HCID 86704550, compound → HCID 86704551, compound

HRID 633464Notes

Reaction equation

HRID 633464 reaction equation
CC1C=CC(S(O[CH2:12][C:13]2([CH2:31][OH:32])[O:18][C:17]3[CH:19]=[CH:20][C:21]([N+:23]([O-:25])=[O:24])=[CH:22][C:16]=3[N:15]3[C:26](=[O:30])[N:27]([CH3:29])[N:28]=[C:14]23)(=O)=O)=CC=1.C([Li])CCC>C1COCC1>[CH3:29][N:27]1[C:26](=[O:30])[N:15]2[C:16]3[CH:22]=[C:21]([N+:23]([O-:25])=[O:24])[CH:20]=[CH:19][C:17]=3[O:18][C:13]3([CH2:12][O:32][CH2:31]3)[C:14]2=[N:28]1

Participants

4

Reactant 2

HCID 86704550HCID 86704550, compoundHCID 178418339Butyllithium

Product 1

HCID 86704551HCID 86704551, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

(4-(Hydroxymethyl)-2-methyl-8-nitro-1-oxo-2,4-dihydro-1H-benzo[b][1,2,4]triazolo[4,3-d][1,4]oxazin-4-yl)methyl 4-methylbenzenesulfonate (1.1 g) was dissolved in anhydrous THF (100 mL). In an ice bath, 2.5 M n-butyl lithium in hexanes (1.05 mL, 1.1 eq.) was added to the reaction. The solution was reacted at 0° C. to room temperature, and then refluxed for three hours. The solvent was removed in vacuo. The residue was partitioned between EtOAc (100 mL) and 5% aqueous sodium bicarbonate (100 mL). The aqueous layer was extracted with EtOAc (2×100 mL). The organic layers were evaporated and purified by Combiflash chromatography (EtOAc in hexanes=20-100%) to give 2-methyl-8-nitrospiro[benzo[b][1,2,4]triazolo[4,3-d][1,4]oxazine-4,3′-oxetan]-1(2H)-one (150 mg, isomer a, m/z=290.92 (M+H)+) and 2-methyl-9-nitro-5H-spiro[benzo[b][1,2,4]triazolo[4,3-d][1,4]oxazepine-4,2′-oxiran]-1(2H)-one (250 mg, isomer b, m/z=290.92 (M+H)+).

Workup

  1. customThe solution was reacted at 0° C. to room temperature
  2. temperaturerefluxed for three hours
  3. customThe solvent was removed in vacuo
  4. customThe residue was partitioned between EtOAc (100 mL) and 5% aqueous sodium bicarbonate (100 mL)
  5. extractionThe aqueous layer was extracted with EtOAc (2×100 mL)
  6. customThe organic layers were evaporated
  7. custompurified by Combiflash chromatography (EtOAc in hexanes=20-100%)

Sources & evidence

ORD record
ord-50e89582958b45c5a8c6086e6dfaba7d
Source dataset
uspto-grants-2016_04
Patent number
US09321763B2

Reaction notes

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