Pyridine → HCID 86704550, compound

HRID 633463Notes

Reaction equation

HRID 633463 reaction equation
[OH:1][CH2:2][C:3]1([CH2:21][OH:22])[O:8][C:7]2[CH:9]=[CH:10][C:11]([N+:13]([O-:15])=[O:14])=[CH:12][C:6]=2[N:5]2[C:16](=[O:20])[N:17]([CH3:19])[N:18]=[C:4]12.N1C=CC=CC=1.[S:29](Cl)([C:32]1[CH:38]=[CH:37][C:35]([CH3:36])=[CH:34][CH:33]=1)(=[O:31])=[O:30].C(N(CC)CC)C>ClCCl>[CH3:36][C:35]1[CH:37]=[CH:38][C:32]([S:29]([O:1][CH2:2][C:3]2([CH2:21][OH:22])[O:8][C:7]3[CH:9]=[CH:10][C:11]([N+:13]([O-:15])=[O:14])=[CH:12][C:6]=3[N:5]3[C:16](=[O:20])[N:17]([CH3:19])[N:18]=[C:4]23)(=[O:31])=[O:30])=[CH:33][CH:34]=1

Participants

6

Reactant 4

HCID 1049PyridineHCID 73974-Toluenesulfonyl chloride2×HCID 8471TriethylamineHCID 86704549HCID 86704549, compound

Product 1

HCID 86704550HCID 86704550, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

4,4-Bis(hydroxymethyl)-2-methyl-8-nitro-2,4-dihydro-1H-benzo[b][1,2,4]triazolo[4,3-d][1,4]oxazin-1-one (1.6 g) and pyridine (0.84 mL, 2 eq.) were dissolved in anhydrous dichloromethane (100 mL). In an ice bath, tosyl chloride (1.2 g, 1.2 eq.) was added to the reaction solution in portions. The reaction was stirred in an ice bath to room temperature overnight. Then triethylamine (1.5 mL, 2 eq.) and more of tosyl chloride (500 mg, 0.5 eq.) were added and stirred at room temperature overnight. LCMS showed mixtures of starting material, mono-tosylated product and bis-tosylated product. The reaction solution was evaporated. The residue was purified by Combiflash chromatography (EtOAc in hexanes=20-100%) to give (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. m/z=462.83 (M+H)+.

Workup

  1. stirringstirred at room temperature overnight
  2. customThe reaction solution was evaporated
  3. customThe residue was purified by Combiflash chromatography (EtOAc in hexanes=20-100%)

Sources & evidence

ORD record
ord-953aad6235e1498a9380efd1b95fcc90
Source dataset
uspto-grants-2016_04
Patent number
US09321763B2

Reaction notes

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