Hoechst Aktiengesellschaft

Bernd Lippsmeier

Klaus Hestermann

Gero Heymer

Hubert Neumaier

Hilmar Roszinski

Martin Reuter

Horst Staendeke

Hans-Werner Stephan

Hartfrid Vollmer

Georg Elsner

Gerhard Hartlapp

Production of quaternary phosphonium halides of the general formula:

Production of quaternary phosphonium halides

Production of tertiary phosphine oxides which contain nitrile groups and correspond to the following general formula I: ##STR1## in which R.sup.1 and R.sub.2 each stand for a straight or branched, identical or different alkyl, cycloalkyl, aryl, alkylaryl or aralkyl group having 1 to 18 carbon atoms, and in which R.sup.1 or R.sub.2 may be identical with R, which stands for a radical of the following general formula II: ##STR2## in which R.sup.3 and R.sup.4 each stand for a straight or branched, identical or different alkyl, cycloalkyl, aryl, alkylaryl or aralkyl group having 1 to 18 carbon atoms, and/or hydrogen atoms. The tertiary phosphine oxides are made by reacting a phosphine of the following general formula III: ##STR3## in which R.sup.5 has the same meaning as R.sup.3 and R.sup.6 has the same meaning as R.sup.4 but is no hydrogen, with an .alpha.,.beta.-unsaturated nitrile of the following general formula IV: ##STR4## in which R.sup.3 and R.sup.4 have the meanings given above. The reaction is effected in a single stage in the presence of water or a water-solvent mixture and the above formula I compounds are separated from the reaction product.

Production of tertiary phosphine oxides

Production of (hydroxymethyl)-alkyl, cycloalkyl or aralkylphosphines of the general formula:

Production of (hydroxymethyl)-alkyl, cycloalkyl and aralkylphosphines

O,O-dialkylthionophosphoric acid chlorides are produced by chlorinating a dialkyldithiophosphoric acid in two stages. In the first stage, the acid is reacted with chlorine in a molar ratio of 1:1.15 to 1:1.50, resulting sulfur is separated, the liquid phase is admixed with a distilled product of a previous batch chlorinated in the second stage and with a further 0.25 to 0.7 mol of O,O-dialkyldithiophosphoric acid per mol of acid initially used, and desirable final product is distillatively separated from said mixture. In the second stage, the distillation residue of the first stage is reacted with a total proportion of 0.9 to 1.0 mol of chlorine per mole of acid initially used, precipitated sulfur is separated from the second stage chlorination product, the liquid phase is distilled off, and resulting distillate is recycled to the first chlorination stage.

Production of O,O-dialkylthionophosphoric acid chlorides

Production of tertiary hydroxyalkylphosphine oxides of general formula (I) ##STR1## in which R.sup.1 and R.sup.2 each stand for organic groups having from 1 to 18 carbon atoms, where R.sup.1 may be identical with R.sup.2 and R.sup.2 may be identical with R which stands for a radical of general formula (II) ##STR2## in which R.sup.3 and R.sup.4 equally stand for organic groups having from 1 to 18 carbon atoms and/or more preferably for hydrogen. The compounds are made from phosphines of general formula (III) ##STR3## in which R.sup.3 and R.sup.4 have the meanings given above, which are reacted in a single step operation with carbonyl compounds of general formula (IV) ##STR4## in which R.sup.3 and R.sup.4 equally have the meanings given above. The reaction is effected while adding at least one substance yielding hydroxyl ions and in the presence of water, and the resulting hydroxyalkylphosphine oxides are separated from the reaction product.

Production of hydroxyalkylphosphine oxides

Production of organophosphines of the general formula R.sub.n PH.sub.3-n, in which R stands for identical or different, substituted or unsubstituted alkyl, cycloalkyl or aralkyl groups having from 1 to 18 carbon atoms, preferably from 1 to 4 carbon atoms, more preferably from 1 to 2 carbon atoms, and n stands for a whole number within the range 1 and 3. The compounds are more particularly produced by continuously reacting hydrocarbon halides of the general formula RX, in which R has the meaning given hereinabove and X stands for halogen, especially for chlorine or bromine, with hydrogen phosphide, and primary or secondary organophosphines at temperatures within the range 100.degree. and 600.degree. C. and under pressures of up to 20 atmospheres in contact with a catalyst being placed in a reactor. Gaseous matter issuing from the reactor is cooled and the resulting organophosphonium halides (R.sub.n PH.sub.4-n)X are hydrolyzed in conventional manner to the corresponding organophosphines.

Production of organophosphines

Production of tertiary (hydroxymethyl)-methylphosphine oxides of the general formula: ##STR1## in which R stands for a branched or unbranched, substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl group having from 1 to 18 carbon atoms. To this end tertiary bis-(hydroxymethyl)-phosphines of the general formula ##STR2## in which R has the meaning given above, are subjected to a thermal rearrangement reaction at temperatures higher than about 90.degree. C or at temperatures within the range -10.degree. and +250.degree. C, in the presence of a catalyst.

Production of tertiary (hydroxymethyl)-methylphosphine oxides

Production of pure dithiophosphoric acid O,O-diesters of the general formula ##STR1## in which the radicals R.sub.1 and R.sub.2, being identical or different, each stand for linear and/or branched alkyl, cycloalkyl, alkenyl, alkinyl, aralkyl or aryl radicals having from 1 to 18 carbon atoms, from their salts of the general formula: ##STR2## in which R.sub.1 and R.sub.2, respectively, have the meanings given hereinabove, M stands for a metal or ammonium cation, and n stands for the valency of the particular cation. The compounds are made by dissolving the salts in the quantity of one or more strong acids necessary to ensure reaction with the resultant formation of two separate liquid phases, and separating the two phases from one another.

Production of dithiophosphoric acid-O,O-diesters

Production of tertiary methylphosphine oxides of the general formula ##STR1## in which R and R' each stand for identical or different, branched or unbranched, substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl groups having from 1 to 18 carbon atoms. The compounds are produced by subjecting tertiary hydroxymethylphosphines of the general formula ##STR2## in which R and R' have the meanings given above, to a thermal rearrangement reaction at temperatures higher than about 90.degree. C or, in the presence of a catalyst, at temperatures within the range -10 and +250.degree. C.

Production of tertiary methylphosphine oxides

Production of halogen-containing tertiary phosphine oxides of the general formula (I) ##STR1## in which R.sub.1 stands for an alkyl, halogenoalkyl, alkenyl, halogenoalkenyl, alkinyl or halogenoalkinyl radical, each of these radicals containing from 1 to 18 carbon atoms, or stands for a cycloalkyl, a halogenated cycloalkyl, an aryl, a halogenated aryl, an aralkyl or a halogenated aralkyl radical, and X stands for halogen. The oxides are made by subjecting a compound of the general formula (II) ##STR2## in which R has the same meaning as R.sub.1 and X stands for halogen, to thermal treatment in the presence of hydrogen halide at atmospheric or at elevated pressure so as to split off water and formaldehyde in vapor form therefrom; by continuously freeing the resulting reaction mixture from the said components in vapor form; by terminating the reaction and thereafter stripping off the hydrogen halide from the reaction mixture by introducing an inert gas thereinto; and by purifying the remaining crude product by distillation or recrystallization.

Production of halogen-containing tertiary phosphine oxides

Production of tertiary phosphine oxides of the general formula (I): ##STR1## in which the substituents R.sub.1 and R.sub.2, being identical or different, each stand for an alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl or aryl radical having from 1 to 18 carbon atoms. The phosphine oxides are made by splitting off formaldehyde and hydrogen halide at temperatures within the range about 150.degree. and 350.degree. C, in the presence of hydrogen halide, from a molten compound of the general formula (II): ##STR2## in which R.sub.1 and R.sub.2 have the meanings given above and X stands for halogen; separating the formaldehyde and hydrogen split off from the reaction mixture, and treating the resulting crude product so as to separate the compound of general formula (I) therefrom.

Methylphosphine oxides of the general formula (I) ##EQU1## are produced from hydroxymethylphosphines of the general formula (II) ##EQU2## in which formulae R and R' each stand for identical or different alkyl-, cycloalkyl-, aralkyl- or aryl groups having from 1 to 18 carbon atoms, or carrying substituents being inert under the reaction conditions. The methylphosphine oxides are more particularly produced by subjecting the hydroxymethylphosphines to a rearrangement reaction with the aid of radical-yielding compounds.

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Hurth-Knapsack, Germany

Bernd Lippsmeier