Benzyltriphenylphosphonium bromide → HCID 86676501, compound

HRID 1854624Notes

Reaction equation

HRID 1854624 reaction equation
[Br-].[CH2:2]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[K].[O-]CCCC.[CH3:34][C:35]1[CH:40]=[CH:39][N:38]=[C:37]([NH:41][C:42]2[N:47]=[C:46]([C:48]3[S:52][C:51]([CH:53]=O)=[N:50][CH:49]=3)[CH:45]=[CH:44][CH:43]=2)[CH:36]=1>C1COCC1.O>[CH3:34][C:35]1[CH:40]=[CH:39][N:38]=[C:37]([NH:41][C:42]2[CH:43]=[CH:44][CH:45]=[C:46]([C:48]3[S:52][C:51](/[CH:53]=[CH:2]/[C:3]4[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=4)=[N:50][CH:49]=3)[N:47]=2)[CH:36]=1

Participants

7

Reactant 4

HCID 2734970Benzyltriphenylphosphonium bromideHCID 5462222PotassiumHCID 12476378Butan-1-olateHCID 53311316HCID 53311316, compound

Product 1

HCID 86676501HCID 86676501, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of benzyltriphenylphosphonium bromide (176 mg, 0.406 mmol) in dry THF cooled at 0° C. under inert atmosphere was added potassium tot-butoxide (1.0M in THF) (675 μL, 675 μmol). The mixture was stirred at 0° C. for 30 mins, then 5-[6-(4-methyl-pyridin-2-ylamino)-pyridin-2-yl]-thiazole-2-carbaldehyde was added in one portion. After stirring at room temperature for 3 hours, the reaction mixture was treated with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4, filtered and evaporated under reduced pressure before purification by column chromatography on SiO2 using combiflash Companion®, eluting with cyclohexane/ethyl acetate. The E-isomer was then further purified by preparative chromatography on silica plate, eluting with 5% methanol in dichloromethane to afford the title compound as a yellow solid. 1H NMR (Acetone-d6, 300 MHz): δ=8.41 (s, 1H), 8.16 (d, J=5.1 Hz, 1H), 8.00 (s, 1H), 7.80-7.70 (m, 3H), 7.65-7.55 (m, 2H), 7.53-7.36 (m, 4H), 7.50 (s, 1H), 6.84 (d, J=5.1 Hz, 1H), 2.47 (s, 3H). (APCI+) m/z 371 (M+H)+.

Workup

  1. stirringAfter stirring at room temperature for 3 hours
  2. extractionextracted with ethyl acetate
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. customevaporated under reduced pressure before purification by column chromatography on SiO2 using combiflash Companion®
  7. washeluting with cyclohexane/ethyl acetate
  8. customThe E-isomer was then further purified by preparative chromatography on silica plate
  9. washeluting with 5% methanol in dichloromethane

Sources & evidence

ORD record
ord-a1f8b7ed3f29499686e87bc76a2693d9
Source dataset
uspto-grants-2015_02
Patent number
US08962665B2

Reaction notes

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