chloro-diethoxy-sulfanylidene-lambda5-phosphane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:42.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: O,O-Diethyl phosphorochloridothioate (11.3 g., 0.06 mole) was added dropwise to a stirred mixture of (1) sodium 3,5,6-trichloro-2-pyridinate (13.2 g., 0.06 mole) in 30 ml. of methylene chloride and 74 ml. of water, (2) 1 mole percent triethylene diamine, (3) 1 mole percent benzyltriethylammonium chloride and (4) a pH buffer consisting of NaOH and sodium borate. The stirred reaction mixture was maintained at 42° C. for 1.5 hours, cooled to room temperature, and the organic phase separated from the aqueous phase. The organic phase was washed once with approximately 30 ml. water and the organic solvent removed under reduced pressure. The title compound was thus obtained in 97 percent yield, based on 100 percent conversion of starting materials. The product was of excellent purity (approximately 99% pure). The stirred reaction mixture cooled to room temperature the organic phase separated from the aqueous phase The organic phase was washed once with approximately 30 ml water and the organic solvent removed under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 12.44 g of diethyl chlorothiophosphate, 6.67 g of triethylamine and 15 g of 2-cyclohexyloxy-4-hydroxy-5-cyano-thiazole was stirred for 3 days and then concentrated to dryness. The residue was added to water and the aqueous phase was extracted with ether. The ether phase was dried and evaporated to dryness. The residue was crystallized from pentane and then isopropyl ether to obtain 10 g of 2-cyclohexyloxy-4-diethoxythiophosphoryloxy-5-cyano-thiazole in the form of white crystals melting at 58° C. concentrated to dryness The residue was added to water the aqueous phase was extracted with ether The ether phase was dried evaporated to dryness The residue was crystallized from pentane

Conditions: temp:42.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: O,O-Diethyl phosphorochloridothioate (11.3 g., 0.06 mole) was added dropwise to a stirred mixture of (1) sodium 3,5,6-trichloro-2-pyridinate (13.2 g., .06 mole) in 30 ml. of methylene chloride and 74 ml. of water, (2) 1 mole percent triethylene diamine, (3) 1 mole percent benzyltriethylammonium chloride and (4) a pH buffer consisting of NaOH and sodium borate. The stirred reaction mixture was maintained at 42° C. for 1.5 hours, cooled to room temperature, and the organic phase separated from the aqueous phase. The organic phase was washed once with approximately 30 ml. water and the organic solvent removed under reduced pressure. The title compound was thus obtained in 97 percent yield, based on 100 percent conversion of starting materials. The product was of excellent purity (approximately 99% pure). The stirred reaction mixture cooled to room temperature the organic phase separated from the aqueous phase The organic phase was washed once with approximately 30 ml water and the organic solvent removed under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Diethyl chlorothiophosphate (25.04 g, supplied by Aldrich Chemical Company Ltd.) was added dropwise with stirring to a saturated solution of ammonia in tetrahydrofuran (250 cm3). Stirring was continued for two hr. The mixture was filtered to remove precipitated ammonium chloride and then concentrated by distillation of the solvent under reduced pressure to a yellow oil (diethyl thiophosphoramide, 21.0 g, 31P NMR in CDCl3, singlet, 67.4 ppm downfield of H3PO4). Without further purification, this amide (8.5 g) was redissolved in tetrahydrofuran (250 cm3) and sodium hydride (13.2 g of a 20% suspension in toluene) was added with stirring. When hydrogen ceased to be evolved, diethyl chlorothiophosphate (9.5 g) was added dropwise during 15 min. The mixture was stirred and heated at 65° C. for 2 hr. and then cooled and filtered. The solvent was distilled under reduced pressure leaving a yellow oil which was dissolved in dichloromethane (250 cm3) and stirred with dilute sulphuric acid (1 molar to ensure that the pH of the suspension was less than pH 2). The organic phase was separated, dried with magnesium sulphate, filtered, and concentrated by distillation of solvent under reduced pressure yielding tetraethyl thioimidodiphosphate (11.2 g, 31P NMR in CDCl3, singlet, 56.4 ppm downfield of H3PO4). The purity was determined by titration of a sample dissolved in 50% tetrahydrofuran--water with 0.1M aqueous sodium hydroxide solution for the acidic (NH or SH) proton, which was 50% neutralised at pH 6.1. By this method the purity was found to be 77% of theoretical based on molecular weight 321. The compound of Formula I in which R1 =R2 =R3 =R4 =ethoxy was examined as an extractant for zinc by Tests 1 and 2, with the results listed in Tables 1 and 2, which show that it is a weak extractant for zinc with high selectivity over iron. The mixture was filtered to remove precipitated ammonium chloride concentrated by distillation of the solvent under reduced pressure to a yellow oil (diethyl thiophosphoramide, 21.0 g, 31P NMR in CDCl3, singlet, 67.4 ppm downfield of H3PO4) Without further purification this amide (8.5 g) was redissolved in tetrahydrofuran (250 cm3) sodium hydride (13.2 g of a 20% suspension in toluene) was added with stirring diethyl chlorothiophosphate (9.5 g) was added dropwise during 15 min The mixture was stirred and then cooled filtered The solvent was distilled under reduced pressure leaving a yellow oil which The organic phase was separated dried with magnesium sulphate filtered concentrated by distillation of solvent under reduced pressure