Benzyl Alcohol → HCID 57228780, compound

HRID 233410Notes

Reaction equation

HRID 233410 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:17]3[C@H]([CH2:10][C@H:11]([C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=4)[CH2:12][C:13]=3[C:14]=1[O:15][CH3:16])[C@H](C(O)=O)[CH2:7][CH2:6]2.C([N:29]([CH2:32]C)[CH2:30][CH3:31])C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:41])C=CC=CC=1.[CH2:51]([OH:58])[C:52]1[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1>C1(C)C=CC=CC=1>[C:32]([NH:29][C@H:30]1[C@H:31]2[C:17]3[C:5](=[CH:4][C:3]([O:2][CH3:1])=[C:14]([O:15][CH3:16])[C:13]=3[CH2:12][C@@H:11]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[CH2:10]2)[CH2:6][CH2:7]1)([O:58][CH2:51][C:52]1[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1)=[O:41]

Participants

6

Reactant 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 18641661[1R*,8S*,9aR*]5,6-Dimethoxy-8-phenyl-2,3,7,8,9,9a-hexahydrophenalene-1-carboxylic acid

Product 1

HCID 57228780HCID 57228780, compoundYield 39%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

[1R *,8S*,9aR*]5,6-Dimethoxy-8-phenyl-2,3,7,8,9,9a-hexahydrophenalene-1-carboxylic acid (0.8 g, 2.3 mmol), from Step 5, and triethylamine (0.32 mL, 2.3 mmol) were dissolved in 16 mL of toluene and 0.55 mL (2.5 mmol) of diphenylphosphoryl azide was added. The reaction mixture was heated at 80° C. for 2.5 h then 0.5 mL (4.8 mmol) of benzyl alcohol was added and heating was continued at 80° C. for an additional 3 h and at 65° C. for 15 h. The reaction mixture was cooled and concentrated under reduced pressure. The residue was dissolved in 25 mL of diethyl ether and the ether solution was washed with 10 mL of 1N aqueous sodium hydroxide solution and brine, dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The product was purified by chromatography on silica gel eluted with 20% ethyl acetate in hexanes to give 0.4 g (39% yield) of the title compound as a white solid; DCI MS: 475 (M+NH4)+, 458 (M+H)+, 367 (M-benzyl+H)+, 324 (M-benzyloxy-carbonyl+2H)+. 1H NMR (CDCl3) δ:1.6-1.7 (m, 3H), 2.2-2.35 (m, 2H), 2.6-2.75 (m, 2H), 2.9-3.0 (m, 3H), 3.2-3.3 (m, 1H), 3.73 (s, 3H), 3.82 (s, 3H), 4.65-4.7 (m, 1H), 5.08 (s, 2H), 6.54 (s, 1H), 7.2-7.4 (m, 10H).

Workup

  1. temperatureheating
  2. temperatureThe reaction mixture was cooled
  3. concentrationconcentrated under reduced pressure
  4. dissolutionThe residue was dissolved in 25 mL of diethyl ether
  5. washthe ether solution was washed with 10 mL of 1N aqueous sodium hydroxide solution and brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe product was purified by chromatography on silica gel
  10. washeluted with 20% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-f5c70f4b2e9144d2a4930c2e5fed16bf
Source dataset
uspto-grants-1997_01
Patent number
US05591884

Reaction notes

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