Hydrochloric Acid → Methyl 4-methyl-4-nitropentanoate

HRID 2061060Notes

Reaction equation

HRID 2061060 reaction equation
[N+:1]([CH:4]([CH3:6])[CH3:5])([O-:3])=[O:2].[C:7]([O:11][CH3:12])(=[O:10])[CH:8]=[CH2:9].Cl.O>O1CCOCC1.[OH-].C([N+](C)(C)C)C1C=CC=CC=1.C(OCC)C>[CH3:5][C:4]([N+:1]([O-:3])=[O:2])([CH3:6])[CH2:9][CH2:8][C:7]([O:11][CH3:12])=[O:10]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 3982-NitropropaneHCID 962WaterHCID 7294Methyl Acrylate

Product 1

HCID 247995Methyl 4-methyl-4-nitropentanoateYield 71.1%

Reagents, catalysts & solvents 3

HCID 66854Benzyltrimethylammonium hydroxideCatalystHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
70 °C

Procedure

According to the method of R. B. Moffett, Organic Syntheses, Coll. Vol. 4, p. 652 (1963), a 250-mL three-necked flask was fitted with a dropping funnel, and a thermometer placed so that the bulb was near the bottom of the flask. A solution of 2-nitropropane (45.5 mL, 0.5 mol) in dioxane (25 mL) and a 40% aqueous solution of benzyltrimethylammonium hydroxide (Triton B, 5 mL, 0.013 mmol) were added to the flask. The flask was heated to 70° C. in an oil bath and methyl acrylate (45 mL, 0.5 mol) was added via a dropping funnel over 15 minutes. The temperature rose to about 100° C. during the addition then dropped to ˜85° C. The mixture was then heated at 100° C. for 4 h. The reaction mixture was cooled to room temperature and acidified with 1 N hydrochloric acid (10 mL). Water (200 mL) and diethyl ether (400 mL) were added to the reaction flask. The mixture was poured into a separatory funnel and organic layer was washed with water (2×200 mL), brine (200 mL), dried over anhydrous MgSO4, filtered and concentrated under reduced pressure to give a yellow liquid. The product was distilled through a short path distillation apparatus to give a pale yellow liquid (62.3 g, 71.1%). 1H NMR (CDCl3, 400 MHz): δ 1.60 (s, 6H), 2.22-2.38 (m, 4H), 3.70 (s, 3H).

Workup

  1. custom652 (1963), a 250-mL three-necked flask was fitted with a dropping funnel
  2. additionThe temperature rose to about 100° C. during the addition
  3. additionthen dropped to ˜85° C
  4. temperatureThe mixture was then heated at 100° C. for 4 h
  5. temperatureThe reaction mixture was cooled to room temperature
  6. additionThe mixture was poured into a separatory funnel
  7. washorganic layer was washed with water (2×200 mL), brine (200 mL)
  8. dry with materialdried over anhydrous MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customto give a yellow liquid
  12. distillationThe product was distilled through a short path distillation apparatus

Sources & evidence

ORD record
ord-0a76bec1b3324e7e95802d71b7dcaa3a
Source dataset
uspto-grants-2012_10
Patent number
US08278482B2

Reaction notes

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