Phenol → (Phenylmethyl)hydrazine

HRID 1993107Notes

Reaction equation

HRID 1993107 reaction equation
OC[P:3](=[O:10])([O:7][CH2:8][CH3:9])[O:4][CH2:5][CH3:6].N1[C:16]([CH3:17])=[CH:15][CH:14]=CC=1C.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.C(OCC1C=CC=CC=1)C1C=CC=CC=1.C1(O)C=CC=CC=1.C([O-])([O-])=O.[Cs+].[Cs+].[CH2:62]([NH:69][NH2:70])C1C=CC=CC=1.[O-]S(C(F)(F)F)(=O)=O>C1COCC1>[CH2:62]([NH:69][NH2:70])[C:9]1[CH:8]=[CH:14][CH:15]=[CH:16][CH:17]=1.[CH2:5]([O:4][PH:3](=[O:10])[O:7][CH2:8][CH3:9])[CH3:6]

Participants

11

Reactant 8

HCID 996PhenolHCID 7657Dibenzyl etherHCID 79372,6-LutidineHCID 10796Cesium carbonateHCID 11157(Phenylmethyl)hydrazineHCID 67749Trifluoromethanesulfonic anhydrideHCID 76513Diethyl phosphonomethanolHCID 2758875Trifluoromethanesulfonate

Product 2

HCID 11157(Phenylmethyl)hydrazineHCID 178476833HCID 178476833, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

Triflate 12 was prepared from diethyl hydroxymethylphosphonate (2 g, 11.9 mmol), 2,6-lutidine (2.1 mL, 17.9 mmol), and trifluoromethanesulfonic anhydride (2.5 mL; 14.9 mmol) as described for compound 9. To a solution of phenol 8 (60 mg, 0.10 mmol) in THF (2 mL) was added Cs2CO3 (65 mg, 0.20 mmol) and triflate 12 (45 mg, 0.15 mmol) in THF (0.25 mL). The mixture was stirred at room temperature for 2 h and additional triflate (0.15 mmol) in THF (0.25 mL) was added. After 2 h the reaction mixture was partitioned between EtOAc and saturated NaCl. The organic phase was dried (MgSO4), filtered, and evaporated under reduced pressure. The crude product was chromatographed on silica gel (EtOAc) to give a residue that was purified by chromatography on silica gel (5% 2-propanol/CH2Cl2) to afford the diethylphosphonate as a foam: 1H NMR (CDCl3) δ 7.66 (d, 2H), 7.10 (d, 2H), 6.94 (d, 2H), 6.82 (d, 2H), 5.60 (d, 1H), 4.97 (d, 2H), 4.23-4.13 (m, 6H), 3.93-3.62 (m, 10H), 3.12-2.68 (m, 7H), 1.84-1.44 (m, 3H), 1.31 (t, 6H), 0.88-0.82 (2d, 6H); 31P NMR (CDCl3) δ 17.7; MS (ESI) 729 (M+H).

Workup

  1. customAfter 2 h the reaction mixture was partitioned between EtOAc and saturated NaCl
  2. dry with materialThe organic phase was dried (MgSO4)
  3. filtrationfiltered
  4. customevaporated under reduced pressure
  5. customThe crude product was chromatographed on silica gel (EtOAc)
  6. customto give a residue that
  7. customwas purified by chromatography on silica gel (5% 2-propanol/CH2Cl2)

Sources & evidence

ORD record
ord-a4cf6324981541a5bc8b87409b2e3536
Source dataset
uspto-grants-2010_01
Patent number
US07649015B2

Reaction notes

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