SU1549960A1 - Method of obtaining dibutoxyphosphin-substituted methyldialkylamines - Google Patents

Abstract

This invention relates to the chemistry of organophosphorus compounds, in particular to the preparation of dibutoxyphosphine substituted methyl dialkylamines Formula [(C ₄ H ₉ O) ₂ P] _3-N CH _N NR ₂ , where R is lower alkyl

N = 1 or 2, which can be used in the preparation of complexes with metal compounds. The goal is to develop a new method of obtaining new compounds. The preparation of the target compound is carried out by the reaction of the alkoxy-substituted methyl dialkylamine formula (R ¹ O) _3-N CH _N NR ₂ , where R ¹ is lower alkyl, R and N are indicated above, respectfully in 10-30% excess of the degree of stoichiometry with dibutoxyphosphine at 50 - 120 ° C in an inert gas atmosphere. 1 hp f-ly.

Description

This invention relates to the chemistry of organophosphorus compounds, namely, to a new method for the preparation of new dibutoxyphosphine substituted methyldialkylamines of the general formula

(C4Vzp vANR2i (I)

where R is lower alkyl;

n - 1 or 2. These compounds include fragmentsN

You can use P-C-N or P-C-P as polydentate ligands in preparing various complexes with metal compounds, as well as for the synthesis of new phosphorus-containing heterocycles and phosphorus analogs of amino acids — new complexing agents and extractants.

The method is prepared with dibutoxyphosphine substituted methyl dialkyl amines and the compounds (I) themselves are not described in the literature and are new.

The purpose of the invention is to develop a simple and universal method for the preparation of dibutoxyphosphine substituted methyl dialkylamines (I) - new key substances for the synthesis of new phosphorus-containing heterocycles and phosphoric analogs.

amino acids.

The goal is achieved by the proposed method for the preparation of dibutoxyphosphine substituted methyl dialkylamines (I), which consists in the fact that the alkoxy substituted methyldialkylamine of the general formula (R CO CHjjNR-, where R1 is lower alkyl; Kip have the above values,

S

this is about

OE

3

interaction with dibutoxyphosphine at 50-12P C in an inert gas atmosphere, and it is desirable to use the alkoxy-substituted methyl-dialkylamine in a 10-30% excess of stoichiometry,

(s) (vio) ph + (R O).

zp

CH.NR ,, -

--e

(Q & A) r R VM CH Fri 2 + (3-n) R OH

where R and R are lower alkyls; n - 1 or 2.

The proposed method for the preparation of the desired products of formula (I) allows these compounds to be obtained in a yield of up to -85% on the basis of readily available alkoxy-substituted methyl dialkylamines and dibutoxyphosphine with different substituents at the nitrogen atom, thereby making it possible to widely use the target products (I) in organic and organo-organic synthesis. The absence of solvents and precipitation make the proposed method preparative and easily reproducible.

The proposed method is based on an original and unexpected reaction: for the first time, it was possible to phosphorylate dibutoxyphosphine alkoxy-substituted methyl dialkylamines in the absence of a catalyst and to avoid the side processes of transesterification and nitrogen-carbon bond melting.

The optimum process conditions are from 50 to 120 ° C. At lower temperatures, the speed of the process slows down dramatically, the yield of the desired products decreases, and at higher temperatures, a decrease in the yield is observed due to significant decomposition of both the initial reagents and the target products.

Carrying out the process in an inert gas atmosphere avoids various side processes as well as oxidation of both the starting and the target products.

Alkoxy-substituted methyl dialkylamine is desirable to use in 10-30% excess of stoichiometry, which allows you to quickly carry out the process and make the most of the introduced dibutoxyphosphine. An increase in the excess of alkoxy-substituted methyl dialkylamine does not lead to an increase in yield, and a decrease in the amount of amine reduces the yield of the target Products (I).

-,

15499604

The obtained compounds (I) - stable liquids, which 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) is confirmed

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data of elemental analysis and NMR

,R.

The synthesis and isolation of the target products (I) was carried out in an atmosphere of dry argon.

Example 1. Dibutoxyphosphino-methyethylamine (1a).

A mixture of 5.5 g (0.031 mol) of dibutoxyphosphine and 534 g (09034 mol, 10% excess) of butoxymethyldiethylamine is maintained at 50 ° C for 1 h, then distilled. 6.6 g of compound (1a) are obtained, yield 81%, m.p., 95 ° C / 1 mm Hg. Fragment of CH2N: it is 2.71 ppm, d, JPK 7.7 Hz; 8C

JPC 7.3 Hz; S

59E56 ppm, de 173.1 ppm

Found,%; C 59.15; R 11.63.

R

H 11.62;

With „NEOYU4R.

C 59.29; H 11.48;

Calculated,%; R 11.76.

Example 2, Dibutoxyphosphinomethyl dimethylamine (16) „

Analogously to Example 1, out of 6.5 g (05036 mol) of dibutoxyphosphine and 5.4 g (0.041 mol, 15% excess) of butoxymethyldimethylamine, at 60 ° C, 7.3 g of compound (16) is obtained, yield 85%, t, kip . 85 ° C / 1 mm Hg

Fragment PCH2N: 0H2,62 ppm, d, JPH 7, C Hz; & 65.19 ppm, d, J ps 9.4 Hz; & p 172.9 ppm

Found,%: C 55.92; H 10.88; R.12,62.

C „W Calculated

R 13.16.

C 56.15; H 11.14;

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Example 3. Dibutoxyphosphinomethyl dipropylamine (1c).

Analogously to example 1, out of 6.5 g (0S037 mol) of dibutoxyphosphine and 8.2 g (0.044 mol, 20% excess) of butoxymethyldipropylamine at 70 ° C, 9.1 g of compound (1c) of 5 yield 85% are obtained, i.e. . 99 ° C / 1 mm Hg 4 Fragment PCH2N: 8H 2.72 ppm, d,

 RI

7.2

Hz; 175 ppm

wed

Found,%: C 61.69; H 12.04; R 10.72.

C SHMN02P.

Calculated,%: C, 61.83; H 11.76; R 10.63.

Example 4. Dibutoxyphosphino-methyethylamine (1a).

Analogously to Example 1, out of 4.9 g (0.028 mol) of dibutoxyphosphine and 4.4 g (0.028 mol, no excess) of butoxymethyl diethylamine at 50 ° C, 5.5 g of compound (1a) are obtained, 75% yield, physicochemical constants are given in example 1.

Example 5. Bis (dibutoxyphosphino) methyldimethylamine (1 g).

Analogously to Example 1, out of 6.3 g (0.036 mol) of dibutoxyphosphine and 2.7 g (0.023 mol, 30% excess) of dimethoxymethyldimethylamine at 120 ° C, 4.5 g of compound (Ir1) are obtained, yield 62%, i.e. . 145 ° C / 1 mm Hg

PCHP fragment: 5M 3.22 ppm, t, lJfh 4.7 Hz; 5C 74.45 ppm, t,% from 31 Hz; 5 p 191 ppm

Found,%: C 55.09; H 10.37; R 15.28.

With „Н4зШ4Рг.

Calculated,%: C 55.46; H 10.53; R 15.05.

Thus, the proposed method allows to obtain the desired products (I) with high yields, is simple, does not require complicated instrumentation and, if necessary, can be easily distributed.

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not on target dibutoxphosphine-substituted methiddialkylamines, of various structures, important intermediates of organophosphorus synthesis, phosphoric analogs of amino acids.

The method is the first example.

creating fragments of CPC and PCC,

including alkoxy substituents on phosphorus atoms, based on the phosphorylation of alkoxy-substituted methyl dialkylamines by dibutoxyphosphine.

Claims (2)

1. A method for preparing dibutoxyphosphine substituted methyl dialkylamines of the general formula (C4HC) 0) .ttCHnNR i, where R is lower alkyl; n 1 or 2 that alkoxy substituted methyldialkylamine of the general formula (R 0) 5 and CH "NKg, where R is lower alkyl; Kip have the indicated values, are reacted with dibutoxyphosphine at a temperature of from 50 to 120 ° C in an inert gas atmosphere. 2. The method according to claim 1, comprising in that alkoxy-substituted methyl dialkylamine is used in 10-30% excess of stoichiometry. Compiled by L. Karunina Editor N. Kishtulinets Tekhred L. Serdyukova Proofreader M. Samborska Order 246 Circulation 311 VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab. 4/5 Subscription