Ammonium Chloride → HCID 21880357, compound

HRID 724352Notes

Reaction equation

HRID 724352 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[C:12]3[C:19](=O)[CH:18]([CH3:21])[CH2:17][C:13]=3[S:14][C:15]=2[CH3:16])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[H-].[Al+3].[Li+].[H-].[H-].[H-].[Cl-].[NH4+]>C(OCC)C>[C:1]([C:5]1[CH:6]=[CH:7][C:8]([C:11]2[C:12]3[CH:19]=[C:18]([CH3:21])[CH2:17][C:13]=3[S:14][C:15]=2[CH3:16])=[CH:9][CH:10]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 21226445Aluminium lithium hydrideHCID 21880350HCID 21880350, compound

Product 1

HCID 21880357HCID 21880357, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution containing 12.9 g (43 mmol) 3-(4-tert-Butyl-phenyl)-2,5-dimethyl-5,6-dihydro-cyclopenta[b]thiophen-4-one dissolved in 100 ml diethyl ether was added 22 mmol lithium aluminum hydride (1M in diethyl ether, 22 ml added) at room temperature. The reaction mixture was stirred for 2.5 h, then a saturated solution of ammonium chloride was slowly added (3 ml). The solids were filtered and the organics were collected with 30% dichloromethane/70% hexane, washed with water, dried over magnesium sulfate, filtered, then solvents removed in vacuo. The partially dehydrated product (12.3 g of a brown oil), was dissolved in 50 ml toluene and a catalytic amount of para-toluenesulfonic acid monohydride (0.25 g) was added, The flask contents were refluxed for 1 h, then stirred at room temperature overnight. The organic fraction was washed with water, dried over magnesium sulfate, filtered, then solvents removed in vacuo. Yield: 10.1 g (77.4%) dark brown oil. Olefin: (2 isomers); 1H NMR (CD2Cl2): δ 7.1–7.7 (m, 4H), 6.4–6.5 (2s, 1H), 3.18, 3.3 (2s, 2H), 2.4–2.6 (m, 3H), 2.18 (m, 3H), 1.4 (s, 12H).

Workup

  1. filtrationThe solids were filtered
  2. customthe organics were collected with 30% dichloromethane/70% hexane
  3. washwashed with water
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. customsolvents removed in vacuo
  7. dissolutionThe partially dehydrated product (12.3 g of a brown oil), was dissolved in 50 ml toluene
  8. additiona catalytic amount of para-toluenesulfonic acid monohydride (0.25 g) was added
  9. temperatureThe flask contents were refluxed for 1 h
  10. stirringstirred at room temperature overnight
  11. washThe organic fraction was washed with water
  12. dry with materialdried over magnesium sulfate
  13. filtrationfiltered
  14. customsolvents removed in vacuo

Sources & evidence

ORD record
ord-1c0253c35a654d33813948b301678235
Source dataset
uspto-grants-2006_11
Patent number
US07141637B2

Reaction notes

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