DE1012611B - Process for the production of nuclear chlorinated phenoxyethyl phosphites - Google Patents

Description

Process for the production of nuclear chlorinated phenoxyethylphosphites These The invention relates to a process for the production of nuclear chlorinated phenoxyethyl phosphites. These substances are new and can be given by the general formulas (ROC.H40) 2P-OH and (ROC.H40) 3P, where R is a chlorine-substituted phenyl radical represents.

The compounds can be prepared according to the invention if 1 mole of phosphorus trichloride with 3 moles of the selected chlorophenoxyethanol in an inert solvent, such as. B. benzene, xylene, or can react in a chlorinated hydrocarbon solvent. The diphosphites are formed in the absence of an acid acceptor, as represented by the following equation: 3ROC.H40H -I- PC13 - + _ - @ (ROC, H40) 2P-OH ± ROC2H4C1 -I- 2HC1 If an equivalent amount of a tertiary amine such as B. pyridine or dimethylaniline, is used as the acid acceptor, then a triphosphite is formed as shown in the following equation: 3ROC., H40H -f- 3C5H5N -I- PCl3 - # - - + - (ROC2H40) 3P -f- 3C5H5N-HCl The practical implementation of the claimed process is shown in the following examples.

Example 1 Preparation of tri- [ß- (2,4-dichlorophenoxy) ethyl] phosphite To a solution of ß- (2,4-dichlorophenoxy) ethanol (63 g = 0.304 mol) and pyridine (25 g = 0.316 mol) in 75 cm3 benzene was a solution of P C13 (13.7 g = 0.10 mol) in 75 cm3 of benzene added dropwise. The mixture was thoroughly stirred at the same time and kept the temperature below 20 ° C, which was achieved by cooling in an ice bath became. Immediately after the addition began, the pyridine chlorohydrate began to precipitate. After the addition was complete, stirring was continued for half an hour. Of the Precipitate was filtered and washed with an additional amount of benzene. The combined filtrates were collected under reduced pressure (0.53 mm) and a bath temperature concentrated from 1.35 ° C. The yield was 98% (64.8 g) and consisted of a viscous one colorless liquid. Refractive index n10 1.5875. Analysis: Theory 32.8% Cl and 4.78% P; found 32.17% Cl and 4.95 0 / a P. Example 2 Tri- [ß- (4-chlorophenoxy) ethyl] phosphite was prepared by the same method as described in Example 1 is, produced, only that the glycol monoether fl - (4 - chlorophenoxy) - ethanol (53 g = 0.307 moles) was used. The filtrate was at a bath temperature of 165 ° C / 0.65 mm concentrated. Yield 95%. Refractive index n "1.5717. Analysis: Theory 19.5'0 / 9C1 and 5.68% P, found 18.8% Cl and 6.08% P.

In the production of other triphosphites according to the invention worked according to Example 1, only that 0.3 mol of another, selected chlorophenoxyethanol was used. The special chlorophenoxyethanols mentioned in all of these Examples used were prepared in the conventional manner by reacting the selected chlorophenol produced with ethylene oxide. The yields, refractive index and analytical data of other triphosphites are as follows: Tri- [ß- (2,4,5-trichlorophenoxy) ethyl] phosphite. Refractive index n2D 1.5920. Analysis: theory 4.121 / o .P and 42.4% Cl; found 4.35% P and 40.94% Cl. Example 3 Preparation of di- [ß- (2,4-dichlorophenoxy) ethyl] phosphite ß- (2,4-Dichlorophenoxy) ethanol (62.1 g = 0.3 mol) was dissolved in 50 cm3 of benzene. A rapid stream of C 02 was initiated and cooled in an ice bath to solution P C13 (13.75 g = 0.1 mol) was added dropwise so that the temperature did not rise above 20 ° C. The introduction of CO 2 was continued for about 2 hours. During this time the temperature was maintained at approximately 0 ° C. The reaction mixture was first concentrated under reduced pressure with the aid of a water pump and finally fractionally distilled at 105 ° C / 0.4 mm (bath temperature of 170 ° C). After 20.3 g of a first run, 47.9 g of a viscous, colorless liquid were obtained obtain. The refractive index n "is 1.5738. Analysis: Theory 30.81 / o Cl and 6.750 / 0 P; found 30.8% Cl and 6.78% P.

In the preparation of other diphosphites according to the invention was worked according to the above method, only 0.3 mol of the corresponding chlorophenoxyethanol were used. The yields were quantitative. Refractive Index and Analytical Data were as follows: Di- [ß- (4-chlorophenoxy) ethyl] phosphite. Analysis: theory 18.1% Cl and 7.91% P; found 18.17% Cl and 7.98% P.

Di- [ß- (2,4,5-trichlorophenoxy) ethyl] phosphite. Refractive index nope 1.5907. Analysis: Theory 40.204C1 and 5.86'0 / 9P; found 39.5% Cl and 5.91% P.

The nuclear chlorinated phenoxyethyl phosphites of the present invention are effective Plant growth regulators.

Claims (1)

PATLNTANSPRUGII: Process for the production of nuclear chlorinated phenoxyethyl phosphites of the general formulas (R O C2 H4 O) 2 P-0 H or (R O C2 H4 O) 3 P, in which R denotes a chlorine-substituted phenyl radical, characterized in that in on known way 3 moles of a nuclear chlorinated phenoxyethanol in the presence of a inert solvent are reacted with 1 mole of phosphorus trichloride, in the case of the preparation of the triester the reaction in the presence of a tertiary amine than Acid acceptor is carried out.