tert-Butanol → tert-butyl N-(pent-4-yn-1-yl)carbamate

HRID 865330Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 865330
C(O)(=O)[CH2:2][CH2:3][CH2:4][C:5]#[CH:6].C([N:11]([CH2:14]C)CC)C.[C:16]([OH:20])([CH3:19])([CH3:18])[CH3:17].C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:28])C=CC=CC=1>CCOCC.O>[C:14]([NH:11][CH2:2][CH2:3][CH2:4][C:5]#[CH:6])([O:20][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:28]

Komponenten

7

Edukt 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 1430365-Hexynoic acidHCID 199401P,P-Diphenylphosphinic azide

Produkt 1

HCID 22904935tert-butyl N-(pent-4-yn-1-yl)carbamateAusbeute 25 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 3283Diethyl EtherLösungsmittel

Versuchsvorschrift

To a magnetically stirred solution of 9.13 grams hex-5-ynoic acid (0.081 mol), 7.12 mL triethylamine (0.051 mol), 30 mL tert-butanol, was added 17.7 mL diphenylphosphoryl azide (0.082 mol) and the mixture heated to reflux for 3 hours. The reaction mixture was allowed to cool to room temperature and poured over a biphasic mixture of 200 mL water and 200 ml ether. The layers were separated and the organic layer was washed 1×50 mL 5% ethylenediaminetetraacetic acid disodium salt, 1×50 mL 10% sodium bicarbonate, 1×50 mL brine, dried over magnesium sulfate and activated carbon, filtered and concentrated in vacuo. The resulting residue was further purified by column chromatography, using silica gel, eluting with 1:1 ether/hexane (TLC, SiO2, 1:3 ethyl acetate/hexane, Rf =0.18, ninhydrin char) to yield 3.8 grams (25%) N-boc-5-amino-1-pentyne. 1H NMR (CDCl3, dTMS) 4.65 (1H, bs, NH), 3.22 (2H, q, 3JHH =6 Hz, NCH2), 2.23 (2H, dt, 3JHH =6 Hz, 4JHH =3 Hz, CH2C∫C), 1.98 (1H, t, 4JHH =3 Hz, C∫CH), 1.73 (2H, p, 3JHH =6 Hz, CH2), 1.42 (9H, s, t-Bu).

Aufarbeitung

  1. temperaturethe mixture heated
  2. temperatureto reflux for 3 hours
  3. customThe layers were separated
  4. washthe organic layer was washed 1×50 mL 5% ethylenediaminetetraacetic acid disodium salt, 1×50 mL 10% sodium bicarbonate, 1×50 mL brine
  5. dry with materialdried over magnesium sulfate and activated carbon
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe resulting residue was further purified by column chromatography
  9. washeluting with 1:1 ether/hexane (TLC, SiO2, 1:3 ethyl acetate/hexane, Rf =0.18, ninhydrin char)

Quellen und Nachweise

ORD-Eintrag
ord-7b2d6005d61348afa9c3f76246de9aee
Quelldatensatz
uspto-grants-1996_10
Patentnummer
US05565449

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