DE1229074B - Process for the production of dodecaboranate and / or. Dodecaborane thioetherates - Google Patents

Description

Process for the production of dodecaboranate and / or. Dodecaborane thioetherates The invention relates to the production of new dodecarboranate and / or. Dodecaborane thioetherates, which have a hydrolytic, oxidative and chemical resistance have, as it normally belongs to aromatic compounds. The twelve boron atoms form a cage in which each boron atom is adjacent to at least four other boron atoms is.

The group in which the 12 boron atoms are contained acts on chemical Reactions as a unit. The hydrogen atoms of this cage can be just like the Hydrogen atoms in aromatic compounds are substituted so that the can attribute an "aromatic" behavior to new compounds.

The dodecaboranate and / or produced according to the invention. Dodecaborane thioetherate have the formula Herein and below, M is an atom or a group which carries one or more positive charges; X is halogen or a carbacyl radical; n is 1 or 2; (2-n) represents the number of groups M contained in the compound; (n - 2) indicates the charge of the group in square brackets; y has a value from 0 to (12-n) and b has a value of at least 1 and is equal to the valence of M; R and R 'are organic groups contained in the thioether used as a reactant.

The compound of the formula (1) can be divided into two groups. For n = 1 the formula is: M [B12H11-yXy. SRR '] b (2) Here y is an integer from 0 to 11.

For n = 2 the formula is: B12H10-yXy 2 SRR '(3) where y is one Number from 0 to 10.

The unsubstituted compounds falling under the formula (1) are represented by the general formula: The compounds of the formula (4) can be divided into two subgroups depending on the value of n. For n = 1 the formula is: M [Bl2Hll SRR '] b (5) For n = 2 the formula is: B12 Hi0 2 SRR' (6) The sulfur atom of the thioethers of the formula SRR 'is capable of attaching an electron pair to the boron cage to be released with the formation of a stable covalent bond.

The nature of the organic groups R and R 'attached to the sulfur are is not critical. So R and R 'can be aliphatic, cycloaliphatic, aryl, Be aralkyl, alkaryl, heterocyclic groups or combinations of these groups. R and R 'can also be carbon chains interrupted by oxygen atoms. R and R 'can be joined to form a ring, the sulfur being a Is part of the ring, e.g. B. tetrahydrothiophene and p-oxathiane. The number of carbon atoms in R and R 'is not critical. Only for reasons of the availability of the thioethers it is recommended that R and R 'aliphatically saturated hydrocarbon groups of up to 18 carbon atoms and that at most one of the groups R and R ' is an aryl group.

X is a halogen atom or the residue of a carboxylic acid.

The group M is defined as an atom or group of atoms, which forms a cation in aqueous solution. It preferably has a valence of at most 4, in particular of 3. The properties of group M are not critical. For example, M can be a proton, hydronium, a metal cation, a metal amine complex, an optionally substituted ammonium or hydrazonium, sulfonium or phosphonium ion be.

The new compounds are obtained by adding a boranthioetherate adduct with diborane (B2H), pentaborane (9) (BsH>) or decaborane (14) (BloHlL) to at least 50 "C heated.

The adducts are from B u r g and W a g n e r, J. Amer. chem. Soc., 76, 3307ff. (1954).

They contain one or more of the characteristic groups = S - BH2.

You can use the adducts for the subsequent reaction with a borohydride used as such, or they can be made in situ. In the case of the latter The adduct is reacted without purification.

With diborane, the process is advantageously carried out by Adds diborane continuously or in sufficient quantities to the thioether at the beginning, to form the adduct and the polyhydropolyborane compound in one go. at In this way of working, the thioether can initially have a temperature which is lower than the final reaction temperature, whereupon the mixture is adjusted to the desired Temperature heated. The starting temperature at which diborane is fed is with regard to the ease with which the adduct (BH2-SRR ') forms, not critical.

The mechanism of the reaction has not yet been clarified. At paragraphwise Procedure diborane and thioether are mixed at a suitable temperature, im generally not above about 35 ° C, and at atmospheric pressure. The temperature is left of the mixture increase until the adduct is formed. This level can be achieved through the Equation can be expressed: 2RR'S + B2H6 2 2RR'S-bras (7) In the by equation (7), no volatile by-products are obtained.

The adduct thus formed is mixed with diborane, pentaborane (9) or decaborane (14) heated to at least 50 "C until hydrogen evolution occurs.

The process can also be carried out continuously.

The products resulting from the crude reaction product of the above process obtained in the stages to be described later consist of new and known ones Links. All products contain nine to twelve interconnected boron atoms. The known boron compounds obtained in the process include adducts of thioethers and nonaborane (13), d. H. B> Hl3 SRR '.

In addition to the compounds according to the invention, compounds of the formulas Mat (B12 H12) bt and M (Bl1H14) are also obtained. In these formulas, M and b are as defined in formula (1), and a 'and b' are the smallest integers corresponding to equation a '. Values of M = 2 are sufficient. The reaction taking place in the process can be represented as follows: B2H6 + RR'S -BH3 warmth Heat, reaction product + H2 > BgHls SRR t times (B12H12) bl + M (BllHl4) b + M ((2 ~ n) [Bl2Hl2-n n SRR '] (n-2) + H2 (8) The composition referred to in equation (8) as the "reaction product" contains a compound of the formula (4) and an ionogenic compound with a cation and a boron-containing anion which contains several boron atoms. The reaction of this reaction product with water or alcohols, which in solution may contain a compound with the cation M, gives one or more ionic polyhydrododecaboranates of the type described above, which contain the cation M and which include the compounds of the formula (5).

Equation (8) shows that hydrogen is a gaseous by-product the reaction is. The amount of hydrogen produced can be considered an approximate Serve a measure of the completeness of the reaction.

The minimum temperature for the reaction is 50 "C.

The yields depend on the products shown in equation (8) to some extent on the reaction temperature. So you get between 50 and 100 ° C as the main product, the Bg compounds; above about 100 ° C the main products are the B12 compounds.

The preferred temperatures vary somewhat with the pressure at which Reactivity of the respective adduct and with the borohydride used. the Increasing the temperature generally leads to a higher rate of reaction. The process is feasible at temperatures up to about 400 ° C, excessively high However, temperatures are not an advantage. A particularly preferred temperature range is between about 60 and 200 "C. The temperature can be gradual or in one Train to be increased to the desired value.

The pressure is not critical; h., the process can be carried out with negative pressure, Perform at normal pressure and at overpressure. It is beneficial to the respondents to be kept in close contact with each other during the procedure. For this reason the process can advantageously be carried out at overpressure if the used Reactants are volatile or have a high vapor pressure at the reaction temperature to have. Pressures of up to 500 ata can be used. In general, with diborane a pressure of at least 5 atmospheres is applied. A precise pressure control is unnecessary. When using a closed reaction vessel, it becomes common the autogenous pressure applied. The borohydride can be used in excess, it can be mixed with inert gases such as nitrogen, argon and helium.

The molar ratio in which the reactants are used, is not critical. The molar ratio of borohydride to adduct is preferably from Thioether and borane at least 1. In the case of diborane and a thioether as reactants the molar ratio of diborane to thioether is preferably greater than 1. In order to achieve high yields to achieve polyboron compounds, it is desirable to use the borohydride in considerable Use excess, especially if diborane is taken as a reactant will. In the case of diborane, for example, the molar ratio of B2H6 to organic sulfide can be greater than 2. The molar ratio in which the reactants are present in the reaction zone are determined to a large extent by the method of operation, i. H. whether one paragraph by paragraph, works continuously or according to a combination of both methods.

The reaction vessel is made of a corrosion-resistant material lined. Ordinary vessels or pressure vessels can be used. The reaction will preferably carried out under substantially anhydrous conditions. The reaction vessel is generally with an inert gas prior to charging the reactants flushed. When using diborane as the borohydride, the vessel is expedient first charged with the thioether and then with the borohydride. If you have a pressure vessel applies, this can be cooled to low temperature and evacuated to the To facilitate loading with a volatile borohydride.

To carry out the process at atmospheric pressure, the reaction vessel equipped with a gas inlet pipe, a reflux condenser and a cooling template which is connected to the reflux condenser.

With decaborane (14) the adduct and the borohydride are simply mixed and heated to reaction temperature, d. H. until a rapid evolution of hydrogen entry.

Mixing the reactants while performing the Procedure can be beneficial.

The response time is not critical. In a batch process the time is generally between about 1 and 50 hours. Generally enough a response time of 5 to 25 hours for batch operation. For a continuous operation, much shorter reaction times can be used, and the unreacted components can be recycled to the reaction zone will.

Optionally, the reaction between the borohydride and the adduct carried out in the presence of an inert solvent. In many cases it is Adduct is liquid at reaction temperature and can also serve as a solvent.

The volatile by-products are added to the work-up of the reaction products generally removed by placing them in a very low temperature (e.g. the temperature of the liquid nitrogen). The by-product Accruing hydrogen is volatile with the other possibly present Products removed. With regard to flammability and toxic hazard The volatile products should vent the reaction vessels accordingly done carefully.

That which remains in the reaction vessel after the volatile components have been removed The crude reaction product is usually a syrup or a mixture of liquid and crystalline components. The raw product gives a gas, mainly hydrogen, if it is exposed to air or if it comes into contact with water or alcohol brings. When working up the product, it is not necessary to exclude air. The crude reaction product is expediently extracted with water or with hot methyl alcohol or ethyl alcohol, in which both the ionic and the non-ionic products are soluble. The non-ionic product (6) falls on cooling the alcoholic Solution and can be separated in the usual way. The ionic product (5), that remains in solution is acidic in character and is expediently in the form of a salt isolated by neutralizing the acidic solution with a base. Possibly the salt is further purified by recrystallization.

Groups X are introduced by relocating a connection of formula (4) with halogens or reactive to Ab carboxylic acid derivatives.

A catalyst can be used in the substitution, e.g. B. Aluminum trichloride, boron trifluoride and polyphosphoric acid.

The implementation of the boron compounds of formulas (5) and (6) with the electrophilic reagent is made in the usual reaction vessels with corrosion-resistant Lining carried out. The boron-containing reactant and optionally an inert liquid solvent are presented. The other respondent is then fed at a temperature and at a rate which is a a controllable response and a full response in a timely manner Implementation lead. The temperature here is generally between about -20 and 2000 C, preferably between about 0 and 150 "C. The reaction generally proceeds quickly, and with thorough mixing of the reactants, the Response time can be very low. In general, a reaction time is between about 10 minutes and 5 hours off.

The reaction can be carried out under pressure. In most In some cases, the reaction proceeds sufficiently quickly at normal pressure. The proportions, in which the reactants are used are not critical. To a To achieve maximum yield of the desired product, it is advisable to at least To use 1 mole of the carboxylic acid derivative or the halogen for each hydrogen atom, which should be suppressed. The compounds are made according to known methods cleaned.

Compounds of the formula (2) are obtained by double reaction, where one z. B. the cesium, triethylammonium or tetraalkylammonium salts are used, which are easily obtainable by the method described above.

Compounds of the formula (2) in which M is an alkali or alkaline earth metal can be subjected to a double rearrangement with other salts in order to to effect a cation exchange.

Compounds produced according to the invention in which M is a metal cation, in particular a transition metal cation or a Werner complex are often included Solvent from crystallization if isolated by conventional methods will.

The new compounds are liquid to solid. You are with the usual resistant to atmospheric temperatures and pressures. They are usually colorless or white and, when solid, usually crystalline. Color and other physical Key figures are determined to a certain extent by the substituent X.

Many of the compounds dissolve in water or alcohols. In relation Two groups can be distinguished in terms of their behavior in water. The connections (2) are ionic in character, while the compounds (3) are neutral and non-ionic are.

The ionogenic compounds generally have a greater solubility in the water as the non-ionic compounds; this solubility difference is used to separate and purify the groups.

The compounds made according to the invention are thermal and chemically unusually resistant.

The compounds (1) are more inorganic in the presence of aqueous solutions Resistant to bases, a property which is unusual for boron compounds.

All of the compounds represented by the formula (1) are considered to be flammable Components of fireworks kits can be used to give the fireworks a pleasant color and to give beautiful glitter.

The compounds prepared according to the invention are also used as impregnating agents suitable for cellulose products in the manufacture of resistors.

The free acids are strong acids; they are particularly useful when there is contamination by sulfate, chloride, bromide, chlorate, phosphate and the like strong acid anions should be avoided. So are the acids of formula (2), in where M is equal to H (or H3O +), for etching metals, for removing rust, for Pickling and suitable for descaling.

The acids are also used as catalysts in the manufacture of esters usable e.g. B. in the implementation of alcohols and organic carboxylic acids. The acids prepared according to the invention are used in the same for this purpose Used way like p-toluenesulfonic acid, sulfuric acid or alcoholic hydrochloric acid.

The acids and many of the salts, especially the alkali and alkaline earth salts, can be used as complexing agents for heavy metals.

The new compounds, especially the acids, the alkali, alkaline earth and ammonium salts, are also valuable as complexing agents for metals in aqueous media.

The substituted ammonium salts and in general all salts of the Nitrogen bases and the phosphonium and sulfonium salts are also used as complexing agents valuable.

The silver salts are light sensitive and therefore used in photography usable.

Example 1 A corrosion-resistant pressure vessel is evacuated (capacity 100 ml) to a pressure of less than 1 torr and cools it by immersion in a bath of solid carbon dioxide and acetone. The cooled vessel is filled with 5 ml of dimethyl sulfide and 1.7 g of diborane charged. The vessel is closed and then with stirring 10 Heated to 100 ° C for hours. The reaction vessel is then cooled to room temperature, and the volatile products are removed by venting. This gives 0.101 Moles of hydrogen. The residue remaining in the reaction vessel is a mixture of Crystals and a syrupy liquid. The solid fraction is filtered off; 0.73 g of a white, crystalline product is obtained which is found in the elemental analysis the following values result: C 21.02, H 9.09, B 39.64, S26.6.

The filtrate is distilled. One receives identifiable products Dimethyl sulfide (unreacted) and BH8 - S (CH3) 2.

The white, crystalline product is boiled in aqueous ethanol, whereby an acidic solution and an insoluble white solid are obtained. the solid mass is filtered off from the hot mixture.

It consists of trimethylsulfonium dimethyl sulfide undecahydrododecaboranate (1-), [(CH3) 3S] + [B12H11. S (CH3) 2] -.

The formula for this compound is usually given without square brackets written: (CH3) 3SBl2Htl S (CH2.

The identity of the compound is indicated by its ultra-red absorption spectrum confirmed.

The hot aqueous ethanol filtrate obtained above is with Triethylamine adjusted to pH 9.

The solution is cooled; an oil separates out, which to a white, solid substance crystallizes.

The solid is filtered off, whereby 0.095 g of triethylammonium dimethyl sulfide undecahydrododecarboranate is obtained (1-), [(C2H5) 3 NH] [B12 H11 5 (CH3) 2] e is obtained. This connection can also be (C2H5) 3NHB12H11 . S (CH3) 2 can be written. The identity of the compound is determined through elemental analysis and ultrared absorption spectrum confirmed.

Analysis for (C2H5) 3NHBl2Hll S (CH3) 2: Calculated ... B 42.53, N 4.60, C 31.47, H 10.81; Found ... B 43.02, N 4.63, C 34.57, H 11.13.

4.74.

The ultrared absorption spectrum in Nujol of (CH3) 8 SB12H 5 (CH3) 2 shows the following bands (omitting those that apply to Nujol), in cm-l: 2500, strong, sharp; 1420, medium, sharp; 1360, weak, sharp; 1330, weak, spicy; 1070, weak, sharp; 1050, weak, sharp; 1005, weak, sharp; 975, medium, hot; 950, weak, broad; 845, weak, broad; 835, weak, sharp and 725, medium, broad. There will be very weak absorption in the 1500 to 2000 cm-1 range noticed.

The ultrared absorption spectrum in nujol of (C2H5) 3NHB12H11 S (CH3) 2 shows the following bands (omitting those that can be assigned to Nujol): 3150, medium, hot; 2500, strong, sharp; 1410, medium, sharp; 1370, medium, sharp; 1360, medium, hot; 1320, weak, sharp; 1300, weak, sharp; 1280, weak, spicy; 1170, medium, sharp with a weak shoulder at 1180; 1150, medium, spicy; 1070, medium, hot; 1040, strong, sharp with shoulder at 1030; 1010, medium, spicy; 995, medium, hot; 965, strong, sharp; 830, medium, hot; 805, weak, spicy; 790, weak, sharp; 720, strong, broad with a shoulder at 735.

The compound (C2Hs NHB, 2 H, 1 S (CH8) 2 in methanolic solution is characterized by a BIl nuclear magnetic resonance spectrum, which consists of a Doublet with a high field portion of a smaller area exists with the center at d = 33 ppm compared to trimethyl borate; the JB-H value is 133 cP. The UV spectrum the compound shows no absorption.

Example 2 A. A corrosion-resistant pressure vessel is evacuated (capacity 400ml) to less than 1 Torr and cools it down by immersing it in a bath of solid carbonic acid and acetone. The vessel is charged with 30 ml of dimethyl sulfide and 25 g of diborane. It is closed and heated to 100 ° C. for 10 hours while shaking. Then cool the vessel off and removes volatile products by venting under reduced pressure. A white, solid residue of 21.3 g remains Vessel. The solid is boiled in water, which contains a small amount of ethanol has been added. One notices a weak evolution of gas. The insoluble Material is filtered off and the hot aqueous filtrate, which is strongly acidic, for the further work-up set aside.

The insoluble fraction is extracted repeatedly with hot ethanol. The ethanol solutions yield 5.9 g of Bl2Hlo 2 5 (CH3) 2 on cooling. Your identity is confirmed by its ultra-red absorption spectrum and by elemental analysis. The product is a white, soft, microcrystalline mass that grows at 220 to 240 ° C melts with decomposition.

Analysis for B12 H, O 2 S (CH3) 2: Calculated ... B 49.15, S 24.27, C 18.18, H 8.40; found . . B 47.27, S 23.54, C 17.87, H 8.22.

47.50, 17.52, 8.66.

The hot aqueous filtrate obtained as above is cooled; It's falling a white, solid mass. This is filtered off and 0.17 g of trimethylsulfoniumdimethylsulfide-undecahydrododecab is obtained orange at (1 -) (CH3) 3SB12H11. S (CH3) 2.

The identity of the compound is indicated by its ultra-red absorption spectrum and confirmed by elemental analysis.

Analysis for (CH3) 3SB12H11. S (CH3) 2: Calculated ... B 46.2, S 22.8, C 21.4, H 9.35; found . . B 46.57, S 23.08, C 21.29, H 9.23.

The cooled filtrate, which after separation of the trimethylsulfonium compound remains, is titrated with triethylamine. As the first solid product fall 4.1 g of triethylammonium dimethyl sulfide undecahydrododecaboranate (1-), (C2H5) 3NHB12H11 . S (CH3) 2 on. As a second solid product that separates out when the filtrate is concentrated, 1.3 g of bis (triethylammonium) dodecahydrododecaboranate (2-), [(C2H5) 3NH] 2B12H12 are obtained.

The yield of the products based on that used in the reaction Diborane is: 9% Bl2Hll 5 (CH3) 2 l derivatives, 3% B12H12-2 derivatives and 15% B12H10 . 2 S (CH3) 2.

B. The procedure described in Part A of this example is carried out using varying amounts of dimethyl sulfide with a constant amount of diborane. In each case, the reaction mixture is heated to 100 ° C. under autogenous pressure for 10 hours. A main product obtained in each case is Bl2Hlo 2 2 S (CH3) 2. Applied amount Melting point Analysis of B12H10. 2 S (CH3) 2 (CH3) 2S B2H6 of the product % B% S% C% H (ml) (g) (° C) 1 1.8 49.05 23.37 16.94 8.23 224 to 225 3 1.8 46.77 24.68 17.79 8.79 193 to 200 17.54 8.59 4.7 1.8 48.37 23.75 19.33 8.82 224 to 230 Example 3 A corrosion-resistant pressure vessel (capacity 400 ml) is evacuated to less than 1 torr and cooled by immersion in a bath of solid carbon dioxide and acetone. The vessel is charged with 30 ml of dimethyl sulfide and 20 g of diborane. The vessel is closed and heated to 150 ° C. for 10 hours while stirring. The vessel is then cooled and volatile products are removed by venting through a receiver that is cooled with liquid nitrogen and suctioning it off to a low pressure.

18 g of a yellow-brown colored semi-solid product remain in the vessel, which becomes solid in the air.

The product is, as described in Example 2, worked up and results in the following compounds: 5.4 g (C2H5) 3NHB12H ,,. S (CH3) 2, 10.1 g B12H10. 2 S (CH3) 2 and about 0.6 g (CH3) 3SB12H11 S (CH3) 2.

The identity of these three products is indicated by their ultra-red absorption spectrum confirmed. The identity by B12H10. 2 S (CH3) 2 is also determined by elemental analysis confirmed.

Analysis for B12H10. 2 S (CH3) 2: Calculated ... B 49.15, S 24.27, C 18.18, H 8.40; Found ... B 48.51, S 24.97, C 18.54, H 8.46.

48.29, 24.83, 18.60, 8.39.

Molecular Weight: Calculated ... 264.18; found ... 256, 271.

The yield of products based on the amount of in the reaction space introduced diborane, is 15% for Bl2Hll. S (CH3) 2 derivatives and 31 0 / o for Bl2Hlo. 2 S (CH3) 2.

A. Using the procedure described in Example 2, Part A is a mixture of 24 g of di-n-propyl sulfide and 10 g of diborane under autogenous pressure Heated to 150 ° C. for 10 hours while stirring.

The vessel is cooled and volatile components are removed by venting under reduced pressure. About 19.7 g of a clear, viscous liquid remain return. The liquid is boiled with water and a development is noticed of gas. An oily layer forms, which is separated by decanting.

The aqueous layer, which is acidic, is filtered off.

The filtrate is neutralized with an aqueous solution of cesium hydroxide. A white precipitate forms, which is filtered off and recirculated twice from water will; 1.12 g of cesium - di - n - propylsuffid - undecahydrododecaboranate (1-) are obtained, CsB12 H11 5 S (C3H7) 2.

The identity of the compound is determined through elemental analysis and through the ultrared absorption spectrum is confirmed.

Analysis for CsBl2Hll 5 S (CsH7) 2: Calculated: Cs 33.9, C 18.38, H 6.43, B 33.10, S 8.18; Found: Cs 31.45, C 17.66, H 6.51, B 32.76, S 8.58.

17.66, 6.52.

The compound's ultra-red absorption spectrum in a nujol trituration shows the following bands (expressed in cm-1 and omitting those that apply to Nujol Bands): 2500, very strong, sharp; 2000 to 1600, four bands, very weak, broad; 1400, medium, hot; 1360, weak, sharp; 1340, very faint, sharp; 1290, very weak, sharp; 1230, weak, sharp; 1100, weak, sharp; 1070, medium, hot; 1050, strong, sharp; 975, medium, hot; 905, weak, broad; 850, shoulder at 840, medium, hot; 780, weak, broad; 720, medium, wide, shoulder at 740.

The oily layer previously separated by decantation is again boiled with water and separated. It will be about 24 under less than 0.1 torr Heated for hours. The BlaHlo 2 S (C3H7) 2 does not crystallize under these conditions Completely. It is soluble in aqueous ethanol and its solution does not reduce the silver ion to free metal.

Analysis for B, 2H, O 2 S (C3H7) 2: Calculated ... C 38.3, H 10.18, B 34.45, S 17.04; Found ... C 37.58, H 10.34, B 35.39, S 17.28.

The adduct RR'S formed as the initial reactant - BH3 can optionally be separated after its production and with BsHg and BloHl4 implemented.

B. A 200 ml reaction vessel which with a reflux condenser, a pipe for introducing solids, a thermometer and magnetic stirrer and is placed in a cold bath of about -78 ° C is located, is charged with 12 mol of dimethyl sulfide.

A vacuum of less than 1 tori is applied.

0.075 mol of diborane is introduced into the cooled vessel, with forms a slurry by reaction with the sulfide. The reaction mixture is left Heat to about 25 "C. The slurry melts to form a clear Liquid. The pressure in the vessel, which is about 100 Torr at this point, becomes reduced to about 30 torr.

With this measure, excess dimethyl sulfide is removed.

Argon gas is introduced into the vessel until the pressure is 1 atmosphere and then connects the vessel with a wet knife through one with mercury sealed washing unit. The pipe for the supply of solids is 4.2 g B, 0H14 charged; a small amount of the compound will be in the reaction mixture given. The mixture will heated to 50 to 80 ° C. with stirring. A yellow color and gas evolution begins. The temperature of the reaction mixture rises to 101 "C, and the mixture boils under reflux.

The remaining part of the B10H, 4 is now slowly added and that Heating of the reaction mixture with stirring continued for about 4 hours. In this Time have about 4.5 liters of gas from the almost colorless solution, which is a white Contains small quantities of solid matter. The mixture is cooled to about 50 to 60 "C and subjects it to reduced pressure to remove volatile products. The non-volatile product is a solid mass weighing 10.3 g.

A portion (6.1 g) of the solid is boiled with water until the gas evolution has stopped. The resulting water-insoluble white solid is filtered off from the hot solution. 2.1 g of bis (dimethyl sulfide) decahydrododecaborane are obtained, B12H, 02 S (CH2) 2.

The hot filtrate obtained above is cooled and the precipitated one white mass filtered off. 0.075 g of trimethylsulfonium dimethylsulfide undecahydrododecaboranate (1-) are obtained, (CH2) 3SB12H ,, S (CH3) 2.

The cold filtrate, which reacts strongly acidic, is mixed with aqueous CsOH neutralized; a white solid mass precipitates out. This mass is filtered off and purified by dissolving them in boiling water and adding the hot solution slowly cools down. 2.2 g of cesium dimethyl sulfide undecahydt ododecab oranat (1-) are obtained, CsB, 2H, 1 S (CH3) 2. lThe identity of the compound is indicated by its ultra-red absorption spectrum confirmed.

A second portion (about 0.5 g) of the in the reaction of BloHl4 with BH S (CH3) 2 obtained non-volatile solid crude product is dissolved in dichloromethane solved. The solution contains [BH2. 2 S (CH3) 2] [B12H11. S (CH3) 2].

Trimethylamine is bubbled through the solution for 5 to 10 minutes, around the cation in [BH2. 2 N (CH3) 3] + to convert. The solution comes in two portions on; divided. A portion is filtered off after standing for a short time.

Water and ethanol are added to the filtrate and this is then added occasional addition of water until the dichloromethane is removed.

The solution is filtered hot and the filtrate is allowed to cool. It's falling a white solid mass which is filtered off; 0.025 g of [BH2 # 2 N (CH3) 3] is obtained [B, 2H11 S (CHs) 2. The identity of the compound is indicated by its ultra-red absorption spectrum (Bands in cm-1, obtained in Nujol) confirmed: 2500, strong, sharp; 1480, weak; 1420, medium, sharp; 1350, 1330, 1310, very faint, sharp; 1240, medium, hot; 1200, shoulder; 1180, medium, hot; 1120, doublet; 1100, weak, sharp; 1070, weak, sharp; 1050, medium, hot; 1000, medium, hot; 975 (shoulder at 985), medium, hot; 910, medium, hot; 850 (shoulder at 830), medium, sharp; 910, weak, broad; 745, weak, broad; 720, medium, wide.

Mix the second portion of the dichloromethane solution with about 1 ml of water and leaves trimethylamine pearl through the mixture. That Mixture is worked up as in the previous paragraph; you get more 0.025 g [H2B. 2 N (CH3) 3] [B12H11. S (CH3) 2].

Example 4 The salt [(C2H5) 3NH] B12H11 obtained according to Examples 1, 2 and 3 S S (CH3) 2 is dissolved in hot water. The aqueous solution is passed through a Column filled with an acidic ion exchange resin (Amherlite IR-12OH), and receives an aqueous solution of HB, 2Hn S (CH3) 2 or, in hydrated form, (H3O) B12H ', S (CH3) 2. The compound is a strong acid and is in boiling Water does not decompose.

The acid, which is in the form of solid crystals by evaporation of the aqueous Solution can be obtained is used to make salts of the monovalent anion [B12H11 . S (CH3) 2]. The acid is expediently used in an aqueous solution. In crystalline form it generally contains water of hydration.

The procedure of Example 4 is typical for the preparation of Compounds of the formula HB12H, 1 SRR '.

The procedure is with any salt using water or alcohols can be used as solvents.

Example 5 A. A portion of the aqueous solution of the acid obtained after Example 4 is obtained is neutralized with an aqueous solution of (CH8) 8SOH, whereby (CH3) 3SB12H11. S (CH3) 2 is formed, which also occurs directly through the conversion of dimethyl sulfide and diborane is obtained. The salt, trimethylsulfonium dimethyl sulfide undecahydrododecaboranate (1-), is a transparent crystalline mass that is soluble in acetone and a little less is soluble in ethanol. It is sparingly soluble in water and insoluble in methylene dichloride. The salt melts at 232 to 233 ° C with decomposition.

B. A portion of the aqueous solution of the acid obtained in Example 4 is, with an aqueous solution of cesium hydroxide to a pH of about 7 set. A white crystalline mass precipitates out almost immediately. The mixture is heated, whereby the solid mass dissolves again. With slow cooling Cesium dimethyl sulfide undecahydrododecaboranate (1-) separates in the form of translucent octahedral crystals. The identity of the compound having the formula CsB12H, 1 S (CH3) 2 is determined by elemental analysis and by ihi ultra-red absorption spectrum confirmed.

Analysis for CsBl2Hll (CH3) 2: Calculated: Cs 39.56, B 38.65, S 9.54, C 7.15, H 5.10; found: Cs 37.0, B 38.85, S 9.58, C 7.26, H 5.45.

The ultrared absorption spectrum of the compound in Nujol shows bands at the following wavelengths, the bands applicable to Nujol being omitted are (in cm-1): 2500, strong, sharp; 1420, medium, sharp; 1370, medium, sharp; 1320, weak, sharp; 1070, weak, sharp; 1045, strong, sharp; 995, medium, hot; 970, strong, sharp, shoulder at 980; 920, weak, sharp; 828, medium, hot, Shoulder at 835; 720, strong, wide.

C. A portion of the aqueous solution of the acid obtained according to Example 4 obtained is treated with an excess aqueous solution of Zn (NH3) 4 (OH) 2. The solution is concentrated by evaporation; a light yellow crystalline mass falls the end. It is filtered off and recrystallized from aqueous ammonia, whereby [Zn (NH3) 4] [B12H11 . S (CH3) 2] 2 is obtained. The compound is obtained in the form of pale yellow crystals. Your identity is confirmed by elemental analysis.

Analysis for Zn (NH3) 4 [B12H11 S (CH2] 2: Calculated. C 8.90, H 8.59, N 10.38; found .. C 9.15, H 8.81, N 10.42.

Example 6 0.3 g of bis (dimethyl sulfide) dodecaborane (10) is dissolved in Methylene chloride and add a small amount of anhydrous sodium carbonate to the solution to. The mixture is stirred and a solution of bromine in methylene chloride is slowly added until the bromine color persists. The mixture is filtered and the clear, light yellow The filtrate was evaporated under reduced pressure. The orange, solid residue is recrystallized from ethanol; a total of 0.25 g of bis (dimethyl sulfide) dibromododecaborane (10) is obtained, B, 2H5Br2 2 S (CH2) 2.

The identity of the compound is determined through elemental analysis and through confirmed their ultrared absorption spectrum.

Analysis for B12 H8 Br2. 2 2 S (CH3) 2: Calculated ... Br 37.9, C 11.4, H 4.74, S 15.1; Found ... Br 38.72, C 11.99, H 4.95, S 13.98, 12.24, 4.75, 14.13.

Example 7 A. Dissolve 1.1 g of (C2H5) 3NHB, 2H11 S (CH3) 2 in methanol and add a small amount of anhydrous sodium carbonate to the solution. Liquid Bromine is slowly added while stirring vigorously until the bromine color is very strong slowly disappears.

The reaction develops considerable heat. The solution is filtered off and the filtrate evaporated, leaving a white semi-solid residue.

By adding water to this residue, a brown, insoluble oil which does not crystallize. The oil is dissolved in methanol and this solution passed through a column covered with an acidic ion exchange resin (Amberlite IR-12OHR) is filled. The strongly acidic eluate contains HBl2H8Br3 S (CH3) 2 and HB, 2H7Br4 S (CH3) 2 in approximately equimolar proportions.

B. A portion of this acidic eluate is mixed with an aqueous solution of trimethylsulfonium hydroxide adjusted to a pH of about 7. The precipitated solid mass is filtered off and recrystallized from aqueous ethanol, whereby an almost white crystalline mass is obtained, which is approximately equimolar Mixture of the following compounds represents: (CH3) 3SB12H8Br3. S (CH3) 2 and (CH3) 3SB12H7Br4 . S (CH3) 2.

These compounds are called Trimethylsulfoniumdimethylsulfid-tribromoctahydrododecaboranat (1-) and trimethylsulfonium dimethyl sulfide - tetrabromohepta -hydrododecaboranate (1-); they are sparingly soluble in water.

Analysis for an equimolar mixture of tribromo and tetrabromo compounds: Calculated: s 11.52, Br 50.57, C 10.79, H 4.08, B 23.34; found: S 12.08, Br 49.45, C 11.30, H 4.21, B 23.40.

10.93, 4.18.

The ultrared absorption spectrum of the product in Nujol shows the following Bands (omitting the bands attributable to Nujol), expressed in cm-l: 2500, strong, sharp; 1410, strong, sharp; 1340, weak, sharp; 1320, very weak, sharp; 1030, strong, sharp; 990, medium, hot; 940, strong, broad; 860, medium, broad; 820, medium, broad; 800, medium, broad; 770, medium, hot; 730, weak, broad.

C. A second portion of the acidic eluate is mixed with aqueous cesium hydroxide adjusted to a pH of about 7. The resulting salt becomes, as in the part B, described worked up, whereby an equimolar mixture of CsB, 2H8Br2 S (CH3) 2 and CsB, 2H7Br4. S (CH3) 2 is obtained. These compounds are white crystalline Masses that are quite readily soluble in water. The identity of the product as one equimolar mixture of the two compounds is confirmed by elemental analysis.

Analysis for an equimolar mixture of tribromo and tetrabromo compounds: Calculated: S 5.24, Br 45.60, C 3.92, H 2.22, B 21.71, Cs 21.71; found: S 5.19, Br 46.08, C 4.56, H 2.48, B 20.73, Cs 20.2, 5.08, 4.26, 2.40, 20.4.

The ultrared absorption spectrum of the product in Nujol shows the following Bands (the Nujol bands omitted), expressed in cm-1: 2500, strong, sharp; 1410, strong, sharp; 1320, weak, sharp; 1030, strong, sharp; 990, medium, hot; 940, strong, broad; 860 medium, broad; 820, strong, broad; 800, strong, broad, shoulder at 780; 735, weak, broad.

D. A portion of the acidic eluate is treated with tetramethylammonium hydroxide solution adjusted to a pH of about 7. The resulting solid product is made from Water-ethanol recrystallized to give an approximately equimolar mixture of (CH3) 4 Obtain N B12H8Br3 S (CH3) 2 and (CH3) 4N B, 2H7Br4 S (CH3) 2. These connections have a limited solubility in water.

Analysis for an equimolar mixture of tribromo and tetrabromo compounds: Calculated: S 5.80, Br 50.54, C 13.82, H 4.64, B 23.47; found: S 5.64, Br 50.69, C 13.24, H 4.82, B 23.23.

5.76, 13.57, 4.62.

The ultrared absorption spectrum of the compound in Nujol shows as follows Bands (omitting the bands attributable to Nujol), expressed in cm-l: 2500, strong, sharp; 1480, strong, sharp; 1420, strong, sharp; 1320, weak, spicy; 1040, medium, hot; 995, medium, hot; 950, strong, broad; 870, medium, wide; 830, medium, broad; 800, medium, broad; 780, medium, broad; 740, weak, broad and 680, weak, broad.

Example 8 A reaction vessel is charged with 3 g of B12H, O 2 S (CH3) 3 and 50 ml of sym.-tetrachloroethane and sets the solution slowly with vigorous stirring liquid bromine until no more bromine is absorbed. The response developed considerable warmth.

When the reaction has subsided, excess bromine is added and heating the mixture to 130-135 ° C for 10 minutes. The solution is cooled and flitred. Carbon tetrachloride is added to the filtrate, producing a white solid mass is precipitated. This is separated and made from a mixture of carbon tetrachloride and dichloromethane recrystallized. Bis (dimethyl sulfide) tetrabromohexahydrod is obtained odecaborane (10).

Analysis for B, 2 H6 Br4 2 2 S (CH3) 2: Calculated ... C 8.3, B 22.4, S. 11.05, Br 55.2; found ... C 8.0, B 18.8, S 9.2, Br 56.6.

Example 9 A reaction vessel is filled with 2.4 g of B, 2H10 2 S (CH3) 2 and 50 ml of sym.-tetrachloroethane are charged. The solution is heated to 60 ° C. and passed Chlorine gas through.

The reaction is exothermic and gummy masses separate from the mixture. When the reaction has stopped, the passage is stopped away from chlorine and heat the mixture to 144 ° C for about 15 minutes. The solution is left cool and filter the precipitated solid product. This solid product will recrystallized from a hot mixture of acetonitrile, carbon tetrachloride and methanol. The compound thus obtained is bis (dimethyl sulfide) tetrachlorohexahydrododecaborane (10).

Analysis for B, 2H6Cl4 2 2 S (CH3) 2: Calculated. . C 11.9, Cl 35.3, B 32.4, S 15.9; found ... G 12.0, Cl 36.2, B 31.4, S 15.9.

Example 10 A reaction vessel is charged with 2.0 g of B12 H, O 2 S (CH3) 2, 30 ml dichloromethane and 30 ml chloroform, stir the mixture and add 13.0 g iodine monochloride added. The mixture is then refluxed for 12 hours and now heated on a steam bath until it is almost dry. The solid residue will mixed with water and potassium iodide and filtered. This treatment is repeated until the filtrate is only slightly yellow in color. The one left behind fixed Mass is dried. Elemental analysis shows that they are mainly from bis (dimethyl sulfide) heptajodotrihydrododecaborane (10), B12H3J7. 2 S (CH3) 2. Elemental analysis: J 68.4, B 11.2, C 8.4, S 5.6.

Example 11 A mixture of 1.5 g of B, 2 H10 2S (CH3) 2, 20 ml benzoyl chloride and 0.1 g AlCl3 for 15 minutes at 80 ° C and 1 minute at 1900C. The mixture is cooled; n-hexane is added with stirring and the resulting solid mass filtered off. The solid mass is purified by putting it in dichloromethane dissolves, precipitates again by adding ether, dissolves again in chloroform and again fails with ether. The product is dried, giving white crystalline Bis (dimethyl sulfide) benzoyl nonahydrododecaborane (10) is obtained.

Analysis for B12H9C (O) C6H5 25 (CH8) 2: Calculated. . C 32.6, S 17.4, B 35.3; Found ... C 31.6, S 18.2, B 36.5.

Claims (2)

Claim: Process for the production of Dodecaboranatund / or. Dodecaborane thioetherates of the general formula M [B12H11-y. Xy. S R R '] b respectively B12H10-y. Xy. 2 S R R 'where M is a cation and X is halogen or carbacyl, R and R' mean organic radicals, y represents a value from 0 to 11 or 10 and b at least 1 and is equal to the valence of M, d u r c h denotes that one Borane thioetherate with diborane, pentaborane (9) or decaborane (14) to at least 50 ° C heated, from the reaction product by extraction with water or alcohol compounds of the formulas M [B12H11. S R R '] b and B12H10. 2 S R R 'wins and this if applicable with halogen or with reactive carboxylic acid derivatives.