Isobutyraldehyde → (R/S)-1-(2,6-dinitrophenyl)-2-methyl-1-propanol

HRID 333477Notes

Reaction equation

HRID 333477 reaction equation
I[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12].C(=O)=O.C(O)(C)C.C1([Mg]Br)C=CC=CC=1.[CH:29](=[O:33])[CH:30]([CH3:32])[CH3:31]>O1CCCC1>[N+:11]([C:3]1[CH:4]=[CH:5][CH:6]=[C:7]([N+:8]([O-:10])=[O:9])[C:2]=1[CH:29]([OH:33])[CH:30]([CH3:32])[CH3:31])([O-:13])=[O:12]

Participants

6

Reactant 4

HCID 6561IsobutyraldehydeHCID 145711842-Iodo-1,3-dinitrobenzeneHCID 86586944Isopropanol carbon dioxideHCID 178418255HCID 178418255, compound

Product 1

HCID 59189411(R/S)-1-(2,6-dinitrophenyl)-2-methyl-1-propanolYield 30%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 1-iodo-2,6-dinitrobenzene (1.55 g, 5.27 mmol) in anhydrous tetrahydrofuran (18 mL) cooled at minus 53° C. (dry ice-isopropanol bath) under nitrogen atmosphere, phenylmagnesium bromide (2 M in THF, 3.16 mL, 6.32 mmol) was added at a rate to keep the temperature at or below minus 45° C. Upon completion of the addition the mixture was stirred for five minutes, then isobutyraldehyde (0.957 mL, 10.54 mmol) was added. The mixture was allowed to gradually warm up to room temperature, then quenched with saturated NH4Cl (5 mL) and poured into water (50 mL)/dichloromethane (100 mL). The organic layer was separated; aqueous layer was extracted three times with dichloromethane (50 mL each). Combined organic extract was washed with water (20 mL), dried over anhydrous Na2SO4, concentrated under reduced pressure, and purified by silica gel column chromatography to yield racemic (RS)-1-(2,6-dinitrophenyl)-2-methyl-1-propanol (0.375 g, 30%) as a light yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.82 (d, 2H, J=8.0 Hz, Ph-H), 7.59 (t, 1H, J=8.0 Hz, Ph-H), 4.84 (dd, 1H, J=7.6 and 9.2 Hz, Ph-CH), 2.87 (d, 1 H, J=7.6 Hz, OH), 2.18 (m, 1H, CHCH(CH3)2), 1.12 (d, 3H, J=6.4 Hz, CH3), 0.77 (d, 3H, J=6.8 Hz, CH3); 13C NMR (100 MHz, CDCl3): δ 150.82 (C), 130.62 (C), 129.31 (CH), 127.30 (CH), 74.52 (CH), 34.19 (CH), 19.84 (CH3), 19.14 (CH3).

Workup

  1. custom45° C
  2. additionUpon completion of the addition the mixture
  3. customquenched with saturated NH4Cl (5 mL)
  4. additionpoured into water (50 mL)/dichloromethane (100 mL)
  5. customThe organic layer was separated
  6. extractionaqueous layer was extracted three times with dichloromethane (50 mL each)
  7. extractionCombined organic extract
  8. washwas washed with water (20 mL)
  9. dry with materialdried over anhydrous Na2SO4
  10. concentrationconcentrated under reduced pressure
  11. custompurified by silica gel column chromatography

Sources & evidence

ORD record
ord-1fa68dbd50a24b729a9875b0a712183e
Source dataset
uspto-grants-2014_11
Patent number
US08877905B2

Reaction notes

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