DE876094C - Process for the production of complex phosphines - Google Patents

Description

Process for the production of complex phosphines The subject of patent 817 909 is, inter alia, the production of complex compounds which consist of a phosphine residue, a heavy metal compound and an organic halogen compound and which are produced by the action of organic halogen compounds on complex compounds of phosphines and heavy metal compounds, e.g. B. carbonyls, halides, pseudohalides, etc. are accessible.

It has now been found that the same complex compounds are obtained when looking at quaternary phosphonium compounds, how they can be obtained by attaching Esters to tertiary phosphines, heavy metals, unsubstituted heavy metal carbonyls and allows free halogen or those carbonyls of heavy metals to act in which some of the CO groups are substituted by organic radicals, in particular phosphine radicals is.

The implementation is shown below using a few equations using the example of triphenyl-benzyl-phosphonium chloride and nickel. From these raw materials arises according to the equation 3'L (C6Hs) aC6H5CH, P] Cl -I- Ni - + - L (C, Hs) sPl2 'NiC12. C, H, CH, C1 (z) (C, HJ3P L C, H5CH, CH.C, H; a triphenylphosphine-nickel chloride-benzyl chloride complex compound and as by-products compounds, those from the withdrawal of the Halogen atom formed from fragments formed from part of the starting material have been. In equation (i), such by-products are triphenylphosphine and dibenzyl have been given; instead of this, however, you can also, for example Stilbene, phenanthrene, etc. are formed and other starting materials thereof various by-products.

If you start from an unsubstituted metal carbonyl, e.g. B. nickel carbonyl, off, the use of free halogen is necessary. The implementation is progressing then according to equation 2 below [(C6H5) 3C.H5CH, P] Cl -I- Ni (C0) 4 + C12 "-> - [(C6H5) 3P] 2 - NiC12. C, H, CH @ C1 (2) -f- 4 CO -} - C, H @ CH, C1.

If a substituted metal carbonyl is used, e.g. B. triphenylphosphine nickel carbonyl, one can assume the following course of the reaction 3 L (C6H5) 3C6H5CH2P] Cl + [(C6H5) 3P] 2N1 (C0) 1 @ '[(C6115) 3P19' Ni C12 # C6 H5 C H2 C1 + 3 (C6 H5) 3 P (3) -f - C6 H5 C H2 C H2 C6 H5 + a CO.

In general, the complex compounds are formed with great ease and it is enough to melt the metal or metal carbonyl or dissolving the quaternary compound at elevated temperature, preferably below Oxygen exclusion, to be entered or vice versa. Examples of suitable solvents are higher aliphatic or alicyclic alcohols, ketones or esters, or even those organic halogen compound which was used to produce the starting material. When choosing the solvent one must also take into account that under certain circumstances the resulting complex compounds are very active catalysts for certain organic compounds Reactions, e.g. B. cyclizing polymerization or carbonylation are, so that reactions between by-products can occur. So z. B. off Alcohols or esters with carbon dioxide are formed. Also the by-products can continue to react with themselves under the influence of the complex compounds, z. B. olefins can be polymerized to cyclic compounds. The education the complex itself is generally not influenced by such side reactions.

The most favorable temperature for the implementation depends in part from the starting materials; in general it is between 100 and 25o °. If necessary you can work under increased pressure, e.g. B. if you have a normally below the most favorable reaction temperature boiling solvent used.

Quaternary compounds that are suitable as starting materials are in particular the alkyl, aralkyl, cycloalkyl or Aryl compounds which have a halogen atom, a cyano or rhodan group as the acid radical contain. Instead of the finished quaternary compounds, one can also use one Starting out mixture of the components required for their formation, e.g. B. from one Mixture of triarylphosphine and butyl bromide instead of triarylbutylphosphonium bromide.

Of the heavy metals, nickel, cobalt, iron, Copper, zinc or cadmium as starting materials. They will be expedient in as much as possible reactive form, especially powder or dust, how to use them z. B. in the decomposition of metal carbonyls, reduction of precipitated oxides or the electrolysis receives.

The substituted metals are even more reactive than the metals themselves Metal carbonyls; however, their use is limited to those metals which are capable of forming carbonyls, in particular nickel and cobalt. as Examples of suitable carbonyls are alkyl, aralkyl, cyclo and arylphosphine nickel carbonyls.

The implementation is complete if you put the starting materials in theoretically required relationship can act on each other, but one can also vary this ratio. - For example, one can in place of the theoretically according to equation (i) required amount of quaternary compound a deficit use thereof and by adding an organic halogen compound or free Halogen for providing the necessary to form the complex compounds Amount of halogen. Equation (4) shows how to e.g. B. by adding benzyl chloride part of the triphenylbenzylphosphonium chloride required according to equation (i) can save.

2 [(C, H5) 3C, H, CH, P] Cl + C, H, CH.Cl - Ni -> - [(C6 @ 5) 3P] 2-NiC12-C, H, CH.Cl . (4) -f- C, H, CH, CH, C, H5.

The same applies if a substituted Metallcarbonvl is used instead of the metal. Here, too, part of the quaternary compound can be saved by adding free halogen or an organic halogen compound, as can be seen from the following equation: [(C6Hs) 3C6H5CH, P] Cl + [(C6H5) sP] 2Ni (C0) 2 -f - C12 (5) -> - [(CIH5) 3P] 2. NiCl2. C, H.CH.C1 -i- (C, H5) 3P +: 2 CO. EXAMPLE i 14.5 parts of nickel powder, such as is obtained from the decomposition of nickel carbonyl, are introduced all at once into a melt of 199 parts of triphenylbutylphosphonium bromide, while stirring and passing in nitrogen. The melt turns dark green. In the course of 6 hours the temperature is increased to 240 °. The hydrocarbons formed as by-products during the reaction, some of which are unsaturated, are distilled directly from the melt and collected separately. 10 parts are obtained thereof, including 3 parts benzene.

After cooling, the melt is dissolved in hot butanol and filtered. From the one when it cools down of the filtrate precipitating crystal pulp the excess solution poured off and the precipitate again from 100 parts Recrystallized ethanol. In this way, 130 parts of the green triphenylphosphine nickel bromide-butyl bromide compound are obtained of the composition L (C, Hs) aP] 2NiBr2. C.H. Br (m.: I77 °). Example 2 In the im In the manner described in Example i, triphenylibutylphosphonium bromide is added to a melt of igg parts 16 parts of zinc powder and thus receives 14o parts of the triphenylphosphine-zinc bromide-butyl bromide compound of the composition L (C ,, HS) 3P] 2ZnBr2. C.H, Br (F.: 174 '). Example 3 A mixture of 500 parts of benzyl chloride is mixed with 262 parts of triphenylphosphine with stirring heated to i5o-. Thirty parts of nickel powder are poured into this solution at once. The reaction mixture initially turns brown, then gray-blue and finally dark green. The mixture is then kept at 180 for 6 hours, allowed to cool, and the unreacted benzyl chloride is poured in and dissolves the solid residue in 500 parts of butanol. It is filtered and mixed the filtrate with 3,000 parts of ether. Thereby 32o parts of a green-blue divide Compound from which one sucks off, crushed, slurried in the filtrate and again sucks. The green-blue crystal pulp turns white in the air (water of crystallization). At Zoo 'it turns sky blue again.

After recrystallization from alcohol, the compound melts 1g6 '. It has the following composition: [(CEHS) 3P] 2NiC12. C, HSCH.C1.

The ethereal filtrate is combined with the previously decanted benzyl chloride. After the ether, butanol and benzyl chloride have been distilled off (at the end in vacuo) the residue is distilled at 7 mm Hg under CO. This gives 20 parts of dibenzyl, 3 parts of stilbene and 7 parts of phenanthrene as residue.

EXAMPLE A mixture of 31 g parts of triphenylphosphine nickel carbonyl = (CEHS) 3P] 2Ni (C0) 2 with 399 parts of triphenylbutylphosphonium bromide [(C6 H5) 3 C4 H ;, P] Br in 1000 parts of butyrolactone are stirred for 3 hours at i7o to igo ' heated. After this time, the implementation is complete. The butyrolactone is distilled off in vacuo and the dark green melt that remains is taken up in 1,000 parts of ethyl acetate and heated to boiling under reflux for one hour. Then the undissolved residue is filtered off. A blue-green compound which is insoluble in ethyl acetate remains on the filter (F.: i55 '). It is recrystallized again from 1,000 parts of butanol and thus zoo parts of a blue-green compound (F .: 176-) of the following composition L (C, H;,) 3P] 2NiBr2 # C "H ,, Br.

Concentration of the filtrate gives a further 20 parts of the compound.

After the complex compound has been separated off, the filtrate is in vacuo concentrated further and, on cooling, 3o parts of one in methanol are obtained very well soluble, green-blue compound (F.: z53`), the composition of which is not certain is determined, it is probably a triphenyl-phosphinoxydtriphenylphosphine-nickelbromidv attachment. The ethyl acetate filtrate is obtained by concentration and recrystallization of the residue from 100 parts to 27o parts of triphenylphosphine (F.: 8o '). aside from that 6o parts partially unsaturated hydrocarbons with different boiling points are produced, including 2o parts benzene.

Example 5 63q parts of triphenylphosphine nickel carbonyl JC6Hs) 3P] 2 - Ni (C0) 2 and 786 parts of triphenylphosphine are included in 5ooo parts of cyclohexanone Stir heated to ioo '. It is left at this temperature for 5 hours 372 parts of benzyl chloride are added dropwise. The solution will gradually turn an intense blue. It is allowed to cool and the resulting blue crystalline compound is precipitated by addition of 30oo parts of ether completely. The precipitate is filtered off and after Pre-drying in the air at ioo 'dried in a drying cabinet. So you get 8io Parts of the compound [(C, Hs) 3P] 2NiC12 already described in Example 3. CIHSCH - C1. Triphenylphosphine nickel chloride is also formed in a minor amount in this reaction L '(C6 Ha) .3 P] 2-NL'C'2 (Tp: 2g2-).

The filtrate of the reaction mixture becomes the ether and finally the cyclohexanone largely removed in vacuo. The residue is with a soda-alkaline shaken aqueous solution and mixed with ether. The aqueous layer is separated and acidified with dilute sulfuric acid. Acidification gives 4o parts of phenylacetic acid, probably due to the action of carbon monoxide in the substituted nickel carbonyl on the benzyl chloride was formed. If you evaporate the essential solution, 300 parts of a residue consisting predominantly of triphenylphosphine are obtained.

Claims (3)

PATENT CLAIMS: i. Process for the production of complex phosphines in a further development of the process according to patent 817 gog, characterized in that heavy metals, unsubstituted heavy metal carbonyls and free halogen or those carbonyls of heavy metals in which some of the CO groups are caused by organic residues are allowed to act on quaternary phosphonium compounds in particular phosphine residues, is substituted. 2. The method according to claim i, characterized in that one on mixtures of tertiary phosphines with an organic halogen compound heavy metals or those carbonyls of heavy metals in which some of the CO groups is substituted by organic residues, in particular phosphine residues. 3. Procedure according to claim i, characterized in that part of the quaternary compound replaced by free halogen or an organic halogen compound.