Sodium Carbonate → (S)-Tetrahydrofuran-3-yl (3-nitrobenzyl)carbamate

HRID 1984965

Reaktionsgleichung

Reaktionsgleichung von HRID 1984965
C([O-])([O-])=O.[Na+].[Na+].Cl.[N+:8]([C:11]1[CH:12]=[C:13]([CH:16]=[CH:17][CH:18]=1)[CH2:14][NH2:15])([O-:10])=[O:9].Cl[C:20]([O:22][C@H:23]1[CH2:27][CH2:26][O:25][CH2:24]1)=[O:21].ClC([O-])=O>C1(C)C=CC=CC=1.O>[N+:8]([C:11]1[CH:12]=[C:13]([CH:16]=[CH:17][CH:18]=1)[CH2:14][NH:15][C:20](=[O:21])[O:22][C@H:23]1[CH2:27][CH2:26][O:25][CH2:24]1)([O-:10])=[O:9]

Komponenten

7

Edukt 4

HCID 10340Sodium CarbonateHCID 2724030Benzenemethanamine, 3-nitro-, hydrochloride (1:1)HCID 21226386CarbonochloridateHCID 22876378(3S)-oxolan-3-yl carbonochloridate

Produkt 1

HCID 57718888(S)-Tetrahydrofuran-3-yl (3-nitrobenzyl)carbamateAusbeute 94,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittel2×

Versuchsvorschrift

Added 13.84 g Na2CO3 to a 500 ml three neck round bottom flask equipped with a mechanical stirrer, addition funnel, and thermocouple. Then added 86 ml water and stirred until full dissolution at room temperature. 20 g 3-nitrobenzylamine HCl 2b was then added, followed by 154 ml toluene. The mixture was heated to 50° C. wherein a clear biphasic solution results. Added a 20% w/w solution of (S)-tetrahydrofuran-3-yl chloroformate, 2a (16 g) in toluene (80 ml) dropwise over 45 minutes wherein very little exotherm was noted. The reaction mixture was stirred for an additional 1 hour before the layers were separated at 50° C. The mixture was concentrated to ˜85 ml, cooled to 0° C. and stirred for 1 hour at 0° C. Precipitated product was collected by filtration and dried for 18 hours at 53° C. to give 26.64 g (94.4% yield, 99.90% a/a) of (S)-tetrahydrofuran-3-yl 3-nitrobenzylcarbamate (2c) as a white crystalline solid with consistent 1H NMR (500 MHz, d6-DMSO): 8.10 (m, 2H); 7.90 (m, 1H); 7.70 (d, 1H); 7.62 (t, 1H); 5.10 (br, 1H); 4.30 (d, 2H); 3.72 (m, 4H); 2.10 (m, 1H); 1.87 (m, 1H)ppm.

Aufarbeitung

  1. customequipped with a mechanical stirrer, addition funnel
  2. temperatureThe mixture was heated to 50° C. wherein a clear biphasic solution
  3. customresults
  4. stirringThe reaction mixture was stirred for an additional 1 hour before the layers
  5. customwere separated at 50° C
  6. concentrationThe mixture was concentrated to ˜85 ml
  7. temperaturecooled to 0° C.
  8. stirringstirred for 1 hour at 0° C
  9. filtrationPrecipitated product was collected by filtration
  10. customdried for 18 hours at 53° C.

Quellen und Nachweise

ORD-Eintrag
ord-f70184390aea4dbd9c80c8825a1e13ec
Quelldatensatz
uspto-grants-2009_06
Patentnummer
US07544810B2

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