Acetone → HCID 66920980, compound

HRID 2065867Notes

Reaction equation

HRID 2065867 reaction equation
[Cl:1][C:2]1[CH:25]=[CH:24][C:5]2[O:6][C:7]3[CH:23]=[CH:22][CH:21]=[CH:20][C:8]=3[C@@H:9]([C:15](OCC)=[O:16])[C@H:10]([CH2:11][N+:12]([O-:14])=[O:13])[C:4]=2[CH:3]=1.O1CCCC1.[BH4-].[Na+].CC(C)=O>CO.C1(C)C=CC=CC=1.O>[Cl:1][C:2]1[CH:25]=[CH:24][C:5]2[O:6][C:7]3[CH:23]=[CH:22][CH:21]=[CH:20][C:8]=3[C@@H:9]([CH2:15][OH:16])[C@H:10]([CH2:11][N+:12]([O-:14])=[O:13])[C:4]=2[CH:3]=1

Participants

8

Reactant 4

HCID 180AcetoneHCID 8028TetrahydrofuranHCID 4311764Sodium borohydrideHCID 66921006HCID 66921006, compound

Product 1

HCID 66920980HCID 66920980, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A 180.9 g portion of the ethyl trans-2-chloro-11-(nitromethyl)-10,11-dihydrodibenzo[b,f]oxepin-10-carboxylate obtained in Reference Example 6 (mixture of the initially obtained whitish crystals and subsequently obtained light yellow crystals, 0.5 mol, trans/cis=99.3/0.7) was added to and mixed with a mixture of 904 mL of tetrahydrofuran and 24.6 g of sodium borohydride (0.65 mol, powdered). Next, 134.1 g (45.5 wt %, 0.90 mol) of a boron trifluoride/tetrahydrofuran complex was added dropwise to the obtained mixture under a nitrogen atmosphere, over a period of about 1 hour and 30 minutes. The internal temperature of the mixture during the dropwise addition was 20-26° C. The obtained mixture was stirred at the same temperature for approximately 2 hours, and then stirred at 40° C. for approximately 3 hours. After cooling the reaction mixture with an ice water bath, 58 g of acetone and 452 mL of water were added dropwise in that order, at an internal temperature of 5-10° C. To the obtained mixture there were added 542 mL of toluene and 180 mL of methanol, the mixture was stirred, and liquid separation was performed. The obtained organic layer was washed twice with 250 mL of a methanol/water=1/10 (v/v) mixed solution and once with 300 mL of 10 wt % brine in that order, and then the organic layer was subjected to dehydration treatment with anhydrous magnesium sulfate and concentrated to obtain 158.1 g of crude trans-[2-chloro-11-(nitromethyl)-10,11-dihydrodibenzo[b,f]oxepin-10-yl]methanol as a highly viscous fluid.

Workup

  1. additionmixture of the initially obtained whitish crystals and subsequently obtained light yellow crystals, 0.5 mol, trans/cis=99.3/0.7)
  2. additionwas added to and
  3. additionNext, 134.1 g (45.5 wt %, 0.90 mol) of a boron trifluoride/tetrahydrofuran complex was added dropwise to the obtained mixture under a nitrogen atmosphere, over a period of about 1 hour and 30 minutes
  4. additionThe internal temperature of the mixture during the dropwise addition
  5. customwas 20-26° C
  6. stirringstirred at 40° C. for approximately 3 hours
  7. temperatureAfter cooling the reaction mixture with an ice water bath
  8. stirringthe mixture was stirred
  9. customliquid separation
  10. washThe obtained organic layer was washed twice with 250 mL of a methanol/water=1/10 (v/v)
  11. additionmixed solution
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-6193e1766e6446d79e012a310be54323
Source dataset
uspto-grants-2012_10
Patent number
US08288564B2

Reaction notes

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