Triphenylphosphine → (S)-methyl 5-methyl-2-(pent-4-en-2-yloxy)benzoate

HRID 921119

Reaktionsgleichung

Reaktionsgleichung von HRID 921119
[OH:1][C:2]1[CH:11]=[CH:10][C:9]([CH3:12])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[CH3:13][C@@H:14](O)[CH2:15][CH:16]=[CH2:17].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.CCOCC>[CH3:12][C:9]1[CH:10]=[CH:11][C:2]([O:1][C@H:16]([CH2:15][CH:14]=[CH2:13])[CH3:17])=[C:3]([CH:8]=1)[C:4]([O:6][CH3:7])=[O:5]

Komponenten

7

Edukt 4

HCID 11776TriphenylphosphineHCID 89802Methyl 5-methylsalicylateHCID 5363146Diisopropyl azodicarboxylateHCID 6999724(2R)-pent-4-en-2-ol

Produkt 1

HCID 118307101(S)-methyl 5-methyl-2-(pent-4-en-2-yloxy)benzoateAusbeute 90 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a solution of methyl 2-hydroxy-5-methylbenzoate (1.0 g, 6.02 mmol) in THF (14 ml) were added (R)-(−)-pent-4-en-2-ol (1.037 g, 12.04 mmol) and triphenylphosphine (2.052 g, 7.82 mmol). DIAD (1.521 ml, 7.82 mmol) was added dropwise (exotherm) and the mixture was stirred at rt. After 4.5 h, the mixture was diluted with Et2O and washed with 1N NaOH followed by water (3×'s) then brine, dried (Na2SO4), filtered and concentrated. The yellow oil was purified by flash chromatography (Biotage; 0%-100% EtOAc/hexane; 20 CV) to give (S)-methyl 5-methyl-2-(pent-4-en-2-yloxy)benzoate (1.2664 g, 5.41 mmol, 90% yield) as a yellow oil. 1H NMR (400 MHz, CDCl3) δ 7.58 (d, J=2.2 Hz, 1H), 7.23 (dd, J=8.3, 2.0 Hz, 1H), 6.90 (d, J=8.6 Hz, 1H), 6.03-5.77 (m, 1H), 5.21-4.99 (m, 2H), 4.61-4.35 (m, 1H), 3.89 (s, 3H), 2.60-2.46 (m, 1H), 2.46-2.34 (m, 1H), 2.34-2.25 (m, 3H), 1.34 (d, J=6.1 Hz, 3H).

Aufarbeitung

  1. washwashed with 1N NaOH
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe yellow oil was purified by flash chromatography (Biotage; 0%-100% EtOAc/hexane; 20 CV)

Quellen und Nachweise

ORD-Eintrag
ord-0623d862063447738561a0cabef1b5ef
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09273067B2

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