Bromine → HCID 66696590, compound

HRID 1672531Notes

Reaction equation

HRID 1672531 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[CH:4][C:3]=1[C:12]1[O:16][CH:15]=[N:14][CH:13]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[Br:27]Br.[O-]S([O-])=O.[Na+].[Na+]>O1CCCC1.CN1CCCN(C)C1=O.CCOCC>[Br:27][C:13]1[N:14]=[CH:15][O:16][C:12]=1[C:3]1[CH:4]=[CH:5][C:6]([C:8]([F:11])([F:9])[F:10])=[CH:7][C:2]=1[F:1]

Participants

8

Reactant 4

HCID 24408BromineHCID 24437Sodium SulfiteHCID 2733832Lithium HexamethyldisilazideHCID 66696593HCID 66696593, compound

Product 1

HCID 66696590HCID 66696590, compoundYield 53%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-Solvent

Procedure

A solution of Example 5A (6.46 g, 27.9 mmol) in tetrahydrofuran (48 mL) and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (36 mL) was cooled to −78° C., and then treated slowly with lithium bis(trimethylsilyl)amide (1M in tetrahydrofuran, 34 mL, 34 mmol). The reaction was stirred for 1 hour and then treated dropwise with bromine (1.43 ml, 27.9 mmol). The reaction stirred for another hour at −78° C., and then was poured into 900 mL ether and 270 mL 10% Na2SO3 solution. The phases were separated, and the organic layer was washed with brine, dried over Na2SO4, filtered, and evaporated. The crude material was purified by chromatography (5 to 20% ethyl acetate-hexane) to afford the title compound as a yellow oil (4.58 g, 53% yield). 1H NMR (300 MHz, DMSO-d6) δ 8.74 (s, 1H), 8.02 (m, 2H), 7.81 (m, 1H). MS (DCI+) m/z 312 (M+H)+.

Workup

  1. stirringThe reaction stirred for another hour at −78° C.
  2. customThe phases were separated
  3. washthe organic layer was washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. customevaporated
  7. customThe crude material was purified by chromatography (5 to 20% ethyl acetate-hexane)

Sources & evidence

ORD record
ord-578ac97f13c347beba75917973f87bbb
Source dataset
uspto-grants-2011_08
Patent number
US07998993B2

Reaction notes

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