trichloro(sulfanylidene)-lambda5-phosphane

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

Conditions: temp:22.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a three-necked, 500 ml flask were placed 31 g (0.25 mole) o-hydroxybenzyl alcohol, 56 g (1.0 moles) calcium oxide, a catalytic amount (0.1 g) of acridine, and 600 ml of benzene. To this reaction mixture was added 46.5 g (0.275 mole) of thiophosphoryl trichloride, dropwise, over a period of 120 minutes with stirring. The temperature was maintained at 22° C by use of a water bath. After the addition of the thiophosphoryl trichloride the mixture was stirred overnight. The mixture was then filtered, the solids washed with four equal portions of benzene (total of 200 ml) and the washings combined with the filtrate. The filtrate was then washed with two equal portions of a 5 percent aqueous bicarbonate solution (total of 100 ml), dried over sodium sulfate, filtered, and the volatiles removed under reduced pressure. The residue crystallized, affording 39 g (71%) pf 2-chloro-4H-1,3,2-benzodioxaphosphorin-2-sulfide, m.p.=44°-45° C. Analysis: %Cl, 16.12 (calculated); 16.42 (Found). Into a three-necked, 500 ml flask were placed was stirred overnight The mixture was then filtered the solids washed with four equal portions of benzene (total of 200 ml) The filtrate was then washed with two equal portions of a 5 percent aqueous bicarbonate solution (total of 100 ml) dried over sodium sulfate filtered the volatiles removed under reduced pressure The residue crystallized

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

Procedure: A solution of diisopropylamine (72 mL, 0.512 mole) in 75 mL of anhydrous ether was added dropwise to a cold (ice bath) solution of 106 mL (1.02 moles) of thiophosphoryl chloride in 300 mL of anhydrous ether under an argon atmosphere. The resultant slurry was allowed to slowly warm to room temperature. After filtering to remove isopropylamine hydrochloride, the filtrate was concentrated under vacuum to provide a red oil (45.2 g, 75.4%). After filtering to remove isopropylamine hydrochloride the filtrate was concentrated under vacuum

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

Procedure: A solution of 2-aminobutane (45 mL, 0.449 mol) in 45 mL of anhydrous ether was added dropwise to a solution of 93 mL (0.915 mol) of thiophosphoryl chloride in 200 mL of anhydrous ether at 0° C. under an argon atmosphere. The resultant slurry was stirred while slowly warmed to room temperature. After filtering to remove sec-butylamine hydrochloride (40.6 g), the filtrate was concentrated at reduced pressure to provide 32.3 g (69.7%) of a yellow oil. After filtering to remove sec-butylamine hydrochloride (40.6 g) the filtrate was concentrated at reduced pressure

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

Procedure: A solution of 43.4 mL (0.52 mol) of pyrrolidine in 50 mL of ether was added dropwise to a stirred solution of 116 mL (1.04 mol) of thiophosphoryl chloride in 200 mL of ether at 0° C. (ice bath) under an argon atmosphere. After the addition was completed, the resultant slurry was slowly warmed to room temperature overnight. A trace of pyrrolidinium hydrochloride was removed by filtration and the filtrate was concentrated under vacuum to provide 84.5 g of a clear oil. A portion of this oil (40 g) was distilled at 80° C. (0.25 mm) to provide 18.1 g of the desired dichloride as a clear oil. After the addition A trace of pyrrolidinium hydrochloride was removed by filtration the filtrate was concentrated under vacuum

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of N-benzyl-N-methylamine (2.81 g, 0.32 mol) in 47 mL of ether was added dropwise with stirring to 78.6 g (0.47 mol) of thiophosphoryl chloride in 375 mL of ether at 0° C. under an argon atmosphere. After the addition was complete, the resultant slurry was stirred for 30 min at 0° C., and then for 1 h at 25° C. The amine hydrochloride was removed by filtration and the solvent was concentrated at reduced pressure to provide 28.5 g (92.5%) of a red colored oil. After the addition for 1 h at 25° C The amine hydrochloride was removed by filtration the solvent was concentrated at reduced pressure

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

Procedure: The title compound was prepared in similar fashion as compound 6, substituting phenol for 2,6-dimethylphenol and thiophosphoryl chloride for phosphorus oxychloride. The resulting oily residue was taken to the next step without further purification. The resulting oily residue was taken to the next step without further purification

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

Procedure: 2-isopropyl-5-methylphenol was reacted with sodium hydride and thiophosphoryl chloride using the procedure of Example 21 to form bis(2-isopropyl-5-methylphenyl) chlorothiophosphate (31PNMR, singlet, 57 ppm). This compound was reacted with diphenylphosphonothioic amide by the General Method C(ii) (THF) yielding the compound of Formula I in which R1 =R2 =phenyl and R3 =R4 =2-isopropyl-5-methylphenoxy. Yield 63%; titration purity, 90%, MW593; 31PNMR, quartet 53ppm. Test 2 (Table 2) showed that the product is a very strong extractant for zinc; however on long standing it crystallised from ESCAID® solution.

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

Procedure: 2-isopropyl-5-methylphenol was reacted with sodium hydride and thiophosphoryl chloride using the procedure of Example 21 to form bis(2-isopropyl-5-methylphenyl) chlorothiophosphate (31PNMR, singlet, 57 ppm). This compound was reacted with diphenylphosphonothioic amide by the General Method C(ii) (THF) yielding the compound of Formula I in which R1 =R2 =phenyl and R3 =R4 =2-isopropyl-5-methylphenoxy. Yield 63%; titration purity, 90%, MW593; 31PNMR, quartet 53ppm. Test 2 (Table 2) showed that the product is a very strong extractant for zinc; however on long standing it crystallised from ESCAID® solution.

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

Procedure: 4-chloro-2-methylphenol (142.5 g) was dissolved in a mixture of hexane (200 cm3) and toluene (400 cm3) and sodium hydride (30.0 g of 80% suspension in mineral oil) was added. After stirring for 3 hrs, this suspension was added during 2 hr to a stirred solution of thiophosphoryl chloride (84.5 g) in hexane (100 cm3). The mixture was stirred for a further 18 hrs at ambient temperature, then diluted with ether (1000 cm3), filtered, and concentrated by distillation of solvents under reduced pressure yielding crude bis (4-chloro-2-methylphenyl) chlorothiophosphate, a brown oil (192 g) 31PNMR, singlet, 57 ppm). Some of this compound was converted to the thiophosphoramide by reaction with ammonia as described in Example 9 (31PNMR, singlet 62.7 ppm) sodium hydride (2.07 g, 80% suspension) was added to a stirred solution of the thiophosphoramide (10.4 g) and the chlorothiophosphate (11.4 g) in dry tetrahydrofuran (50 cm3). Stirring at ambient temperature was continued for 18 hrs. The solvent was distilled under reduced pressure and the residue was taken up in hexane and the suspension was filtered. Purification by extraction into 5% aqueous methanol and back extraction as described in Example 15, gave tetrakis (4-chloro-2-methylphenyl) thioimidodiphosphate (9.4 g), (31P NMR, singlet, 49.3 ppm) a brown oil of 81% purity as estimated by titration (MW711). The product of Formula I in which R1 =R2 =RB=R4 =4-chloro-2-methylphenoxy was examined as an extractant by Tests 2 and 3 with the results listed in Tables 2 and 3 respectively, which show that it is a stronger extractant for zinc than the substituted phenoxy derivatives of Examples 9, 14 and 15 and that it has has good selectively over iron. was added The mixture was stirred for a further 18 hrs at ambient temperature filtered concentrated by distillation of solvents under reduced pressure yielding crude bis (4-chloro-2-methylphenyl) chlorothiophosphate Stirring at ambient temperature was continued for 18 hrs The solvent was distilled under reduced pressure the suspension was filtered Purification by extraction into 5% aqueous methanol and back extraction

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

Procedure: 4-chloro-2-methylphenol (142.5 g) was dissolved in a mixture of hexane (200 cm3) and toluene (400 cm3) and sodium hydride (30.0 g of 80% suspension in mineral oil) was added. After stirring for 3 hrs, this suspension was added during 2 hr to a stirred solution of thiophosphoryl chloride (84.5 g) in hexane (100 cm3). The mixture was stirred for a further 18 hrs at ambient temperature, then diluted with ether (1000 cm3), filtered, and concentrated by distillation of solvents under reduced pressure yielding crude bis (4-chloro-2-methylphenyl) chlorothiophosphate, a brown oil (192 g) 31PNMR, singlet, 57 ppm). Some of this compound was converted to the thiophosphoramide by reaction with ammonia as described in Example 9 (31PNMR, singlet 62.7 ppm) sodium hydride (2.07 g, 80% suspension) was added to a stirred solution of the thiophosphoramide (10.4 g) and the chlorothiophosphate (11.4 g) in dry tetrahydrofuran (50 cm3). Stirring at ambient temperature was continued for 18 hrs. The solvent was distilled under reduced pressure and the residue was taken up in hexane and the suspension was filtered. Purification by extraction into 5% aqueous methanol and back extraction as described in Example 15, gave tetrakis (4-chloro-2-methylphenyl) thioimidodiphosphate (9.4 g), (31P NMR, singlet, 49.3 ppm) a brown oil of 81% purity as estimated by titration (MW711). The product of Formula I in which R1 =R2 =RB=R4 =4-chloro-2-methylphenoxy was examined as an extractant by Tests 2 and 3 with the results listed in Tables 2 and 3 respectively, which show that it is a stronger extractant for zinc than the substituted phenoxy derivatives of Examples 9, 14 and 15 and that it has has good selectively over iron. was added The mixture was stirred for a further 18 hrs at ambient temperature filtered concentrated by distillation of solvents under reduced pressure yielding crude bis (4-chloro-2-methylphenyl) chlorothiophosphate Stirring at ambient temperature was continued for 18 hrs The solvent was distilled under reduced pressure the suspension was filtered Purification by extraction into 5% aqueous methanol and back extraction

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

Procedure: Sodium hydride (38.0 g of 80% suspension in mineral oil) was added to a stirred solution of 2-isopropylphenol (139.2 g) and thiophosphoryl chloride (84.5 g) in toluene (500 cm3) at such a rate that the reaction temperature did not rise above 65° C. After stirring for a further 0.5 hr at ambient temperature, the solution was extracted twice with water (250 cm3 portions), separated, dried (MgSO4) and concentrated by distillation of solvents under reduced pressure yielding crude bis(2-isopropylphenyl) chlorothiophosphate, a brown oil (164.2 g); 31P NMR in CDCl3, singlet 53.0 ppm downfield of H3PO4). Of this material, 54.0 g were reacted with ammonia by the procedure of Example 9 yielding crude bis(2-isopropylphenyl)thiophosphoramide) (50.0 g; 31PNmr, singlet δ=58.8 ppm). did not rise above 65° C the solution was extracted twice with water (250 cm3 portions) separated dried (MgSO4) concentrated by distillation of solvents under reduced pressure