Triphenylphosphine → Diphenyl Ether

HRID 1369951Notes

Reaction equation

HRID 1369951 reaction equation
C([C:5]1[CH:6]=[C:7](C2OC=C(CCO)N=2)[CH:8]=[C:9](C(C)(C)C)[C:10]=1[OH:11])(C)(C)C.C(N(C(=O)CC)CC[C:29]1[CH:34]=[CH:33][C:32](O)=[CH:31][CH:30]=1)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O>O1CCCC1>[C:29]1([O:11][C:10]2[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 69946721HCID 69946721, compoundHCID 135509425HCID 135509425, compound

Product 1

HCID 7583Diphenyl EtherYield 109.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a stirred solution of 2-(3,5-di-t-butyl-4-hydroxyphenyl)-4-(2-hydroxyethyl)oxazole (5.51 g, 17.38 mmole) in tetrahydrofuran (47 ml) was added N-ethyl,N-propionyl tyramine (3.5 g, 15.8 mmole) and triphenylphosphine (4.55 g, 17.38 mmole). After cooling to 0° C., a solution of diethylazodicarboxylate (2.73 ml, 17.38 mmole) in tetrahydrofuran (16 ml) was added dropwise over 10 minutes. The reaction was allowed to warm to room temperature and stir for 22 hours, evaporated, and triturated with methylene chloride (50 ml) and filtered The filtrate was chromatographed on silica gel twice using methylene chloride-ethyl acetate and hexane-acetone gradients to give the intermediate phenyl ether (2.95 g, 36%):

Workup

  1. temperatureto warm to room temperature
  2. customevaporated
  3. customtriturated with methylene chloride (50 ml)
  4. filtrationfiltered The filtrate
  5. customwas chromatographed on silica gel twice using methylene chloride-ethyl acetate and hexane-acetone gradients

Sources & evidence

ORD record
ord-0aa5f9eb361d438ba4d5ba720715f5bb
Source dataset
uspto-grants-2003_06
Patent number
US06579871B2

Reaction notes

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