(Trimethylsilyl)acetonitrile → HCID 58361484, compound

HRID 2076448Notes

Reaction equation

HRID 2076448 reaction equation
C(O[Li])(C)=O.[C:6]1([S:12]([O:15][C:16]2[C:25]([Br:26])=[C:24]3[C:19]([CH:20]=[CH:21][C:22]([CH:27]=[O:28])=[N:23]3)=[CH:18][CH:17]=2)(=[O:14])=[O:13])[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[Si]([CH2:33][C:34]#[N:35])(C)(C)C>CN(C=O)C>[C:6]1([S:12]([O:15][C:16]2[C:25]([Br:26])=[C:24]3[C:19]([CH:20]=[CH:21][C:22]([CH:27]([OH:28])[CH2:33][C:34]#[N:35])=[N:23]3)=[CH:18][CH:17]=2)(=[O:14])=[O:13])[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

5

Reactant 3

HCID 87557(Trimethylsilyl)acetonitrileHCID 58361485HCID 58361485, compoundHCID 178506943lithium acetate

Product 1

HCID 58361484HCID 58361484, compoundYield 50.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a stirred solution of AcOLi (27 mg, 0.41 mmol) in DMF (1 mL) were added successively a solution of 8-bromo-2-formylquinolin-7-yl benzenesulfonate (1.60 g, 4.08 mmol) in anhydrous DMF (10 mL) and TMSCH2CN (465 mg, 4.11 mmol) at 0° C. And the reaction mixture was slowly warmed to room temperature. The mixture was stirred for 12 h at the same temperature and quenched with 15% citric acid (5.0 mL) and MeOH (5.0 mL). After the removal of MeOH in vacuo, the mixture was extracted with AcOEt and organic layer was washed with brine and dried over anhydrous Na2SO4, and evaporated. Purification by silica gel chromatography (Hexanes/EtOAc=2/1) gave S0187 as a yellow gum (0.89 g, 2.05 mmol, 50% yield). 13CNMR (ppm, 500 MHz, CDCl3, 298 K) δ: 159.989, 148.716, 144.388, 138.493, 135.675, 135.042, 129.556, 128.819, 128.189, 127.380, 123.481, 119.173, 118.419, 117.117, 68.926, 26.812. 1HNMR (ppm, 500 MHz, CDCl3, 298 K) δ: 8.262 (d, 1H, J=8.5 Hz), 7.968 (d, 2H, J=8.0 Hz), 7.836 (d, 1H, J=9.0 Hz), 7.716 (t, 1H, J=7.0 Hz), 7.633 (d, 1H, J=9.0 Hz), 7.588-7.545 (m, 3H), 5.224−5.188 (m, 1H), 5.126 (d, 1H, J=6.0 Hz), 3.031−2.929 (m, 2H). MS-ESI (m/z): [M+H]+ calculated for C18H14BrN2O4S, 433.0 (79Br) and 435.0 (81Br); found 432.9 (79Br) and 434.9 (81Br).

Workup

  1. customquenched with 15% citric acid (5.0 mL) and MeOH (5.0 mL)
  2. customAfter the removal of MeOH in vacuo
  3. extractionthe mixture was extracted with AcOEt and organic layer
  4. washwas washed with brine
  5. dry with materialdried over anhydrous Na2SO4
  6. customevaporated
  7. customPurification by silica gel chromatography (Hexanes/EtOAc=2/1)

Sources & evidence

ORD record
ord-bd331bc8ec2b4441b4e835916a3257b3
Source dataset
uspto-grants-2011_04
Patent number
US07923562B2

Reaction notes

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