Sodium Carbonate → 2-(4,4-Dimethyl-cyclohex-1-enyl)-3-nitro-pyridine

HRID 1711270Notes

Reaction equation

HRID 1711270 reaction equation
[CH3:1][C:2]1([CH3:11])[CH2:7][CH2:6][C:5](B(O)O)=[CH:4][CH2:3]1.Cl[C:13]1[C:18]([N+:19]([O-:21])=[O:20])=[CH:17][CH:16]=[CH:15][N:14]=1.C([O-])([O-])=O.[Na+].[Na+]>C1(C)C=CC=CC=1.CCO.CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][C:2]1([CH3:11])[CH2:7][CH2:6][C:5]([C:13]2[C:18]([N+:19]([O-:21])=[O:20])=[CH:17][CH:16]=[CH:15][N:14]=2)=[CH:4][CH2:3]1

Participants

8

Reactant 3

HCID 10340Sodium CarbonateHCID 796132-Chloro-3-nitropyridineHCID 441195554,4-Dimethylcyclohexen-1-ylboronic acid

Product 1

HCID 685051192-(4,4-Dimethyl-cyclohex-1-enyl)-3-nitro-pyridineYield 61%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 894 mg (3.78 mmol) of 4,4-dimethyl-cyclohex-1-enylboronic acid and 0.500 g (3.15 mmol) of 2-chloro-3-nitro-pyridine in toluene (20 mL) and EtOH (10 mL) was treated with 12.6 mL (25.2 mmol) of 2.0 M aqueous Na2CO3. The mixture was degassed via sonication, placed under Ar, treated with 364 mg (0.315 mmol) of Pd(PPh3)4, and heated to 80° C. for 2 h. The mixture was cooled to RT, diluted with EtOAc (50 mL), and washed with saturated aqueous NaHCO3 (1×40 mL) and water (1×40 mL). The aqueous layer was extracted with EtOAc (40 mL), and the combined organic layers were dried (MgSO4) and concentrated in vacuo. Silica gel chromatography of the residue with CH2Cl2 afforded 446 mg (61%) of the title compound as a yellow solid: 1H-NMR (CDCl3; 400 MHz): δ 8.73 (dd, 1H, J=4.8, 1.6 Hz), 8.02 (dd, 1H, J=8.4, 1.6 Hz), 7.32 (m, 1H), 5.83 (sept, 1H, J=2.0 Hz), 2.50-2.44 (m, 2H), 1.98-1.93 (m, 2H), 1.56 (t, 2H, J=6.0 Hz), 1.00 (s, 6H).

Workup

  1. customThe mixture was degassed via sonication
  2. temperatureThe mixture was cooled to RT
  3. washwashed with saturated aqueous NaHCO3 (1×40 mL) and water (1×40 mL)
  4. extractionThe aqueous layer was extracted with EtOAc (40 mL)
  5. dry with materialthe combined organic layers were dried (MgSO4)
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-bc8a2f9809c94afdb222a7bb3caed8e4
Source dataset
uspto-grants-2010_09
Patent number
US07790724B2

Reaction notes

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