SU1735304A1 - Method for producing (dimethylalkosilyl)methyl phosphonites or diamidophosphonites - Google Patents

Abstract

Use: as intermediates for the synthesis of graft catalysts. SUMMARY OF THE INVENTION: Product: (dimethyl / ethoxy / silyl) methyl / di / iso / propyl / phosphonite (CH3) 25 (OC2H5) CH2P (OSNH7-, yield 63%, bp 73-74 ° C 1.5 mmHg, d420 0.9245. (Dimethyl / iso / propoxy / silyl) methyl / di / ethyl / phosphonite. (CH3) 25 (OSSH7-ISO) -CH2P (OC2H5) 2, OUTPUT 67%, bp 82-84 ° C 3 mmHg, d4 0.9252, (Dimethyl / ethoxy / silyl) meth, silt / tetra / ethyl / d and / amido / phosphonite ((OC2H5UNH2RCHKS2N5Y2 47% yield, bp 83-84 ° C 1 mmHg, 0.9959. Reagent 1: (CH3) 2Si (OR) CH2CI, where R is the primary or secondary alkyl. Reagent 2: Magnesium. Reagent 3: X2PCI, where X is an alkoxy or dialkylamino group. Reaction conditions: in medium tetra agidrofurana at minus 78- 0 °.. C 5 straight CO

Description

This invention relates to the chemistry of organophosphorus compounds, and specifically to a process for the preparation of (dimethyl alkoxy silyl) methylphosphonites and diamidophosphonites of the general formula

M62SiCH2PX2

/

OR

where R is primary or secondary lower alkyl;

X is an alkoxy or dialkylamino group.

(Dimethylalkoxysilyl) methylphosphonites and diamidophosphonites of the indicated general formula are new compounds, a characteristic feature of which is the presence of a reactive alkoxy group on the silicon atom, which makes it possible to use them, like so- grafted catalysts. The presence of the tri-coordinated phosphorus atom in these compounds, as well as the reactive alkoxy and dialkylamino groups at this center, makes it possible to use the above-mentioned phosphonites and diamide phosphonites as synthons to create new silicon phosphorus-containing monomers and polymers with valuable properties, as well as new coupling compounds .

The known method of synthesis of (dimethylalkoxysilyl) methyl-substituted phosphines from dimethylalkoxychloromethylsilane and the corresponding lithium phosphide is not suitable for the preparation of phosphonous derivatives

V | WITH SL 00

g

acids, since phosphides like (AlkO) aPI-l and (Alk2N) 2PLi do not exist.

The purpose of the invention is to develop a method for producing (dimethyl alkoxysilyl) methylphosphonites and diamidophosphonites of the indicated general formula, which are promising for use in various fields of technology.

The goal is achieved by the fact that from dimethylalkoxychloromethyl silane and magnesium, boiling in tetrahydrofuran is used to obtain a Grignard reagent of the type

Me2SiCH2MgCI

I OR

followed by the interaction of this organomagnesium compound with dialkyl or tetraalkyldiamidochlorophosphite at a temperature of from -78 to 0 ° C and a 1: 1 ratio of reagents in a solution of tetrahydrofuran in an inert gas atmosphere.

The Grignard reagent used, which contains an alkoxyl group at the silicon atom, is stable and interacts with such strong electrophilic reagents, as chlorophosphites and diamido-chlorophosphites, only at the carbon atom. The reaction of phosphonous acid chlorides at the oxygen center of the Grignard reagent, leading to the formation of trialkylphosphites or diamidoalkylphosphites, practically does not occur under these conditions. Carrying out the process at a lower temperature is impractical because it does not lead to an increase in yield and is difficult technically. At higher temperatures, the yield of the target products falls due to side reactions.

Example 1. (Dimethylethoxysilyl) methyl diisopropylphosphonite.

To 1.2 g (0.05 g-at) magnesium chips in 250 ml of absolute tetrahydrofuran (THF), 7.63 g (0.05 mol) of dimethyl ethoxychloromethylsilane and a crystal of iodine are added and the mixture is boiled under reflux at stirring for 3 hours. The process is carried out in an inert gas atmosphere. After dissolving the magnesium, the reaction mixture is cooled to -20 ° C and 9.23 g (0.05 mol) of diisopropylchlorophosphite is added over 0.5 h. The mixture was stirred at the same temperature for 1 h, then THF was distilled off, the precipitate was extracted with hexane (3 x 100 ml) and centrifuged. Hexane is distilled off, the residue is distilled in vacuum. Yield 8.38g (63%); Bp 73-74 ° C / 1.5 mm Hg; her 20 0.9245.

NMR31R d, ppm: 180.4.

0

five

0

5 0 5 0

5 0 5

NMR13 C- {1H} (d, ppm): 0.61 (d, 3J (PC), 3.40 Hz, (CHafeSi); 16.91 (s, CH3CH2); 25.02 (d, 3J (PC) 4.60 Hz, (); 26.13 (d, 1J (PC) 29.78 Hz, SiCH2P); 58.25 (s, CH20); 70.30 (d, 2J (PC) 16 , 07 Hz, CHO).

Found,%: C 49.17; H 10.11.

CnH2703PSi.

Calculated,%: C 49.62; H 10.15.

Example 2. (Dimethylethoxysilyl) methyl diisopropylphosphonite.

Grignard reagent is prepared analogously to example 1 from 0.05 g-at mg of magnesium and 0.05 mol of dimethylethoxychloromethyl silane. After the solution was cooled to -78 ° C, 9.23 g (0.05 mol) of diisopropylchlorophosphite was added over 0.5 h, after which the synthesis was carried out as described in Example 1.

Yield 7.32 g (55%). Physico-chemical constants and data of NMRR spectra and C- {H} are given in example 1.

Example 3. (Dimethylethoxysilyl) methyl diisopropylphosphonite,

To a solution of 0.05 mol (dimethylethoxysilyl) methylmagnesium chloride, obtained in the same way as in Example 1, 9.23 g (0.05 mol) of diisopropylchlorophosphite was added at 0 ° C for 0.5 h, after which the synthesis was carried out the method of example 1. The output of 6.26 g (47%).

Physico-chemical constants and spectral characteristics shown in example 1.

Example 4 (Dimethylisopropoxysilyl) methyldichylethylphosphonite.

(Dimethylisopropoxysilyl) methylmagnesium chloride is obtained in a manner similar to that described in Example 1 from 1.2 g (0.05 g-at) magnesium and 8.33 g (0.05 mol) of dimethyl isopropoxychloromethyl-silane. Then the solution is cooled to -20 ° C, 7.83 g (0.05 mol) of diethylchlorophosphite is added over 0.5 h and the product is isolated according to the procedure of Example 1. Yield 8.34 g (67%). Bp 82-84 ° C / 3 mmHg); d2 ° 4 0.9252.

NMR31P ((3, ppm): 184.3.

NMR295 (d, ppm): 4.774 (2J (Si) 14.76 Hz.

NMR 13C- {1H}. (d, ppm): 1.21 (d, 3H (PC) 2.94 Hz, (CH3) 251); 17.74 (d, 3J (PC) 5.90 Hz, CH 3 CH 2); 25.55 (d, 1J (PC) 35.19 Hz, SICH2P); 26.45 (s, (CH3HCH); 62.33 (d, 2J (PC) 13.58 Hz, CH2OP); 65.14 (s, CHO). Found:% C 4734; H 9, 57.

CioH2503PSi.

Calculated,%: C 47.62; H 9.92.

Example 5 (Dimethylethoxysilyl) methyl tetraethyl diamidophosphonite.

The synthesis is carried out analogously to example 1, but 10.53 g (0.05 mol) of tetraethyl diamido chlorophosphite are added to the Grignard reagent solution cooled to -20 ° C. Exit 6.87

g (47%). 0.9959.

Bp 83-84 ° C / 1 mm Hg; d4

.20

flMPJ1P d, ppm: 108.1.

NMR 13C- {1H} d, ppm: -0.28 (d, 3J (PC) 5.38 Hz, (CH3) 250; 1.17 (s, CH3CH2N); 17.60 (d, 1J (PC) 25.45 Hz, SiCH2P); 19.04 (s, CH3CH20); 42.62 (d, 2H (PC) 16.79 Hz, CH2N); 58.25 (s, CH20).

Found,%: C 53.17; H 11.19.

С1зНззМ2ОР51

Calculated,%: C 53.42; H 11.30.

Thus, the proposed method for the synthesis of (dimethyl alkoxysilyl) methyl dialkyl phosphonites and diamido phosphonites based on (dimethyl alkoxysilyl) methyl mg chloride and the corresponding chlorophosphite or diamine dochlorophosphite allows obtaining, with yields up to 67% of readily available starting materials, promising monomers for the monomers created for the monomers created for the projects. heterogeneous catalytic systems including phosphonite and diamidophosphonite phosphorus atoms.

Claims (1)

Invention Formula The method of obtaining (dimethylalkoxysilyl) methylphosphonites or diamidophosphonites of the general formula .20 (СН3) 281СН2РХ.г OR where R is primary or secondary lower alkyl; X is an alkoxy or dialkylamino group, in which dimethylalkoxychloromethylsilane is reacted with magnesium in tetrahydrofuran medium at boiling to form an organomagnesium compound of the general formula (СН3) 281СНгКдС1 OR they are treated with dialkyl- or diamido-chlorophosphite of the general formula X2PC1, where R and X have the indicated values, with the equimolar ratio of the reactants in tetrahydrofuran medium at a temperature of from -78 to 0 ° C in an inert gas atmosphere.