N,N,N',N'-Tetramethylazodicarboxamide → O-(Diphenylphosphinyl)hydroxylamine

HRID 73648

Reaction equation

HRID 73648 reaction equation
[OH-:1].[Na+].CN(C(N=NC(N(C)C)=O)=O)C.Cl.[NH2:16]O.[C:18]1([P:24](Cl)([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[O:25])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>O.O1CCOCC1>[NH2:16][O:25][P:24](=[O:1])([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

7

Reactant 4

HCID 4278N,N,N',N'-TetramethylazodicarboxamideHCID 14798Sodium HydroxideHCID 73910Diphenylphosphinic chlorideHCID 443297Hydroxyamine hydrochloride

Product 1

HCID 10955453O-(Diphenylphosphinyl)hydroxylamineYield 82.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A 5 L 4-neck round bottom flask (rbf) fitted with an overhead stirrer & a thermocouple was charged with; (1) a solution of NaOH (60.85 g, 1.52 mol, 2.4 eq) in 180 mL water, (2) a solution of hydroxylamine-HCl (110.12 g, 1.58 mol, 2.5 eq) in 180 mL water and (3) 180 mL dioxane. The mixture was cooled in an ice/acetone bath to 0° C. 150 g of ice was added, followed by a precooled (to about 10° C.) solution of diphenylphosphinic chloride (150.0 g, 0.634 mol, 1 eq) in 180 mL dioxane (added all at once). The reaction became very thick with a white precipitate, requiring vigorous stirring. The internal temperature rose to 22° C. After 5 additional minutes stirring (10 minutes maximum), the reaction mixture was diluted with 2.5 L of ice cold water and filtered thru a large fritted funnel (15 cm diameter). The crude material was left on the frit to drain for one hour, then transferred back into the 5 L rbf. The solid was suspended in 500 mL ice cold 0.25N NaOH solution and vigorously stirred for five minutes (no more than 10 min), then filtered again, washing 2× with ice cold water and left to dry overnight on the fritted filter. The partially dried material was dried for 12 h in a vacuum oven (50° C., 0.1 torr) and then well crushed with a mortar & pestal. An additional 16 h of drying in the vacuum oven afforded 122 g (82%) the above compound as a white powder.

Workup

  1. customA 5 L 4-neck round bottom flask (rbf) fitted with an overhead stirrer
  2. additiona thermocouple was charged with
  3. additionadded all at once)
  4. customrose to 22° C
  5. filtrationfiltered
  6. waitThe crude material was left on the frit
  7. waitto drain for one hour
  8. stirringvigorously stirred for five minutes (no more than 10 min)
  9. filtrationfiltered again
  10. washwashing 2× with ice cold water
  11. waitleft
  12. customto dry overnight on the fritted filter
  13. customThe partially dried material was dried for 12 h in a vacuum oven (50° C., 0.1 torr)
  14. customwell crushed with a mortar & pestal
  15. customAn additional 16 h of drying in the vacuum oven

Sources & evidence

ORD record
ord-b2e4355bacd546f2952490ef96acf714
Source dataset
uspto-grants-2014_09
Patent number
US08829185B2

Linked notes

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