Tetrahydrofuran → 1-Ethyl-4-(4-nitro-phenyl)-perhydro-1,4-azaphosphorine 4-oxide

HRID 472668Notes

Reaction equation

HRID 472668 reaction equation
[CH:1]([P:3]([CH:14]=[CH2:15])([C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][CH:6]=1)=[O:4])=[CH2:2].[OH-].[Na+].O1CCCC1.Cl.[CH2:24]([NH2:26])[CH3:25].C(=O)(O)[O-].[Na+]>O>[CH2:24]([N:26]1[CH2:2][CH2:1][P:3](=[O:4])([C:5]2[CH:6]=[CH:7][C:8]([N+:11]([O-:13])=[O:12])=[CH:9][CH:10]=2)[CH2:14][CH2:15]1)[CH3:25]

Participants

7

Reactant 5

HCID 8028TetrahydrofuranHCID 11198Ethylamine hydrochloride2×HCID 14798Sodium HydroxideHCID 516892Sodium BicarbonateHCID 580713594-(Divinyl-phosphinoyl)nitro benzene

Product 1

HCID 674791721-Ethyl-4-(4-nitro-phenyl)-perhydro-1,4-azaphosphorine 4-oxide

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
105 °C

Procedure

A mixture of 4-(Divinyl-phosphinoyl)nitro benzene (1.69 g, 7.56 mmol), water (10 mL), 1.0 M of sodium hydroxide in water (7.56 mL, 7.56 mmol) and tetrahydrofuran (10.0 mL, 123 mmol) was treated with ethylamine hydrochloride (678 mg, 8.32 mmol) then heated at 105° C. for one hour. An additional portion of ethylamine hydrochloride was added and the reaction was heated for an additional 2 hours. The reaction was cooled, poured into saturated sodium bicarbonate solution and extracted with dichloromethane. The aqueous layer was treated with solid sodium chloride and extracted and additional 4 times to isolate all the product. The combined organic layers were dried over magnesium sulfate, filtered and evaporated. The residue was purified via chromatography (40 g silica gel and 0%→10% methanol in dichloromethane). 1-Ethyl-4-(4-nitro-phenyl)-perhydro-1,4-azaphosphorine 4-oxide was isolated as yellow oil (300 mg, 10%). 1H NMR (400 MHz, (D3C)2SO, δ, ppm): 8.34 (d, J=8.4 Hz, 2H), 8.11 (t, J=18.46, 9.15 Hz, 2H), 2.91-2.75 (m, 4H), 2.51-2.46 (m, 2H), 2.29 (m, 2H), 1.96 (m, 2H), 1.01 (t, J=14.4, 7.5 Hz, 3H). MS=269 (MH)+.

Workup

  1. temperaturethe reaction was heated for an additional 2 hours
  2. temperatureThe reaction was cooled
  3. extractionextracted with dichloromethane
  4. additionThe aqueous layer was treated with solid sodium chloride
  5. extractionextracted
  6. customadditional 4 times to isolate all the product
  7. dry with materialThe combined organic layers were dried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified via chromatography (40 g silica gel and 0%→10% methanol in dichloromethane)

Sources & evidence

ORD record
ord-948da4f95f504aa1b484d72557bb87ae
Source dataset
uspto-grants-2014_01
Patent number
US08633173B2

Reaction notes

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