Hydrogen Bromide → 9-(8-azabicyclo[3.2.1]octan-3-ylidene)-N,N-diethylxanthene-3-carboxamide

HRID 733051Notes

Reaction equation

HRID 733051 reaction equation
C(OC([N:6]1[CH:11]2[CH2:12][CH2:13][CH:7]1[CH2:8][C:9](=[C:14]1[C:27]3[CH:26]=[CH:25][C:24]([C:28](=[O:34])[N:29]([CH2:32][CH3:33])[CH2:30][CH3:31])=[CH:23][C:22]=3[O:21][C:20]3[C:15]1=[CH:16][CH:17]=[CH:18][CH:19]=3)[CH2:10]2)=O)C.Br>C(O)(=O)C>[CH2:32]([N:29]([CH2:30][CH3:31])[C:28]([C:24]1[CH:25]=[CH:26][C:27]2[C:14](=[C:9]3[CH2:10][CH:11]4[NH:6][CH:7]([CH2:13][CH2:12]4)[CH2:8]3)[C:15]3[C:20]([O:21][C:22]=2[CH:23]=1)=[CH:19][CH:18]=[CH:17][CH:16]=3)=[O:34])[CH3:33]

Participants

4

Reactant 2

HCID 260Hydrogen BromideHCID 578392423-(3-Diethylcarbamoyl-xanthen-9-ylidene)-8-aza-bicyclo[3.2.1]octane-8-carboxylic acid ethyl ester

Product 1

HCID 469181419-(8-azabicyclo[3.2.1]octan-3-ylidene)-N,N-diethylxanthene-3-carboxamideYield 56.6%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

A sample of compound 8a (16.0 g, 34.8 mmol) was dissolved in 35 mL acetic acid and 100 mL of 30% HBr in acetic acid was added to the reaction under Argon before heating on a steam bath for 1 h. The reaction was cooled, added to ice cold NaOH and extracted with CH2Cl2. The combined organics were washed with brine and dried over potassium carbonate. Evaporation of the solvent provided 12 g of crude Compound 10a, which was purified by column chromatography with 7% 2 N NH3 in methanol/93% CH2Cl2. to give 7.66 g (19.7 mmol) of Compound 10a. MS m/z=389.3 (M+1); 1H NMR 300 MHz (CDCl3) δ 1.1-1.4 (m, 6H), 1.7 (m, 2H), 2.7-3.0 (m, 4H), 3.4 (br s, 4H), 3.5-3.7 (m, 4H), 7.0-7.3 (m, 7H).

Workup

  1. temperaturebefore heating on a steam bath for 1 h
  2. temperatureThe reaction was cooled
  3. additionadded to ice cold NaOH
  4. extractionextracted with CH2Cl2
  5. washThe combined organics were washed with brine
  6. dry with materialdried over potassium carbonate
  7. customEvaporation of the solvent
  8. customprovided 12 g of crude Compound 10a, which
  9. customwas purified by column chromatography with 7% 2 N NH3 in methanol/93% CH2Cl2

Sources & evidence

ORD record
ord-b24ecdc91ead4b6bb9a9f3fcfd532cb1
Source dataset
uspto-grants-2009_09
Patent number
US07589103B2

Reaction notes

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