Hydrochloric Acid → HCID 178507154, compound

HRID 32489Notes

Reaction equation

HRID 32489 reaction equation
[NH2:1][C:2]1[N:7]([C:8]2[CH:13]=[CH:12][C:11]([N+:14]([O-])=O)=[CH:10][CH:9]=2)[CH2:6][N:5]=[C:4]2[S:17][CH:18]=[CH:19][C:3]=12.Cl.[Sn].[OH-].[NH4+]>C(OCC)(=O)C>[NH2:1][C:2]1[N:7]([C:8]2[CH:9]=[CH:10][C:11]([NH2:14])=[CH:12][CH:13]=2)[CH2:6][N:5]=[C:4]2[S:17][CH:18]=[CH:19][C:3]=12

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 14923Ammonium HydroxideHCID 5352426Tin atomHCID 178507160HCID 178507160, compound

Product 1

HCID 178507154HCID 178507154, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

4-Amino-3-(4-nitrophenyl)thieno[2,3-d]pyrimidine (11.6 g; 272 g/mole; 42.6 mmoles) was treated with 500 mL HCl 6N and 15 g elemental tin at room temperature. After 15 minutes the reaction was complete by TLC (product has Rf=0.50 in 100% ethyl acetate). The system was placed in an ice bath and treated with concentrated ammonium hydroxide to pH 10 (˜300 mL). At this point, extensive precipitation was observed. Precipitate (A) was collected by filtration and reserved, and the clear solution was treated with 1 L methylene chloride. The aqueous layer was then back-extracted with 3×200 mL methylene chloride. The organic layers were combined, dried over anhydrous sodium sulfate, and filtered. Precipitate (A), consisting of a mixture of tin salts and product, was extracted with boiling methanol until washings showed no more product by TLC. The resulting solution was combined with the previously reserved organic layers, filtered, concentrated to dryness and dried overnight, generating desired product 4-Amino-3-(4-aminophenyl)thieno[2,3-d]pyrimidine (242 g/mole; nearly quantitative yield), which was recrystallized from methanol.

Workup

  1. customThe system was placed in an ice bath
  2. customAt this point, extensive precipitation
  3. filtrationPrecipitate (A) was collected by filtration
  4. additionthe clear solution was treated with 1 L methylene chloride
  5. extractionThe aqueous layer was then back-extracted with 3×200 mL methylene chloride
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. additionPrecipitate (A), consisting of a mixture of tin salts and product
  9. extractionwas extracted with boiling methanol until washings
  10. filtrationfiltered
  11. concentrationconcentrated to dryness
  12. customdried overnight
  13. customnearly quantitative yield), which was recrystallized from methanol

Sources & evidence

ORD record
ord-2446ca64e986480c9b6691611e026eec
Source dataset
uspto-grants-2008_09
Patent number
US07427623B2

Reaction notes

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