Dichloromethane → HCID 131732934, compound

HRID 2170235Notes

Reaction equation

HRID 2170235 reaction equation
ClCCl.[CH:4]([C:6]1[C:7]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[C:8]([CH3:19])[N:9]([CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])[CH:10]=1)=O.[N+:25]([CH2:28][C:29]([O:31][CH2:32][CH3:33])=[O:30])([O-:27])=[O:26].CN1CCOCC1.[Cl-].[NH4+]>O1CCCC1.[Ti](Cl)(Cl)(Cl)Cl>[CH2:32]([O:31][C:29](=[O:30])[C:28]([N+:25]([O-:27])=[O:26])=[CH:4][C:6]1[C:7]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[C:8]([CH3:19])[N:9]([CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])[CH:10]=1)[CH3:33]

Participants

8

Reactant 5

HCID 6344DichloromethaneHCID 79724-MethylmorpholineHCID 25517Ammonium ChlorideHCID 69379Ethyl nitroacetateHCID 90387295HCID 90387295, compound

Product 1

HCID 131732934HCID 131732934, compound

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

A flask equipped with stirbar was charged with 4 mL tetrahydrofuran and cooled in an ice bath. Titanium(IV) chloride, 1M solution in dichloromethane (2.1 mL, 2.100 mmol) was added by syringe, providing a suspension. After 15 minutes, a solution of Example 93c (0.322 g, 1.034 mmol) and ethyl 2-nitroacetate (0.115 mL, 1.034 mmol) in tetrahydrofuran (0.5 mL) was added. After an additional 15 minutes, a solution of 4-methylmorpholine (0.45 mL, 4.09 mmol) in tetrahydrofuran (0.3 mL) was added dropwise. The solution was allowed to warm to ambient temperature and stirred for 18 hours. The heterogeneous reaction mixture was poured into aqueous ammonium chloride and extracted twice with ether. The combined organics were washed with saturated aqueous sodium chloride then dried over anhydrous magnesium sulfate. Filtration, solvent removal, and chromatography on a 12 g silica gel cartridge eluting with 0-60% ethyl acetate/heptane provided the title compounds as a 2.5:1 mixture of olefin isomers.

Workup

  1. customA flask equipped with stirbar
  2. temperaturecooled in an ice bath
  3. customproviding a suspension
  4. waitAfter an additional 15 minutes
  5. extractionextracted twice with ether
  6. washThe combined organics were washed with saturated aqueous sodium chloride
  7. dry with materialthen dried over anhydrous magnesium sulfate
  8. filtrationFiltration, solvent removal, and chromatography on a 12 g silica gel cartridge
  9. washeluting with 0-60% ethyl acetate/heptane

Sources & evidence

ORD record
ord-f22df2ccfddc45f2a2580c18e71eb351
Source dataset
uspto-grants-2015_06
Patent number
US09050346B2

Reaction notes

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