2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane

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

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

Procedure: To phosphorus trichloride (775.4 g, 5.5 M, 10% molar excess) was added dropwise with stirring over two hours a solution of neopentylene glycol (520.8 g, 5.0 M) in chloroform (1200 ml). After the slight endotherm and evolution of HCl had subsided, the clear colorless solution was freed of most of the chloroform and excess PCl3 by distillation at atmospheric pressure to a pot temperature of 100° C. Distillation of the residue through a short vacuum-jacketed Vigreaux column yielded 803.6 g (95.3% yield) of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane (III), bp 65° C./10 mm nD25 1.4738, % Cl found 20.71 (21.03 calculated). by distillation at atmospheric pressure to a pot temperature of 100° C Distillation of the residue through a short vacuum-jacketed Vigreaux column

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

Procedure: To phosphorus trichloride (775.4 g, 5.5 M, 10% molar excess) was added dropwise with stirring over two hours a solution of neopentylene glycol (520.8 g, 5.0 M) in chloroform (1200 ml). After the slight endotherm and evolution of HCl had subsided, the clear colorless solution was freed of most of the chloroform and excess PCl3 by distillation at atmospheric pressure to a pot temperature of 100° C. Distillation of the residue through a short vacuum-jacketed Vigreaux column yielded 803.6 g (95.3% yield) of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane (III), bp 65° C./10 mm nD25 1.4738, % Cl found 20.71 (21.03 calculated). by distillation at atmospheric pressure to a pot temperature of 100° C Distillation of the residue through a short vacuum-jacketed Vigreaux column

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

Procedure: 18.4 g of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane are added dropwise, at room temperature, with stirring, to a solution of 19.7 g (0.1 mol) of 4-butylamino1,2,2,6,6-pentamethylpiperidine in 100 ml of triethylamine. After heating at the reflux temperature for 15 hours, the mixture is diluted with toluene and the precipitated hydrochloride is filtered off. Evaporation of the filtrate gives 2-[N-butyl(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-5,5-dimethyl-1,3,2-dioxaphosphorinane as an oil which boils at 120° under 40 Pa (Compound No. 1). After heating at the reflux temperature for 15 hours the precipitated hydrochloride is filtered off Evaporation of the filtrate

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

Procedure: 18.4 g of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane are added dropwise, at room temperature, with stirring, to a solution of 19.7 g (0.1 mol) of 4-butylamino1,2,2,6,6-pentamethylpiperidine in 100 ml of triethylamine. After heating at the reflux temperature for 15 hours, the mixture is diluted with toluene and the precipitated hydrochloride is filtered off. Evaporation of the filtrate gives 2-[N-butyl(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-5,5-dimethyl-1,3,2-dioxaphosphorinane as an oil which boils at 120° under 40 Pa (Compound No. 1). After heating at the reflux temperature for 15 hours the precipitated hydrochloride is filtered off Evaporation of the filtrate

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

Procedure: 4.85 g (29.0 mmol) of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane are added dropwise over a period of about 15 minutes to a solution of 6.6 g (27.0 mmol) of 6-(cyclohexen-1-yl)-2-tert-butyl-4-methylphenol (compound(102), Example 1)and 4.0 ml (29.0 mmol) of triethylamine in 25 ml of mesitylene (1,3,5-trimethylbenzene). The reaction mixture is then refluxed for 18 hours, cooled, filtered, and the filtrate is concentrated on a vacuum rotary evaporator. Crystallization of the residue from dry acetonitrile gives 5.8 g (57%)of 2-[6-(cyclohexen-1-yl)-2-tert-butyl-4-methyl-phenoxy]-5, 5-dimethyl-1,3,2-dioxaphosphorinane, m.p. 97°-102° C. (compound(201), Table 2). The reaction mixture is then refluxed for 18 hours cooled filtered the filtrate is concentrated on a vacuum rotary evaporator Crystallization of the residue from dry acetonitrile

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

Procedure: 4.85 g (29.0 mmol) of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane are added drop-wise over a period of about 15 minutes to a solution of 6.6 g (27.0 mmol) of 6-(cyclohexen-1-yl)-2-tert-butyl-4-methylphenol (compound (102), Example 1) and 4.0 ml (29.0 mmol) of triethylamine in 25 ml of mesitylene (1,3,5-trimethylbenzene). The reaction mixture is then refluxed for 18 hours, cooled, filtered, and the filtrate is concentrated on a vacuum rotary evaporator. Crystallization of the residue from dry acetonitrile gives 5.8 g (57%) of 2-[6-(cyclohexen-1-yl)-2-tert-butyl-4-methyl-phenoxy]-5,5-dimethyl-1,3,2-dioxaphosphorinane, m.p. 97°-102° C. (compound (201), Table 2). The reaction mixture is then refluxed for 18 hours cooled filtered the filtrate is concentrated on a vacuum rotary evaporator Crystallization of the residue from dry acetonitrile

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

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

Procedure: 4.85 g (29.0 mmol) of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane are added dropwise over a period of about 15 minutes to a solution of 6.6 g (27.0 mmol) of 6-(cyclohexen-1-yl)-2-tert-butyl-4-methylphenol (compound(102), Example 1)and 4.0 ml (29.0 mmol) of triethylamine in 25 ml of mesitylene (1,3,5-trimethylbenzene). The reaction mixture is then refluxed for 18 hours, cooled, filtered, and the filtrate is concentrated on a vacuum rotary evaporator. Crystallization of the residue from dry acetonitrile gives 5.8 g (57%)of 2-[6-(cyclohexen-1-yl)-2-tert-butyl-4-methyl-phenoxy]-5, 5-dimethyl-1,3,2-dioxaphosphorinane, m.p. 97°-102° C. (compound(201), Table 2). The reaction mixture is then refluxed for 18 hours cooled filtered the filtrate is concentrated on a vacuum rotary evaporator Crystallization of the residue from dry acetonitrile

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

Procedure: 4.85 g (29.0 mmol) of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane are added drop-wise over a period of about 15 minutes to a solution of 6.6 g (27.0 mmol) of 6-(cyclohexen-1-yl)-2-tert-butyl-4-methylphenol (compound (102), Example 1) and 4.0 ml (29.0 mmol) of triethylamine in 25 ml of mesitylene (1,3,5-trimethylbenzene). The reaction mixture is then refluxed for 18 hours, cooled, filtered, and the filtrate is concentrated on a vacuum rotary evaporator. Crystallization of the residue from dry acetonitrile gives 5.8 g (57%) of 2-[6-(cyclohexen-1-yl)-2-tert-butyl-4-methyl-phenoxy]-5,5-dimethyl-1,3,2-dioxaphosphorinane, m.p. 97°-102° C. (compound (201), Table 2). The reaction mixture is then refluxed for 18 hours cooled filtered the filtrate is concentrated on a vacuum rotary evaporator Crystallization of the residue from dry acetonitrile

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

Procedure: 18.4 g of 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane are added dropwise, at room temperature, with stirring, to a solution of 19.7 g (0.1 mol) of 4-butylamino-1,2,2,6,6-pentamethylpiperidine in 100 ml of triethylamine. After heating at the reflux temperature for 15 hours, the mixture is diluted with toluene and the precipitated hydrochloride is filtered off. Evaporation of the filtrate gives 2-[N-butyl(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-5,5-dimethyl-1,3,2-dioxaphosphorinane as an oil which boils at 120° under 40 Pa (Compound No. 1). After heating at the reflux temperature for 15 hours the precipitated hydrochloride is filtered off Evaporation of the filtrate

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

Procedure: A solution of 8.45 g of 2-chloro-5,5-dimethyl[1,3,2]dioxaphosphinane in 50 ml of toluene is added dropwise, in the course of 15 minutes and at a temperature between 20° and 30° C., to a solution of 28.65 g of 3,5-bis-[3',5'-ditert.-butyl-4'-hydroxybenzyl]-2,4,6-trimethylphenol and 25.3 g of triethylamine in 150 ml of toluene. The reaction mixture is heated under reflux for 24 hours. After cooling to room temperature, the residue is filtered off and the filtrate is evaporated to dryness. This gives 35 g of a colourless product having a melting point of 190° C. The reaction mixture is heated under reflux for 24 hours the residue is filtered off the filtrate is evaporated to dryness