2-adamantyl Chloroformate → Carbonate Ion

HRID 54844Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 54844
[CH3:1][C@:2]([C:14]([NH:16][C@H:17]([CH2:25][OH:26])[CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:15])([CH2:4][C:5]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[NH:7][CH:6]=1)[NH2:3].[CH:27]12[CH2:36][CH:31]3[CH2:32][CH:33]([CH2:35][CH:29]([CH2:30]3)[CH:28]1[O:37][C:38](Cl)=[O:39])[CH2:34]2>C1COCC1.C(OCC)(=O)C>[CH:29]12[CH2:35][CH:33]3[CH2:32][CH:31]([CH2:36][CH:27]([CH2:34]3)[CH:28]1[O:37][C:38](=[O:39])[NH:3][C:2]([CH2:4][C:5]1[C:13]3[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=3)[NH:7][CH:6]=1)([CH3:1])[C:14]([NH:16][CH:17]([CH2:25][OH:26])[CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:15])[CH2:30]2.[C:38](=[O:39])([O-:15])[O-:37]

Komponenten

6

Edukt 2

HCID 108785372-adamantyl ChloroformateHCID 54471265alpha-methyl-D-tryptophyl-L-phenylalaninol

Produkt 2

HCID 19660Carbonate IonAusbeute 20 %HCID 10165354Tricyclo[3.3,1.13,7]dec-2-yl-[2-[[1-(hydroxymethyl)-2-phenylethyl]amino]-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl]carbamate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A solution of the α-methyl-D-tryptophyl-L-phenylalaninol (0.5 g, 1.42 mmol) and 4-N,N-dimethylaminopyridine (0.2 g, 1.64 mmol), in anhydrous THF (20 mL) was treated dropwise with a solution of 2-adamantylchloroformate (1.4 mmol) in anhydrous THF (20 mL) at room temperature. The reaction was monitored by IR spectroscopy. Once complete, the reaction mixture was diluted with ethyl acetate and washed with 1M citric acid solution, then water. The dried (MgSO4) organic phase was evaporated to dryness and chromatographed over silica using 2% MeOH:98% CH2Cl2 as eluant. This gave the required compound (65% along with 20% carbonate impurity. NOTE: Some of the more acid labile urethanes required chromatography on neutral stationary phases. mp 96°-100° C. (EtOAc-hexane); IR (KBr) 3316, 1695 and 1658 cm-1 ; NMR (CD3OD) δ1.28 (3H, s), 1.55 (2H, m), 1.68-2.06 (12H, m), 2.76 (2H, ABx, J 13.5 and 17Hz), 3.31 (2H, Abq, J 14.5Hz), 3.45 (2H, m), 4.12 (1H, m), 4.78 (1H, br.s) and 6.8-7.5 (10H, m); Anal (C32H39N3O4), C, H, N.

Aufarbeitung

  1. washwashed with 1M citric acid solution
  2. dry with materialThe dried (MgSO4) organic phase
  3. customwas evaporated to dryness
  4. customchromatographed over silica using 2% MeOH

Quellen und Nachweise

ORD-Eintrag
ord-41ed5fb5f01245898410dd7345481174
Quelldatensatz
uspto-grants-1997_04
Patentnummer
US05622983

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