Hydrochloric Acid → HCID 11727549, compound

HRID 429802Notes

Reaction equation

HRID 429802 reaction equation
[CH:1]1([C:4]2[NH:12][C:11]3[C:10](=S)[NH:9][C:8](=[S:14])[N:7]([CH2:15][CH2:16][CH3:17])[C:6]=3[N:5]=2)[CH2:3][CH2:2]1.[N:18]1[CH:23]=[CH:22][C:21]([CH2:24][NH2:25])=[CH:20][CH:19]=1.Cl.C(=O)(O)[O-].[Na+]>O>[CH:1]1([C:4]2[NH:12][C:11]3[C:10]([NH:25][CH2:24][C:21]4[CH:22]=[CH:23][N:18]=[CH:19][CH:20]=4)=[N:9][C:8](=[S:14])[N:7]([CH2:15][CH2:16][CH3:17])[C:6]=3[N:5]=2)[CH2:3][CH2:2]1

Participants

6

Reactant 4

HCID 313Hydrochloric Acid2×HCID 773174-PyridinemethanamineHCID 516892Sodium BicarbonateHCID 10934421HCID 10934421, compound

Product 1

HCID 11727549HCID 11727549, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

5.33 g (20 mmoles) of 8-cyclopropyl-3-n-propyl-2,6-dithioxanthine and 21.3 ml (200 mmoles) of 95% 4-picolylamine were heated under argon to 150-5° C. After 14 hours the cooled solution was poured into 100 ml of water, acidified with 19 ml of 10N HCl and 1N HCl to pH 6, where an orange colored gum was formed. With sodium bicarbonate the mixture was neutralized to pH 7. With time the gum crystallized and the solid is collected and washed. The residue was suspended in acetone and the crystals collected: 3.92 (57.6%) of crude product. The filtrate was evaporated to dryness, dissolved in 40 ml of 0.5N NaOH, extracted 4 times with methylene-chloride, and acidified again with 5N HCl to pH 6. Again the gum crystallized over 48 hours and the mixture was neutralized to pH 7 with bicarbonate and the solid collected: 1.75 g (25.7%) of crude product. Both parts were dissolved in 30 ml of methylenechloride and filtered through 30 g of silicagel in a column. 150 mg (2.8%) of starting material was recovered first, then 5.04 g (74.0%) of product was recovered with 5% of methanol, which was dissolved in 32 ml of 1N HCl, treated with 250 mg of charcoal, filtered, and neutralized with 7.5 ml of 2N NaOH and sodium bicarbonate solution to pH 7-8. The water phase was decanted from the gum and the latter washed with water and crystallized from acetone: 4.08 g (59.9%) of thioisoguanine with mp 204-210° C. with decomposition.

Workup

  1. customwas formed
  2. customWith time the gum crystallized
  3. customthe solid is collected
  4. washwashed
  5. customthe crystals collected
  6. customThe filtrate was evaporated to dryness
  7. dissolutiondissolved in 40 ml of 0.5N NaOH
  8. extractionextracted 4 times with methylene-chloride
  9. customAgain the gum crystallized over 48 hours
  10. customthe solid collected
  11. dissolutionBoth parts were dissolved in 30 ml of methylenechloride
  12. filtrationfiltered through 30 g of silicagel in a column
  13. custom150 mg (2.8%) of starting material was recovered first
  14. custom5.04 g (74.0%) of product was recovered with 5% of methanol, which
  15. dissolutionwas dissolved in 32 ml of 1N HCl
  16. additiontreated with 250 mg of charcoal
  17. filtrationfiltered
  18. customThe water phase was decanted from the gum
  19. washthe latter washed with water
  20. customcrystallized from acetone

Sources & evidence

ORD record
ord-dfca0ce76cb8415295aa1eeba32a6aee
Source dataset
uspto-grants-2001_11
Patent number
US06319928B1

Reaction notes

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