Heptane → HCID 90012346, compound

HRID 2207059Notes

Reaction equation

HRID 2207059 reaction equation
[H-].[H-].COCCO[Al+]OCCOC.[Na+].[CH2:15]([N:22]([CH2:30][CH:31]([C:37](OCC)=[O:38])[C:32](OCC)=[O:33])[CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.CCCCCCC>C1(C)C=CC=CC=1>[CH2:15]([N:22]([CH2:30][CH:31]([CH2:37][OH:38])[CH2:32][OH:33])[CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1

Participants

5

Reactant 3

HCID 8900HeptaneHCID 21584525Sodium bis(2-methoxyethoxy)aluminiumhydrideHCID 90011506HCID 90011506, compound

Product 1

HCID 90012346HCID 90012346, compoundYield 69.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Conditions

Temperature
35 °C

Procedure

A flask is charged with toluene (160 mL) and sodium bis(2-methoxyethoxy)aluminum dihydride (Red-Al, 137.9 g, 443.4 mmol, 65 wt. % in toluene). The solution is heated to 35° C. and treated with a solution of 2 (54.6 g, 369.5 mmol) in toluene (110 mL) at a rate sufficient to maintain the reaction temperature between 35-42° C. The reaction is stirred while cooling gradually at about 30° C. for 2 hours. The reaction is further cooled to 5° C. and quenched with ethyl acetate (10.3 mL) followed by 1.85N aqueous NaOH solution (176 mL), and the layers are separated. The organic phase is treated with a solution of sodium potassium tartrate (13.65 g) in water (112 mL), and the mixture is heated at 50° C. for about 15 minutes. After cooling at about 25° C., the layers are separated. The organic phase is washed with water (180 mL), and then concentrated by distillation under vacuum at about 50-55° C. to an oil. Toluene (30 mL) is added and the resultant solution is seeded with crystals of 3 (see below) and stirred at about 25° C. for 1 hour. At this point a thick slurry is obtained. Heptane (250 mL) is added dropwise over 30 minutes, stirred an additional 2 hours, and filtered. The solid is washed with heptane and dried under vacuum to provide 3 as a white solid. Yield: 30.4 g, 69.8% yield: Purity: 96.8 wt. %.

Workup

  1. temperatureto maintain the reaction temperature between 35-42° C
  2. temperaturewhile cooling gradually at about 30° C. for 2 hours
  3. temperatureThe reaction is further cooled to 5° C.
  4. customquenched with ethyl acetate (10.3 mL)
  5. customthe layers are separated
  6. additionThe organic phase is treated with a solution of sodium potassium tartrate (13.65 g) in water (112 mL)
  7. temperaturethe mixture is heated at 50° C. for about 15 minutes
  8. temperatureAfter cooling at about 25° C.
  9. customthe layers are separated
  10. washThe organic phase is washed with water (180 mL)
  11. concentrationconcentrated by distillation under vacuum at about 50-55° C. to an oil
  12. additionToluene (30 mL) is added
  13. stirringstirred at about 25° C. for 1 hour
  14. customAt this point a thick slurry is obtained
  15. stirringstirred an additional 2 hours
  16. filtrationfiltered
  17. washThe solid is washed with heptane
  18. customdried under vacuum

Sources & evidence

ORD record
ord-619d3679d5bf4efd8b7cc8555a66bf19
Source dataset
uspto-grants-2016_06
Patent number
US09376409B2

Reaction notes

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