DE1493638A1 - Process for the production of organic phosphorus compounds - Google Patents

Description

Process for the production of organic phosphorus compounds Es is already known, carbonyl compounds, especially aldehydes, with phosphine in To convert the presence of a lot of hydrogen chloride to tetra-alkoxy-phosphonium salts.

However, it was not known whether the implementation had been carried out in absentia of hydrogen chloride or, in the presence of only slight acids, of acids. Halogen-substituted Aldehydes have not yet been used for this reaction, presumably because disturbances of the aldehyde addition by intra- or extramolecular halogen quaternization were feared.

The subject of DBP 1 035 135 is a process for the production of Trioxymethylphosphine, in which one 1 ol formaldehyde, advantageously in the presence of cup, in the presence of small amounts of finely divided, not to the alkali or @rdalkali metals belonging to metals and / or their compounds with phosphine reat alkylating can, and / or of their phosphine reaction products Reacts with 1/3 mole of phosphine.

In further. Design of this process are in accordance with the additional patent 1 075 610 organic phosphorus compounds obtained in a smooth reaction by that one uses other aldehydes or substituted aldehydes in place of the formaldehyde.

In a further refinement of this procedure, it has now been found that # organic phosphorus compounds are also used in the presence of phosphine and aldehydes of small amounts of finely divided, not belonging to the alkali or alkaline earth metals Metals and / or their compounds that can react with phosphine and / or of their phosphine reaction products if one @ -branched aldehydes with 1/3 mol of phosphine in the presence of acids.

# -Branched aldehydes are those in patent specification 1,075 610 named representative, e.g. B. isobutyraldehyde, isovaleraldehyde, 2-ethyl @ hexanal, Cxysynthesis aldehydes, furfural or mixtures of these. Come as catalysts the products mentioned in the patent specification 1 035 135 into consideration.

Suitable acids are organic and inorganic acids, e.g. B. hydrochloric acid, Lactic acid, but also acidic sentences such as B. iron-3-chloride, sodium hydrogen sulfate. Highly volatile aliphatic carboxylic acids @ such. B. Acetic acid.

Substoichiometric amounts of acid are generally sufficient, z. B. 1/100 - 1/3 mole per mole of ihosphine depending on the type of acid. It can also be called "Solid acids", i.e. cation exchangers, are used, z. B. Phenolic resin sulfonic acids (cf. A. P. 2 566 559; also P. @astagli, Comptes rendus Vol. 236 (1953) p. 616 and Vol. 237 (1954). 187). However, if necessary larger amounts of the acids can also be used, e.g. B. 1 to 3 moles per phosphine.

Mol The addition of acids in Umnetzwli: the aldehydes with 1/3 Moles of phosphine bring about a significant increase in the rate of reaction, and surprisingly without the formation of quaternary phosphonium compounds, such as They arise from Mm formaldehyde according to DP 1 044 078.

In the present case, too, the procedure can be carried out in the presence or absence * carried out v: earth.

Conotitution of the resulting from the present procedure organic phosphorus compounds has not yet been fully clarified. Anyway included the reaction products the carbon atoms of 3 moles of aldehyde per @ hosphor- @ tom, but without entry of the added acids.

The reaction products depend on the type of aldehyde used medium to high r. iedenfle oils or waxy Steffe. They are all in lower ones Alcohols are soluble in oil, but not in water. They can be used as anti-parasitic agents or used as intermediates.

Example 144 g of isobutyraldehyde are mixed with 100 cc of acetonitrile, in the 0,5 @ ital4 are solved, vrdännt; 15 g of glacial acetic acid are added to the empty solution and then its phosphine is trimmed through a frit under a steady stream; the The exhaust gases are passed through a low temperature reflux cooler (-40 ° C). The temperature of solvents rises rapidly to 360 C and during implementation is kept at this value by cooling. After two hours of initiation, the exothermic reaction essentially ended; 1 hour to complete Phosphine passed through at room temperature. Before working up, it is in the reaction solution 1 g of hydroquinone dissolved to prevent oxidation by the oxygen in the air. From the externally homogeneous solution, 150 g of an oily underlayer separate overnight after distilling off the solution by means of 146 g of an oil at 1 mm Hg / 40 ° C supplies.

The oil distills undecomposed and uniformly at 880 C / 0.5 mm Hg @nd has only a faint onion odor. A sample is distilled at normal pressure at 2050 C. The oil is insoluble in water, over with methanol, benzene, thylacetate and gasoline can be mixed.

In the mild oxidation of the reaction product in methanolic Ionization with hydrogen oxide results in a good yield of a water-insoluble, methanol-soluble, uniform crystallized phosphorus compound with a melting point 1570 C with acid number 218. Elemental analysis gives the gross formula C12H2503P compared to C12H25O2P in the case of the oily phosphorus compound. Presumably that's above described oily, distillation-resistant phosphine is a formed in an acidic medium Acetal from 1 tol primarily formed bis - @ - hydroxyisobutylphosphine with 1 @ol isobutyraldehyde. This acetal (c12H2402) PI! with a hydrogen atom bonded to the phosphorus atom was terribly oxidized with H2O2 to crystallized phosphinic acid (C12H24O2) POH.

DaP presumably acetal-like phosphine is identical to that of 5. . Buckler in Journ. At the. Chem. Soc. 1958, p. 6455 in the absence of heavy metal catalysts Phosphine made from isobutyraldehyde and hydrochloric acid.

The acetal-like phosphine is suitable due to its gasoline solubility and low odor as well as the possibility of distilling it undecomposed at normal pressure to be able to, advantageous as an additive for fuels for internal combustion engines. It is known organic phosphorus compounds to Otto fuels, especially in Presence of anti-knock agents such as tetraethyl lead to be added, for example Tricresyl phosphate or chloropropylthionophosphate. One tries with this to achieve that in spark ignition spark ignition engines there is less deposit-related or "surface" ignitions step on and that the spark plugs clog less.

The rotor should work more efficiently, as a result of irregular ones Combustion induced loss is reduced. As the one with the well-known phosphorus compounds If the effects are only slightly softened, the addition has already been added in their place proposed by trialkylphosphines, the alkyl groups of which contain 1 to 5 carbon atoms. However, these substances have the disadvantage of a very strong phosphine odor, the their handling is extremely difficult and their practical use has hitherto been prevented Has. It is also known to use trialkylphosphines as an additive to diesel fuels to be used for compression ignition engines. This is intended to make the ignition period more such Motors are shortened. The disadvantage of the very strong one also applies here Phosphine smell.

The added amounts of the presumably acetal-like phosphine from inobutyraldehyde to the fuels are expediently in the range from about 0.01 to 3 percent by weight. In the case of diesel fuels for compression ignition engines, men are preferably used Additions of about 0.1 to 3 percent by weight, which accelerate the ignition of the compressed fuel and a considerable increase in performance. With petrol you generally come with additional amounts between about 0.01 and 0.2 percent by weight and thereby achieved, in particular in the presence of anti-inflammatory agents, a reduction in the known deposits on the spark plugs and inside the combustion chamber. This also increases the number the "surface" -ZunduntZen diminishes. Thus there is a considerable increase the quietness of the engine, especially due to the fact that the initial volume the combustion chamber is not reduced or is only slightly reduced during prolonged operation0 The fuels used are hydrocarbons or hydrocarbon mixtures and have a boiling range between about 400 C and about 2000, depending on the type of engine C for Otto fuels and around 1500 C to 3500 C for diesel fuels. The octane range in the case of Otto fuels, the aliphatic, cycloaliphatic or aromatic, preferably may contain mononuclear aromatic hydrocarbons is in the range of about 60 to above 100, with an addition of customary anti-knock agents, for example about 0.02 to about 0.2 ffi tetraethyl lead or tetramethyl lead can be carried out. The cetane number range for diesel fuels is between about 25 and about 70.

In addition, the propellant mixtures according to the invention can be used for everyone known internal combustion engines, especially for gasoline and diesel engines, in the higher Compression area can be used. Working with Otto engines is preferred in the compression range between 1: 5 and 1:12 or possibly even higher and for diesel engines in a compression range between 1:10 and 1:30.

A car gasoline, for example, serves as the basis with a boiling range of 50 - 200 ° C and a specific weight of 0.73 from about 50, paraffins, 20% olefins, 10% aromatic hydrocarbons and 20% naphthene. To this end, 0.8 ccm @ tetraethyl lead is added. This anti-knock agent was used as a common odor derived from 1 thcor. Unit of ethylene chloride and 0.5 theoretical units of ethylene bromide blended tetraethyl lead.

(It is well known that 1 theor. Unit of a Halogenepül means for tetraethyl lead that amount which contains just enough halogen to convert the lead quantitatively into corresponding. Lead dihalide). The octane number is about 90 (Researoh method). a) 0.1 g / l tributylphosphine are dissolved in the above-mentioned high-octane gasoline, in order to reduce the irregular ignitions caused by the ager. Here shows a very unpleasant phosphine-Greuch, which is still at 10 taoher dilution with same gasoline is noticeable. b) If you work as indicated under a), you solve aur to reduce the irregular ignitions caused by deposits instead of tributylphosphine 0.1 g / l of the above acetal-like phosphines from isobutyraldehyde in the gasoline suf, so there is no odor change, even when adding larger amounts up to 1 g / l. Of course, there is also no odor change with smaller ones Additions, for example between 0.01 and 0.08 g / l of this acetal-like phosphine, also not with a modified lead content, for example at 0.3 ccm / l or 1.5 ccm / l tetraethyl lead or mixtures such as tetraethyl lead or tetramethyl lead in a ratio of 9: 1 or 3: 2 or 1: 3. Instead of the car gasoline marked at the beginning You can also use other commercially available car petrol, for example, with the same result with a composition of 50% aromatic hydrocarbons, 30th % Paraffin, 10% olefins and 10% naphthenes can be used.

Furthermore, for example, in a diesel fuel pus the catalytic Cracking with an aniline point of 500 C, an ignition point of 1000 C, a cetane number 33 and an A.P.I. density of 29 under the same conditions, 1 each of the following Phosphines dissolved: a) tri-n-butyl-phosphine, b) acetal-like phosphine from isobutyraldehyde.

While solution (a) has a very disgusting phosphine odor, solution (b) still smells similar to petroleum. This even applies to the addition the double amount, nlso of 2% of the phosphine in question in experiment (b), while in these experiments with a reduction of the phosphine additions only 0.2 % no ugly change @ appearance. On the other hand, if you reduce the amount of phosphine added in the case of mixture (a) from 1% to 0.2%, this mixture also still adheres penetrating phosphine smell. This is true even with an addition of only 0.02 ffi tributylphosphine to the diesel oil.

The same odor phenomena occur with a paraffinic diesel fuel observed with a boiling range of 200 to 3500 C, without cracking by direct Oestillation of EnÖl is made.

Claims (1)

Claim Further embodiment of the process for production of organic phosphorus compounds from phosphine and aldehydes in the presence of small amounts of finely divided, not belonging to the alkali or frdalkali metals Metals and / or their compounds that can react with phosphine and / or of their phosphine reaction products according to patent 1 075 610, characterized in that that in-position branched aliphatic aldehydes with 1/3 mole of phosphine in the presence of acids.