Benzene → 2,3-Dihydroperimidine

HRID 1167577

Reaction equation

HRID 1167577 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 mL), 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): δ 28.00, 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-fec9a00476814354b6c2c88458f2a5d0
Source dataset
uspto-grants-2003_09
Patent number
USRE038251E1

Linked notes

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