Tert-Butyl nitrite → HCID 58687906, compound

HRID 1988572Notes

Reaction equation

HRID 1988572 reaction equation
N[C:2]1[CH:15]=[C:14]2[C:5]([S:6][C:7]3[C:8]([C:16]4[O:17][C:18]([N:23]5[CH2:28][CH2:27][O:26][CH2:25][CH2:24]5)=[CH:19][C:20](=[O:22])[CH:21]=4)=[CH:9][CH:10]=[CH:11][C:12]=3[CH2:13]2)=[CH:4][CH:3]=1.F[B-](F)(F)F.[H+].N([O:37][C:38](C)(C)C)=O.C([SiH](C(C)C)C(C)C)(C)C>C(O)C.C(OCC)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[N:23]1([C:18]2[O:17][C:16]([C:8]3[CH:9]=[CH:10][CH:11]=[C:12]4[C:7]=3[S:6][C:5]3[CH:4]=[CH:3][C:2]([CH:38]=[O:37])=[CH:15][C:14]=3[CH2:13]4)=[CH:21][C:20](=[O:22])[CH:19]=2)[CH2:28][CH2:27][O:26][CH2:25][CH2:24]1

Participants

8

Reactant 4

HCID 10906Tert-Butyl nitriteHCID 28118Tetrafluoroboric acidHCID 138754Silane, tris(1-methylethyl)-HCID 221394022-(7-Amino-9H-thioxanthen-4-yl)-6-morpholin-4-yl-pyran-4-one

Product 1

HCID 58687906HCID 58687906, compoundYield 76.1%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of 2-(7-amino-9H-thioxanthen-4-yl)-6-morpholin-4-yl-pyran-4-one (1)(0.50 g, 1.27 mmol) in ethanol (4 mL) at room temperature was added tetrafluorboric acid (supplied as 54 wt % in diethyl ether, 0.35 mL, 2.54 mmol). The solution was then cooled to 0° C., when t-butyl nitrite (750 μL, 6.33 mmol) was added. After 1 hr, the reaction was diluted with diethyl ether (10 mL), and after 20 mins the precipitate was filtered and washed with diethyl ether. The orange coloured salt was then dissolved in MeCN:Et2O (1:1) (15 mL), when triisopropylsilane (222 mg, 1.40 mmol) and Pd(OAc)2 (5.47 g, 24.37 mmol) were added successively. A CO pressure of 10 atm was then applied for 10 minutes, after which the reaction was filtered. The organic layer was washed with saturated NaHCO3 then brine, dried over MgSO4, filtered and concentrated in vacuo. The resulting yellow/orange solid was dried under vacuum at 50° C. to give the crude title compound (0.392 g, 75%, 2 steps) which was used without any further purification. m/z (LC-MS, ESP), RT=3.40 min, (M++1)=406.3

Workup

  1. filtrationafter 20 mins the precipitate was filtered
  2. washwashed with diethyl ether
  3. dissolutionThe orange coloured salt was then dissolved in MeCN:Et2O (1:1) (15 mL)
  4. filtrationafter which the reaction was filtered
  5. washThe organic layer was washed with saturated NaHCO3
  6. dry with materialbrine, dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe resulting yellow/orange solid was dried under vacuum at 50° C.

Sources & evidence

ORD record
ord-7638747ed6cc4c6db45e3af79dcaf7df
Source dataset
uspto-grants-2010_01
Patent number
US07642254B2

Reaction notes

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