SU1097632A1 - Process for preparing biphosphorylated vinylalkyl esters - Google Patents

Abstract

1. METHOD FOR OBTAINING BISPHOSPHORIZED VINIPALKYL ETHERS OF THE GENERAL FORMULA GR2R-CH C (oR "| pi 2x; alkoxyacetylene at a temperature of minus 35 to plus in an inert organic solvent medium in an inert gas atmosphere 2. Method POP.1, consisting in that diethyl or petroleum ether is used as an inert organic solvent

Description

110 The invention relates to the chemistry of organophosphorus compounds with a C-P bond, namely to a new method for producing bisphosphorylated vinyl alkyl esters of the general formula C (,, (; where R is ethyl, isopropyl R is alkyl., X is chlorine, bromine, iodine. These compounds are not described in the literature, are new and can be used as intermediates for organophosphorus synthesis. There is a known method for obtaining bisdiethylphosphinoethylene by hydrogenation of bisdiethylphosphinoethine over a nickel-Rene catalyst in ethyl alcohol at atmospheric pressure. The target product is 57% f1. There is also known a method for producing bisdiphenylphosphinoethylene by reacting diphenylphosphide lithium with 1,2-dichloroethyshenane when heated in tetrahydrofuran, the yield of the desired product is 80% 2. The same method was used to obtain bisbutylphosphinoethylene (25%) 3. Compound, containing two phosphorus atoms of different coordination (bisdibutylphosphine ethylene monoxide), obtained in two ways: by addition of dibutylphosphine to dibutyltintilene phosphine oxide in a sealed ampoule at 150160 C for 24 hours (22% yield) or V, / (.IV-AliIAV. r lb "./a / attachment of dibutylphosphorous acid to dibutylethynylphosphine in the presence of azobisisobutyronitrile (a radical addition catalyst) in a sealed ampoule at 110 ° C (17% yield) 23. Also known is a method for producing monophosphorylated vinylalkyl ether in zymellane zymete 17% 23. esters, followed by the decomposition of the resulting complex with sulfur dioxide or acetic acid 4. However, all these methods do not allow the proposed bi-phosphorylated vinylalkyl esters to be obtained and ry. The purpose of the invention is the development of an accessible general method for the synthesis of compounds of a new type — the bisphosphorylating vinyl alkyl esters of 1-alkoxy dialkylphosphinoethenyl diphyl halophosphonium halides. 2 The goal is achieved according to the method for preparing bisphosphorylated vinylalkyl ethers of the general formula (1), which consists in reacting the dihydrohalphosphine with terminal alkoxyacetylenes at minus 35 to plus 25c in inert organic solvent in an inert atmosphere. As an inert organic solvent, it is desirable to use diethyl or petroleum ether. The proposed method is not described in the literature and allows obtaining new types of organophosphorus compounds of bisphosphorylated vinyl alkyl ethers. Production of bisphosphorylized vinyl alkyls values, and is the first example of the conjugate addition of di, alkylhalogenophosphines in multiples of s. The reaction follows the ur vneny regardless of the number of alkoksiatsetilena taken, i.e. with a dialkyl halophosphine: alkoxy acetylene ratio of 1: 1 (i.e., a two-fold excess of alkoxy acetylene), the same desired product is formed, and apkoxy acetypene is returned unreacted. The selected temperature range is due to the fact that at a temperature below minus the reaction rate is small and, therefore, the use of lower temperatures is impractical, while at-temperatures above the target products are decomposed and rearranged. The target products are low-melting crystalline compounds or oils that are stable when stored in the absence of moisture and oxygen of the air for a long time do not change. The data of elemental analysis, IR, PMR, NMR and P-spectroscopy confirm the composition and structure of the target products. All reactions are carried out in an inert gas (dry argon) atmosphere in absolute solvents. Example 1. To a solution of 4.5 g (0.02 mol) of diisopropyl iodophosphine in 30 ml of absolute diethyl ether, cooled to minus 35 ° C, a solution of 0.9 g (0.013 mol) of ethoxyacetylene is added dropwise with stirring in 10 ml of diethyl ether. The reaction mixture is stirred at this temperature for 10 minutes, the temperature is raised to room temperature, the precipitated precipitate is decanted, rinsed with 10 ml of diethyl ether, dried in a vacuum desiccator, 5.5 g (quantitatively) of 1-ethoxy-2-diisopropylphosphinoethenyl diisopropyl iodophosphonium iodide are obtained ( J), m.p. 84-85 ° C. Example 2. To a solution of 1.2 g (0.012 mol) of butoxyacetylene in 25 m of absolute petroleum ether, cooled before, while stirring, adding 81 t of dropwise within 10 min a solution of 4.5 g (0.02 mol) of diisopropyliodophosphine in 15 ml absolute petroleum ether. The temperature of the reaction mixture was raised to room temperature. The precipitated precipitate was decanted by washing with 10 ml of petroleum ether, dried in a vacuum desiccator, and 5.8 g (quantitatively) of 1-butoxy-2-diisopropylphosphinoethenyl diisopropyl iodosphonyl iodide (P) was obtained, mp. 80-81 ° C. Example 3. To a solution of 0.8 g (0.012 mol) of ethoxyacetylene in 10 ml of diethyl ether at 20–25 ° C with an intensive stirring, a solution of 4.0 (0.02 mol) diisopropyl bromophosphine in 20 ml of diethyl ether. The reaction mixture is stirred at this temperature for 3-4 hours, the precipitated precipitate is decanted, washed with 10 ml of diethyl ether, dried in a vacuum desiccator, 4.6 g (quantitatively) of 1-ethoxy-2-diisopropylphosphinoethenyl diisopropyl bromophosphonium bromide (III) are obtained. square 78-79 ° C. Example 4. To a solution of 4.6 g (0.03 mol) of diisopropyl chlorophosphine at 25 ° C and stirring, a solution of 2.0 g (0.02 mol) of butoxyacetylene in 10 ml of diethyl ether. The reaction mixture is stirred at this temperature for 48 hours, the solvent is distilled off in vacuo, to obtain 6.0 g (quantitatively) of 1-butoxy-2-diisopropylphosphinoethenyldiisopropylchlorophosphonium chloride (iv), in the form of a non-crystallizing oil. Example 5. To a solution of 1.7 g (0.03 mol) of methoxyacetylene in 50 ml of petroleum ether, cooled to minus 20 ° C, a solution of 6.45 g (0.03 mol) is added dropwise with stirring over 15 minutes. a) diethyl iodophosphine in 50 ml of petroleum ether. The reaction mixture is stirred at this temperature for 15 minutes, the temperature is raised to room temperature, the precipitated precipitate is decanted, washed. twice with 10 ml of petroleum ether, dried in a vacuum desiccator, 7.2 g (quantitatively) of 1-methoxy-2-diethylphosphinoethenyl diethyl iodophosphonium iodide (V) are obtained, mp. 92 C. The data of elemental analysis, IR and NMR spectroscopy of the compounds obtained are given in Tables 1 and 2. Table 1

Compound (iso.SD) RS (H) C (.JI {ieo-SzN) (M3 -CjHj2PC (((J .. II ("-CjH-tlj, tg Вг -с., (((G, ( SzN)

Found,%;

M.p.

Yield,% D1T 84-5 34.79 6.34 Amount. 80-1 36.91 6.20 Colich. 78-9 41.42 7.30 Colich.

se

/

VIII (C Hjl P HIzCioc H-HlP cr Quant.

)

IX (., RS (H) C () P g- Kolich.

(from-SzN)

Continued table. one

48.49

8.65

43.77

7.76

I +

(sec), (

n

((sns), 2

 5.43 N OCHjCH CH CM

,,, ((%%., 01

IIIc CBr °° 1

N. OtHjCHj

, ce +

IV (C "32C 2Pv (CH3), 6.22

WITH .

H OCH2CHN CHCH

V () 2Px ,, () 2- ,. . 5.21

n ozn se

VI WjCHj P (CH3), 26

with cr /

- n OS2SNz (CH.eH.ljPv Р (СН2СНз) 2 n «vi .. (CHjCH IjP Р (СН2СНз), нOCHjCHjjj (CH, y, j51.0

n

table 2

5,36О19,04,48 3,0

o19,04,37 2,0

1.3 26.04.55 3.0

1.5 28.34.42 3.0

1.0 20.04.08

1.5 27.54.46 3.0 5.95 1.0 25.04.58 2.0 2.0 28.04.40 2.0 27.04.40 2.0

- Compounds VI -tX are prepared analogously (Tables 1 and 2).

Thus, the inventive method allows to obtain compounds not previously described in high yield. The method is simple and does not require complex instrumental etching. The resulting organophosphorus compounds contain two phosphorus atoms in one molecule, which makes it possible to use the target products as starting compounds for the preparation of a number of

derivatives (for example, phosphine oxides), possessing high complexing ability and interest as potential complexones and flotation reagents. In addition, the target products are functionally saturated compounds and as a result, they can be considered as useful intermediates in the synthesis of new types of organophosphorus compounds containing three- and four-coordination coordinating phosphorus.

Claims (2)

1. METHOD FOR PRODUCING BISPHOSPHORILATED VINYPALKYL ETHERS of the general formula [r ₂ p-ch = p ₽ ₂ xjx- ₍ where R is ethyl, isopropyl; - alkyl C ₄ ~ C ₄ , X is chlorine, bromine, iodine, including that dialkylhalogenphosphine is reacted with terminal alkoxyacetylene at a temperature of minus 35 to plus 25 ° C in an inert organic solvent in an inert gas atmosphere. 2. The method of pop. 1, concluding with the fact that diethyl or petroleum ether is used as an inert organic solvent. SU .. "1097632