EP0000694B1 - Procédé de préparation d'hydroxydes de phosphonium quaternaires - Google Patents

Procédé de préparation d'hydroxydes de phosphonium quaternaires Download PDF

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Publication number
EP0000694B1
EP0000694B1 EP78100226A EP78100226A EP0000694B1 EP 0000694 B1 EP0000694 B1 EP 0000694B1 EP 78100226 A EP78100226 A EP 78100226A EP 78100226 A EP78100226 A EP 78100226A EP 0000694 B1 EP0000694 B1 EP 0000694B1
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Prior art keywords
mol
water
aqueous medium
trimethylphosphine
reaction
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EP78100226A
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German (de)
English (en)
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EP0000694A1 (fr
Inventor
Klaus Dr. Hestermann
Vollmer Dr. Hartfried
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5407—Acyclic saturated phosphonium compounds

Definitions

  • the invention relates to a process for the preparation of quaternary phosphonium hydroxides of the general formula
  • the R is either hydrogen or an aliphatic or an aromatic hydrocarbon having 1 to 12 carbon atoms, in particular having 1 to 6 carbon atoms, and n is 1 or 2, by reacting di- or trimethylphosphine with epoxides of the general formula in which R has the above meaning, in an aqueous medium.
  • a disadvantage of this method is that after the starting substances have been brought together, the reaction only begins with a long delay, but then proceeds very stormily. The result of this is that the reaction mixture is heated rapidly in the course of the exothermic reaction and some of the volatile di- or trimethylphosphine is expelled from the reaction vessel before it is able to react with the epoxide.
  • the known procedure for the preparation of the quaternary phosphonium hydroxides can be improved if the aqueous medium is adjusted to a pH ß 12 using bases before the starting components are mixed with one another in this medium.
  • Water alone or in a mixture with an organic solvent, can be used as the aqueous medium.
  • the reaction is preferably carried out at temperatures between -10 and + 35 ° C. It emp. it is necessary to use 1 to 10 mol, preferably 3 to 5 mol, of water per mol of di- or trimethylphosphine and to use the epoxide in excess of the methylphosphine, based on the stoichiometric amount required to form the desired phosphonium hydroxides.
  • the pH of the aqueous medium is adjusted in particular with the aid of an alkali metal hydroxide.
  • the process according to the invention is carried out in such a way that in a reactor which is equipped with a stirrer, a thermometer, a pH meter, a gas inlet tube, a reflux condenser with a gas outlet and a dropping funnel, as the working medium is initially charged.
  • This consists either of water or of a mixture of water with an organic solvent that is soluble in water. for example an alcohol or which is insoluble in water, for example an ether. It is recommended that at least 1 mole of water is specified per mole of dimethylphosphine or trimethylphosphine.
  • the water is then adjusted to a pH equal to or greater than 12 with a small amount of a base, in particular NaOH.
  • the amount of epoxides added can of course be greater than the stoichiometric amount required to form the desired phosphonium hydroxide. However, there is then the risk that the excess of epoxides will continue to react under the reaction conditions to polyglycols, which are known to be difficult to separate from the desired phosphonium hydroxide. It is therefore preferred to react 1 or 2 moles of epoxide per mole of alkylphosphine. It is also advantageous to work with an excess of alkylphosphine, since this can easily be separated off at T> 40 ° C. after the end of the reaction and used again.
  • the separation of the solvents from the quaternary phosphonium hydroxide formed is carried out in a known manner under gentle conditions by distillation, possibly. at negative pressure.
  • the quaternary phosphonium hydroxides are obtained as oily, extremely hydroscopic, colorless liquids.
  • a particular advantage of the process according to the invention is that any quaternary phosphonium salt can be prepared with respect to the anion by neutralization with the corresponding acid.
  • the invention which is naturally not limited to the generally described embodiment, enables simple manufacture for the first time Provision of methyl-2-hydroxyalkyl (aralkyl) phosphonium hydroxides, which are widely used in the form of their salts as flame retardants, vulcanization accelerators, phase transfer catalysts, crop protection agents or pharmaceuticals.
  • the other part of the original reaction product was neutralized with aqueous HCl solution.
  • the solvent H 2 O was evaporated at 110 ° C. and 20 torr.
  • the crystalline solid obtained was treated with 150 ml of ethanol, the phosphonium salt going into solution and being separated from the undissolved NaCl.
  • Trimethyl-2-hydroxyethyl-phosphonium chloride was converted from the alcoholic solution by adding 1000 ml of acetone deposited as colorless crystals. A total of 70 g of the chloride were obtained, which corresponds to a yield of 89.7%.
  • connection had a melting point of 267 ° C.
  • Example 1 The reaction according to Example 1 was repeated, with the difference that a mixture of 5 mol of H 2 O and 5 mol of isopropanol was used as the working medium and the reaction temperature was 30 ° C.
  • the phosphonium hydroxide solution obtained was neutralized with hydrochloric acid and as in Example 1 worked up. 137 g of end product were obtained, corresponding to a yield of 87.5%.
  • Example 2 The reaction according to Example 1 was repeated, with the difference that a suspension of 10 mol of H 2 O and 3 mol of diethyl ether was used as the working medium and the reaction temperature was 0 ° C.
  • the aqueous phosphonium hydroxide solution obtained was separated from the ether, neutralized with hydrochloric acid and, as in Example 1, " worked up. 121 g of end product were obtained, corresponding to a yield of 77.3%.
  • the compound had a melting point of 169 ° C.
  • the phosphonium hydroxide solution obtained was neutralized with hydrochloric acid and opened worked up. However, the compound could not be obtained as a crystalline substance, but only as a syrupy mass. 180 g of end product were obtained, corresponding to a yield of 77.7%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (7)

1. Procédé de préparation d'hydroxydes de phosphonium quaternaires de formule générale:
Figure imgb0029
dans laquelle R représente soit l'hydrogène, soit un hydrocarbure aliphatique ou aromatique en C,-C,2, de préférence C1―C6, et n représente 1 ou 2, par réaction de di- ou triméthylphosphine avec des époxydes de formule générale:
Figure imgb0030
dans laquelle R a la signification déjà donnée, en ,milieu aqueux, caractérisé en ce que l'on établit, dans le milieu aqueux, une valeur de pH égale ou supérieure à l'aide d'une base, et on mélange ensuite les composants de départ dans ce milieu.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise, comme milieu aqueux, l'eau seule ou en association avec un solvant organique.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on effectue la réaction à des températures comprises entre -10 et +35°C.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on utilise 1 à 10 moles d'eau par mole de di- ou triméthylphosphine.
5. Procédé selon la revendication 4, caractérisé en ce que l'on utilise 3 à 5 moles d'eau par mole de di- ou triméthylphosphine.
6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on utilise l'epoxyde en excès, par rapport à la' quantité steochiométrique de méthylphosphine nécessaire pour la formation de l'hydroxide de phosphonium recherché.
7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on établit la valeur de pH dans le milieu aqueux à l'aide d'un hydroxide alcalin.
EP78100226A 1977-07-20 1978-06-23 Procédé de préparation d'hydroxydes de phosphonium quaternaires Expired EP0000694B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772732751 DE2732751A1 (de) 1977-07-20 1977-07-20 Verfahren zur herstellung von quartaeren phosphoniumhydroxiden
DE2732751 1977-07-20

Publications (2)

Publication Number Publication Date
EP0000694A1 EP0000694A1 (fr) 1979-02-21
EP0000694B1 true EP0000694B1 (fr) 1980-09-17

Family

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EP78100226A Expired EP0000694B1 (fr) 1977-07-20 1978-06-23 Procédé de préparation d'hydroxydes de phosphonium quaternaires

Country Status (5)

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US (1) US4189449A (fr)
EP (1) EP0000694B1 (fr)
CA (1) CA1102824A (fr)
DE (2) DE2732751A1 (fr)
IT (1) IT7850344A0 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO175842C (no) * 1985-08-06 1994-12-21 Albright & Wilson Biocid sammensetning for anvendelse ved vannbehandling
GB8527793D0 (en) * 1985-11-11 1985-12-18 Albright & Wilson Control of bryophytes lichens algae & fern
JPS62212397A (ja) * 1986-03-12 1987-09-18 Hokko Chem Ind Co Ltd 第４級ホスホニウムヒドロキシドの製造法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3251883A (en) * 1962-07-20 1966-05-17 American Cyanamid Co Process for preparing 2-hydroxyalkylphosphines and 2-hydroxyalkylphosphonium salts
US3452098A (en) * 1966-04-18 1969-06-24 Hooker Chemical Corp Hydroxymethyl,beta-hydroxyalkylene phosphonium salts and the preparation thereof
US3681126A (en) * 1969-11-25 1972-08-01 Monsanto Co Flame retardant article containing tris-(3 - halo - 2-hydroxypropyl)-hydroxymethylphosphonium chloride

Also Published As

Publication number Publication date
US4189449A (en) 1980-02-19
EP0000694A1 (fr) 1979-02-21
IT7850344A0 (it) 1978-07-18
CA1102824A (fr) 1981-06-09
DE2732751A1 (de) 1979-02-01
DE2860167D1 (en) 1980-12-18

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