SU1659416A1 - Method for obtaining n,n-tetrasubstituted o-trimethylsilylbis-(aminomethyl) phosphinates - Google Patents

Abstract

The invention relates to organometallic compounds, in particular, the preparation of NN-tetrasubstituted 0-trimethylsilylbis (aminomethyl) phosphinates of the formula (CH3) 3SiOP (0) CH2NRR fe, where R-R1 is lower alkyl or R is methyl R is acetyl or R and R is (CHa) s or (CH2) C (O), which can be used in the synthesis of phosphorus-containing compounds. The goal is to simplify the process and expand its scope. The preparation is carried out by the reaction of bis- (trimethylsiloxy) phosphine with M-disubstituted chloromethylamine in the form of CICH2NRR, where R and R are indicated, at a molar ratio of 1: 2 under an inert gas atmosphere, in an organic solvent in the presence of triethylamine (preferably in 5-10% excess of stoichiometry) at room temperature. 1 hp f-ly.

Description

This invention relates to the chemistry of organophosphorus compounds, namely, to a new method for the preparation of N.N-tetra-substituted 0-trimethylsilyl bis (amino methyl) phosphinates of the general formula

(CHjbSiOlMCHjNBR h (i)

n

where R R is lower alkyl, or R is methyl, R1 is acetyl, or R and R are (CH2) s or (CH2) 3C (0).

Compounds (I) include a fragment of NCPCN, phosphoryl and carbonyl groups and can be used as polydentate ligands in various complexes with metal compounds, for the synthesis of phosphorus-containing heterocycles and unusual phosphorus analogues of amino acids, new complexing agents or extractants.

The aim of the invention is to simplify the process and expand its scope.

According to the proposed method for the preparation of N.N-tetra-substituted 0-trimethylsilyl-bis- (aminomethyl) phosphinates of formula (I) bis (trimethylsiloxy-phosphine) is reacted with N-disubstituted chloromethylamine of the general formula

CICH2NRR

where R and R have the indicated values, with a polar ratio of the reactants equal to 1: 2, and the process is carried out in an organic solvent medium in the presence of triethylamine at room temperature under an inert gas atmosphere. In the reaction, it is desirable to use triethylamine in 5-10% of the excess stoichiometry.

The process can be represented by the following scheme.

ABOUT

ate about

J

sixteen

(SNZ) + 2С1Сн КК

. ". (CHjbSlO-PlCH RR) - (. CHsJjSiCl

- (C8H5) jH-HCl

where R and R have the indicated meanings.

The method of obtaining the target products (I) allows to obtain these compounds in a yield of up to 90% based on readily available reagents with various substituents at the nitrogen atom, including carbonyl groups, due to which it becomes possible to widely use the target products in organoelemental synthesis. The mild process conditions make the process preparative and easy to produce.

The proposed method is based on the original reaction of the double aminomethylorranium bis- (trmemethylsiloxy) phosphine with the creation of two phosphorus bonds — carbon, the ease of flow of which is associated with the high reactivity of N-disubstituted chloromethylamine.

The optimal process conditions are to carry it out in an organic solvent medium in the presence of triethylamine at room temperature; Mild conditions contribute to the highest reaction rates and prevent the formation of by-products. Carrying out the process in an inert gas atmosphere avoids the oxidation and hydrolysis of the starting and desired products. The use of triethylamine in 5-10% excess of stoichiometry allows you to quickly complete the process and make the most of the initial and reagent formed in the reaction mixture. An increase in the excess of triethylamine does not lead to an increase in the yield of the target products (I), and a decrease in the amount of triethylamine somewhat reduces the yield.

The preparation of compound (I) —stable liquids that are distilled under reduced pressure — can be stored in an inert gas atmosphere for a long time. The composition and structure of the target products (I) are confirmed by elemental analysis data and 1H, 13C, 31P NMR.

The synthesis and isolation of the target products was carried out in an atmosphere of dry argon using absolute solvents.

Example 1. 0-Trimethylsilylbis (diethylaminomethyl) phosphinate (la).

To a solution of 6.5 g (0.031 mol) of bis- (trimethylsiloxy) phosphine and 3.4 g (0.034 mol, 10% excess) of triethylamine in 30 ml of diethyl ether, a solution of 7.5 is added dropwise with stirring. g (0,062 mol) of chloromethylamine in 50 ml of chloride

1659416

methylene, the mixture is stirred for 1.5 hours at room temperature, the solvent is distilled off in vacuo, 150 ml of diethyl ether are added to the residue, the precipitate is separated, the solvent is distilled off, the residue is distilled. 8.5 g of compound (la) are obtained, yield 90%, t. Kip. 92 ° C (1 mm Hg). Fragment PCH2N: (5H 2.77 ppm, ppm ABX; ds51.8 ppm, d, 1Jpc 112.8 Hz; (5P40 ppm Physico-chemical constants of the compound (la) coincide with literary data.

Example 2. 0-Trimethylsilylbis- (dimethylaminomethyl) phosphinate (16).

Analogously to example 1 of 7.6 g (0.036 mol) of bis- (trimethylsiloxy) phosphine and 3.7 g (0.037 mol, 5% excess) of triethylamine in 40 ml of diethyl ether and 6.7 g (0.072 mol) of chloromethyldimethylamine in 50 ml of methylene chloride gave 7.7 g of compound (16), yield 85%, t. 73 ° C (1 mm Hg). Fragment of PCHaM: dn 2.64 ppm, m of AVH; 5C57.18 ppm, d., 1J re 114.2 Hz; dr 37.8 ppm The physicochemical constants of compound (16) coincide with the lit data.

Example 3. Otrimethylsilylbis (diisobutylaminomethyl) phosphinate (1c).

Analogously to example 1, a g (0.029 mol) of bis- (trimethylsiloxy) phosphine and 3.1 g (0.031 mol, 7% excess) of triethylamine in 45 ml of diethyl ether and 10.1 g (0.058 mol) of chloromethyl (diisobutyl) amine 9.9 g of compound (c) are obtained in 50 ml of methylene chloride, yield 83%, t. bales. 134 ° C (1 mm Hg),

n ° 1,4490. Fragment RSNaM; d 2.75 ppm, m. ABH; dfc 54.83 ppm, d., 1JPC 104.9 Hz; dp 39.17 ppm

Found,%; C 59.72, H 11.59.

C21H49N202PSI

Calculated,%: C 59.96, H 11.74.

Example 4. 0-Trimethylsilyl-bis- (piperidinomethyl) phosphinate (g).

Analogously to example 1 of 6.5 g (0.031 mol) of bis- (trimethylsiloxy) phosphine and 3.3 g (0.33 mol, 8% excess) of triethylamine in 30 ml of diethyl ether and 8.3 g (0.062 mol) N-chloromethylpiperidine in 75 ml of methylene chloride gives 8.9 g of compound (g), yield 86%, t. Bale. 137 ° C (1 mm

Hg), 1.4740. PCH2N fragment; D 2,75 ppm, m. ABH; 5C57.02 ppm, D.J. p. 114 Hz; br 40.03 ppm

Found,%: C 54.37, H 10.07.

CisH33N202PS

Calculated,%: C 54.19, H 10.00.

Example 5. 0-Trimethylsilylbis- (N- methyl-M-acetylaminomethyl) phosphinate (d).

Analogously to example 1 of 7.4 g (0.035 mol) of bis- (trimethylsiloxy) phosphine and 3.9 g

(0.039 mol, 10% excess) with triethyla-high and good yields. It is offered in 40 ml of diethyl ether and 8.6 g (the 0.070green method is simple, not

mol) N-methyl-M-chloromethylacetamide requires 75.4 grams of methylene chloride to make a complex apparatus of formalmethyl methylene chloride and can be easily spread to

Dineni (d), yield 40%, t. Kip. 175 ° C (1 mm of compound (I) of various structures of mercury), n & 1.4830. Fragment RSNaM: unusual phosphoric analogues of amino acids 5n 3.61 ppm and 3.77 ppm m. AVH ;. ds 47.37 ppm, lot-potential ligands. complexones,

d. JPC 97.9 Hz and 50.68 ppm. X, 94.7 Hz; extractants.

dr 34.61 ppm and 35.16 ppm. - a mixture of two 4P Sposo6 is the "first example

PRPMCHPMRGYUI 1-410 Double aminomethylation of bis- (trimeUGUrfounnCL / vD i, "

Found% C 42 59 H 8 29thylsiloxy) phosphine under mild conditions with ICSiN25 # 04P51 using highly correctedCalculated,%: C 42.84; H 8.17. Of the capable N-disubstituted chlormethime Example 6. 0-Trimethylsilyl-alami abis (pyR-rolidon-2-yl-1-methyl) -phosphinate 15 Phromylase and 6 timeste | e) Method of producing NN-tetrazameshanin analogously to example 1 of 7 g (0.033 O-tRimethylsilylbis (aminomethyl) phosmol) bis- (tRimethylsiloxy) phosphine and 3.7 g of inates of total F ° R "Y ™ (0.037 mol, 10% excess of) triethylamine- / l "cinvfroi who is M

on in 40 ml of methylene chloride and 8.9 g (0.066 5 1i | Ng "YL / 2

mol) M-chloromethylpyrrolidone-2. in 75 mlp

methylene chloride get 4.7 g of Compound-D g, -pp

Neni (1e, yield 42%. T. Kip. 182 ° C (1 mm where R R lower alkyl. or R-methyl, R

. Ampl, - acetyl, or R and R, are (CHaJs or

Hg), pb 1.4935. Fragment PCH2N: 25 (CH2) C (0),

Dns 3.62 ppm, m. ABH; 5C 45.80 ppm, D. Jpc interaction of bis- (trimethylsilox100, 2 Hz; others 33.86 ppm) phosphine with -substituted tertiary amine. Found: C 46.69, H 7.39 under an inert atmosphere gas, differing from 25 to 04R31y u and with the fact that, in order to simplify

Calculated,%: With 46,97, H 7.58.30 process and expansion of its region of example. Example 7. 0-Trimethylsilyl-bis (di-neni, M-disubstituted is used as the oL -substituted tertiethylaminomethyl) phosphinate (la).

Analogously to example 1 of 7.2 g (0.034 chloromethylamine of the general formula mol) of bis- (trimethylsiloxy) phosphine and 3.5 g of CICH2NRR,

(0.034 mol, no excess) of triethylamine in 40 35 where R and R. have the above values

ml of diethyl ether and 8.3 g (0.068 mol) at a molar ratio of reagents, equal to chloromethylethylethium in 50 ml with chloro 1: 2. and the process is conducted in an environment of organic methylene; 7.7 g of compound (la) are obtained;

yield 72%, physico-chemical constants of triethylamine at room temperature, which is given in Example 1. 40 2. The method according to claim 1, characterized by

Thus, the proposed method that triethylamine is used in 5-10% allows to obtain the target products (I) with a slight excess of stoichiometry.

Claims (1)

15 Formula of the invention A method for producing Ν, тет-tetrasubstituted O-trimethylsilylbis- (aminomethyl) phosphinates of the general formula 20. (CH ₃ ) s $ 1OP (SNDO11 ') 2 Oh where R = R ’is lower alkyl, or R is methyl, R ' - acetyl, or R and R! constitute (CH ₂ ) 5 or 25 (CH ₂ ) sC (O). the interaction of bis- (trimethylsiloxy) phosphine with a CX-substituted tertiary amine in an inert gas atmosphere, characterized in that, in order to simplify the process 30 and expand its scope, Y-disubstituted chloromethylamine of the general formula CICH ₂ NRR is used as an oC-substituted tertiary amine \ 35 where R and R ‘, have the above meanings, with a molar ratio of reactants equal to 1: 2, and the process is conducted in an organic solvent in the presence of triethylamine at room temperature. 40 2. The method of pop. 1, characterized in that triethylamine is used in a 5-10% excess of stoichiometry.