1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 13957672, compound

HRID 847454Notes

Reaction equation

HRID 847454 reaction equation
[F:1][C:2]([F:27])([F:26])[C:3]1[NH:4][C:5]([C:22](F)([F:24])[F:23])=[C:6]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH:7]([CH:14]2[CH2:16][CH2:15]2)[C:8]=1[C:9]([O:11][CH2:12][CH3:13])=[O:10].C1CCN2C(=NCCC2)CC1>C1COCC1>[F:24][CH:22]([F:23])[C:5]1[C:6]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[C:7]([CH:14]2[CH2:15][CH2:16]2)[C:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:3]([C:2]([F:27])([F:1])[F:26])[N:4]=1

Participants

4

Reactant 2

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 15018589HCID 15018589, compound

Product 1

HCID 13957672HCID 13957672, compoundYield 85%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 40 g (0.0916 mole) of diethyl 2,6-bis(trifluoromethyl)-2,6-dihydroxy-4-cyclopropyl-tetrahydropyran-3,5-dicarboxylate in 200 ml of THF is introduced 55.5 g (3.26 moles) of ammonia. The reaction mixture is concentrated to give 38.5 g (96.7%) of a solid. A portion (28 g) of this material is stirred with 27.08 g (0.129 mole) of trifluoroacetic anhydride for one day. The reaction mixture is concentrated and diluted with ether. The ether solution is washed with saturated sodium bicarbonate, dried (MgSO4), and concentrated to give 21 g (81.3%) of an oil, nD25 1.4460. This oil is identified as diethyl 2,6-bis(trifluoromethyl)- 4-cyclopropyl-1,4-dihydro-pyridine-3,5-dicarboxylate. A portion (18 g) of this oil and 150 ml of THF is treated with 6.82 g (0.0449 mole) of DBU. The reaction mixture is held at reflux for 24 hours and concentrated. The residue is stirred with water and extracted with ether. The ether extract is washed with diluted HCl, dried (MgSO4), and concentrated. The residue is crystallized to give 13 g (76.0%) of crude product. A portion (2.0 g) of this product is recrystallized from petroleum ether at low temperature to give 1.17 g (85%) of desired product, m.p. 30°-32° C.

Workup

  1. temperatureat reflux for 24 hours
  2. concentrationconcentrated
  3. extractionextracted with ether
  4. extractionThe ether extract
  5. washis washed with diluted HCl
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. customThe residue is crystallized
  9. customto give 13 g (76.0%) of crude product
  10. customA portion (2.0 g) of this product is recrystallized from petroleum ether at low temperature

Sources & evidence

ORD record
ord-1ed95a7d92364941b08928d63a2bf0d9
Source dataset
uspto-grants-1992_08
Patent number
US05142055

Reaction notes

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