Sodium Hydroxide → Methyl N-[[[methyl[[(2-methylpropyl)(2-thioxo-1,3,2-benzodioxaphosphol-2-yl)amino]thio]amino] carbonyl]oxy]ethanimidothioate

HRID 1995767

Reaction equation

HRID 1995767 reaction equation
[CH3:1][N:2]([S:6][N:7]([CH2:18][CH:19]([CH3:21])[CH3:20])[P:8]1(=[S:17])[O:12][C:11]2[CH:13]=[CH:14][CH:15]=[CH:16][C:10]=2[O:9]1)[C:3](F)=[O:4].[OH:22][N:23]=[C:24]([S:26][CH3:27])[CH3:25].[OH-].[Na+]>C(Cl)Cl.[Cl-].C([N+](CC)(CC)CC)C.O>[CH3:1][N:2]([S:6][N:7]([CH2:18][CH:19]([CH3:21])[CH3:20])[P:8]1(=[S:17])[O:12][C:11]2[CH:13]=[CH:14][CH:15]=[CH:16][C:10]=2[O:9]1)[C:3]([O:22][N:23]=[C:24]([S:26][CH3:27])[CH3:25])=[O:4]

Participants

7

Reactant 3

HCID 14798Sodium HydroxideHCID 92243Methyl N-hydroxyethanimidothioateHCID 53825165N-methyl[[(2-methylpropyl)(2-thioxo-1,3,2-benzodioxaphosphol-2-yl)amino]thio]carbamic fluoride

Product 1

HCID 54174186Methyl N-[[[methyl[[(2-methylpropyl)(2-thioxo-1,3,2-benzodioxaphosphol-2-yl)amino]thio]amino] carbonyl]oxy]ethanimidothioate

Reagents, catalysts & solvents 3

HCID 5946Tetraethylammonium ChlorideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of N-(2-methylpropyl)-2-thioxo-1,3,2-benzodioxaphosphol-2-amine (16.2 g, 66.6 mmol) and triethylamine (7.3 g, 72 mmol) in tetrahydrofuran (50 ml) is added dropwise over 10 minutes to a solution of sulfur dichloride (8.1 g, 78.7 mmol) in tetrahydrofuran (50 ml) with cooling to maintain a temperature of -5° to 0°. After the addition, the mixture is stirred for two hours then diluted with ether (100 ml). The reaction mixture is filtered under nitrogen and the filtrate concentrated in vacuo. The residue is dissolved in dimethyl formamide (50 ml) and N-methyl carbamoyl fluoride (5.8 g, 75.3 mmol) added at once followed by dropwise addition of triethylamine (7.3 g, 72 mmol) in dimethyl formamide (10 ml) over 10 minutes with cooling in a bath at -25°. After the addition the mixture is stirred for two hours in a bath at 0°. The mixture is diluted with ether, washed with ice cold water, dried and concentrated to leave a crude N-methyl[[(2-methylpropyl)(2-thioxo-1,3,2-benzodioxaphosphol-2-yl)amino]thio]carbamic fluoride II"'. The carbamic fluoride is dissolved in methylene chloride (50 ml) and a solution of methyl N-hydroxyethanimidothioate (7.00 g, 66.6 mmol), tetraethylammonium chloride (1.00 g, 6.04 mmol) and sodium hydroxide (3.20 g, 80 mmol) in water (50 ml) is added at once. The mixture is stirred for 20 hours at room temperature, the phases separated, and the organic phase washed with water, dried over magnesium sulfate and concentrated under reduced pressure. The residual oil is triturated with ether to precipitate the product methyl N-[[[methyl[[(2-methylpropyl)(2-thioxo-1,3,2-benzodioxaphosphol-2-yl)amino]thio]amino]carbonyl]oxy]ethanimidothioate I"'.

Workup

  1. customthe phases separated
  2. washthe organic phase washed with water
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe residual oil is triturated with ether
  6. customto precipitate the product methyl N-[[[methyl[[(2-methylpropyl)(2-thioxo-1,3,2-benzodioxaphosphol-2-yl)amino]thio]amino]carbonyl]oxy]ethanimidothioate I"'

Sources & evidence

ORD record
ord-74e106a483ce4e5fab0c87bc20183ae7
Source dataset
uspto-grants-1983_09
Patent number
US04405796

Linked notes

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