Hydrochloric Acid → HCID 86747346, compound

HRID 256544Notes

Reaction equation

HRID 256544 reaction equation
[ClH:1].[OH:2][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]2[C:18]=1[C:17]1=[C:19]3[C@@H:9]([N:10]([CH3:20])[CH2:11][CH2:12][C:13]3=[CH:14][CH:15]=[CH:16]1)[CH2:8]2.C[Mg+].[Br-].CN(C)P(N(C)C)N(C)C.C=O.Cl.[C:37]([O-])(O)=[O:38].[Na+]>C1C=CC=CC=1>[ClH:1].[CH:37]([C:4]1[C:3]([OH:2])=[C:18]2[C:7]([CH2:8][C@H:9]3[C:19]4[C:13](=[CH:14][CH:15]=[CH:16][C:17]2=4)[CH2:12][CH2:11][N:10]3[CH3:20])=[CH:6][CH:5]=1)=[O:38]

Participants

8

Reactant 6

HCID 313Hydrochloric Acid3×HCID 712FormaldehydeHCID 15355Hexamethylphosphorous triamideHCID 516892Sodium BicarbonateHCID 67857954HCID 67857954, compoundHCID 178418689HCID 178418689, compound

Product 1

HCID 86747346HCID 86747346, compoundYield 46%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent4×

Procedure

This reaction was performed in a dry box under N2 (10% relative humidity). A suspension of 0.228 g (0.908 mmol) of 9 in 10 mL of benzene was added in 0.5 mL portions over 20 min to a solution of 0.45 mL (1.36 mmol) of MeMgBr (3.0M in Et2O) in 10 mL of benzene. The mixture was stirred at room temperature for 30 min. A solution of 0.243 g (1.36 mmol) of hexamethylphosphorous triamide in 1 mL of benzene was added. The mixture was stirred for 15 min, then a suspension of 0.273 g (9.08 mmol) of paraformaldehyde in 2 mL of benzene was added. The mixture was heated under reflux for 4 h, cooled, and transferred to a 1 L beaker. Two hundred milliliters of 5% HCl was added and the resulting mixture was stirred for 10 min. The mixture was made basic with solid NaHCO3 and was extracted with 100 mL of Et2O, then with four 75 mL portions of CHCl3. The combined extracts were dried (Na2SO4) and volatiles were removed under reduced pressure to produce a green oil which was converted into its HCl salt with ethereal HCl. The salt was washed with two 5 mL portions of abs EtOH to give 0.130 g (46%) of a white solid, mp 255°-258° C. (decomp). Lit1 mp of (R) enantiomer 260°-262° C. (decomp).

Workup

  1. customThis reaction was performed in a dry box under N2 (10% relative humidity)
  2. stirringThe mixture was stirred for 15 min
  3. additionwas added
  4. temperatureThe mixture was heated
  5. temperatureunder reflux for 4 h
  6. temperaturecooled
  7. stirringthe resulting mixture was stirred for 10 min
  8. extractionwas extracted with 100 mL of Et2O
  9. dry with materialThe combined extracts were dried (Na2SO4) and volatiles
  10. customwere removed under reduced pressure
  11. customto produce a green oil which
  12. washThe salt was washed with two 5 mL portions of abs EtOH

Sources & evidence

ORD record
ord-42830d3ab3ff4bd8bb051f4b717cd0e2
Source dataset
uspto-grants-1993_11
Patent number
US05258384

Reaction notes

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