Di-tert-butyl dicarbonate → Methyl 2-(bis((tert-butoxy)carbonyl)amino)prop-2-enoate

HRID 1177720

Reaktionsgleichung

Reaktionsgleichung von HRID 1177720
COC(=O)C(NC(OC(C)(C)C)=O)CO.C(OC(OC(OC(C)(C)C)=O)=O)(C)(C)C.[CH3:31][O:32][C:33](=[O:59])[CH:34]([N:44]([C:52]([O:54][C:55]([CH3:58])([CH3:57])[CH3:56])=[O:53])[C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])[CH2:35]OC(OC(C)(C)C)=O>C(#N)C.CN(C)C1C=CN=CC=1>[CH3:31][O:32][C:33](=[O:59])[C:34]([N:44]([C:52]([O:54][C:55]([CH3:58])([CH3:57])[CH3:56])=[O:53])[C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])=[CH2:35]

Komponenten

6

Edukt 3

HCID 90495Di-tert-butyl dicarbonateHCID 495564Methyl N-(tert-butoxycarbonyl)serinateHCID 588642662-(Di-tert-butoxycarbonylamino)-3-tert-butoxycarbonyloxy-propionic acid methyl ester

Produkt 1

HCID 10870342Methyl 2-(bis((tert-butoxy)carbonyl)amino)prop-2-enoate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

To a solution of 2-tert-butoxycarbonylamino-3-hydroxy-propionic acid methyl ester (10.0 g, 39 mmol) and di-tert-butyl-dicarbonate (21.8 g, 2.6 equiv.) in acetonitrile (40 mL) was added 4-dimethylaminopyridine (0.48 g, 0.1 equiv) at room temperature. The solution was stirred overnight and concentrated. The residue was dissolved in diethyl ether, washed sequentially with 1 M potassium hydrogen sulfate (2×), saturated sodium bicarbonate, brine, dried over magnesium sulfate, and concentrated to give 15.6 g (quant.) as an oil. Inspection of the 1H NMR showed a mixture of the title compound and 2-(di-tert-butoxycarbonylamino)-3-tert-butoxycarbonyloxy-propionic acid methyl ester. As it was later found that both react with secondary amines to give the same products, the mixture was used without separation. 2-(Di-tert-butoxycarbonylamino)-acrylic acid methyl ester: 1H-NMR (CDCl3) δ 1.45 (s, 18H), 3.78 (s, 3H), 5.63 (s, 1H), 6.33 (s, 1H). Mass spec.: 324.14 (M+Na)+. 2-(Di-tert-butoxycarbonylamino)-3-tert-butoxycarbonyloxy-propionic acid methyl ester: 1H-NMR (CDCl3, 500 MHz) δ 1.46 (s, 9H), 1.49 (s, 18H), 3.72 (s, 3H), 4.42 (dd, J=11.6, 9.2, 1H), 4.75 (dd, J=11.3, 4.6, 1H), 5.30 (dd, J=9.2, 4.6, 1H). Mass spec.: 442.21 (M+Na)+.

Aufarbeitung

  1. concentrationconcentrated
  2. dissolutionThe residue was dissolved in diethyl ether
  3. washwashed sequentially with 1 M potassium hydrogen sulfate (2×), saturated sodium bicarbonate, brine
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated
  6. customto give 15.6 g (quant.) as an oil

Quellen und Nachweise

ORD-Eintrag
ord-cfc12a12e08e43a1940843127c115370
Quelldatensatz
uspto-grants-2010_11
Patentnummer
US07842808B2

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