Dichloromethane → HCID 21309671, compound

HRID 1416625Notes

Reaction equation

HRID 1416625 reaction equation
[C:1]([N:8]1[CH2:11][CH2:10][C@H:9]1[CH2:12][O:13][C:14]1[CH:15]=[N:16][C:17]([CH3:20])=[CH:18][CH:19]=1)(OC(C)(C)C)=O.C(O)(C(F)(F)F)=O.C([O-])([O-])=O.[K+].[K+].C(Cl)[Cl:35]>>[ClH:35].[ClH:35].[CH3:1][N:8]1[CH2:11][CH2:10][C@H:9]1[CH2:12][O:13][C:14]1[CH:15]=[N:16][C:17]([CH3:20])=[CH:18][CH:19]=1

Participants

5

Reactant 4

HCID 6344DichloromethaneHCID 6422Trifluoroacetic acidHCID 11430Potassium CarbonateHCID 21309664HCID 21309664, compound

Product 1

HCID 21309671HCID 21309671, compound

Conditions

Temperature
0 °C

Procedure

A 1.3 g sample of the compound from step 59a above was dissolved in 6 mL of methylene chloride, the solution was cooled to 0° C., and 4 mL of TFA was added. The reaction mixture was stirred at 0° C. for 3 hours, then poured into a satd solution of K2CO3. The organic layer was separated, the aqueous layer extracted with additional methylene chloride, the organics combined, and the solvent removed. The residue was dissolved in ethanol, the solution was cooled to 0° C., and excess NaCNBH3 was added. Two mL of HCHO were added, the pH was adjusted with acetic acid, using bromocresol as an indicator, and the reaction mixture was stirred for 16 hours. The reaction was quenched by pouring it into satd K2CO3 solution. The mixture was extracted with methylene chloride, the extract was dried over MgSO4, and the solvent was removed. The residual oil was purified by chromatography on silica gel, eluting with 100: 1 to 95:5 CHCl3 :methanol containing 0.5% NH4OH. This compound was treated with HCl in ether according to Example 14c to afford 362 mg of the title compound. MS (DCI/NH3) m/e: 193 (M+H)+. 1H NMR (D2O, 300 MHz) δ: 8.33 (d, J=2.2 Hz, 1H), 7.92 (dd, J=2.6, 8.8 Hz, 1H), 7.66 (d, J=8.8 Hz, 1H), 7.66 (d, J=8.8 Hz, 1H), 4.87-4.77 (m, 1H), 4.57-4.44 (m, 2H), 4.33-4.23 (m, 1H), 4.01 (q, J=9.6 Hz, 1H), 3.00 (s, 3H), 2.73-2.61 (m, 2H), 2.64 (s, 3H). Anal. Calc. for C11H16N2O·2 HCl·0.4 H2O: C, 49.88; H, 6.84; N, 10.56; Found C, 48.25; H, 6.96; N, 10.28.

Workup

  1. customThe organic layer was separated
  2. extractionthe aqueous layer extracted with additional methylene chloride
  3. customthe solvent removed
  4. dissolutionThe residue was dissolved in ethanol
  5. temperaturethe solution was cooled to 0° C.
  6. additionexcess NaCNBH3 was added
  7. additionTwo mL of HCHO were added
  8. stirringthe reaction mixture was stirred for 16 hours
  9. customThe reaction was quenched
  10. additionby pouring it into satd K2CO3 solution
  11. extractionThe mixture was extracted with methylene chloride
  12. dry with materialthe extract was dried over MgSO4
  13. customthe solvent was removed
  14. customThe residual oil was purified by chromatography on silica gel
  15. washeluting with 100: 1 to 95:5 CHCl3
  16. additionThis compound was treated with HCl in ether according to Example 14c

Sources & evidence

ORD record
ord-28cb2c09e444470389a1c9ca53c72978
Source dataset
uspto-grants-1999_06
Patent number
US05914328

Reaction notes

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