Triphenylphosphine → HCID 67485203, compound

HRID 2233365Notes

Reaction equation

HRID 2233365 reaction equation
[CH3:1][C:2]1[O:3][C:4]2[CH:10]=[C:9]([C:11]([O:13][CH3:14])=[O:12])[CH:8]=[C:7]([OH:15])[C:5]=2[CH:6]=1.[S:16]1[CH:20]=[CH:19][C:18]([CH2:21][CH2:22]O)=[CH:17]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)(C)C)=O)=NC(OC(C)(C)C)=O>C(Cl)Cl>[CH3:1][C:2]1[O:3][C:4]2[CH:10]=[C:9]([C:11]([O:13][CH3:14])=[O:12])[CH:8]=[C:7]([O:15][CH2:22][CH2:21][C:18]3[CH:19]=[CH:20][S:16][CH:17]=3)[C:5]=2[CH:6]=1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 83731Thiophene-3-ethanolHCID 97268Di-tert-butyl azodicarboxylateHCID 46941595Methyl 4-hydroxy-2-methyl-1-benzofuran-6-carboxylate

Product 1

HCID 67485203HCID 67485203, compoundYield 8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
5 °C

Procedure

To a solution of 2-methyl-4-hydroxy-6-methoxycarbonylbenzofuran (Method 12; 1.24 g, 6.0 mmol) and 2-(3-thienyl) ethanol (768 mg, 0.67 ml, 6.0 mmol) in DCM (DCM, 50 ml) was added polymer-supported triphenyl phosphine (2.5 g, ca 3 mmol/g, 1.5 eq), and the suspension cooled to 5° C. under an argon atmosphere. To this was added di t-butyl azodicarboxylate (1.725 g, 7.5 mmol, 1.5 eq), and the reaction mixture stirred overnight, allowing to warm to ambient temperature. It was then filtered through diatomaceous earth, washed through with DCM, and the filtrate and washings evaporated in vacuo to ˜50 ml total volume. To this was added trifluoroacetic acid (2 ml), and the solution evaporated in vacuo to give a red oil. This was chromatographed (70 g Bondelut, eluting with hexane containing ethyl acetate, 0-50%) to give a red solid; this was re-chromatographed (as previous) to give the title compound as a colourless crystalline solid (150 mg, 8% yield). NMR: 2.46 (s, 3H), 3.10 (t, 2H), 3.83 (s, 3H), 4.33 (t, 2H), 6.64 (s, 1H), 7.12 (dd, 1H), 7.28 (s, 1H), 7.32 (d, 1H), 7.46 (dd, 1H), 7.66 (s, 1H).

Workup

  1. temperatureto warm to ambient temperature
  2. filtrationIt was then filtered through diatomaceous earth
  3. washwashed through with DCM
  4. customthe filtrate and washings evaporated in vacuo to ˜50 ml total volume
  5. additionTo this was added trifluoroacetic acid (2 ml)
  6. customthe solution evaporated in vacuo
  7. customto give a red oil
  8. customThis was chromatographed
  9. wash(70 g Bondelut, eluting with hexane containing ethyl acetate, 0-50%)
  10. customto give a red solid
  11. customthis was re-chromatographed (as previous)

Sources & evidence

ORD record
ord-13bf0ad13d49493bbc9a47651c6540d4
Source dataset
uspto-grants-2010_05
Patent number
US07709505B2

Reaction notes

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