p-Toluenesulfonic acid → HCID 57853812, compound

HRID 1041786Notes

Reaction equation

HRID 1041786 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[CH2:13][CH2:12][CH2:11][NH:10][C:9](=S)[C:8]=2[CH:15]=1)([O-:3])=[O:2].CO[CH:18](OC)[CH2:19][NH2:20].C1(C)C=CC(S(O)(=O)=O)=CC=1>C1COCC1.[Hg](OC(C)=O)OC(C)=O>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[CH2:13][CH2:12][CH2:11][N:10]3[C:9](=[N:20][CH:19]=[CH:18]3)[C:8]=2[CH:15]=1)([O-:3])=[O:2]

Participants

6

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 89728Aminoacetaldehyde dimethyl acetalHCID 57853831HCID 57853831, compound

Product 1

HCID 57853812HCID 57853812, compoundYield 15%

Reagents, catalysts & solvents 2

HCID 16683746DiacetyloxymercuryCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
25 °C

Procedure

A solution of 8-nitro-2,3,4,5-tetrahydro-benzo[c]azepine-1-thione (2 g, 9 mmol) and 2,2-dimethoxy-ethylamine (4.7 g, 45 mmol, 5.0 eq.) in THF (100 mL) was treated with Hg(OAc)2 (4.3 g, 13.5 mmol, 1.5 eq.) at 5° C. The mixture was warmed to 25° C. and stirred for 2 hours, then concentrated. The residue was dissolved in toluene/water (11:1, 150 mL) and treated with p-toluenesulfonic acid (0.76 g, 4 mmol). This mixture was then heated at 65° C. for 24 h and subsequently concentrated under vacuum. The resulting residue was dissolved in methanol/HCl solution (2:1, 100 mL) and heated at 90° C. for 12 hours. Solvent evaporation and purification with silica gel chromatography (DCM/MeOH (9:1)) gave 9-nitro-5,6-dihydro-4H-1,3a-diaza-benzo[e]azulene (300 mg, 1.3 mmol, 15%). 1H NMR (300 MHz, CD3OD) δ 8.50 (d, 1H), 8.23 (dd, 1H), 7.61 (d, 1H), 7.32 (d, 1H), 7.12 (d, 1H), 4.05 (t, 2H), 2.85 (t, 2H), 2.42 (pent, 2H); MS (m/e) 230 (M+1).

Workup

  1. concentrationconcentrated
  2. dissolutionThe residue was dissolved in toluene/water (11:1, 150 mL)
  3. temperatureThis mixture was then heated at 65° C. for 24 h
  4. concentrationsubsequently concentrated under vacuum
  5. dissolutionThe resulting residue was dissolved in methanol/HCl solution (2:1, 100 mL)
  6. temperatureheated at 90° C. for 12 hours
  7. customSolvent evaporation and purification with silica gel chromatography (DCM/MeOH (9:1))

Sources & evidence

ORD record
ord-f6f5ff6c4ca04ca98fee5809d19d9323
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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