Benzene → 2,3-Dihydroperimidine

HRID 395240Notes

Reaction equation

HRID 395240 reaction equation
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

Participants

7

Reactant 4

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

Product 1

HCID 124409652,3-DihydroperimidineYield 127.3%

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 962WaterSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-b4d95c85973b43c8abd60863429191a6
Source dataset
uspto-grants-2003_08
Patent number
US06605416B2

Reaction notes

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