4-chloro-2-methylphenol

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:; See reaction.notes.procedure_details.

Procedure: Sodium hydride (60% in mineral oil, 1.08 g, 27 mmol) was washed 3× with hexanes then a solution of 4-chloro-2-methylphenol (3.50 g, 24.5 mmol) dissolved in tetrahydrofuran (40 mL) was added. The solution was stirred for 20 minutes then 2-chloro-3-methyl-5-nitropyridine (4.02 g, 23.3 mmol) was added and the reaction mixture was heated to reflux for 3 hours. After cooling, the mixture was concentrated in vacuo then dissolved in ethyl acetate and washed with water, 3× with saturated NaHCO3 and saturated NaCl then dried over Na2SO4 and concentrated in vacuo. was added the reaction mixture was heated to reflux for 3 hours After cooling the mixture was concentrated in vacuo then dissolved in ethyl acetate washed with water, 3× with saturated NaHCO3 and saturated NaCl then dried over Na2SO4 concentrated in vacuo

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

Procedure: 4-Chloro-2-methylphenol (101 mg, 0.71 mmol) was dissolved in tetrahydrofuran (2.1 mL) and the solution was treated with sodium hydride (60% dispersed in mineral oil, 31 mg, 0.78 mmol). After stirring for 30 minutes at 22° C., 2-chloro-5-nitropyridine (101 mg, 0.64 mmol) was added and the reaction mixture was heated to reflux for 1 hour. The solution was cooled to ambient temperature, quenched with saturated aqueous NH4Cl and concentrated in vacuo. The residue was redissolved in ethyl acetate then washed 2× with saturated NaHCO3, saturated NaCl, dried over anhydrous Na2SO4 and concentrated in vacuo. the reaction mixture was heated to reflux for 1 hour The solution was cooled to ambient temperature quenched with saturated aqueous NH4Cl concentrated in vacuo The residue was redissolved in ethyl acetate then washed 2× with saturated NaHCO3, saturated NaCl dried over anhydrous Na2SO4 concentrated in vacuo

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

Procedure: 106.5 g (0.75 mol) 4-chloro-2-methylphenol and 45.67 g (0.25 mol) 4-tert. butylbenzylchloride are dissolved in 200 ml chloroform, and 22.5 g water-free zinc chloride are added as Friedel-Crafts catalyst. Thereafter the reaction mixture is stirred, whereby indeed at room temperature to the start of the reaction intense gas development, i.e. intense reaction, is to be noted. Subsequently the reaction mixture is stirred at 60° C. 5-6 h and washed three times each with 200 ml water for the purpose of removing the zinc chloride. The organic phase is dried across magnesium sulfate and the chloroform is driven off in a vacuum. At 182°-185° C./0.3 Torr the 4-chloro-2-methyl-6-(4'-tert. butylbenzyl)-phenol distills over as water-clear, viscous, nearly odorless liquid. whereby indeed at room temperature to the start of the reaction intense gas development, i.e. intense reaction Subsequently the reaction mixture is stirred at 60° C 5-6 h and washed three times each with 200 ml water for the purpose of removing the zinc chloride The organic phase is dried across magnesium sulfate At 182°-185° C./0.3 Torr the 4-chloro-2-methyl-6-(4'-tert. butylbenzyl)-phenol distills over as water-clear

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: 25.1 g of diethyl-2-chloro-propionyl-malonate and 14.2 g of 4-chloro-o-cresol are dissolved in 100 ml dimethyl formamide. The mixture is stirred at 60° C. for 48 hours in the presence of 13.8 g of potassium carbonate. The reaction mixture is filtered and the filtrate is evaporated. The residue is dissolved in 100 ml of benzene and washed successively with 100 ml of a saturated aqueous sodium bicarbonate solution and 100 ml of water. The benzene phase is evaporated to yield 28 g of the desired compound, yield 80%. The reaction mixture is filtered the filtrate is evaporated The residue is dissolved in 100 ml of benzene washed successively with 100 ml of a saturated aqueous sodium bicarbonate solution and 100 ml of water The benzene phase is evaporated

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

Procedure: 25.1 g of diethyl-2-chloro-propionyl-malonate and 14.2 g of 4-chloro-o-cresol are dissolved in 100 ml dimethyl formamide. The mixture is stirred at 60° C. for 48 hours in the presence of 13.8 g of potassium carbonate. The reaction mixture is filtered and the filtrate is evaporated. The residue is dissolved in 100 ml of benzene and washed successively with 100 ml of a saturated aqueous sodium bicarbonate solution and 100 ml of water. The benzene phase is evaporated to yield 28 g of the desired compound, yield 80%. The reaction mixture is filtered the filtrate is evaporated The residue is dissolved in 100 ml of benzene washed successively with 100 ml of a saturated aqueous sodium bicarbonate solution and 100 ml of water The benzene phase is evaporated