Ammonia → HCID 57680997, compound

HRID 386266Notes

Reaction equation

HRID 386266 reaction equation
[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][NH:8][C:4]=2[N:5]=[CH:6][N:7]=1.[C:12]1(B(O)O)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.N1C=CC=CC=1.N>C(Cl)Cl.CC([O-])=O.CC([O-])=O.[Cu+2]>[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][N:8]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[C:4]=2[N:5]=[CH:6][N:7]=1

Participants

7

Reactant 4

HCID 222AmmoniaHCID 1049PyridineHCID 66827Phenylboronic AcidHCID 148092816-Chloro-7-iodo-7-deazapurine

Product 1

HCID 57680997HCID 57680997, compound

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A mixture of 4-chloro-5-iodo-7H-pyrrolo[2,3-d]pyrimidine (prepared according to: L. B. Townsend et al., J. Med. Chem. 1990, 33 (7), 1984-92) (280 mg, 1.00 mmol), phenylboronic acid (244 mg, 2.00 mmol), pyridine (165 μL, 161 mg, 2.04 mmol), and Cu(OAc)2 (272 mg, 1.50 mmol) in CH2Cl2 (5 mL) was stirred under air at ambient temperature for 12 d. Aqueous ammonia (1 M) and CH2Cl2 were added, the solids were filtered off, the layers of the filtrate were separated, the aqueous layer was extracted with CH2Cl2 (2×30 mL), the combined CH2Cl2 layers were washed with 1 M aqueous ammonia (2×), 2 M NaOH (2×), and brine and dried over MgSO4. The crude material was adsorbed onto Hydromatrix and chromatographed on silica gel [Jones Flashmaster, 20 g/70 mL cartridge, eluting with CH2Cl2], yielding the title compound as off-white solid. 1H NMR (CDCl3, 400 MHz): δ=7.43-7.48 (m, 1H), 7.54-7.60 (m, 2H), 7.61-7.65 (m, 2H), 7.69 (s, 1H), 8.68 (s, 1H). MS (ES+): m/z 355.9/357.9 (100/35) [MH+]. HPLC: tR=3.8 min (OpenLynx, polar—5 min).

Workup

  1. filtrationthe solids were filtered off
  2. customthe layers of the filtrate were separated
  3. extractionthe aqueous layer was extracted with CH2Cl2 (2×30 mL)
  4. washthe combined CH2Cl2 layers were washed with 1 M aqueous ammonia (2×), 2 M NaOH (2×), and brine
  5. dry with materialdried over MgSO4
  6. customchromatographed on silica gel [Jones Flashmaster, 20 g/70 mL cartridge, eluting with CH2Cl2]

Sources & evidence

ORD record
ord-b37a5d990812416abf34030be0920f9f
Source dataset
uspto-grants-2013_02
Patent number
US08367826B2

Reaction notes

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