatureat reflux for 20 h under nitrogen
  2. temperatureAfter cooling
  3. extractionextracted with three portions of ether
  4. washwashed with a 10% aqueous solution of potassium hydrogensulfate
  5. dry with materialdried over anhydrous Na2SO4
  6. concentrationconcentrated
  7. customThe crude was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-8f62784bbb0f4e268a4134b278053753
Source dataset
uspto-grants-2012_04
Patent number
US08158675B2

Reaction notes

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