Triethylamine → N-(4-Chlorobutyl)-N-methylphosphoramidic dichloride

HRID 346440Notes

Reaction equation

HRID 346440 reaction equation
Cl.[CH3:2][NH:3][CH2:4][CH2:5][CH2:6][CH2:7][Cl:8].[P:9](Cl)([Cl:12])([Cl:11])=[O:10].C(N(CC)CC)C.[Cl-].[NH4+]>C(Cl)Cl>[CH3:2][N:3]([CH2:4][CH2:5][CH2:6][CH2:7][Cl:8])[P:9]([Cl:12])([Cl:11])=[O:10]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 24813Phosphorus oxychlorideHCID 25517Ammonium ChlorideHCID 553025604-Chloro-N-methylbutan-1-amine--hydrogen chloride (1/1)

Product 1

HCID 11644381N-(4-Chlorobutyl)-N-methylphosphoramidic dichlorideYield 85%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-40 °C

Procedure

N-methyl-N-(4-chlorobutyl)amine hydrochloride (2.0 g, 12.73 mmol) was dissolved in 20 mL of anhydrous CH2Cl2 and cooled to −40° C. Phosphorous oxycloride (1.2 mL, 12.73 mmol) was added neat followed by the drop wise addition of triethyl amine (3.6 mL, 25.46 mmol) in 5 mL of CH2Cl2. Warmed reaction to 0° C. and slowly to room temperature. Allowed reaction to stir at room temperature for 6 hours. The reaction mixture was poured over ice, added saturated ammonium chloride and separated layers. Extracted water layer 3× with CH2Cl2, combined organic layers, dried over anhydrous sodium sulfate and concentrated under reduce pressure. Purified by silica gel flash chromatography (3:1 Hex/EtOAc) to yield a clear oil (2.57 g, 85%).

Workup

  1. temperatureWarmed
  2. customreaction to 0° C.
  3. customslowly to room temperature
  4. customAllowed reaction
  5. additionThe reaction mixture was poured over ice
  6. customseparated layers
  7. dry with materialdried over anhydrous sodium sulfate
  8. concentrationconcentrated
  9. customPurified by silica gel flash chromatography (3:1 Hex/EtOAc)

Sources & evidence

ORD record
ord-e7039ddf8f3b4248b144eddecba0c8d8
Source dataset
uspto-grants-2007_02
Patent number
US07173020B2

Reaction notes

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