Triphenylphosphine → HCID 154041574, compound

HRID 1194879Notes

Reaction equation

HRID 1194879 reaction equation
[CH3:1][C@H:2]1[CH2:7][C@@H:6]([OH:8])[C@H:5]([CH:9]([CH3:11])[CH3:10])[CH2:4][CH2:3]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.O[N:44]=[C:45]([C:51](=[O:53])[CH3:52])[C:46]([O:48][CH2:49][CH3:50])=[O:47]>O1CCCC1>[CH3:1][C@H:2]1[CH2:7][C@H:6]([O:8]/[N:44]=[C:45](/[C:51](=[O:53])[CH3:52])\[C:46]([O:48][CH2:49][CH3:50])=[O:47])[C@H:5]([CH:9]([CH3:11])[CH3:10])[CH2:4][CH2:3]1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 16666(-)-MentholHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 178472877HCID 178472877, compound

Product 1

HCID 154041574HCID 154041574, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

(1R, 2S, 5R-)-(-)-Menthol (7.3 g, 45 mmol) and triphenylphosphine (8.65 g, 33 mmol) in dry tetrahydrofuran under argon were cooled in an ice bath and diethyl azodicarboxylate (5.2 ml, 5.7 g, 33 mmol) in dry tetrahydrofuran (30 ml) was added dropwise over 15 minutes. The ice bath was removed and ethyl 2-hydroxyimino-3-oxobutyrate (4.77 g, 33 mmol) in dry tetrahydrofuran (30 ml) was added dropwise over 20 min. The mixture was stirred at room temperature for 18 h and then warmed at 50° C. for 1.5 h. The mixture was cooled and the tetrahydrofuran was removed by evaporation in vacuo. Toluene was added to the residue and evaporated in vacuo. The residual yellow oil was chromatographed on silica gel, eluting with carbon tetrachloride, followed by hexane, followed by hexane/ethyl acetate mixtures. After evaporation of relevant fractions the title compound was obtained as an oil, νmax (CH2Cl2) 2945, 2920, 2860, 1740, 1685, 1365, 1315, 1235, 1070 and 1005 cm-1 ; δ (250 MHz, CDCl3) 0.87 (3H, d, J 7.3 Hz), 0.90 (3H, d, J 6.8 Hz), 0.92 (3H, d, J 6.3 Hz), 0.95-1.14 (2H, m), 1.14-1.35 (1H, m), 1.32 (3H, t, J 7.2 Hz), 1.49-1.63 (2H, m), 1.63-1.80 (2H, m), 2.13 (1H, m), 2.40 (3H, s), 4.34 (2H, q, J 7.1 Hz), 4.70 (1H, broad s).

Workup

  1. customThe ice bath was removed
  2. temperaturewarmed at 50° C. for 1.5 h
  3. temperatureThe mixture was cooled
  4. customthe tetrahydrofuran was removed by evaporation in vacuo
  5. additionToluene was added to the residue
  6. customevaporated in vacuo
  7. customThe residual yellow oil was chromatographed on silica gel
  8. washeluting with carbon tetrachloride
  9. customAfter evaporation of relevant fractions the title compound
  10. customwas obtained as an oil, νmax (CH2Cl2) 2945, 2920, 2860, 1740, 1685, 1365, 1315, 1235, 1070 and 1005 cm-1

Sources & evidence

ORD record
ord-4c05039b0a3d4c58b923003c3678f4f6
Source dataset
uspto-grants-1989_03
Patent number
US04816452

Reaction notes

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