DE1062244B - Process for the production of organometallic or organometallic acetylene compounds - Google Patents

Description

Process for the production of organometallic or organometallic acetylene compounds Connections of organically substituted metals with the Äthingruppe are so far hardly known. Only acetylene derivatives of organosubstituted mercury and one Organosilicon acetylene compounds have hitherto been described in the literature. The mercury compounds were made alkaline-alcoholic by introducing acetylene Suspensions of alkyl mercury halides have been obtained. The silicon-acetylene compound was made by reacting acetylenedimagnesium dibromide with trimethylsilicon chloride, but only in the presence of catalysts such as CuCl.

The introduction of acetylene in organometallic compounds so far The methods described are on the one hand not generally feasible, on the other hand because of the use of the relatively rapidly decomposing acetylenedimagnesium dibromide difficult in technology.

It has now been found that one can use organometallic or organometallic acetylene compounds in which the hydrogen atoms of acetylene are replaced by organosubstituted metals or metalloids are replaced when partially organosubstituted halides of an ordinal number of over 7 having elements of the IV. and V main group of the periodic system, whose valences are not saturated by halogen atoms directly are bonded to the carbon, reacts with alkali acetylides.

In contrast to acetylenedimagnesium dibromide, alkali acetylides are Easily accessible from a technical point of view and can be kept indefinitely under exclusion of moisture.

The reaction with the alkali acetylides can depending on the stability the organosubstituted compounds in the presence of solvents or suspending agents, such as liquid ammonia, chloroform-ether mixtures, or carried out in melt flow will. It is advisable to exclude the presence of moisture.

As can be seen from the above reaction conditions, the Reaction in a fairly wide range of temperatures, e.g. B. below the boiling point of ammonia, or at a higher temperature, e.g. B. performed at the melting temperature will. The reaction product can e.g. B. when working in the presence of solvents or suspending agents after their evaporation by treatment with new solvents, such as diethyl ether, benzene or other solvents free of hydroxyl groups, worked up will.

In the above reactions, the reactants in stoichiometric amount can be implemented, but one of the components be used in excess.

Because of the incorporation of acetylene into the organometallic compounds whose activity is weakened, d. H. the connections are stabilized and Substituted lead acetylides in particular can reduce their toxicity can be used as an anti-knock agent. Further are the compounds in question as pesticides as well as due to their high energy content, in particular the Boracetylide, suitable as rocket propellants. Optionally, the compounds also find use as catalysts or as stabilizers for plastics.

Example 1 Bis (triethyltin) acetylene 2 (C, H5) 3SnC1 + 2 NaC, H _ (C.H ..) 3Sn-C-C-Sn (C, H ") 3 + C, H2 + 2NaC1 Triethyltin chloride is suspended in liquid ammonia and the equivalent or better double the molar amount of monosodium or monolithium acetylide added. After vigorous shaking, the cooling is removed and the N H3 is evaporated.

The evaporation residue is boiled with diethyl ether, the solution Poured off of formed alkali chloride and possibly excess alkali acetylide and filtered clear.

That left after evaporation of the organic solvent Bis (triethyltin) acetylene can be purified by vacuum distillation, whereby it is advisable to feed the boiling capillary with N2.

Most of the reaction product is at 123 ° C and 0.05 mm Hg above. Yield: 69% of theory. Example 2 bis (triphenylsilicon) acetylene 2 (C ,; HS) 3 SiBr + 2NaC, H - (C, Hs) s Si C = C-Si (C, Hs) 3; C, Hz -I-2 NaBr triphenyl silicon bromide is mixed with an excess of monosodium acetylide or monolithium acetylide and if moisture is excluded, heated for a long time with frequent stirring. The reaction is ended when there are no gas bubbles in the melt from the acetylene being released educate more. The mass is then cooled, pulverized and boiled in benzene. After the solution has cooled, the undissolved material is filtered off. By evaporation dcs Crude bis (triphenylsilicon) acetylene is obtained in the filtrate. The connection leaves z. B. by recrystallization from chloroform and alcohol mixture or from ligroin, further purify by chromatography and vacuum distillation.

The pure product melts at 156 ° C (from ligroin). Yield: 58% the theory.

Example 3 Bis (tribenzyltin) acetylene 10 g of tribenzyltin chloride are suspended in 200 ml of liquid ammonia and with 2 g of monosodium acetylide offset. Frequent shaking takes place during the evaporation of the ammonia. The evaporation residue is extracted twice with benzene. The benzene solution is suspended from sodium chloride and monosodium acetylide separated and evaporated completely. The residue is in dissolved in absolute chloroform and bis (tribenzyltin) acetylene with cold absolute Alcohol precipitated and recrystallized from ligroin.

The product is obtained in a yield of 700%. M.p. = 94 ° C.

Example 4 bis (di-a-naphthyl arsenic) acetylene 2 g of di-a-naphthyl arsenic chloride are dissolved in 40 ml of liquid ammonia and mixed with 0.4 g of monosodium acetylide. Frequent shaking takes place during the evaporation of the ammonia. The evaporation residue is extracted several times with benzene. The combined benzene extracts are used for separation of the suspended sodium chloride and monosodium acetylide by one with a 1 mm high asbestos layer covered glass frit filtered. That after distilling off of the benzene remaining bis- (di-a-naphthylarsen) acetylene is repeatedly removed Recrystallized chloroform.

The product is obtained in a yield of 500/0. M.p. = 232 ° C.

Example 5 bis (diphenyl arsenic) acetylene 1 g of diphenyl arsenic chloride is used suspended in 10 ml of liquid ammonia and stirred with 0.6 g of monosodium acetylide offset. The work-up is carried out as described above for the preparation of the naphthyl compound already described way. Only the purification is done by reprecipitation from one Chloroform-alcohol mixture.

The product is obtained in a yield of 74%. M.p. = 100.5 ° C.

Example 6 Bis (dimethyl antimony) acetylene 35 g of dimethyl antimony bromide without a solvent (the melting point is 89 ° C, but can be easily a supercooled melt is obtained because the substance is slow and incomplete crystallized) in a solution of 19.4 g of monosodium acetylide (= three times the stoichiometric Amount) in 350 ml of liquid ammonia added dropwise with stirring. After evaporation of the ammonia, the residue is extracted with ether and the solvent is evaporated off and the remaining oil is distilled under reduced pressure.

The product is obtained in a yield of 4001. Bp 18 = 120 ° C. Example 7 Mono- (diethylantimony) acetylene and bis (diethylantimony) acetylene 25 g Diethyl antimony bromide are dissolved in 150 ml of tetrahydrofuran and vigorously Stir into a slurry of 14.4 g (= three times the stoichiometric amount) of monosodium acetylide added dropwise to 50 ml of tetrahydrofuran. The mixture only heats up a little. The mixture is stirred for a further 2 hours and to separate off the suspended monosodium acetylide and sodium bromide filtered through a narrow-pore glass frit. The solvent is drawn off and the remaining oil is distilled under reduced pressure. You get two fractions.

The mono- (diethylantimony) acetylene is obtained in a yield of 35,5 ° / o.

Bp; 9 - 87 ° C.

The bis (diethylantimony) acetylene is obtained in a yield of 48.8 0/0.

Bp 1.5 = 122 ° C.

Example 8 bis (diphenyl antimony) acetylene 3 g monosodium acetylide are dissolved in 250 ccm of liquid ammonia.

This suspension is constantly stirred, and 5 g of diphenylstibine chloride, dissolved in a little ether, added slowly. The heat of reaction is low. It will now stirred until the ammonia has completely evaporated. The white residue is extracted with benzene and the benzene solution is decanted. The pale brown colored solution is filtered once through asbestos powder and then through an aluminum oxide column given. After this treatment the solution is clear and colorless. Now the benzene sucked off.

The bis (diphenyl antimony) acetylene is obtained in the form of small white ones Needles. To recrystallize, dissolve in as little chloroform as possible and precipitate Petroleum ether. After or up to five recrystallization, the substance is pure at its melting point.

The product is obtained in a yield of 54.1 ° F. = 1110C.

Example 9 Bis (triphenylgermanium) acetylene 7.5 g triphenylgermanium bromide are dissolved in 200 cc of tetrahydrofuran. 7 g of monosodium acetylide are put into this Solution added in portions. The mixture is refluxed for 11/2 hours while stirring. After cooling, it is filtered through asbestos wool. Obtained from the clear solution after stripping off the tetrahydrofuran in vacuo, a crude product consisting of benzene lets recrystallize well and then gives a white crystalline substance.

The product is obtained in a yield of 640/0. M.p. = 126.7 ° C.

Example 10 Bis (diphenyl bismuth) acetylene 8 g of monosodium acetylide are suspended in 400 ml of liquid ammonia. 25 g of diphenyl bismuth chloride dissolved in 350 ml of absolute tetrahydrofuran and added dropwise with stirring for 30 minutes admitted. The ammonia is left stirring for about 6 hours at room temperature evaporate. To dissolve the bis (diphenyl bismuth) acetylene from the residue, is extracted several times with absolute benzene. Under nitrogen is made by asbestos wool filtered until the solution became clear. After about the half of the benzene is removed in vacuo, crystals appear. By adding absolute Petroleum ether, the product is completely precipitated. Under nitrogen the voluminous Sucked off precipitate and dried in the flask on the oil pump for about 2 hours. To After drying, the bis (diphenyl bismuth) acetylene is melted down under nitrogen.

The product is obtained in a yield of 55%. F. = 153 to 154 ° C (with decomposition).

Example 11 Mono- and bis- (dibutylphosphorus) acetylene 5.2 g monosodium acetylide are slurried in 250 cc of tetrahydrofuran. 16 g of dibutyl phosphorus chloride, dissolved in 50 cc of tetrahydrofuran, slow down. in the course of 3 hours the stink stirred Slurry added dropwise. The reaction mixture is boiling for a short time heated of the solvent. The reaction products are then worked up. the Black-brown tetrahydrofuran solution becomes, when cold, of unreacted monosodium acetylide and sodium chloride decanted and the solvent evaporated.

A red-brown oil remains as a residue, which is a fractionated Is subjected to distillation. All work is carried out under nitrogen as a protective gas.

The first fraction of Kp.3 = 9 "C C is the mono- (dibutylphosphorus) -acetylene, which is obtained in a yield of 4.3 g = 28.5% of theory.

The second fraction of boiling point 3 = 162 ° C is bis (dibutyl-phosphorus) -acetylene, which is obtained in a yield of 3.2 g = 23.05% of theory. Example 12 Bis (triphenyl lead) acetylene 10.6 g of triphenyl lead bromide are dissolved in a solution of 2.6 g of Na C, H in 80 cc of liquid NH3 registered. After the ammonia has evaporated, the residue is dissolved with benzene extracted, the benzene evaporated and the remaining crude bis (triphenyl lead) acetylene first recrystallized from acetone, then from ligroin. Yield: 6.27 g (C, HS) 3Pb - CC - Pb (C, HS) 3.

Mp = 138.5 ° C.

Claims (1)

PATENT CLAIM: Process for the production of organometallic or metalloid organic Acetylene compounds, in which the hydrogen atoms of the acetylene are substituted by organos Metals or metalloids are replaced, characterized in that partially organic, nosubstituted Halides of elements of main group IV and V having an atomic number greater than 7 of the periodic system, which are not saturated by halogen atoms or hydroxyl groups Valences are bonded directly to the carbon, can be reacted with alkali acetylides. References considered: Gilman, H.,) Organic Chemistry, An Advanced Realize, "New York, 1938, Vol. I, p. 440; U.S. Patent No. 2,551,924; journal of the American chemical Society, 1952, p. 4853 ff.