DE1157617B - Process for the preparation of uniform tin alkyl compounds - Google Patents

Description

A number of processes have been proposed for the preparation of alkali compounds of tin, e.g. B. the action of Grignard's magnesium compounds on tin tetrachloride, a reaction that does not proceed very uniformly, because even when using 4 molecules of magnesium haloalkyl, due to the tetravalence of tin, in addition to tin tetraalkylenes, three rows of tin alkyl compounds are formed, which - using the example of Chlorides formulated - RSnCl ₃ , R ₂ SnCl ₂ , R ₃ SnCl are to be written. In the reaction between tin tetrachloride and z. B. Magnesium haloalkylene are also regularly obtained in addition to the tin tetraalkylene dialkyltin dichlorides and trialkyltin monochlorides. Cumbersome separation processes are then necessary to produce the pure substances from such mixtures.

It has already been proposed to obtain tin tetraalkyls from tin difluoride and aluminum trialkyls. Here - assuming the correct proportions - the reaction proceeds largely uniformly, what should be based on the fact that in this case one of the reaction products is the stable, sparingly soluble Forms aluminum fluoride. This method is not applicable to tin tetrachloride because the reaction runs inconsistently again, as the following example shows:

45.6 g of aluminum triethyl become very with the exclusion of air, good cooling and vigorous stirring Carefully add a total of 78.1 g of tin tetrachloride (molar ratio 4: 3) drop by drop. To When the mixture is complete, the cooling is removed and the reaction is allowed to continue for a further 2 hours at room temperature. If you now hydrolyze a sample of the reaction mixture, about 30% of the ethyl groups originally bound to aluminum in the form of ethane free. Ethyl groups on tin are not hydrolyzed under these conditions, so they cannot deliver ethane. One hydrolyzes then the entire reaction mixture, 7 g of tin tetraethyl containing 10% of the amount used are obtained Tin, 53.4 g, d. H. 74% of the tin originally used, as tin triethyl chloride and 5.9 g - 8% of the tin used as diethyltin dichloride. The result stays the same when you consider benzene Solvent used or the reaction mixture at the end at 80 or even 120 ° C for some time reheated.

In the published German patent application K 20 071 IVb / 12o, page 1, lines 18 to 26, reference is made to this inconsistent course of the reaction. The reaction, the manufacturing process, is similarly inconsistent
of uniform tin alkyl compounds

Applicant:

Dr. Dr. eh Karl Ziegler,
Mülheim / Ruhr, Kaiser-Wilhelm-Platz 1

Dr. Wilhelm Paul Neumann, Giessen,
has been named as the inventor

when aluminum trialkyls are allowed to react with tin tetrachloride in a molecular ratio of 1: 1. Under one could in accordance with these circumstances with a smooth stoichiometric reaction

AlR ₃ + SnCl ₄

R ₃ SnCl + AlCl ₃

expect the smooth formation of trialkyltin monohalides. In the case of ethyl compounds, however, only 82.5% of the _{tin used as SnCl 4 is obtained} in the form of organic tin compounds, and these consist of 30% Cl ₂ Sn (C ₂ Hj) ₂ and 68% ClSn (C ₂ Hj) ₃ and 2% from Sn (C ₂ Hg) ₁ . The experiment is no different, according to

2AlR., + 3SnCL

3R ₂ SnCl ₂ -i 2AlCl ₃

to make uniform dialkyltin dichlorides. In the case of the ethyl compounds, 24% of the SnCl _{4 was obtained} unchanged in this way, along with 37% ClSn (C ₂ H ₅ ) and only 33% SnCl ₃ (C ₂ H ₅ ) ₂ .

In the case of the tetraalkyl compounds of tin, the German Auslegeschrift 1048275 a uniform course of the reaction by adding alkali chlorides to the reaction mixtures obtain. The special effect of the alkali metal chloride in this process is based on the fact that in the Mixture of Aluminiunitrialkyl and tin tetrachloride set equilibria at which on the side of the Aluminum aluminum chloride and also alkyl aluminum chloride involved. Together with the alkali chlorides, these two substances are quite stable Complex compounds. They are removed from the equilibrium in the form of these complex compounds, therefore the reaction is then complete

309 749/424

3 4

these auxiliaries according to the invention in the direction of an extensive transition of the reaction phase

Alkyl groups on the tin. Requirement for to be used. You can use the

The feasibility of this process is obvious, etherates or aminates of the organoaluminum

that at least four alkyl compounds work per tin atom or that ethers are available as solution groups, as used in the 5 medium or even at the beginning in the

Examples of German Auslegeschrift 1 048 275 add reaction mixture. Finally you can

is also always given. The alkali chloride complexes but also the main reaction in the absence of

Aluminum trichloride or the monoalkylaluminum ether or amine can be played and then on

dihalides represent solid crystal masses of higher degree ether or tertiary amine in a quantity Melting points, which are difficult to clog from the reaction, are at least those of the aluminum used

have the vessels removed. is equivalent. In this last case it changes

It has now been found that the ether rate of the originally very complex composition of the

Alkylaluminum compounds in the reaction with reaction mixture subsequently with formation

the tin tetrachloride behave quite differently than the uniform reaction products. Appropriately heated ether-free alkyl aluminum compounds. In this case, after adding the ether resp.

war of ether, it is possible by suitable choice of tertiary amine for some time afterwards, so that the

the proportions of the starting materials, d. H. also occur in the event of changes in the reaction mixture

Use of approximately stoichiometric amounts of the can.

Reaction constituents, dialkyl tin dichlorides, trialkyl example 1 tin monochlorides and tin tetraalkyls in largely 20

Uniformly proceeding reactions each in and of itself in To 46.0 g of aluminum triethyl are left in

high yields without significant contamination, stirring and initial cooling to 0 ° C 78.2 g

tin tetrachloride drip through the other organotin compounds. Then add 45 cm ³

to manufacture. Diethyl ether and heats the mixture to

The invention relates to a process for completing the reaction to 80 ° C. Distillation Production of uniform tin alkyl compounds at 10 Torr gives pure tin without pre- and post-carriage from tin tetrachloride and aluminum alkyl compound tin tetraethyl, which passes over at 62 to 68 ° C. Ausgen, which is characterized in that you get tin booty: 68.1 g (97% of theory). The product is Tetrachloride in the presence of ethers or tertiary chlorine-free and goes into unit-amines with repeated distillation and aluminum alkyl compounds in stoichio- 30 Hch below 10 Torr at 62 ° C above, converts metric quantities. Suitable tertiary amines

are e.g. triethylamine, tributylamine, dimethyl- Example 2 cyclohexylamine, dimethylaniline, pyridine or quinoline.

46.0 g of triethyl aluminum are gradually added as alkylating organoaluminum compounds are not only aluminum trialkyls but also dialkylaluminum 35 with 78.2 g tin tetrachloride and 45 g dry

niummonochloride, sesquichloride and monoalkyl triethylamine. Initial cooling enables one

suitable for aluminum dichlorides. The ether or ter- rapid implementation of the reaction at 8O ⁰ C

tertiary amines are found at the end of the reaction in is terminated. The contents of the flask then remain the same

Form of their compounds with aluminum chloride. Liquid at room temperature. The reaction product is of these, the organotin reaction 4 ° below 10 Torr exaggerated (boiling point 62 to 73 ⁰ C)

products, insofar as their boiling points permit, and consists of pure tin tetraethyl, free of

be distilled off directly. The remaining chloride and triethylamine. Yield: 61.9 g = 88.2%

Aluminum chloride compounds of the ether or the theory,

Tiary amines are liquids or low-melting points substances that can easily be found in the distillation 45

have the vessels removed. The reaction can be added. 53 g of aluminum triisobutyl are gradually added

products can also be worked up simply by hydrolysis, adding 51.8 g of tin tetrachloride and then adding 28 cm ³

the ethers or tertiary amines from the hydro-diethyl ether too. Distillation from the reaction

lysis products can be recovered. mixture yields 66.1 g (95.4% of theory) at 10 Torr

For the production of dialkyltin preferably 5 ° to chlorine-free Zinntetraisobutyl that at 130 to 132 ⁰ C.

dichloride one has to pass one for each tin tetrachloride.

Amount of the organic aluminum compound - Example 4 set that as exactly as possible two alkyl groups

Are available, ie either 2 moles of monoalkyl- To 39.6 g of aluminum tri-n-butyl are added dropwise 39.1 g of aluminum dichloride or 1 mole of dialkylaluminum tin tetrachloride and then 30 g of dibutyl ether. monochloride or _^2/3 mole of aluminum trialkyl. The decomposition with water and hydrochloric acid should not mean that the external cooling is painstakingly separated, the phases in the vagina are separated according to the stoichiometric ratio down to the funnel and the organic layer of the per mil must be strictly adhered to. Natural distillation at 12 torr. After dibutyl you have here a certain freedom and does not need 60 (bp. To 50 ⁰ C) is the tetra-n-butyl at 149 ⁰ C greater care to use, as they generally above. Yield: 46.7 g = 90% of theory, which is necessary for normal organic preparative work. Even if you deviate example 5 by about 10% from the equivalence in each direction, you get

one still quite uniform reaction products. 65 80 g of tin tetrachloride are gradually added

As described, the presence of 22.8 g of aluminum triethyl and then with 25 cm ^{3 of} di-

of ethers or tertiary amines is essential. It's ethyl ether. At 10 Torr, the diethyltin formed goes

however, it does not matter in which way and in which dichloride at 100 to 102 ⁰ C after a forerun

of 2 g (Kp. to 8O ⁰ C). Yield: 68.1 g = 91.8% of theory.

Example 6

53 g of tin tetrachloride are reacted with 22.8 g of aluminum triethyl. Then 25 cm ^{3 of} dry diethyl ether are added and the mixture is distilled at 10 torr. At 90 to 93 ^° C. 45, Ig = 93.5% of theory go over to triethyltin chloride. Chlorine content: 14.6%.

Example 7

The mixture is left 52 g of tin tetrachloride with 39 g Aluminiumdiäthylchloriddiäthylätherat react and subsequently distilled, the resulting Diäthylzinndichlorid under reduced pressure (bp. _Lo = 101 ° C). 45 g (90.6% of theory) of the compound are obtained; Mp. 85 ⁰ C.

Example 8

From 130 g of tin tetrachloride and 124 g of Ätyhlaluminiumsesquichlorid with a procedure according to Example 2 after adding 101 g of triethylamine, a total of 110 g (91.4%) of pure triethyltin monochloride with 14.8% chlorine (bp. _Lo = 92 ° C). The residue consists of aluminum trichloride triethylaminate.

Example 9

78 g of tin tetrachloride are allowed to react with 53 g of aluminum di-n-butyl monochloride at room temperature. 30 cm ^{3 of} diethyl ether are then added, and after brief heating to 100 ^° C., 85 g (94.5% of theory) of di-n-butyltin dichloride (melting point 38 ^° C.) are obtained by distillation under reduced pressure.

Example 10

82 g of crystallized tin chloride etherate are added in portions to 22.8 g of aluminum triethyl. The reaction mixture was heated to 6O ⁰ C, then filtered off excess ether radicals and drives from the resulting triethyltin. Bp. ₁₂ = 93 to 95 ° C. Yield: 44.8 g = 93% of theory.

45

Example 11

22.8 g of aluminum triethyl are added dropwise to 81 g of tin tetrachloride with stirring and cooling to 0 ^{° C.} 26 g of dry dimethylcyclohexylamine are then added, the mixture partially solidifying. Distillation from the reaction mixture at 12 torr gives, after a small forerun, 65.4 g (88% of theory) of diethyltin dichloride, which solidifies immediately.

Example 12

41 g of tin tetrachloride are gradually mixed with 19.8 g of aluminum tri-n-butyl and then with 19 g of dry tributylamine. 42 g (90% of theory) of dibutyltin dichloride can be distilled off from the mixture. Kp. _{0) 15} = 88 ⁰ C.

Example 13

^{19.5 g of tin tetrachloride and then 25 cm 3 of} diethyl ether are added dropwise to 36.6 g of aluminum tri-n-octyl. Upon heating to 6O ⁰ C the mixture separates into two layers. The upper, colorless, is siphoned off and shaken with 10 cm ^{3 of} dilute hydrochloric acid and then with water _{to remove traces of AlCl 3.} After the organic phase has been separated off and dried, 39.4 g (92% of theory) of tin tetra-n-octyl are obtained. Chlorine content: Less than 0.1%. Instead of diethyl ether, an equimolar amount of diisopropyl ether can also be used.

Example 14

43.8 g of powdered tin ^{tetrabromide are mixed with 20 cm 3 of} diethyl ether, some of the etherate formed precipitating out. Then 18.8 g of aluminum triethyl etherate are added dropwise with stirring, the mixture is allowed to react for about 30 minutes and the excess ether is filtered off with suction. Distillation at 12 torr gives crude triethyltin bromide, which is separated from a high-boiling tail by fractionation. Yield:

24.3 g = 85% of theory; Bp ₁₂ = 96 to 97 ° C; Tin content: 41.3% · The result of the approach is similar if the equimolar amount of triethylamine is used instead of the ether.

Example 15

37.6 g of aluminum triethyl etherate are added dropwise to 123.3 g of dry, finely crystalline tin tetraiodide at about ⁰ ° C., the mixture liquefying. The volatile components are driven off at 12 to 15 Torr (bath temperature up to 180 ^° C.) and fractionated. Yield: 54.2 g of triethyltin iodide (83% of theory); Bp ₁₅ = 120 to 122 ° C; Tin content: 35.3%; Iodine content:

38.4%.

Example 16

To 104.2 g (0.4 mol) of tin tetrachloride are gradually added, with thorough mixing, 26.0 g (0.2 mol) of ethoxyaluminum diethyl and then 25 ecm of ether, left to react for IV2 hours (conversion is then complete, a sample does not develop any gas during alcoholysis) and the resulting ethyltin trichloride is distilled off. Bp ₁₂ = 86 ^° C. Yield 95.5 g = 94% of theory. The compound contains 41.75% chlorine (calculated 41.84%) and is stable if moisture is excluded.

Claims (2)

PATENT CLAIMS: 1. A process for the preparation of uniform tin alkyl compounds from tin tetrachloride and aluminum alkyl compounds, characterized in that tin tetrachloride is reacted in the presence of ethers or tertiary amines with aluminum alkyl compounds in stoichiometric amounts. 2. The method according to claim 1, characterized in that in the layer separation process the Aluminum chloride complex precipitates in the organic phase. 1 309 749/424 11.63