Triphenylphosphine → HCID 68062013, compound

HRID 1427486Notes

Reaction equation

HRID 1427486 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C.[F:34][C:35]([F:57])([F:56])[C:36]1[CH:41]=[CH:40][C:39]([C:42]2[N:43]=[CH:44][C:45]([NH:48][C:49](=[O:55])[O:50][C:51]([CH3:54])([CH3:53])[CH3:52])=[N:46][CH:47]=2)=[CH:38][CH:37]=1.O[CH:59]([C:63]1[CH:73]=[CH:72][C:66]([C:67]([O:69][CH2:70][CH3:71])=[O:68])=[CH:65][CH:64]=1)[CH2:60][CH2:61][CH3:62]>C(Cl)Cl.[Cl-].[NH4+].C1COCC1>[C:51]([O:50][C:49]([N:48]([C:45]1[CH:44]=[N:43][C:42]([C:39]2[CH:38]=[CH:37][C:36]([C:35]([F:34])([F:56])[F:57])=[CH:41][CH:40]=2)=[CH:47][N:46]=1)[CH:59]([C:63]1[CH:73]=[CH:72][C:66]([C:67]([O:69][CH2:70][CH3:71])=[O:68])=[CH:65][CH:64]=1)[CH2:60][CH2:61][CH3:62])=[O:55])([CH3:52])([CH3:53])[CH3:54]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 67981039Ethyl 4-(1-hydroxybutyl)benzoateHCID 68081043HCID 68081043, compound

Product 1

HCID 68062013HCID 68062013, compoundYield 98.3%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×HCID 25517Ammonium ChlorideSolvent

Procedure

A round bottom flask was charged with triphenylphosphine (2.64 g, 10.0 mmol), diisopropylazodicarboxylate (1.99 mL, 10.0 mmol) and THF (23 mL) at 0° C. After the yield crashed out of solution (less than 10 minutes), tert-butyl (5-(4-(trifluoromethyl)phenyl)pyrazin-2-yl)carbamate (3.10 g, 9.10 mmol) and (±)-ethyl 4-(1-hydroxybutyl)benzoate (2.03 g, 9.14 mmol) followed by THF (10 mL). Reaction stirred at room temperature overnight. Reaction diluted with DCM and ammonium chloride solution (aq. sat.) and transferred to an extraction funnel. Aqueous extracted twice with DCM. Combined organic layers washed with brine (1×), dried over sodium sulfate, filtered and concentrated to provide the crude material. Purification by silica gel flash chromatography (MeOH/DCM) provide the title compound as a yellow gum (4.86 g, 98.0%). 1H NMR (400 MHz, CHLOROFORM-d) δ 0.96 (t, 3H) 1.36 (s, 9H) 1.37-1.54 (m, 5H) 2.06-2.18 (m, 1H) 2.23-2.35 (m, 1H) 4.38 (q, J=7.24 Hz, 2H) 5.77 (dd, J=9.10, 6.55 Hz, 1H) 7.51 (d, J=8.61 Hz, 2H) 7.76 (d, J=8.61 Hz, 2H) 7.95-8.02 (m, 2H) 8.12 (d, J=8.22 Hz, 2H) 8.74 (d, J=1.37 Hz, 1H) 8.83 (d, J=1.56 Hz, 1H); MS (M+1): 544.5.

Workup

  1. customReaction
  2. customReaction
  3. customtransferred to an extraction funnel
  4. extractionAqueous extracted twice with DCM
  5. washCombined organic layers washed with brine (1×)
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto provide the crude material
  10. customPurification by silica gel flash chromatography (MeOH/DCM)

Sources & evidence

ORD record
ord-2e8dbbc82fde4157b08ebc8360a5a18c
Source dataset
uspto-grants-2015_01
Patent number
US08933104B2

Reaction notes

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