Triphenylphosphine → HCID 69301070, compound

HRID 902443Notes

Reaction equation

HRID 902443 reaction equation
N(C(OCC)=O)=NC(OCC)=O.[OH:13][C:14]1[CH:15]=[CH:16][C:17]2[CH2:24][CH:23]3[C:25](=[O:26])[CH:20]([CH2:21][CH2:22]3)[CH2:19][C:18]=2[CH:27]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O[CH2:48][CH2:49][N:50]1[CH2:55][CH2:54][O:53][CH2:52][CH2:51]1>C(Cl)Cl>[N:50]1([CH2:49][CH2:48][O:13][C:14]2[CH:15]=[CH:16][C:17]3[CH2:24][CH:23]4[C:25](=[O:26])[CH:20]([CH2:21][CH2:22]4)[CH2:19][C:18]=3[CH:27]=2)[CH2:55][CH2:54][O:53][CH2:52][CH2:51]1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 611632-MorpholinoethanolHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 130264432-Hydroxy-5,6,7,8,9,10-hexahydro-6,9-methanobenzo[8]annulen-11-one

Product 1

HCID 69301070HCID 69301070, compoundYield 57.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Diethyl azodicarboxylate (1.07 g, 6.16 mmol) in DCM (5 ml) was added at a dropwise rate to a stirred solution of 2-hydroxy-11-oxo-5,6,7,8,9,10-hexahydro-6,9-methanobenzocyclooctene (J. Org. Chem. 1982 4329, 829 mg, 4.10 mmol), triphenylphosphine (1.61 g, 6.16 mmol) and 4-(2-hydroxyethyl)morpholine (806 mg, 6.16 mmol) in DCM (45 ml). The mixture was stirred at room temperature for 2 hours and then concentrated to dryness. The crude product was purified by column chromatography on silica eluting with 40:1 DCM: 2M ammonia in methanol. The chromatographed material was taken up in the minimal volume of ethyl acetate and diluted with diethyl ether. 1M HCl in diethyl ether was added. The precipitate was filtered washing the solid with ethyl acetate and diethyl ether. The white solid was taken up in DCM and washed with 1M sodium hydroxide (aq). The organic phase was dried over sodium sulphate, filtered and concentrated to dryness to give 5-(2-morpholin-4-yl-ethoxy)-tricyclo[8.2.1.03,8]trideca-3(8),4,6-trien-13-one as a colourless oil 740 mg (57%).

Workup

  1. concentrationconcentrated to dryness
  2. customThe crude product was purified by column chromatography on silica eluting with 40:1 DCM
  3. additiondiluted with diethyl ether
  4. addition1M HCl in diethyl ether was added
  5. filtrationThe precipitate was filtered
  6. washwashing the solid with ethyl acetate and diethyl ether
  7. washwashed with 1M sodium hydroxide (aq)
  8. dry with materialThe organic phase was dried over sodium sulphate
  9. filtrationfiltered
  10. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-f7231c3fac894c51aaff78bb6993e917
Source dataset
uspto-grants-2008_04
Patent number
US07365196B2

Reaction notes

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