SU1074878A1 - Methylenebis(alpha-hydroxyalkyl)phosphonic acids - Google Patents

Abstract

METHYLENBIS (oi -OXYALKSH1) PHOSPHINE ACIDS of the general formula cn 2 - O R, I in I, R-C-P-CHf-F-d-K it is mm where R is hydrogen, methyl or ethyl; R is Cf-Cg-alkyl or phenyl. W

Description

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This invention relates to the chemistry of organophosphorus compounds, specifically to the new methylenevis L-ox alkylphosphine | acids of the formula it "o o k2 R-c-f-CHrP-fj-ii I II" OH OH he he, where R is hydrogen, methyl or ethyl; R - Sz-Sz-glkyl or phenyl. Methylenebis (oboxyalkyl) phosphinic acids can be used as complexones and extracts of cations of various metals and as starting compounds for the synthesis of new types of methylenediphosphoroorganic compounds. The compounds of formula (I) have a fundamentally new structure, since they contain two phosphorus atoms, divided by a methylene unit, each of which has the BOC-position of an ox group. It can be expected that, along with the general properties determined by phosphine groups, methylenebis (o (, - o sialkyl) phosphinic acids) will have a higher selectivity as analytical reagents compared to their analogues, due to the presence in this structure of two potentially capable of coordinating hydroxyl groups. Mono- and diphosphorus-containing compounds of the following types are known: (X-hydroxyalkyl (aryl) phosphonic acid (type I); QL-oxyalkyl (aryl) phosphinic acids (type II) and L-hydroxyalkane diphosphonic acids (type III) : 0 sn-he (type I) where X is OH, OR, R and R are alkyl, RT — CH — OH (type II) BUT R where R and R are alkyl, aryl / OKO H IR (type III XgP — C — rXg where X is OH, OR, R and R are alkyl, Ari One of the methods for the synthesis of Oi-hydroxy alkyl (aryl) phosphinic and phosphoic acids containing one phosphorus atom (type I, II) is based on the reaction of hydrolysis of chlorohydride chloroyl kil (aryl) phosphonic and phosphonic acids obtained by the reaction of phosphorus trichloride and alkyl (aryl) dichlorofoofins with fatty aldehydes. It is known that under severe conditions phosphorus trichloride and alkyl; aryl) dichlorophosphines form adducts with aldehyde w, which, after hydrolysis, lead to oi-oxyalkyl (aryl) phosphine and -phosphonic acids (type I and II) 1, fti-Oxyalkyl ( Aryl) phosphinic and et-phosphonic acids are also obtained by hydrolysis of the acid chlorides to α, ω-oxyalkyl (aryl) phosphinic and α-phosphonic acids, which can be easily synthesized in good yields by the interaction of phosphorus trichloride or dichlorophosphines with ketones in the presence of protic chemicals ( Alcohol, carboxylic acid, or the corresponding phosphonic acid) 2. Oxyalkanediphosphonic acids (type III) are obtained by acylation of phosphorous acid or phosphorus trichloride with carboxylic acids, they are anhydrided or by acid halides and .4. Of the studied compounds, 1-hydroxyethylidene diphosphonic acid (HEDP) is of the greatest interest, which is determined by the availability of the raw material and the comparative simplicity of the synthesis, which made the practical production of these compounds realistic. For the synthesis of HEDP, the reactions of phosphorus trichloride with acetic acid were used. The aim of the invention is the synthesis of organophosphorus compounds of a new structure. This goal is achieved by new methylenebis (L-hydroxyalkyl) phosphino1 amino acids of formula (I), which are a new type of methylenediphosphorus-containing compounds having two phosphorus atoms separated by a methylene unit, each of which has an oxy group in its o-position. These compounds can be used as alkaline and alkaline earth metal complexones. The method for producing methylenebis (o-oxyalkyl) phosphinic acids is that carbon tetrachloride methylenediphosphine is treated with aliphatic or aromatic aldehydes or ketones (the latter are taken in acetic acid) under an inert gas atmosphere 20-40 ° C, followed by hydrolysis to form; their acid chlorides methylenebis (oi-chloroalkyl) phosphinic or methylenebis 06-hydroxyl) phosphinic acids 2N hydrochloric acid. The reaction is described by the following equation: kS1gRS1% RScfr; about L CHiOOOH ch4-gagna ksn4-onl1s1-k 01 C11 S1C1on he he 1) H to kgf- | -sn, 4-ok to "- RVe-p-OHrf-ciiR IIII t I he he on he C1 he

where R, R, R is alkyl or phenyl.

The yield of the desired product after recrystallization 63-89%.

The synthesized compounds are stable oils or white crystalline substances, purified by reprecipitation of benzene with pentane or recrystallization from ethyl alcohol.

The composition and structure of the compounds obtained are confirmed by elemental, analysis and spectroscopy data.

Example 1. Methylenebis (l-hydroxybenzyl) phosphinic acid.

In a three-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel, 10.55 g (0.05 g-mol) of tetrachloromethylene diphosphine are placed ./ 11.7 g (0.11 g-mol) of base aldehyde are added slowly with stirring so that the temperature the reaction mixture did not exceed 35-40 C. At the end of the exothermic reaction, leave the reaction mixture for a day. Then 30 ml of 2N hydrochloric acid are added dropwise and the reaction mixture is left again for a day. The precipitated methylenebis (ω-oxybenzyl) phosphinic acid crystals are filtered off and then purified by recrystallization from ethyl alcohol. 12.8 g (72%), so pl. S 32.14 ppm, 5; 31.90 ppm (meso and d-, 1-forms

Found,%: C 50.26; H 5.19; R 17.96.

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Calculated,%: C 50.57; H 5.09; R 17.39.

Example 2. Methylenebis (a, β-hydroxybutyl) phosphinoBa acid.

The substance is obtained according to the described procedure, from 10.55 g (0.05 g mol) of tetrachloromethylene diphosphine and 7.92 g (0.11 g mol) of oily aldehyde with a yield of 10.8 g (75%). M.p. 203 С NMR spectrum Р 8.36, 23 ppm, $ d 36.12 ppm (meso and d, 1 form).

Found,%: C 37.99; H 7.78; R 21.49.

Calculated,%: C 37.51; H 7.69; R 21.45.

Example 3. Methylenebis (o4-hydroxy-isoamyl) phosphinic acid.

The substance is obtained according to the procedure described above, from 10.55 g (0.05 g-mol) of tetrachloromethylenedi-5 phosphine and 9.46 g (0.11 g-mol) of isovaleriandehyde with a yield of 10 g- (63%), tons. square NMR spectrum 35.93 ppm 5, 36.09 ppm (meso and d, 1 form).

0

Found,%: C 41, .58; H 8.49; P 19.59

Cjfi HjiOgP / j.

Calculated,%: C, 41.78; H 8.29; R 19.59.

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Example 4. MethiLenbis (o-oxy-o1 methylethyl) phosphinic acid.

In a three-neck flask equipped with

10.55 g (0.05 g-mol) of tetrachloromethylenediphosphine and 5.8 g of 0.1 g-mol) acetone are placed with a stirrer, reflux condenser, and addition funnel. After 0.5 h, 10 ml are added dropwise.

5 glacial acetic acid. The reaction mixture is left for a day, the acetic acid is distilled off, the residue is hydrolyzed with 25 gl of 2N hydrochloric acid (2 h). The precipitated oil is precipitated from benzene with pentane. The yield of g (89%), oil spectrum 47.0.07 M. D, S. 47.32 Md. (meso and d-, 1-forms).

Found,%: C 31.98; H 7.05; R 23.50.

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C | H48 PjOg.

C 32.32; H 6.97;

Calculated% R 23.81.

Example 5. Methylenebis (ot-hydroxy- {L-ethylpropyl) phosphinic acid.

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According to the described procedure, from 10.55 g (0.05 g-mol), those of trachloromethylenediphosphine and 8.6 g of 10.1 g-mol) of diethyl ketone are obtained in a yield of 13.1 g (83%) of the product, mp. , spectrum

5 8, 38.42 MD, 8 38.30 ppm (meso and d, 1 form).

Found,%: C 42.31; H 8.12; R 19.64.

C-ViHjgPjO.

0

Credited,%: C 41.78; H 8.29; R 19.59.

Example 6. Methylenebis (ob-hydroxy-methyl-benzyl) phosphinic acid.

The substance is obtained according to the method described above from 10.55 g (0.05 g-mol)

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tetrachloro methyledidephosphine and 12 g (O.Dg-mol) of acetophvion with a yield of 12, (63%), so pl. 25 ,, NMR P S 26.40 MD, & j 24.89 ppm (meeo and a-, 1-f01 sh),

Found,% 1 C 52.80} I 6.10 R 16.37

WITH ON, Rlo, L.

Isleno T%: C 53.13 H 5.77; R 16,12.,.

Thus, a new class of methylenediphosphorus-containing compounds has been synthesized - methylenebis (e6-hydroxyalkyl) phosphinic acids, two phosphorus atoms separated by a methylene unit, of which oxygroup is in et-position.

The target products can be used as complexones and extractants of various metal cations and as starting compounds for the synthesis of new methylenediphosphorus-containing compounds.

Claims (1)

(54) METHYLENBIS (ci-OXYALKYL) PHOSPHIC ACIDS of the general formula R ² 0 0 R ² . I th I 1 R ^ CF-CHr-FCK II ^with IIon he onon ^where ~ ⁱⁿ ° D ° R ° Dg methyl or ethyl; R is Cf-Cg alkyl or phenyl. m oo m X The invention relates to the chemistry of organophosphorus compounds, specifically to new methylenebis alkyl phosphinic acids of the formula