Triphenylphosphine → HCID 178460553, compound

HRID 1062539Notes

Reaction equation

HRID 1062539 reaction equation
O[CH:2]1[CH2:6][CH2:5][C:4]([CH2:7][PH:8](=[O:13])[O:9][CH:10]([CH3:12])[CH3:11])=[CH:3]1.CCOC(/[N:19]=N/C(OCC)=O)=O.N=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC=CC=1.C1COCC1.O>[NH2:19][CH:2]1[CH2:6][CH2:5][C:4]([CH2:7][PH:8](=[O:13])[O:9][CH:10]([CH3:12])[CH3:11])=[CH:3]1

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 24530Hydrazoic acidHCID 5462977Diethyl azodicarboxylateHCID 178460555HCID 178460555, compound

Product 1

HCID 178460553HCID 178460553, compoundYield 68.7%

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (±)-isopropyl (3-hydroxycyclopentenyl)methylphosphinate (3) (2.5 g, 12.25 mmol), DEAD (4.0 cm3,26.95 mmol) and HN3 (12.9 cm3 of a 1.9 M solution in benzene) in anhydrous THF (100 cm3) at 0° C. was added triphenylphosphine (12.8 g, 49 mmol) in small portions over a period of 1 h. The reaction mixture was allowed to warm to room temperature and stirring continued for 12 h. The reaction mixture was then heated to 50° C. for 3 h after which time water (2 cm3) was added and heating continued for a further 2 h. The reaction mixture was cooled to room temperature and the solvent removed in vacuo. The residue was partitioned between HCl (1M, 40 cm3) and DCM (40 cm3). The organic layer was separated and further extracted with water (3×30 cm3). The combined aqueous fractions were washed with DCM (2×30 cm3) and concentrated in vacuo. The crude product was purified by ion exchange chromatography (Dowex 50 H+ form), eluting first with water until the eluate was neutral and then with aqueous ammonium hydroxide (1 M) collecting ninhydrin positive fractions. The solvent was removed in vacuo to yield the title compound as a pale yellow oil (8) (1.71 g, 68%): 1H NMR (300 MHz; CD3OD) δ 1.26 and 1.27 (3H, d, J=6.0 and 6.0 Hz, POCHCH3), 1.31 and 1.32 (3H, d, J=6.3 and 6.3 Hz, POCHCH3), 1.51 and 1.53 (3H, d, J=14.4 and 14.1 Hz, PCH3) 1.59-1.79 (1H, m, C(4)—H, 2.33-2.55 (2H, m, C(5)—H, C(5)—H′), 2.54-2.72 (1H, m, C(4)—H′) 4.05 (1H, m, C(3)—H), 4.48 (1H, m, C(2)—H), 6.52 (1H, dm, J=9.9 Hz, PCCH), 13C NMR (75.46 MHz, CD3OD) δ 13.92 and 14.10 (PCH3, d, JPC=102.1 and 101.6 Hz), 24.54 and 24.60 (POCHCH3, 2×d, 3JPOCC=46 Hz), 24.9 (POCHCH3, d, 3JPOCC=3.4 Hz), 32.86 and 32.88 (C(4), d, 3JPC=12.6 and 12.3 Hz), 35.0 and 35.13 (C(5), 2×d, 2JPC=10.0 Hz) 59.83 and 60.07 (POCHCH3, d, 2JPOC=5.7 and 5.7 Hz), 71.36 and 71.39 (C(3), d, 3JPC=6.3 and 6.3 Hz), 137.96 (C(1), d, JPC=125.7 Hz), 150.84 and 150.95 (C(2), d, 2JPC=10.9 and 11.1 Hz), 31 P NMR (121 MHz, CD3OD) δ 45.9, MS (EI) m/z 204 (38%) (MH+), 147 (30), 105 (100) (ESI) 204.1151 (MH+-C9H19NO2P requires 204.1153).

Workup

  1. additionwas added
  2. temperatureheating
  3. waitcontinued for a further 2 h
  4. temperatureThe reaction mixture was cooled to room temperature
  5. customthe solvent removed in vacuo
  6. customThe residue was partitioned between HCl (1M, 40 cm3) and DCM (40 cm3)
  7. customThe organic layer was separated
  8. extractionfurther extracted with water (3×30 cm3)
  9. washThe combined aqueous fractions were washed with DCM (2×30 cm3)
  10. concentrationconcentrated in vacuo
  11. customThe crude product was purified by ion exchange chromatography (Dowex 50 H+ form)
  12. washeluting first with water until the eluate
  13. customwith aqueous ammonium hydroxide (1 M) collecting ninhydrin positive fractions
  14. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-c172eebceec246329de549f1a6d00987
Source dataset
uspto-grants-2005_11
Patent number
US06962907B2

Reaction notes

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