4-Toluenesulfonyl chloride → 2-amino-6,7-dihydro-5H-benzo[6,7]cyclohepta[1,2-d]pyrimidin-4-yl 4-methylbenzenesulfonate

HRID 1027883Notes

Reaction equation

HRID 1027883 reaction equation
[NH2:1][C:2]1[N:3]=[C:4]([OH:17])[C:5]2[CH2:12][CH2:11][CH2:10][C:9]3[CH:13]=[CH:14][CH:15]=[CH:16][C:8]=3[C:6]=2[N:7]=1.[S:18](Cl)([C:21]1[CH:27]=[CH:26][C:24]([CH3:25])=[CH:23][CH:22]=1)(=[O:20])=[O:19].C(N(CC)CC)C>C(Cl)Cl.CN(C)C1C=CN=CC=1>[CH3:25][C:24]1[CH:26]=[CH:27][C:21]([S:18]([O:17][C:4]2[C:5]3[CH2:12][CH2:11][CH2:10][C:9]4[CH:13]=[CH:14][CH:15]=[CH:16][C:8]=4[C:6]=3[N:7]=[C:2]([NH2:1])[N:3]=2)(=[O:20])=[O:19])=[CH:22][CH:23]=1

Participants

6

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 178508870HCID 178508870, compound

Product 1

HCID 251291732-amino-6,7-dihydro-5H-benzo[6,7]cyclohepta[1,2-d]pyrimidin-4-yl 4-methylbenzenesulfonate

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

The product from Example 59B (1.37 g, 6 mmol) was suspended in CH2Cl2 (100 mL), treated with TsCl (2.28 g, 12 mmol), treated with 4-dimethylaminopyridine (100 mg, 0.82 mmol), treated with triethylamine (2.2 mL. 16 mmol), and heated at reflux for 4 hours. The mixture was washed with H2O, dried (MgSO4), concentrated under reduced pressure and chromatographed on silica gel eluting with EtOAc:hexanes (25:75) to provide the title compound. 1H NMR (DMSO-d6) δ 1.99 (t, J=6.95 Hz, 2H), 2.23 (t, J=6.95 Hz, 2H), 2.45 (s, 3H), 2.47 (m, 2H), 6.91 (bs, 2H), 7.31 (m, 1H), 7.4 (m, 2H), 7.55 (dd, J=7.29, 1.87 Hz, 1H), 7.5 (d, J=8.48 Hz, 2H), 8.03 (d, J=8.14 Hz, 2H). MS (M+H)+ m/z 382.

Workup

  1. temperatureheated
  2. temperatureat reflux for 4 hours
  3. washThe mixture was washed with H2O
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated under reduced pressure
  6. customchromatographed on silica gel eluting with EtOAc:hexanes (25:75)

Sources & evidence

ORD record
ord-9bf5cdf9906b496f94b27d88ff286bcc
Source dataset
uspto-grants-2014_05
Patent number
US08735411B2

Reaction notes

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