Methomyl → HCID 86736972, compound

HRID 1395029Notes

Reaction equation

HRID 1395029 reaction equation
[CH3:1][C:2]1([CH3:13])[CH2:7][O:6][P:5]([NH:9][CH:10]([CH3:12])[CH3:11])(=[S:8])[O:4][CH2:3]1.C(N(CC)CC)C.[S:21](Cl)Cl.[CH3:24][NH:25][C:26]([O:28][N:29]=[C:30]([S:32][CH3:33])[CH3:31])=[O:27]>O1CCCC1.O>[CH3:1][C:2]1([CH3:13])[CH2:3][O:4][P:5]([N:9]([CH:10]([CH3:11])[CH3:12])[S:21][CH2:24][NH:25][C:26]([O:28][N:29]=[C:30]([S:32][CH3:33])[CH3:31])=[O:27])(=[S:8])[O:6][CH2:7]1

Participants

7

Reactant 4

HCID 4109MethomylHCID 8471Triethylamine2×HCID 25353Sulfur dichlorideHCID 20333949HCID 20333949, compound

Product 1

HCID 86736972HCID 86736972, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of 5,5-dimethyl-2-isopropylamino-2-thioxo-1,3,2-dioxaphosphorinane (3.00 g, 13.4 mmol) and triethylamine (1.9 ml, 13.5 mmol) in tetrahydrofuran (20 ml) is added dropwise over 20 minutes to a stirred solution of sulfur dichloride (1.00 ml, 15.7 mmol) in tetrahydrofuran (20 ml) at room temperature. Following the addition the mixture is stirred at room temperature for 1 hour. Cuprous chloride (0.25 g) is added to the mixture followed by dropwise addition of a solution of Methyl N-[[(methylamino)carbonyl]oxy]ethanimidothioate (2.17 g, 13.4 mmol) and triethylamine (1.90 ml, 13.5 mmol) in tetrahydrofuran (20 ml.). The mixture is stirred for two hours at room temperature then diluted with water and extracted with ethyl acetate. The organic phase is washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The residual oil is chromatographed over silica gel eluting with a mixture of ethyl acetate - Skellysolve B in the ratio of 2 to 3. The chromatographed product is recrystallized from ethyl acetate, to give Methyl N-[[[[[(5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)isopropylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate as a white solid of melting point 114°-115° C. The nmr and ir spectra are consistent with the expected structure.

Workup

  1. additionthe addition the mixture
  2. stirringThe mixture is stirred for two hours at room temperature
  3. extractionextracted with ethyl acetate
  4. washThe organic phase is washed with water
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residual oil is chromatographed over silica gel eluting with a mixture of ethyl acetate - Skellysolve B in the ratio of 2 to 3
  8. customThe chromatographed product is recrystallized from ethyl acetate

Sources & evidence

ORD record
ord-615e5487724347108e85f3bd81356f03
Source dataset
uspto-grants-1980_05
Patent number
US04201733

Reaction notes

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