Phosphoric Acid → Aldicarb [ISO]

HRID 477278Notes

Reaction equation

HRID 477278 reaction equation
[CH3:1][C:2]([S:7][CH3:8])([CH3:6])[CH:3]=[N:4][OH:5].C(N(CC)CC)C.[CH3:16][N:17]=[C:18]=[O:19].P(=O)(O)(O)O>O>[CH3:16][NH:17][C:18]([O:5][N:4]=[CH:3][C:2]([CH3:6])([S:7][CH3:8])[CH3:1])=[O:19]

Participants

6

Reactant 4

HCID 1004Phosphoric AcidHCID 8471TriethylamineHCID 12228Methyl Isocyanate2×HCID 154362-Methylthio-2-methylpropionaldoxime2×

Product 1

HCID 2086Aldicarb [ISO]Yield 89.1%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent4×

Procedure

Into a one liter glass resin kettle equipped with a metal pitched-blade agitator, a pressure-equalizing dropping funnel with Teflon® tube for subsurface addition, a thermometer and a dry ice/acetone cooled condenser was added 66.5 grams (0.50 mole) of 2-methyl-2-(methylthio) propionaldehyde oxime and 112 milliliters of water. After cooling the mixture to a temperature of 2° C.-3° C. with a water/salt/ice bath, 0.52 grams (0.005 mole) of triethylamine was added to the kettle under a nitrogen atmosphere. A stoichiometric amount of methyl isocyanate (29.5 milliliters, 0.50 mole) was then added over a period of 30 minutes at a temperature of 4° C.-14° C. with vigorous stirring. The water/salt/ice bath was removed and the mixture was stirred for an additional 75 minutes at a temperature of 10° C.-18° C. after which an additional 2.0 milliliters (0.03 mole) of methyl isocyanate was added and the mixture stirred for an additional period of 30 minutes. The water/salt/ice bath was then put back in place and 2.9 grams of phosphoric acid in 10 milliliters of water was added in a slow stream subsurface. The resulting solid product was filtered off on a sintered glass funnel and rinsed with hexane to give 104.4 grams (wet weight) of a fluffy white powder. High pressure liquid chromatographic analysis (internal standard) indicated the following: 84.00 percent 2-methyl-2-(methylthio) propionaldehyde O-(methylcarbamoyl) oxime (89.1 percent yield based on aldicarb oxime) and 2.38 percent 2-methyl-2-(methylthio) propionaldehyde oxime; 13.62 percent water content was determined by Karl Fischer titration.

Workup

  1. additionfor subsurface addition
  2. additionwas added to the kettle under a nitrogen atmosphere
  3. customThe water/salt/ice bath was removed
  4. additionwas added
  5. additionwas added in a slow stream subsurface
  6. filtrationThe resulting solid product was filtered off on a sintered glass funnel
  7. washrinsed with hexane
  8. customto give 104.4 grams (wet weight) of a fluffy white powder

Sources & evidence

ORD record
ord-bf0100b43b1b4e58a06ffacf85729388
Source dataset
uspto-grants-1989_12
Patent number
US04886913

Reaction notes

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