Methanol → HCID 59733775, compound

HRID 132102Notes

Reaction equation

HRID 132102 reaction equation
C1(P([N:15]=[N+]=[N-])(C2C=CC=CC=2)=[O:8])C=CC=CC=1.[C:18]([C:22]1[CH:23]=[C:24]([C:28]2(C(O)=O)[CH2:33][CH2:32][CH2:31][C:30](=[CH2:34])[CH2:29]2)[CH:25]=[CH:26][CH:27]=1)([CH3:21])([CH3:20])[CH3:19].C([N:40](CC)CC)C.CO>C1(C)C=CC=CC=1>[OH-:8].[NH4+:15].[C:18]([C:22]1[CH:23]=[C:24]([C:28]2([NH2:40])[CH2:33][CH2:32][CH2:31][C:30](=[CH2:34])[CH2:29]2)[CH:25]=[CH:26][CH:27]=1)([CH3:21])([CH3:20])[CH3:19]

Participants

7

Reactant 4

HCID 887MethanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 597337311-(3-Tert-butyl-phenyl)-3-methylene-cyclohexanecarboxylic acid

Product 2

HCID 14923Ammonium HydroxideHCID 59733775HCID 59733775, compoundYield 2.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Diphenylphosphoryl azide (0.53 mL, 2.46 mmol) was added to a solution of 1-(3-tert-butyl-phenyl)-3-methylene-cyclohexanecarboxylic acid (554 mg, 2.03 mmol) and triethylamine (0.43 mL, 3.08 mmol) in toluene (4 mL). After stirring at ambient temperature for 18 h, the solution was placed into a preheated oil bath at 80° C. Bubbling was observed. After stirring for 1 h at 80° C., the bubbling had ceased and the solution was cooled to ambient temperature. 10% aqueous hydrochloric acid was added and stirred vigorously for 3 h. The aqueous layer was made alkaline with aqueous 3 N NaOH and extracted with methylene chloride. The combined organic extracts were dried over magnesium sulfate, filtered, and concentrated. The residue was flash chromatographed with 99:1:0.1, 49:1:0.1, 24:1:0.1, and 23:2:0.2 methylene chloride:methanol:concentrated ammonium hydroxide as the eluant to yield 12 mg (2% yield) of 1-(3-tert-butyl-phenyl)-3-methylene-cyclohexylamine.

Workup

  1. customthe solution was placed into a preheated oil bath at 80° C
  2. customBubbling
  3. stirringAfter stirring for 1 h at 80° C.
  4. temperaturethe solution was cooled to ambient temperature
  5. addition10% aqueous hydrochloric acid was added
  6. stirringstirred vigorously for 3 h
  7. extractionextracted with methylene chloride
  8. dry with materialThe combined organic extracts were dried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customchromatographed with 99:1:0.1, 49:1:0.1, 24:1:0.1, and 23:2:0.2 methylene chloride

Sources & evidence

ORD record
ord-0ba0571fd228428cbe2b7f0195beb714
Source dataset
uspto-grants-2008_06
Patent number
US07385085B2

Reaction notes

Loading…