Ethyl Acetate → N-(7'-Bromo-4-methoxy-3',4'-dihydro-1'H-spiro[cyclohexane-1,2'-naphthalene]-1'-ylidene)-2-methylpropane-2-sulfinamide

HRID 1468231Notes

Reaction equation

HRID 1468231 reaction equation
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][C:8]3([CH2:17][CH2:16][CH:15]([O:18][CH3:19])[CH2:14][CH2:13]3)[C:9]2=O)=[CH:4][CH:3]=1.[CH3:20][C:21]([S:24]([NH2:26])=[O:25])([CH3:23])[CH3:22].CCOC(C)=O>[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC.O>[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][C:8]3([CH2:17][CH2:16][CH:15]([O:18][CH3:19])[CH2:14][CH2:13]3)[C:9]2=[N:26][S:24]([C:21]([CH3:23])([CH3:22])[CH3:20])=[O:25])=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 8857Ethyl AcetateHCID 3382465Tert-ButanesulfinamideHCID 581971077'-Bromo-4-methoxy-3',4'-dihydro-1'H-spiro[cyclohexane-1,2'-naphthalen]-1'-one2×

Product 1

HCID 86706708N-(7'-Bromo-4-methoxy-3',4'-dihydro-1'H-spiro[cyclohexane-1,2'-naphthalene]-1'-ylidene)-2-methylpropane-2-sulfinamideYield 20.5%

Reagents, catalysts & solvents 2

HCID 76524Titanium tetraethoxideCatalystHCID 962WaterSolvent

Procedure

7′-Bromo-4-methoxy-3′,4′-dihydro-1′H-spiro[cyclohexane-1,2′-naphthalen]-1′-one (Intermediate 9, 2.26 g, 6.99 mmol), 2-methylpropane-2-sulfinamide (1.27 g, 10.5 mmol) and titanium ethoxide (2.88 mL, 14.0 mmol) were dissolved in 2-Me THF (15 mL) and heated to reflux over the weekend. The reaction was stopped and cooled to r.t. EtOAc (30 mL) and water (15 mL) were added under stirring. The mixture was then let to stand without stirring for 1 h. The organic phase was collected by filtration, dried using a phase separator and concentrated in vacuo. The product was purified by flash column chromatography using a gradient of 0-100% EtOAc in heptane to give the title compound (0.61 g, 20% yield): MS (ES+) m/z 426.11 [M+H]+.

Workup

  1. temperatureheated
  2. temperatureto reflux over the weekend
  3. stirringwithout stirring for 1 h
  4. filtrationThe organic phase was collected by filtration
  5. customdried
  6. concentrationconcentrated in vacuo
  7. customThe product was purified by flash column chromatography

Sources & evidence

ORD record
ord-d83022f744a14a8a8b121e79dd443ffa
Source dataset
uspto-grants-2015_04
Patent number
US09000184B2

Reaction notes

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