Allyl bromide → 9-(8-Allyl-8-aza-bicyclo[3.2.1] oct-3-ylidene)-9H-xanthene-3-carboxylic acid diethylamide

HRID 733054Notes

Reaction equation

HRID 733054 reaction equation
[CH2:1]([N:3]([CH2:28][CH3:29])[C:4]([C:6]1[CH:7]=[CH:8][C:9]2[C:10](=[C:20]3[CH2:26][CH:25]4[NH:27][CH:22]([CH2:23][CH2:24]4)[CH2:21]3)[C:11]3[C:16]([O:17][C:18]=2[CH:19]=1)=[CH:15][CH:14]=[CH:13][CH:12]=3)=[O:5])[CH3:2].C(=O)([O-])[O-].[K+].[K+].[CH2:36](Br)[CH:37]=[CH2:38]>C(#N)C.O>[CH2:28]([N:3]([CH2:1][CH3:2])[C:4]([C:6]1[CH:7]=[CH:8][C:9]2[C:10](=[C:20]3[CH2:26][CH:25]4[N:27]([CH2:38][CH:37]=[CH2:36])[CH:22]([CH2:23][CH2:24]4)[CH2:21]3)[C:11]3[C:16]([O:17][C:18]=2[CH:19]=1)=[CH:15][CH:14]=[CH:13][CH:12]=3)=[O:5])[CH3:29]

Participants

6

Reactant 3

HCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 469181419-(8-azabicyclo[3.2.1]octan-3-ylidene)-N,N-diethylxanthene-3-carboxamide

Product 1

HCID 114531349-(8-Allyl-8-aza-bicyclo[3.2.1] oct-3-ylidene)-9H-xanthene-3-carboxylic acid diethylamideYield 26.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

To a sample of compound 10a (0.37 g, 0.95 mmol) in 6 mL acetonitrile was added potassium carbonate (0.53 g, 3.81 mmol) and allyl bromide (80 μL, 0.95 mmol). The mixture was stirred at room temperature for 20 h. The reaction was diluted with water and extracted with CH2Cl2. The combined organic extracts were dried over magnesium sulfate and concentrated. The product was purified by flash column chromatography on silica gel, eluting with 10% 0.5 M NH3 in methanol/CH2Cl2 to yield 0.11 g (0.25 mmol) of Compound 14a. The product was converted into its HCl salt using ethereal hydrogen chloride. MS m/z=429.0 (M+1); 1H NMR 300 MHz (CDCl3) δ 1.1-1.4 (m, 6H), 1.7 (m, 2H), 2.3 (m, 2H), 3.1 (m, 2H), 3.4 (m, 2H), 3.6 (m, 4H), 4.0 (m, 2H), 4.4 (m, 2H), 4.7 (m, 2H), 5.5-5.9 (m, 4H), 6.3 (m, 2H), 7.1-7.4 (m, 7H).

Workup

  1. extractionextracted with CH2Cl2
  2. dry with materialThe combined organic extracts were dried over magnesium sulfate
  3. concentrationconcentrated
  4. customThe product was purified by flash column chromatography on silica gel
  5. washeluting with 10% 0.5 M NH3 in methanol/CH2Cl2

Sources & evidence

ORD record
ord-7713ea29ec9749558b24b06ee016c9e3
Source dataset
uspto-grants-2009_09
Patent number
US07589103B2

Reaction notes

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