SU1715811A1 - Method for the synthesis of n-disubstituted 0,0,0,0-tetraethylaminomethylene-diphosphonites - Google Patents

Abstract

The invention relates to the chemistry of organophosphorus compounds, in particular the preparation of N-disubstituted 0,0,0,0-tetraethylaminomethylene diphosphonites of the general formula (C2Hs02) P 2CH-NRR, where R is the lowest alkyl, or (R) 2 group - (CH2) s- or - (CH2) 2- 0- (CH2) 2-, - semi-products for the synthesis of phosphorus-containing heterocycles or as polyadent ligands in complexes with metal compounds. The goal is to create a new method of obtaining new substances of the specified class. Synthesis is carried out by the reaction of 0,0-diethylpivaloylphosphonite with N-disubstituted amino diethoxy methane in ethanol at 100-130 ° C in the presence of a zinc chloride catalyst, in an amount of 2-5% of stoichiometry, in an inert gas atmosphere. 1 hp ff.

Description

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WITH

This invention relates to the chemistry of organophosphorus compounds, namely, to new methods for the preparation of new N-disubstituted 0.0.0.0-tetraethylamino-methylenediphosphonites of the general formula

(C2H50) 2P 2CHNR2

ABOUT)

where R is lower alkyl or 2R is (CH2) 5 or (CH2) 20 (CH2) 2.

Compounds (I) include an R-C (N) -R fragment and can be used as polydentate ligands in the preparation of

2 (C4H90) 2PH - KC4H90) 2PbCHN (CH3) 2

various complexes with metal compounds, as well as intermediates for the synthesis of new phosphorus-containing heterocycles; phosphoric analogues of amino acids, new complexing agents and extractants, biologically active compounds.

The compound 0,0,0,0-tetrabutyldimethylaminomethylene diphosphonite is obtained by reacting dibutoxyphosphine with dimethylamino (dimethoxy) methane at 120 ° C in an inert gas atmosphere with a yield of 62%.

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The proposed method provides the yield of the target products () up to 77% on the basis of readily available reagents with various substitutes for nitrogen nitrogen, including cyclic structure. The presence of ethoxyl admixtures in the atom of Phosphorus makes the target products (0 especially valuable intermediates of elemental synthesis. Gog.1Ge1-; wear and tear w insignificant amount of organic solution /: - ethanol, provide the processability and reproducibility of the method The proposed method is the basis: -; NU of the original and unexpected reaction: for the first time, it is possible to carry out the emulation of OO Dis-pylpizaloylphosphoi - with the disconnection of the Р-С connection in the initial connections and the PC Fragment (NVP in the target products ah (}.

It is about heating and dosing from 100 to 130 ° C to ethanol, which ensures the homogeneity of the medium. At lower temperatures, the speed of proc s and a dramatically slows down the yield of the target products decreases: at higher temperatures, a decrease in the yield is observed due to decomposition of the initial reagents –l of the target products t about a

The catalyst of the process is zinc chloride, must be used in an amount of from 2 to 5 mol.% Of stoichiometry. Smaller amounts of the catalytic agent lead to a significant slowdown in the reaction with pzdzheniyu the yield of target products, the large number of CL 3 o -humps leads to a significant decrease in the yield of the target: health outcomes of the original

compounds and the occurrence of side processes.

The inert gas atmosphere avoids hopping of the source and target products and ensures the activity of kata-: and; 5 fire.

N-Displaced zmino (diethoxy) mV-hg is better used in 10-20% of the Tite from stoichiometry. Increase in excess: -: Egfizodit to increase the yield of the target; x products, h reducing the excess reduces the yield of target products (i).

The compounds obtained () are stable, colorless liquids, and distillation, it can be stored in an argon atmosphere for a long time without change. The composition and structure of the target products () psdgyeO Kdeny by elemental analysis data and NM: 1H, 13C, 31P,

All reactions and the isolation of the target products () are carried out in a dry argon atmosphere using absolute reagents and solvents,

PRI me R 1. 0,0,0,0-Tetraethyldimethymeminomethyl versus phosphonite (la).

A mixture of 6 g (0.0291 mol), 0.0-diethyl piva-psiflofonite, 2.5 g (0.0171 mol, 20% excess) dimethylam / 1 (diethoxy) methane. ml of ethanol and 0.04 g (2.93 mol, 2 mol.%) of zinc chloride are kept at 100 ° C with distillation of light substances for; , 5 h, then distilled. 3.3 g of co-reactions are obtained (a).

Yield 77%, i.e., 90 ° C (1 mm Hg).

Fragment PCHP: bn 3.19 ppm, t., 2JpH 42 Hz; bs 74.1D ppm, t., 1Jpc 31.09 Hz: d-f 186.7 orgl,

Found,%: C 44.01; H 9.03; R 20.91.

C11H27N04P2Calculated,%: C 44.15; H 9.01; R 20.70.

PRI me R 2, 0,0,0,0-tetraethyldmpropilzminomethylene and amphosphonite (16).

Analogously to Example 1, out of 5.8 g (0.0281 mol) of 0.0-dmztilpivaloylphosphonite, 3.2 g (0.0159 mol, 15% excess) of dipropylamino (diethoxy) methane, 2 ml of ethanol and 0577 g (4.2-10 mol, 3 mol,%) of zinc chloride at a process temperature of 130 ° C, 3.4 g of compound (16) are obtained.

Yield 72% b.k. 102 ° C (1 mm Hg).

Fragment PCHP: bn 3.40 ppm, t., 2Jpn 3.30 Hz; ds 71.90 ppm, t., 1Jpe 29.84 Hz; 6p 187.5 ppm.

Found,%: C 50.55; H 9.89; R 17.16,

C15H35N04P2.

Calculated,%: C 50.69; H 9.93; R 17.33.

Example 0,0,0,0-Tetraethylpiperidinomethylenediphosphonite (c).

Analogously to Example 1 of 5.8 g (0.0281 mol) of a 0.0-distilpivaloyl phosphate phonite, 3 g (0.016 mol, 15% excess) of piperidino (diethoxy) methane, 1.5 ml of ethanol and 0.076 g (5.61 mol, 4 mol.%) zinc chloride at a process temperature of 120 ° C. get 3.4 g of compound (c).

Yield 71% b.k. 10b ° C (1 mm Hg).

Fragment PCHP; d 3.16 ppm., t., 2JpH 3.73 Hz; (5c 75.48 ppm., M., LRS 31.67 Hz; dp 184.7 ppm.

Found,%: C 49.64; H 9.18; R 18.43.

C14H311 04P2 (

Calculated,%: C 49.55; H 9.21; R 18.25.

PRI me R 4. 0,0,0,0-tetraethylmorpholino methylene diphosphonite (g).

Similar to Example 1 of 5.3 g (0.0257 mol) of 0.0-diethylpivaloylphosphonite, 2.6 g (0.0134 mol, 10% excess) of morpholino (diethoxy) methane, 1.5 ml ethanol and 0.087 g (6 mol, 5 mol.%) zinc chloride at a process temperature of 110 ° C get 3.2 g of compounds (I g).

Yield 71% b.k. 116 ° C (1 mm Hg).

Fragment PCHP; bottom 3.06 ppm., t., 2JpH 4.73 Hz; c5s 74.65 ppm., t., 1Jpc 31.47 Hz; dr 185.1 ppm .. Found,%: C 45.81; H 8.56; R 18,32.

C13H29NCMP2

Calculated,%: 45.75; H 8.56; P 18.15.

Approx. 5. 0,0,0,0-Tetraethyldimethylaminomethylene diphosphonite (la).

Analogously to example 1 of 6 g (0.0291 mol) of 0,0-diethylpivaloylphosphonite, 2.1 g (0.0145 mol, no excess) of dimethylamino (diethoxy) methane, 2 ml of ethanol and 0.04 g (2, 93 -10 mol, 2 mol.%) Zinc chloride at a process temperature of 100 ° C get 2.8 g of compound (la), yield 65%, physicochemical constants are the same as in example 1.

Thus, the proposed method allows to obtain the desired products (I) in high yields, is simple, does not require complex instrumentation and, if necessary, can be used to obtain products (I) of various structures - semi-organophosphorus synthesis products, unusual phosphorus analogs of amino acids .

The method is an example of creating a fragment of P-C (N) -P on the basis of the original aminomethylenation of 0,0-diethylpivaloylphosphonite, which is accompanied by rupture of the P – C bond and the preservation of the three-coordinated phosphorus atom.

Claims (2)

1. Method of obtaining N-disubstituted 0,0,0,0-tetrazethylaminomethylene diphosphonitol of the general formula (C2HsO) 2PbCHNRR. where R is lower alkyl or 2R is (CH2) 5 OR (CP2) 20 (CH2) 2. DIFFERENT in that 0,0-diethylpivaloylphosphonite is reacted with M-disubstituted amino (distoxy) methane formulas {C2H50) 2CHNRR, where R has the indicated values in ethanol at a temperature of from 100 to 130 ° C in the presence of a catalyst, zinc chloride, taken in an amount of 2-5 mol.% of stoichiometry, in an inert gas atmosphere. 2. A method according to claim 1, characterized in that N-disubstituted amino (diethoxy) methane is used in a 10-20% excess of stoichiometry.