DE1768914B - Process for the preparation of alkyl or cycloalkyl tin halides - Google Patents

Description

In the industrial production of alkyl tin halides, the direct reaction of metallic tin with alkyl halides offers significant advantages over the already known processes which tin tetrachloride is used as a starting material, which is added either with a Grignard compound or an aluminum alkyl compound to the Tetraalkyltin compound is reacted, from which then the desired alkyltin halide in one second process run is obtained by a disproportionation reaction with tin tetrahalide.

A number of processes for the direct reaction of metallic tin with alkyl halides are known which use highly reactive alkyl halides, particularly iodides. In most cases, however, these iodines are too expensive for the industrial production of alkyltin halides. There is therefore a need for a process in which the cheaper alkyl bromides and especially the alkyl chlorides can be converted directly to the corresponding alkyl tin halides in high yield. According to a known method, this can be achieved using arsenic or antimony halides as catalysts for the reaction, but the main aim of this method is the conversion of higher alkyl halide homologs. z. B. alkali halides in which the alkyl group contains more than 4 carbon atoms. In another known method, the reaction is carried out in the presence of an alcohol, an ether, a lister or tetrahydrofuran and in the presence of certain metals and / or alkyl metal halides. However, the need to use special solvents is a major disadvantage of this known method.

A process has now been found for the preparation of alkyl or cycloalkyl tin halides at an elevated temperature in the presence of antimony compounds. Thereafter, the reaction at 160 to 18O ⁰ C in the presence of organoantimony compounds of the formulas R ₃ Sb, R ₂ SbX ₁ R ₃ SbX ₂ or [R ₄ Sb] A, where R is a n-alkyl group having 4 to 8 C atoms or the phenyl radical, X a halogen atom and A a halide anion or a tetrahalometalate anion

ίο mean, in an amount of 1 to 8 mole percent, based on the tin used.

This process can be carried out with good yield and without the need for special solvents use, perform.

Usually the dialkyl or dicycloalkyltin dihalides are obtained as the main product, whereas the monoalkyl or monocycloalkyltin trihalides are formed as by-products, as well as - usually in small quantities - the

Trialkyl or tricydoalkyl tin monohalides.

The aforementioned organoantimony compounds are compounds of trivalent or pentavalent antimony in which the residues of one another can be different.

Examples of the organoantimony compounds used as catalysts according to this invention are:

Triethylantimony, Tri-n-butylantimony,

Triisobutyl antimony, Di-n-butylantimony bromide, Di-n-butylantimony chloride,

Ethyldibutylantimony, Tetrabutylantimony bromide,

Tributyl antimony dibromide, Tri-n-octylantimony, Di-n-octyl antimony bromide,

Divinyl antimony bromide, Tricyclohexylantimony,

Triphenylantimony, Diphenylantimony chloride, Tetraphynylantimony bromide, Bis (tetrabutylantimony) mercury iodide

[{(H ₉ C ₄ ) ₄ Sb} ₂ · HgJ ₄ ],

Bis (tetraphenylantimony) germanium iodobromide _{[((C 0} Hg) ₄ Sb) _{2 -GeJ 2} Br ₂ ].

In the method according to this invention

the organoantimony compounds are usually added in amounts of 3 to 5 mol percent, calculated on the tin used.

It is usually expedient to use, as the catalyst, an organoantimony compound in which the organic group (s) is (are) the same as the alkyl or cycloalkyl group in the halide to be reacted.

It is also advantageous if you can implement the less reactive alkyl or cycloalkyl halides, e.g. B. the bromides and chlorides wants to improve this a small amount of elemental .Iodine or an inorganic iodide or an alkyl iodide. z. B. an amount of 0.5 to 1.0 mole percent, preferably 1 to 3 mole percent.

based on the bromide or chloride present, to be added. So it is advantageous to use an alkyl or To add cyeloalkyl iodide in which the organic group is the same. like those in the alkyl or

Cycloalkyl chloride that is used. The iodide can also be in the form of an alkyl or cycloalkyl tin iodide be added, e.g. B. as dialkyltin iodide or tin tetraiodide. The proportion from alkyl or cycloalkyl halide to tin can vary within wide limits.

The shape and quality of the tin used as the starting material is essential for carrying out the process not decisive. In most cases a very good implementation can be achieved if The tin is applied in the form of fine chips, but it is also possible to use finer or coarser to use powdered tin as the starting material.

The process can take place both in a closed system under pressure and in an open one System to be carried out under atmospheric pressure; in this case it becomes the evaporating liquid returned via a reflux condenser. In the latter case, however, it is expedient, especially in the conversion of lower alkyl halides to add solvents with a high boiling point in order to to increase the reaction temperature.

Also, if an air sensitive catalyst is used, it is important to take the reaction off inert atmosphere, e.g. B. to perform under nitrogen.

The reaction mixture obtained can be treated further, as can the alkyl or cycloalkyl tin halides can by known methods, for. B. be purified by distillation. To the analytical Gas chromatography can be used to determine the composition of the mixture.

Any alkyl or cycloalkyl halide which is used in excess can practically completely recovered by distillation and used for another batch, as well as that added solvents. The antimony-containing residue from the distillation can often be used advantageously as a catalyst can be used for a further reaction.

The alkyl and cycloalkyl tin halides, respectively, obtained by the process of the present invention especially the dialkyl or dicycloalkyltin halides are valuable intermediates for the production of alkyl or cycloalkyltin compounds, which among other things as Find plastic additives use. The monoalkyl or monocycloalkyltin trihalides and the trialkyl or tricycloalkyltin monohalides, the Process by-products are also valuable intermediates, but it is It is also possible to convert these compounds into the dialkyl or dicycloalkyltin halides by means of a disproportionation reaction to transform.

The following examples are intended to explain the invention in more detail:

example 1

(■>, () g of pure tin in the form of shavings (0.1 to 0.3 mm thick) and 21.0g n-butylbmmide are in brought a Carius tube. After replacing the air with nitrogen, 0.5 g of di-n-butyl antimony bromide is added added and the tube is then heated to 180 ° C for 16 hours under its own pressure, whereby the tin goes completely into solution.

The tube contents are filtered off after cooling and the butyl bromide excess is reduced Pressure removed. Part of the residue is quantitatively methylated and the mixture obtained Methylbutyltin compounds analyzed by chromatography.

The analysis result shows that of the added tin 63.0% to di-n-butyltin bromide and 24.8% were converted to n-butyltin tribromide and that no detectable amount of tri-n-butyltin bromide was formed.

6.0 g of tin and 21.0 g of n-butyl bromide are heated in the same way without any further addition. Even after 16 hours no tin has converted. This clearly shows the catalytic Effect of the organoantimony compound.

Example 2

A mix of

6.0 g tin,
21.0 g n-butyl bromide,
2.0 g of n-buryl iodide and
0.5 g of tri-n-butyl antimony

is 16 hours under its own pressure in a Carius tube in which the air is replaced by nitrogen was replaced, heated to 180 ° C. After completion of the experiment, the reaction mixture is in the same Way further treated as described in Example 1.

The analysis result shows that of the added tin 70.6% to di-n-butyltin dibromide and 14.3% were converted to n-butyltin tribromide and that no detectable amount of tri-n-butyltin bromide was formed. In comparison to Example 1, this result shows the favorable effect of the added alkyl iodide to the formation of dialkyltin dihalide.

Example 3

With a mixture of the following composition:

6.0 g tin,

14.1g n-butyl chloride,

2.0 g of n-butyl iodide and

0.5 g of tri-n-butyl antimony

individual tests are carried out in a Carius tube at temperatures of 140 or 160 or 180 or

200 ⁰ C carried out every 16 hours. The following table shows the yields of butyltin chlorides, calculated from the analytical results of the reaction mixtures obtained, based on the amount of tin added.

n-butyltin trichloride

Di-n-butyltin dichloride

Tri-n-butyl tin chloride

Total amount of butyltin chlorine

Kill ( ISO C 2 (1 (1 ( 1 1.5 "(, 12.5 "., 7.5 "υ 5Ϋ8 "" 72.7 "■" 2-1.4 "" ¹ year 5 "ι, ^! 76, X "" S5.2 ".. 31.9 "ι. 140 C not individually definitely Ή) "η

5 6

tribromide, based on the amount of tin added,

Example 4 was achieved while undetectable amounts of A mixture of the same composition as tri-n-octyltin bromide was formed

in example 3, where however the tri-r.-butyiantimon ... · ι ο

is replaced by triphenylantimony, results after 5 e ι s ρ ι e

16 hours of heating to 180 ° C, the following In an autoclave with a stirrer

booty, based on the added tin quantity: Di- is equipped, a mixture of

n-butyltin dichloride 53.8%, n-butyltin trichloride _10Q q _tin (p _u i _{ver VO} n 0.1 to 0.3 mm

19.6% and tri-n-butyltin chloride nothing. 'Grain size)

Example 5 ^1O 235.0 g of n-butyl chloride,

33.0 g of n-butyl iodide and

A mixture of _{95 g of} tri- _{n-butylantimony}

ι λ λ Ϊ Jt ^. 'etc. ™ * after the air in the autoclave has been

A ⁸ vi ^y i _ri η ¹ S substance was replaced. The autoclave will now run for 3 hours

AI S AI the heated to 175 ° C, with the stirrer

0.6 g of Tn-n-butylantimony _{rotates at a speed of 480} rpm. Select

is 16 hours in a Carius tube, in the end of the reaction, the pressure rises to about

the air is replaced by nitrogen, to 180 ° C - 9 kg / cm ² .

heats. After the end of the experiment, 90% of the tin is reduced. After cooling, the contents of the autoclave are removed

been set, and a yield of 65.4 ⁰ Zo Di-η- treated further, as in the previous examples

butyltin dichloride and 6.2% n-butyltin triols. The test results show that

chloride, based on the amount of tin converted, 85.7% of the amount of tin added was converted

has been reached. the, with a yield of 71.5% di-n-butyl-

25 tin dichloride, 12.8% n-butyltin trichloride and

Example 6 9.0% tri-n-butyltin chloride was obtained. A mix of

6.0g tin, example 10

24.9 g n-octyl bromide, a mixture of

2.0 g of n-octyl iodide and ³ °

0.5 g tri-n-butylantimony J? '" ^G ■""" ·.,.,

^{6 J} 21.0 g n-butyl bromide,

is 16 hours in a Carius tube on 2.0 g of butyl iodide and

Heated to 180 ° C. in the same manner as above 0.5 g of tri-n-butylantimone dibromide

described. An overall yield of 80.2% n-Ok- 35 * _{1 £ Ε} -. j. ™ 1 · ·

tyltin bromide, based on the converted tin ™ ^approx . 16. ^StUn £ ^e "™ ter autogenous printing in one

³ , '. ,, ^{5 6} Carius tubes in which the air is replaced by nitrogen

amount, was achieved. _replaces ^ _{on lgQ0 Q & rh [m} ^ _{conclusion of the}

Example 7 experiment is the reaction mixture in the same Treated in the same way as in the previous 40 ^W ™ ^& as in Example 1. Examples is a mixture of ^The analysis result shows that of the tensile

put tin 73.4% to di-n-butyltin dibromide and

6.0 g tin, 15.1% converted to n-butyltin tribromide and none

24.5 g of cyclohexyl bromide and a detectable amount of tri-n-butyltin bromide were formed

0.5 g, tributyl antimony.

in a Carius tube for 16 hours at 180 ° C , based on an identical mixture of each

heated. After the end of the experiment it turns out that 45% £ ^OC J? ^without addition of n-butyl iodide, are the same

of the added amount of tin in a mixture of conditions of the added tin 57 to 4%

Cyclohexyltin bromides was implemented. Di-n-butyltin bromide and 27.4% to n-butyltin An experiment with a simple mixture that converted ₅ o bromide and also not a detectable one

1.38 g of iodine were still added, shows an amount of Tn-n-butyltin bromide formed.

Settlement of 48.3% of the added amount of tin. . ^ ₁₁₁ ^{B eis} P ^{[ e l 8} A mixture of A mixture of 55 _{6) 0 g} tin,

6.0 g tin (shavings from 0.1 to 0.3 mm), 14.1 g n-butyl chloride,

58.0 g of n-octyl bromide and 0.35 g of germanium iodide and

2.0 μ bis (tclra-n-butylantiinone) - 1.1 g tetiaphenvlanuir.onbromide

quccksilbLMiodide. ,,. .

60 in hours under nitrogen in a canister

is heated in a flask with a RüeklUißküliler uebiaelu rope tube to 180 C, see that

and heated to KSO C for 5 hours, with vigorously ee- Üis- (telraphaiylantimon) -gennaniuinjodidbromii.i HiI-

riilirt and nitrogen is passed over clic mixture. dot.

After filtering off , the mixture obtained is The analytical result shows that i depend on the converted

treated in the same way. as in the second Zimimenge 75.7 "," to di-n-bdtylzimidiclilorid

game 1 is described. S7 "0 of the added tin and 22.6" Ό to n-biitytin tin chloride umgj: ctzi and

amount were implemented. A yield of 57.4 "» no detectable amount of Ύπ-n-butyltin chloride

ni-n-OklvlzinnbiOinid and \ on 28.9 ¹¹ O n-Oktvlzinn- have been formed.

example
A mix of

12th

6.0 g tin, 14.1 g n-butyl chloride, 1.0 g tetra-n-butyl antimony iodide and 1.5 g n-butyl iodide

35

6.0 g tin,

21.0 g of n-butyl bromide and 0.5 g of diphenyl antimony chloride

is heated to 160 ° C for J6 hours under autogenous pressure in a Carius tube in which the air has been replaced by nitrogen. After the experiment has ended, the reaction mixture is treated in the same way as in Example 1.

The analysis result shows that of the added tin 13.7% to n-butyltin tribromide, 56.3% have been converted to di-n-butyltin dibromide and 5.2% to tri-n-butyltin bromide.

Example 13 A mixture of

6.0 g tin,

14.1 g n-butyl chloride,

1.1 g of tetraphenylantimony bromide and 2.0 g of n-butyl iodide

is heated to 180 ° C under nitrogen in a Carius tube for 16 hours.

The analysis result shows that of the converted amount of tin 52.8% to di-n-butyltin dichloride, 11.3% have been converted to n-butyltin trichloride and 6.3% to tri-nbulyltin chloride.

Example 14 A mixture of

is heated to 1 75 ° C. in a Carius tube under nitrogen for 16 hours.

The analysis result shows that of the converted amount of tin f> 9.5% to di-n-butyltin dichloride and 1 (p. 1% converted to n-Buivl / .mntrichlorid and no detectable amount of tri-n-vinyl chloride formed have been.

Example 15 A mix of

6.0 g tin, 14.1 g n-butyl chloride, 0.6 g of tri-n-butylantimony and 1.38 g of iodine

is heated to 180 ° C under nitrogen in a Carius tube for 16 hours.

The analysis result shows that 59.0% of the converted amount of tin is di-n-butyltin chloride and 22.8% converted to n-butyltin trichloride and no detectable amount of tri-n-butyltin chloride was formed.

Example 16 With a mixture of the following composition:

6.0 g tin, 14.1 g n-butyl chloride, 2.0 g of butyl iodide and 0.6 g of tri-n-butyl antimony

experiments are carried out twice in Canus tubes at different temperatures for 16 hours each accomplished. The following table shows the yields of butyltin chlorides. calculated from the Analysis results of the educated reaction mixtures, based on the amount of tin converted.

180 ° C a 'b 17O ⁰ C
a; b

160 ^? C.
Ah

n-butyltin trichloride .. Di-n-butyltin dichloride Tri-n-butyl tin chloride. Total yield

18.6%

72.7% 18.7% 70.3%

12.8% 75.4%

12.9% 74.1%

91.3% ; 89.0% 88.2% j 87.0%

j 1.0 · 0

69.9%

7.0%

11.4%

70.8%

5.9%

88.5% 88.1%

309537 / S

Claims (3)

Patent claims: 1. A process for the preparation of alkyl or cycloalkyl tin halides by reacting tin with alkyl or cycloalkyl halides at elevated temperature in the presence of antimony compounds, characterized in that the reaction is carried out at 160 to 180 ° C in the presence of organoantimony compounds of the formulas R ₃ Sb , R ₃ SbX, R ₃ SbX ₂ or [R ₄ Sb] A, where R is an n-alkyl radical having 4 to 8 carbon atoms or the phenyl radical, X is a halogen atom and A is a halide anion or tetrahalometallate anion, in an amount of 1 up to 8 mol percent, based on the tin used. 2. The method according to claim 1, characterized in that the reaction mixture organoantimony compounds are added, their organic radicals are the same as the alkyl or cycloalkyl groups to be reacted Alkyl or cycloalkyl halides. 3. The method according to claim 1 and 2, characterized in that in the implementation of Alkyl or Cacloalkylbromiden or -Chloriden the reaction mixture in addition and on the Bromides or chlorides related to 0.5 to 10 mol percent iodine in elemental form or in the form an inorganic or an alkyl iodide is added.