SU1505950A1 - Method of producing 1-alkoxy-1,1-bis(dialkylphosphono)ethanes - Google Patents

Abstract

This invention relates to the chemistry of organophosphorus compounds with a C-P bond, in particular, to the preparation of 1-alkoxy-1,1-bis (dialkylphosphino) ethanes of the general formula [(R) ₂ P] ₂ C (OR ₁ ) CH ₃ , where R and R ₁ are lower alkyls of normal structure, which can be used as bidentate ligands, as well as for the synthesis of new phosphorus-containing heterocycles and biologically active substances. The goal is to develop a new method of obtaining new compounds. The synthesis is carried out by the interaction of dialkylphosphines with a trialkyl orthoacetate in the presence of 3-5 mol.% Of the catalyst - BF ₃ ^. (C ₂ H ₅ ) ₂ O at room temperature in an inert gas atmosphere, the trialkyl ortho-acetate being used in a 50-100% excess. Yield,%, b.p., ^C (mm Hg), gross formula: a) 51, 109 (1), C ₁₆ H ₃₆ OP ₂

b) 49, 131 (1), C ₁₈ H ₄₀ OP ₂

c) 60, 133 (1), C ₂₀ H ₄₄ OP ₂ . The method allows to obtain these compounds based on readily available products under mild conditions. 1 hp f-ly.

Description

The invention relates to the chemistry of organophosphorus compounds, namely to a method for producing new 1-alkoxy-1,1-bis (dialkylphosphino) ethanoB of the general formula

(RjP) C (O) CH3,

where R and R are the lower levels of normal structure,

and can be used as bidentate ligands in the preparation of various complexes with metal compounds, as well as for the synthesis of new phosphorus-containing heterocycles and methylenediphosphorus-containing compounds — new complexing agents: and extractants.

The aim of the invention is to develop a new, simple and universal process for the preparation of 1-alkoxy-1,1-bis (dialkylphosphino) ethanes.

The goal is achieved according to the method, in which diatylphosphine is reacted with trialkyl orthoacetate in

:P

l cd

31505

in the presence of a catalyst, boron trifluoride etherate, taken in an amount of from 3 to 5 mol.% of stoichiometry at room temperature in an inert gas atmosphere, and it is desirable to use trialkyl orthoacetate in a 50-100% excess of stoichiometry.

f

i

2R, PHMR 0), CCH,

20

25

thirty

() 4C (OR) CH3

de R and R are nioeshe alkyls normal- 5

it is built.

The catalyst of the process - boron etheretate etherate should be used in the amount of 3-5 mol.% Of stoichiometry. Smaller amounts of the analyzer lead to a dramatic reaction retardation, which significantly reduces the yield and complicates the process. Large amounts of catalyst lead to a significant increase in the rates of side reactions and the formation of inseparable mixtures of decomposition products of both target substances and starting compounds.

Carrying out the process at room temperature in an inert gas atmosphere avoids side processes and oxidation of both the starting and the target products.

It is advisable to use trialkyl orthoacetate in 50–100% excess of stoichiometry, which allows the process to be carried out quickly and maximally use dialkylphosphine. An increase in the excess of the trialkyl orthoacetate does not lead to an increase in the yield, and a decrease in the amount of the trialkyl orthoacetate reduces the yield of the target products.

The compounds obtained are stable liquids that are distilled at a lower pressure of 45 and can be stored in an inert gas atmosphere for a long time. The composition and structure of the target products are confirmed by the data of elemental analysis and NMR

 n, h, p.

All reactions and separations of the target products were carried out in a dry argon atmosphere using absolute reagents.

jg

55

PRI mme R 1. 1-ETOXI-1,1-bis (dibutylphosphino) ethane.

0

five

A mixture of 5.9 g (0.04 mol) of dibutylphosphine, 6.5 g (0.04 mol), 100% excess) of triethyl orthoacetate and 0.2 g (0.0016 mol, 4 mol.%) Of etherate boron trifluoride is stirred for 4 hours at room temperature, then distilled. 4.4 g of compound are obtained, yield 60%, m.p. 133 C (1 mm Hg).

HMR spectrum: 8 (, CHj), 0.72-1.82 MD, m, 42H; S () 3, A5m.d., K, Ptsn 7 Hz.

NMR С: О () 60.27 ppm, t, 1 7.6 Hz; S (PCP) 79.27 ppm, t.

five

0

50

Calculated,%: C, 66.26; H 12.33; P 17.09.

Example 2. 1-Ethoxy-1,1-bis (dipropylphosphino) ethane.

Analogously to Example 1, out of 5.8 g (0.049 mol) of dipropyl phosphine, 6.8 g (0.042 mol, 70% excess) of triethyl orthoacetate and 0.3 g (0.00245 mol, 5 mol.%) Of boron trifluoride etherate are obtained 3 , 8 g of compound, yield 51%, t. Kip. 109 C (1 mm Hg).

PMR spectrum: S (CH,) 0.75-2.01 MD, m, 34H; 5 () 3.48 ppm, K, 7 Hz, 2H.

 C: U (CH, 0) 60.07 MD, t, P „„ 7.01 Hz; S (PCP) 78.96 ppm, t, 28.1 Hz.

 R: So - 13.23 MD, p.

Found,%: C 62.58; H 11.95; R 20.59.

C. “NlOR,

C 62.72; H 11.48;

pc

PC NMR

Mb. Calculated, R 20,22.

PRI mme R 3. 1-Butoxy-1,1-bis (dipropylphosphino) ethane.

Analogously to Example 1, out of 6.5 g (0.055 mol) of dipropyl phosphine, 10.1 g (0.041 mol, 50% excess) of tributyl orthoacetate and 0.2 g (0.00165 mol, 3 mol.%) Of boron trifluoride etherate 4.5 g of compound are obtained, yield 49%, b.p. (1 mm Hg).

PMR spectrum: Y (H-CjH, CH,) 0.85-2.05 MD, m, 38H; J () 3.66 ppm, g. 1 "n 6 Hz, 2H.

NMR R: (Ur - 11.25 MD, p.

Found,%: C 64.71; H 12.21; P 18.19. ,

- “and W ORA

C, BH

Calculated,%: C 6A, 6A; H 12.05; P 18.52.

PRI me R 4. 1-Ethoxy-1,1-bis (dibutylphosphino) ethane.

AnsGrogly Example 1 of 3.8 g (0.026 mol) of dibutylphosphine, 2.1 g (Oj013 mol, no excess) of triethyl orthoacetate and 0.1 g (0.00065 mol, 5 mol.%) Of boron trifluoride etherate are obtained , 2 g of compound, 25Z yield, physicochemical constants are given in Example 1.

Thus, the proposed method of obtaining the desired products allows to obtain these compounds in a yield of up to 60% based on the readily available dialkyl |} yusphins and trialkyl orthoacetate with various substitutions of normal structure. The mild process conditions (room temperature, lack of solvents and precipitation) make the proposed method preparative and easily reproducible.

1505950

F o

rmula of invention

1. Method of producing 1-alkoxy-1,1-bis (dialkylphosphino) ethanes of the general formula

() 2С (ОК) СНд,

where R and R are the lower alkyls of normal structure,

that is, dialkylphosphine is reacted with trialkyl orthoacetate in the presence of a catalyst, boron trifluoride etherate, taken in an amount of 3 to 5 mol% of stoichiometry at room temperature under an inert gas atmosphere.

2. The method of Claim 1, wherein the trialkyl ortho-acetate is used in a 50-100% excess of stoichiometry.

Compiled by L. Karunina Editor N. Gun'ke Tehred M. Khodanych

Order 5390/25

Circulation 338

VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab., A / 5

Production and publishing plant Patent, Uzhgorod, st. Gagarin, 101

Proofreader O.Iiple

Subscription

Claims (2)

Claim 1. The method of obtaining 1-alkoxy- 1,1-bis (dialkylphosphino) ethanes of the general formula (R ₁ P) _i C (0R ') CH ₃ , I where R and R are lower alkyls of normal structure, consisting in the fact that dialkylphosphine is reacted with trialkyl orthoacetate in the presence of a catalyst, boron trifluoride etherate, taken in an amount of 3 to 5 mol% of stoichiometry at room temperature in an inert gas atmosphere. 2. The method according to claim 1, which consists in the fact that trialkyl orthoacetate is used in a 50-100% excess of stoichiometry.