Dichloromethane → HCID 178433084, compound

HRID 1371112Notes

Reaction equation

HRID 1371112 reaction equation
Cl[C:2]1[N:7]=[C:6]([CH3:8])[NH:5][C:4]2=[CH:9][C:10]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)=[N:11][C:3]=12.[CH3:18][CH:19]1[CH2:24][CH:23]([CH3:25])[CH2:22][NH:21][CH2:20]1.C([O-])([O-])=O.[K+].[K+].C(Cl)Cl>O>[CH3:18][C@H:19]1[CH2:24][C@H:23]([CH3:25])[CH2:22][N:21]([C:2]2[N:7]=[C:6]([CH3:8])[NH:5][C:4]3=[CH:9][C:10]([C:12]4[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=4)=[N:11][C:3]=23)[CH2:20]1

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 1182593,5-DimethylpiperidineHCID 178432852HCID 178432852, compound

Product 1

HCID 178433084HCID 178433084, compoundYield 50%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
140 °C

Procedure

To a mixture of 4-chloro-2-methyl-6-phenyl-pyrrolo[3,2-d]pyrimidine (Example 1(e)) (83.8 mg, 0.34 mmol) and 3,5-dimethylpiperidine (cis/trans, Aldrich Chemical Company) (250 μL, 1.72 mmol) was added a solution of K2CO3 (0.19 g, 1.36 mmol) in H2O (2.0 mL). This mixture was stirred at 140° C. in a closed-capped Wheaton vial for 2.0 h. After cooling, CH2Cl2 (10 mL) and H2O (10 mL) were added. The organic solution was removed and the aqueous solution washed with CH2Cl2 (10 mL). The combined organic solutions were washed with saturated NaCl (15 mL), dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (3% MeOH:CHCl3 on silica gel) and then recrystallized from MeOH/CH2Cl2 to give 85 mg (78%) as a beige colored solid. This material was recrystallized from hot MeOH/CH2Cl2 to give 54 mg (50%) of the title compound as a 95:5 mixture of isomers as colorless crystals. Mp: 225.5-227° C. MS m/z: 321 (M+1). 1H NMR (DMSO-d6; 400 MHz) (for major isomer): δ 0.90 (m, 2), 0.91 (d, 6, J=6.5), 1.73 (m, 2), 2.40 (s, 3), 2.42 (br s, 2), 4.42 (br d, 1, J=8.2), 6.74 (s, 1), 7.40 (m, 1), 7.49 (br s, 2), 7.89 (d, 2, J=7.4), 11.06 (s, 1). Anal. Calcd for C20H24N4: C, 75.00; H, 7.50; N, 17.50. Found: C, 74.87; H, 7.56; N, 17.38.

Workup

  1. temperatureAfter cooling
  2. customThe organic solution was removed
  3. washthe aqueous solution washed with CH2Cl2 (10 mL)
  4. washThe combined organic solutions were washed with saturated NaCl (15 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by flash chromatography (3% MeOH:CHCl3 on silica gel)
  9. customrecrystallized from MeOH/CH2Cl2
  10. customto give 85 mg (78%) as a beige colored solid
  11. customThis material was recrystallized from hot MeOH/CH2Cl2

Sources & evidence

ORD record
ord-df3e5870cf9c41e0b0cc0fffe6ad343e
Source dataset
uspto-grants-2003_06
Patent number
US06583154B1

Reaction notes

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