Methanol → HCID 135404972, compound

HRID 1684108Notes

Reaction equation

HRID 1684108 reaction equation
O([CH2:8][C:9]1[NH:10][C:11](=[O:36])[C:12]2[C:13]([N:35]=1)=[C:14]([O:33]C)[C:15]1[C:16](=[O:32])[NH:17][C:18]([CH2:24]OC3C=CC=CC=3)=[N:19][C:20]=1C=2OC)C1C=CC=CC=1.B(Br)(Br)[Br:38].[CH3:41][OH:42].[K+].[Br-:44]>C1C=CC=CC=1.C(Cl)Cl.C(O)CCC.C(O)(=O)C.O>[Br:44][CH2:8][C:9]1[NH:10][C:11](=[O:36])[C:12]2[C:13]([N:35]=1)=[C:14]([OH:33])[C:15]1[C:16](=[O:32])[NH:17][C:18]([CH2:24][Br:38])=[N:19][C:20]=1[C:41]=2[OH:42]

Participants

8

Reactant 4

HCID 887MethanolHCID 25134Boron tribromide2×HCID 253877Potassium BromideHCID 135525454HCID 135525454, compound

Product 1

HCID 135404972HCID 135404972, compound

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 6344DichloromethaneSolventHCID 22056973Butanol acetic acid waterSolvent

Procedure

To a solution of 217 mg (0.447 mmol) of 14 in 50 mL of dry benzene, was added 3.2 mL (3.20 mmol) of 1 M BBr3 in methylene chloride. The resulting mixture was refluxed for 5 hours. Additional BBr3 (1.3 mL, 1.3 mmol) was then added to the reaction mixture, and the mixture was refluxed for an additional 5 hours. After cooling the reaction mixture to room temperature, methanol was added to destroy the excess BBr3, and the solvents were removed in vacuo. The yellowish-red solid residue was redissolved in 5 mL methanol and 75 mL of water added to the solution resulting in precipitation of a greenish-yellow solid. Filtration, and washing the solids with water, and then washing with diethyl ether gave pure 18: 137 mg (71%) yield; dec pt >285° C.; TLC (n-butanol/acetic acid/water [5:2:3]), Rf =0.42; IR (KBr pellet) 3328, 3024, 1649, 1669, 1419, 1271, 1245, 1225, 1038, 800 cm-1 ; 1H NMR (dimethyl-d6 sulfoxide) δ4.45 (4H, s, methylenes); mass spectrum, (EI solids probe), m/z 430, 432, and 434 (P+ for the 79Br, 79Br; 79Br, 81Br; 81Br, 81Br combinations, respectively, at an intensity ratio of 1:2:1). Anal. Calcd for C12H8Br2N4O4.0.5H2O: C, 32.68; H, 2.05; N, 12.70. Found: C, 32.84; H, 1.89; N, 12.10.

Workup

  1. temperatureThe resulting mixture was refluxed for 5 hours
  2. temperaturethe mixture was refluxed for an additional 5 hours
  3. customto destroy the excess BBr3
  4. customthe solvents were removed in vacuo
  5. dissolutionThe yellowish-red solid residue was redissolved in 5 mL methanol
  6. addition75 mL of water added to the solution
  7. customresulting in precipitation of a greenish-yellow solid
  8. filtrationFiltration
  9. washwashing the solids with water
  10. washwashing with diethyl ether
  11. customgave pure 18
  12. custom137 mg (71%) yield

Sources & evidence

ORD record
ord-c0045a0a8e9645e890c0a672217b30fa
Source dataset
uspto-grants-1997_06
Patent number
US05639881

Reaction notes

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