Hexamethyldisilazane → HCID 10021156, compound

HRID 1828851Notes

Reaction equation

HRID 1828851 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:23](=[CH:24][CH:25]=1)[C:7]1[NH:8][N:9]=[C:10]([C:11]3[C:12]([C:17]4[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=4)=[N:13][O:14][C:15]=3[CH3:16])[C:6]=1[CH2:5]2.C[Si](C)(C)N[Si](C)(C)C.C(N(C(C)C)CC)(C)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C[N:74]1CCCN(C)[C:75]1=[O:81]>CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:16][C:15]1[O:14][N:13]=[C:12]([C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C:11]=1[C:10]1[NH:9][N:8]=[C:7]2[C:23]3[C:4]([CH2:5][C:6]=12)=[CH:3][C:2]([C:75]([NH2:74])=[O:81])=[CH:25][CH:24]=3

Participants

7

Reactant 5

HCID 13838HexamethyldisilazaneHCID 812191,3-Bis(diphenylphosphino)propaneHCID 81531DiisopropylethylamineHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-HCID 178434983HCID 178434983, compound

Product 1

HCID 10021156HCID 10021156, compoundYield 19%

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
100 °C

Procedure

A solution of 6-bromo-3-(5-methyl-3-phenylisoxazol-4-yl)-1,4-dihydroindeno[1,2-c]pyrazole (250 mg, 0.6 mmol), hexamethyldisilazane (0.9 ml, 4.2 mmol), diisopropylethylamine (0.2 ml, 1.2 mmol) and 1,3-bis(diphenylphosphino)propane (25 mg, 0.06 mmol) in 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (5 ml) was degassed with nitrogen for 0.5 h, Pd(OAc)2 (13 mg, 0.06 mmol) was added and carbon monoxide was bubbled through the reaction whilst heating to 100° C. After 2 h the stream of carbon monoxide was replaced with a balloon of carbon monoxide and the reaction was heated at 100° C. for 16 h. The reaction was cooled, partitioned between H2O and EtOAc and the organic layer washed with H2O (×10), dried (MgSO4) and evaporated. The residue was chromatographed on silica, eluting with 3% methanol/dichloromethane to give a yellow oil which was crystallised from CDCl3 to give the title compound as a white solid (40 mg, 19%). 1H NMR (360 MHz, CDCl3) δ 7.92 (s, 1H), 7.81 (s, 1H), 7.51 (d, J=6.8 Hz, 2H), 7.47–7.37 (m, 3H), 3.33 (s, 2H), 2.60 (s, 3H), m/z (ES+) 357 (M+H)+.

Workup

  1. customcarbon monoxide was bubbled through the reaction
  2. temperaturethe reaction was heated at 100° C. for 16 h
  3. temperatureThe reaction was cooled
  4. custompartitioned between H2O and EtOAc
  5. washthe organic layer washed with H2O (×10)
  6. dry with materialdried (MgSO4)
  7. customevaporated
  8. customThe residue was chromatographed on silica
  9. washeluting with 3% methanol/dichloromethane
  10. customto give a yellow oil which
  11. customwas crystallised from CDCl3

Sources & evidence

ORD record
ord-ed59cc2f3f9f4b349355f01c9d3b51d7
Source dataset
uspto-grants-2006_06
Patent number
US07060710B2

Reaction notes

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