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2,6-Diisopropyl-4-(4-fluorophenyl)-5-pentyl-3-pyridine-carboxaldehyde → 2,6-Diisopropyl-3-ethenyl-4-(4-fluorophenyl)-5pentylpyridine

HRID 324837
Notes
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Reaction equation

HRID 324837 reaction equation
[CH2:1]([Li])CCC.[CH:6]([C:9]1[C:14]([CH:15]=O)=[C:13]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)[C:12]([CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])=[C:11]([CH:29]([CH3:31])[CH3:30])[N:10]=1)([CH3:8])[CH3:7]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH:6]([C:9]1[C:14]([CH:15]=[CH2:1])=[C:13]([C:17]2[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=2)[C:12]([CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])=[C:11]([CH:29]([CH3:31])[CH3:30])[N:10]=1)([CH3:8])[CH3:7]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 2

HCID 220049662,6-Diisopropyl-4-(4-fluorophenyl)-5-pentyl-3-pyridine-carboxaldehydeHCID 178418339Butyllithium

Product 1

HCID 220052272,6-Diisopropyl-3-ethenyl-4-(4-fluorophenyl)-5pentylpyridineYield 66%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028
Tetrahydrofuran
Solvent
2×

Conditions

Temperature
-78 °C

Procedure

Methyl triphenylphosphonium bromide was suspended in 15 mL of dry THF under argon and stirred at −78° C. Butyllithium (1.6M, 0.42 mL) was added dropwise over 2 min. and then the reaction mixture was allowed to stir at 0° C. for 1.5 hours. The solution was cooled again to −78° C., treated dropwise with a solution of 2,6-diisopropyl-4-(4-fluorophenyl)-5-pentyl-3-pyridinecarboxaldehyde (Example 114, Step A) in 5 mL of dry THF, and then stirred at 0° C. for 2.5 hours. The reaction was quenched with water (10 mL) and the THF evaporated in vacuo. Diethyl ether was added and the mixture was washed with water (2×20 mL), brine (1×20 mL), and dried with MgSO4. Filtration, concentration and flash chromatography (30% CH2Cl2/hexanes) yielded a solid (0.132 g, 0.37 mmol, 66%). 1H NMR (300 MHz, CDCl3) δ 7.08 (m, J=1.1 Hz, 4 H), 6.34, 6.28 (d, J=11.4 Hz, J=11.4 Hz, 1 H), 5.19 (d, J=1.8 Hz, 1 H), 4.96 (d, J=1.8 Hz, 1 H), 3.39 (septet, J=6.6 Hz, 1 H), 3.24 (septet, J=6.6 Hz, 1 H), 2.30 (t, J=5.2 Hz, 2 H), 1.20 (m, J=2.2 Hz, 18 H), 0.979 (t, J=6.0 Hz, 3 H). FAB-MS: calcd for (C24H32FN) 353, found 354 (M+H). Anal. Calcd for C24H32FN: C, 81.54; H, 9.12; N, 3.96; F, 5.37. Found: C, 81.46; H, 9.06; N, 3.78; F, 5.59. mp 44-46° C. Rf=0.7 (30% CH2Cl2/hexanes).

Workup

  1. stirringto stir at 0° C. for 1.5 hours
  2. temperatureThe solution was cooled again to −78° C.
  3. stirringstirred at 0° C. for 2.5 hours
  4. customThe reaction was quenched with water (10 mL)
  5. customthe THF evaporated in vacuo
  6. additionDiethyl ether was added
  7. washthe mixture was washed with water (2×20 mL), brine (1×20 mL)
  8. dry with materialdried with MgSO4
  9. filtrationFiltration, concentration and flash chromatography (30% CH2Cl2/hexanes)

Sources & evidence

ORD record
ord-16eabe2b5a7e4b65a8753fb204e3696d
Source dataset
uspto-grants-2001_04
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06218431B1

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes