4-Chloro-3-nitrotoluene → 4-Methyl-2-nitro-1-(1-propen-2-yl)benzene

HRID 62039

Reaction equation

HRID 62039 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[CH3:12][C:13]1(C)[C:17](C)(C)OB(C(C)=C)O1.C(=O)([O-])[O-].[Na+].[Na+]>O.O1CCOCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:8][C:5]1[CH:6]=[CH:7][C:2]([C:13]([CH3:17])=[CH2:12])=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

Participants

7

Reactant 3

HCID 69764-Chloro-3-nitrotolueneHCID 10340Sodium CarbonateHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane

Product 1

HCID 897388014-Methyl-2-nitro-1-(1-propen-2-yl)benzeneYield 95.4%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
140 °C

Procedure

1-Chloro-4-methyl-2-nitrobenzene (0.771 mL, 5.83 mmol), 4,4,5,5-tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane (1.32 mL, 6.99 mmol), bis(triphenyl phosphine)palladium(II) chloride (0.327 g, 0.466 mmol), sodium carbonate (0.741 g, 6.99 mmol) in water (2.9 mL) and dioxane (11.4 mL) was capped in two separate 10-20 mL vials and heated on a Biotage Initiator® microwave reactor for 30 minutes at 140° C., with external IR-sensor temperature monitoring from the side of the vessel. The contents of the two vials were combined and diluted with ethyl acetate and washed with water. The aqueous layer was extracted with ethyl acetate (2×). The combined organic layers were dried over magnesium sulfate, filtered, and concentrated. Purification by flash column chromatography using 1-5% ethyl acetate/hexanes provided the title compound as a yellow oil (0.986 g, 95%): IR (thin film) 3084 (w), 2976 (m), 2919 (w), 1641 (w), 1560 (w), 1526 (vs), 1349 (s) cm−1; 1H NMR (400 MHz, CDCl3) δ 7.68-7.65 (m, 1H), 7.37-7.32 (m, 1H), 7.21 (d, J=7.9 Hz, 1H), 5.15 (p, J=1.5 Hz, 1H), 4.91 (p, J=1.0 Hz, 1H), 2.42 (s, 3H), 2.06 (t, J=1.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 148.06, 142.71, 138.30, 136.15, 133.38, 130.32, 124.29, 115.17, 23.32, 20.81.

Workup

  1. customseparate 10-20 mL vials
  2. additiondiluted with ethyl acetate
  3. washwashed with water
  4. extractionThe aqueous layer was extracted with ethyl acetate (2×)
  5. dry with materialThe combined organic layers were dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification by flash column chromatography

Sources & evidence

ORD record
ord-2131dcd688744a948c8f0f8a8e0001c8
Source dataset
uspto-grants-2016_09
Patent number
US09445594B2

Linked notes

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