4-Toluenesulfonyl chloride → (+/-)-2-(Azidomethyl)-2,3-dihydronaphtho[1,2-b]furan

HRID 13929

Reaktionsgleichung

Reaktionsgleichung von HRID 13929
[O:1]1[CH:5]([CH2:6]O)[CH2:4][C:3]2[CH:8]=[CH:9][C:10]3[C:15]([C:2]1=2)=[CH:14][CH:13]=[CH:12][CH:11]=3.C1(C)C=CC(S(Cl)(=O)=O)=CC=1.C(N(CC)CC)C.CC1C=CC(S(OCC2OC3C4C(C=CC=3C2)=CC=CC=4)(=O)=O)=CC=1.S(C1C=CC(C)=CC=1)([O-])(=O)=O.[N-:70]=[N+:71]=[N-:72].[Na+]>CN(C)C1C=CN=CC=1.CS(C)=O.O>[N:70]([CH2:6][CH:5]1[O:1][C:2]2[C:15]3[C:10]([CH:9]=[CH:8][C:3]=2[CH2:4]1)=[CH:11][CH:12]=[CH:13][CH:14]=3)=[N+:71]=[N-:72]

Komponenten

10

Edukt 6

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 33557Sodium AzideHCID 85570p-ToluenesulfonateHCID 68584837(2,3-Dihydronaphtho[1,2-b]furan-2-yl)methanolHCID 86598549(+/-)-2,3-Dihydronaphtho[1,2-b]furan-2-ylmethyl 4-methylbenzenesulfonate

Produkt 1

HCID 86047400(+/-)-2-(Azidomethyl)-2,3-dihydronaphtho[1,2-b]furanAusbeute 71 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 679Dimethyl SulfoxideLösungsmittelHCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

Treatment of (±)-tert-butyl(2,3-dihydronaphtho[1,2-b]furan-2-ylmethoxy)dimethylsilane (2.70 g; 8.59 mmol) with tetrabutylammonium fluoride (9.4 mL, 1.0 M solution in tetrahydrofuran) generally according to the procedure described for Intermediate 6 gave (±)-2,3-dihydronaphtho[1,2-b]furan-2-ylmethanol. Treatment of the alcohol with p-toluenesulfonyl chloride (1.64 g, 8.59 mmol), 4-(dimethylamino)pyridine (0.105 g, 0.86 mmol), and triethylamine (1.67 g, 12.89 mmol) generally according to the procedure described for Intermediate 14 provided (±)-2,3-dihydronaphtho[1,2-b]furan-2-ylmethyl 4-methylbenzenesulfonate. To a solution of the tosylate in dimethylsulfoxide (50 mL) was added sodium azide (0.558 g, 8.59 mmol) and the reaction mixture was allowed to stir at 70° C. for 12 h, cooled to room temperature, diluted with water (200 mL) and extracted with diethyl ether (2×100 mL). The combined organic extracts were washed with water (4×75 mL), saturated aqueous sodium chloride (75 mL), dried (magnesium sulfate), and the solvent was removed in vacuo to provide a crude oil. Purification by flash column chromatography (silica, ethyl acetate:hexanes 1:9) provided 1.38 g (71%) of (±)-2-(azidomethyl)-2,3-dihydronaphtho[1,2-b]furan as a colorless oil. Rf=0.46 (silica, ethyl acetate:hexanes 1:9); Anal. calcd. for C13H11N3O.0.1H2O: C, 68.77; H, 4.97; N, 18.51. Found: C, 68.4; H, 4.62; N, 18.12.

Aufarbeitung

  1. temperaturecooled to room temperature
  2. extractionextracted with diethyl ether (2×100 mL)
  3. washThe combined organic extracts were washed with water (4×75 mL), saturated aqueous sodium chloride (75 mL)
  4. dry with materialdried (magnesium sulfate)
  5. customthe solvent was removed in vacuo
  6. customto provide a crude oil
  7. customPurification by flash column chromatography (silica, ethyl acetate:hexanes 1:9)

Quellen und Nachweise

ORD-Eintrag
ord-c09f7df325dd4ba9bce1faf352f68534
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07728155B2

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