Ammonium Chloride → HCID 131713995, compound

HRID 2118907Notes

Reaction equation

HRID 2118907 reaction equation
O[CH:2]1OC2=CC(C(C)(C)CCCCCC)=CC3=C2C(CC(C)(C)O3)C1.[CH3:26][O:27][C:28]1[CH:33]=[C:32]([CH2:34][NH:35][CH2:36][CH2:37][CH2:38][NH:39][CH2:40][CH2:41][CH2:42][CH2:43][NH:44][CH2:45][CH2:46][CH2:47][NH2:48])[CH:31]=[CH:30][C:29]=1[OH:49].[OH:50][CH:51]1[CH:60]2[CH2:61][CH2:62][O:63][C:58]3=[C:59]2[C:54](=[CH:55][C:56]([C:64]([CH3:72])([CH3:71])[CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH3:70])=[CH:57]3)[O:53][C:52]1([CH3:74])[CH3:73].C[Mg]I.[Cl-].[NH4+]>C(OCC)C>[CH3:26][O:27][C:28]1[CH:33]=[C:32]([CH2:34][NH:35][CH2:36][CH2:37][CH2:38][NH:39][CH2:40][CH2:41][CH2:42][CH2:43][NH:44][CH2:45][CH2:46][CH2:47][NH2:48])[CH:31]=[CH:30][C:29]=1[OH:49].[OH:50][CH:51]1[CH:60]([CH2:61][CH:62]([OH:63])[CH3:2])[C:59]2[CH:58]=[CH:57][C:56]([C:64]([CH3:72])([CH3:71])[CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH3:70])=[CH:55][C:54]=2[O:53][C:52]1([CH3:74])[CH3:73]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 19848769HCID 19848769, compoundHCID 131713997HCID 131713997, compoundHCID 178418373HCID 178418373, compound

Product 1

HCID 131713995HCID 131713995, compoundYield 58.3%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

The hemiacetal obtained in Example 6, dl-5-hydroxy-2,2-dimethyl-8-(1,1-dimethylheptyl)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran, (491 mg, 1.42 mmole) was dissolved in 10 ml of diethyl ether and cooled in an ice bath for 15 minutes. From a syringe 1.58 ml of 2.9M methylmagnesium iodide was added slowly with stirring. The reaction mixture was allowed to warm to room temperature and stirred for three hours. Ammonium chloride crystals (ca. 100 mg) was added to consume the unreacted Grignard reagent and the mixture stirred for 20 minutes. Ethyl acetate, 75 ml, and water, 50 ml, were added, the mixture stirred for a few minutes, and the layers separated. The aqueous layer was extracted with 50 ml of ethyl acetate and the combined organic layers washed with 50 ml each of water, brine and water again. The organic layer was dried over anhydrous magnesium sulfate and solvent evaporated in vacuo to provide 525 mg of crude oil. The oil was chromatographed on a pair of 2 mm thickness silica gel plates employing an ethyl acetate/pentane (1:3 by volume) solvent system. The region with Rf 0.09-0.21 was extracted with 200 ml of ethyl acetate for 2-3 hours to afford 300 mg of product (58.3%).

Workup

  1. temperaturecooled in an ice bath for 15 minutes
  2. stirringstirred for three hours
  3. customto consume the unreacted Grignard reagent
  4. stirringthe mixture stirred for 20 minutes
  5. additionEthyl acetate, 75 ml, and water, 50 ml, were added
  6. stirringthe mixture stirred for a few minutes
  7. customthe layers separated
  8. extractionThe aqueous layer was extracted with 50 ml of ethyl acetate
  9. washthe combined organic layers washed with 50 ml each of water, brine and water again
  10. dry with materialThe organic layer was dried over anhydrous magnesium sulfate and solvent
  11. customevaporated in vacuo
  12. customto provide 525 mg of crude oil
  13. customThe oil was chromatographed on a pair of 2 mm thickness silica gel plates
  14. extractionThe region with Rf 0.09-0.21 was extracted with 200 ml of ethyl acetate for 2-3 hours

Sources & evidence

ORD record
ord-6893057b9a31442386ebd25025b714aa
Source dataset
uspto-grants-1987_07
Patent number
US04680404

Reaction notes

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