Benzene → 2,3-Dihydroperimidine

HRID 395240

Reaktionsgleichung

Reaktionsgleichung von HRID 395240
OC[C:3]1(CO)[NH:14][C:13]2[C:15]3[C:9]([CH:10]=[CH:11][CH:12]=2)=[CH:8][CH:7]=[CH:6][C:5]=3[NH:4]1.C1C=CC=CC=1.[OH-].[Na+].BrCC(OC(C)(C)C)=O>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.O>[NH:4]1[C:5]2=[C:15]3[C:9](=[CH:8][CH:7]=[CH:6]2)[CH:10]=[CH:11][CH:12]=[C:13]3[NH:14][CH2:3]1

Komponenten

7

Edukt 4

HCID 241BenzeneHCID 14798Sodium HydroxideHCID 79177tert-Butyl bromoacetateHCID 111955781H-Perimidine-2,2(3H)-dimethanol

Produkt 1

HCID 124409652,3-DihydroperimidineAusbeute 127,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 94433Tetrabutylammonium hydrogen sulfateKatalysatorHCID 962WaterLösungsmittel

Versuchsvorschrift

A mixture of 2,2-bis(hydroxymethyl)-2,3-dihydro-1H-perimidine (4.14 g, 18.0 mmol), benzene (45 nL), 50% aqueous sodium hydroxide (37.5 mL), tetrabutylammonium hydrogen sulfate (1.0 g, 2.94 mmol), and t-butyl bromoacetate (5.85 mL, 39.6 mmol) was vigorously stirred at room temperature for 18 hours using a mechanical stirrer. The reaction mixture was diluted with water (150 mL.) and then extracted twice with chloroform (150 mL each). The chloroform extracts were combined and washed with brine (100 mL). The chloroform layer was dried using anhydrous magnesium sulfate, filtered, and then concentrated to give a tan solid. The solid was recrystallized with methanol to yield 3.90 g of 1,3-dihydroperimidine derivative I as tan crystals; m.p. 152-154° C.; 1H NMR (500 Mz; CDCl3): δ 1.46 (s, 18H); 3.70 (s, 4H); 4.01 (s, 5H); 5.20 (s, 2H); 6.51 (δ, 2H, J=7.3 Hz); 7.12 (δ, 2H, J=8.1 Hz); 7.21 (t, 2H, J=7.8 Hz); 13C{1H} NMR (125 Mz; CDCl3): δ28.00, 67.09, 69.43, 72.53, 81.75, 105.88, 112.33, 116.87, 126.92, 134.34, 138.74, 169.56.

Aufarbeitung

  1. extractionextracted twice with chloroform (150 mL each)
  2. washwashed with brine (100 mL)
  3. dry with materialThe chloroform layer was dried
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give a tan solid
  7. customThe solid was recrystallized with methanol

Quellen und Nachweise

ORD-Eintrag
ord-b4d95c85973b43c8abd60863429191a6
Quelldatensatz
uspto-grants-2003_08
Patentnummer
US06605416B2

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