Methylenecyclohexane → HCID 67515548, compound

HRID 1754336Notes

Reaction equation

HRID 1754336 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:9]2[CH2:13][C:12]3([CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]3)[O:11][N:10]=2)[CH:5]=[CH:6][C:7]=1[CH3:8].CC1C=C(C=CC=1C)C=NO.C=C1CCCCC1.C1C(=O)N([Br:44])C(=O)C1>C(Cl)(Cl)Cl.CC(N=NC(C#N)(C)C)(C#N)C>[Br:44][CH:13]1[C:12]2([CH2:14][CH2:15][CH2:16][CH2:17][CH2:18]2)[O:11][N:10]=[C:9]1[C:4]1[CH:5]=[CH:6][C:7]([CH3:8])=[C:2]([Br:1])[CH:3]=1

Participants

7

Reactant 4

HCID 14502MethylenecyclohexaneHCID 67184N-bromobutanimideHCID 53395410N-[(3,4-Dimethylphenyl)methylidene]hydroxylamineHCID 67515835HCID 67515835, compound

Product 1

HCID 67515548HCID 67515548, compoundYield 23.9%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 6212ChloroformSolvent2×

Procedure

To a solution of 3-(3-bromo-4-methylphenyl)-1-oxa-2-azaspiro[4.5]dec-2-ene (2.0 g, 6.49 mmol, 1.0 eq) (prepared by following the procedure described for step-2 of the intermediate 27 by the reaction of 3-methyl-4-methylbenzaldehyde oxime with methylenecyclohexane) in chloroform (20 mL) was added NBS (1.15 g, 6.49 mmol, 1.0 eq) followed by catalytic amount of AIBN (21 mg, 0.13 mmol, 0.02 eq). The resulting mixture was stirred at room temperature overnight. The reaction was diluted with chloroform (50 mL) and washed with water (50 mL) and brine (50 mL). The organic layer was dried (Na2SO4) and filtered. The filtrate was concentrated under vacuum. The crude product was purified by flash column chromatography (silica gel, ethyl acetate and hexane) to afford 600 mg of the title product as a white solid. 1HNMR (400 MHz, CDCl3) δ 7.97 (d, J=2.0 Hz, 1H), 7.65 (dd, J=8.0, 2.0 Hz, 1H), 7.29 (d, J=8.0 Hz, 1H), 5.14 (s, 1H), 2.43 (s, 3H), 2.13-2.10 (m, 1H), 2.01-1.99 (m, 1H), 1.82-1.76 (m, 4H), 1.65-1.62 (m, 1H), 1.52-1.45 (m, 3H); ESI-MS (m/z) 386, 388, 390 [(MH)+ Br79,81].

Workup

  1. washwashed with water (50 mL) and brine (50 mL)
  2. dry with materialThe organic layer was dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated under vacuum
  5. customThe crude product was purified by flash column chromatography (silica gel, ethyl acetate and hexane)

Sources & evidence

ORD record
ord-3e8ddc976ece4129adfe4225724b923a
Source dataset
uspto-grants-2015_10
Patent number
US09169242B2

Reaction notes

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