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Triphenylphosphine → Phenylmethyl 4-[(3-methyl-4-nitrophenyl)oxy]-1-piperidinecarboxylate

HRID 419313
Notes
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Reaction equation

HRID 419313 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([OH:11])[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O[CH:32]1[CH2:37][CH2:36][N:35]([C:38]([O:40][CH2:41][C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)=[O:39])[CH2:34][CH2:33]1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C(Cl)Cl>[CH3:1][C:2]1[CH:3]=[C:4]([O:11][CH:32]2[CH2:37][CH2:36][N:35]([C:38]([O:40][CH2:41][C:42]3[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=3)=[O:39])[CH2:34][CH2:33]2)[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 174123-Methyl-4-nitrophenolHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 2794620Benzyl 4-Hydroxy-1-piperidinecarboxylate

Product 1

HCID 59452627Phenylmethyl 4-[(3-methyl-4-nitrophenyl)oxy]-1-piperidinecarboxylateYield 87%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

3-Methyl-4-nitrophenol (1.74 g, 11.4 mmol), triphenylphosphine (5.98 g, 22.8 mmol), and phenylmethyl 4-hydroxy-1-piperidinecarboxylate (3.99 g, 17.0 mmol) were dissolved in DCM with stirring and cooled to 0° C. Diisopropyl azodicarboxylate (3.35 mL, 17.0 mmol) was added via syringe. The reaction was stirred for 10 min and allowed to warm to rt. The reaction was stirred overnight and adsorbed onto silica gel. The crude material was purified by flash chromatography, and fractions containing product were concentrated in vacuo. The material was contaminated with 3-methyl-4-nitrophenol. The material was dissolved in diethyl ether and washed with 2N NaOH solution (3×), H2O, and brine. The organic layer was dried over MgSO4, filtered, and concentrated in vacuo to provide 3.67 g (87%) of the title compound. 1H NMR (400 MHz, DMSO-d6) δ 8.02 (d, J=9.0 Hz, 1H), 7.42-7.24 (m, 5H), 7.06 (d, J=2.4 Hz, 1H), 7.01 (dd, J=9.1, 2.7 Hz, 1H), 5.07 (s, 2H), 4.76 (ddd, J=7.7, 4.2, 4.0 Hz, 1H), 3.81-3.64 (m, 2H), 3.31 (br. s., 2H), 2.52 (s, 3H), 2.01-1.88 (m, 2H), 1.63-1.49 (m, 2H).

Workup

  1. stirringThe reaction was stirred for 10 min
  2. temperatureto warm to rt
  3. stirringThe reaction was stirred overnight
  4. customThe crude material was purified by flash chromatography, and fractions
  5. additioncontaining product
  6. concentrationwere concentrated in vacuo
  7. dissolutionThe material was dissolved in diethyl ether
  8. washwashed with 2N NaOH solution (3×), H2O, and brine
  9. dry with materialThe organic layer was dried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-d6bad6fa66c74a7881dd631728f4e66b
Source dataset
uspto-grants-2012_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08093239B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes