DE1618223B1 - Process for the preparation of complex organic sodium aluminum hydrides - Google Patents

Description

Various processes for the preparation of these compounds have been made already described.

One of the difficulties that one faces in making this Connections and encountered in their application consists in the fact that they only exist in a very great way a few organic solvents are soluble, e.g. B. in diethyl ether, but not in solvents which are more conveniently available and which are also less dangerous are to be handled. So z. B. it is not possible to substitute the above-mentioned Dissolve sodium hydrides in benzene.

That in Liebigs Annalen der Chemie, Vol. 607 (1957), pp. 24 to 35, Sodium triethoxyaluminum hydride described is also in addition to diethyl ether soluble in tetrahydrofuran, but this complex of sodium hydride and Aluminum ethylate reduces its solubility in other solvents such as aromatic hydrocarbons.

This limited solubility brings benefits both during manufacture There are also difficulties and dangers involved in using these products.

Other hydrides, e.g. B. the decaboranes are in non-polar solvents soluble, but the solutions of these hydrides have no reducing properties.

The object of the present invention is to solve the aforementioned difficulties and disadvantages to be overcome and a process for the production of organically substituted Sodium aluminum hydrides can be found in an easy and economical way Manner carried out in a non-polar medium in which they are optionally soluble can be.

This object is achieved by the invention.

The invention therefore relates to a method for production complex, organic sodium aluminum hydrides of the general formula NaAlHxZ4-x in which x is an integer from 1 to 3 and Z has the meaning given below, by reacting a sodium hydride with an aluminum trial alcoholate at increased Temperature in the presence of an inert organic solvent, which is characterized is that you can use trisodium aluminum hexahydride or sodium aluminum tetrahydride a compound of the general formula A1Z3 or NaAlZ4 or with one of the latter Formula corresponding mixture of compounds of the general formula NaZ and AlZ3 in which Z is the radical of one of the following alcohols: (1) Tetrahydrofurfuryl alcohols, (2) tetrahydropyranyl alcohols, (3) ether alcohols obtained by alkylating a hydroxyl group have been obtained in diols, (4) polyether alcohols obtained by condensation of Ether alcohols and diols, but each with splitting off a water molecule have been obtained, (5) amino alcohols of the general formula R2N- (CH2) yOH wherein R denotes identical or different alkyl, aryl or alkoxyalkyl, where the The alkyl radical contains 1 to 4 carbon atoms and the aryl radical contains 6 to 8 carbon atoms and y is an integer from 2 to 4.

Na3AIH6 can e.g. B. be prepared by the method described in the Czechoslovak patent specification 117 768 is described.

Compounds of the general formula AIZ3 and also the general Formula NaZ, which can also be used as an additional reactant, such as will be described in detail later, by reacting the alcohol concerned ZH with the metal, sodium or aluminum, or with the relevant hydrides, sodium hydride or aluminum hydride. There is no difficulty with that Preparation of derivatives substituted by dialkylamino and alkylamino groups are. In general, the reactions are carried out in a liquid medium, such as hydrocarbons, Ethers (diethyl ether, monoglyme, tetrahydrofuran), or an excess of the ZH compounds carried out.

The NaZ compounds produced in this way are insoluble in the reaction medium, so that a suspension must be made.

Before these compounds in the above-described inventive Methods are applied, e.g. B. according to equations (7) described below to (13) and (15) to (19), the NaZ connections must pass from the suspension Filtration and subsequent drying are separated. The dry product thus obtained can be used directly as starting material for the process according to the invention and does not require any further cleaning. The impurities classified as metallic Sodium may be present, but it does not interfere with the reaction as these are contaminants are insoluble in the reaction medium, while that by the method according to the invention end product obtained is soluble in the reaction medium concerned. If but a compound of the NaZ type is established when NaH is used as the starting product and therefore the NaZ produced in this way may contain a remainder of NaH, then In some cases it is advantageous to reduce the amount of sodium aluminum hydride and of the AlZ3 beyond the theoretically necessary amount.

The production of alcoholates and amino alcoholates of the AlZ3 type is also easy.

Conventional methods can be used for the production of these derivatives, those of aluminum or aluminum hydride and the corresponding alcohol or amino alcohol starting from the formula ZH. All substituted according to the invention N / A- Triumaluminum hydrides are soluble in hydrocarbons and ethers; the unchanged Aluminum or aluminum hydride can be easily removed by filtration prior to isolation of the End product can be removed.

Another advantageous method for the production of aluminum alcoholates of the type AlZ3 is based on the following reaction equations: Al (OCH3) 3 + 3ZH # AlZ3 + 3CH3OH (1) Al (OR) 3 + 3ZH- + AlZ3 + 3ROH (2) It is advantageous to have an excess of ZH and the reaction with simultaneous removal of CM3 OH (or ROH), the boiling point of which must be lower than that of ZN, which is generally the case is. The removal of CM3 OH or (ROH) can be done in the usual way with the help of a rectification column can be carried out.

The starting compounds for carrying out the reaction, the aluminum alcoholates, can easily be obtained in pure form, even on an industrial scale. It is most advantageous to start from Al (OCH3) 3, because this z. B. in hydrocarbons is insoluble and therefore the separation of an unchanged amount of the reaction mixture is very relieved. The reaction product AlZ3 can easily be removed by removing the Solvent and the excess of ZH are isolated.

The starting compounds of the type NaZ AIZ3 can by the following reactions the following can be produced: Na + Al + 4ZH> NaAIZ4 + 2H2 (3) NaH + AlH3 + 4ZH # NaAlZ4 + 4H2 (4) NaAlH4 + 4ZH-> NaAlZ4 + 4H2 (5) NaAl (OCH3) 4 + 4ZH # NaAlZ4 + 4CH3OH (6) The complex Alcoholates of the NaZ AlZ3 type are generally easily soluble in ethers and also in aromatic hydrocarbons. You can just as easily according to the above given equations are prepared under the same conditions as when simple alcoholates of the type NaZ + AlZ3 are assumed.

The method of the present invention can be used in accordance with the following equations.

Na3AlH6 + 3 NaZ + 4AlZ3 e 6 NaAIHZ3 (7) Na3AlH6 + 2A1Z3 # 3 NaAIH2Z2 (8) 3 Na3AIH6 + 2AlZ3 + AlCl3 -> 6NaAlH3Z + 3NaCl (9) NaAlH4 + 3A1Z3 + 3NaZ # 4NaAlHZ3 (10) NaAlH4 + AlZ3 + NaZ # 2NaAlH2Z2 (11) NaAlH4 + 2NaH + 2A1Z3 # 3NaAlH2Z2 (12) 3NaAlH4 + AlZ3 + NaZH4NaAlH3Z (13) Similarly, in accordance with the below cited equations (14) to (18) complex compounds of the general formula NaZ A1Z3 can be used instead of AlZ3.

Na3AlH6 + 3 [NaZ A1Z3] + 2A1Z3 # 6NaAlHZ3 (14) NaAlH4 + 3 [NaZ # AlZ3] # 4NaAlHZ3 (15) NaAlH4 + NaZ AlZ3 ~ 2NaAIH2Z2 (16) NaAlH4 + 3 [NaZ AlZ3] + 2NaH + 2AlZ3 # 6NaAlHZ3 (17) 3NaAlH4 + NaZ # AlZ3 # 4NaAlH3Z (18) The liquid reaction medium in which the reactions described above according to the invention guided preferably belongs to the group of aromatic hydrocarbons and ethers, whose boiling point at atmospheric pressure is lower than the decomposition temperature the substituted sodium aluminum hydride to be produced.

One suitable type of procedure is to reflux the reaction run at the boiling point of the reaction mixture. Benzene is used as the reaction medium or toluene are preferred, but the reaction media described above can also be used will.

The groups of compounds falling within the scope of the present invention are as follows: NaAIHx (OCH2CH20R) 4-x NaAlHx (OCH2CH2CH2OR) 4 -naAlHx [O (CH20zO (CH2) w OR] 4x NaAlHxEO (CH2) yNR2] 4x where w and z are integers from 2 to 4, x is an integer from 1 to 3 and R denotes identical or different alkyl, aryl or alkoxyalkyl, the alkyl radical having 1 to 4 carbon atoms and the Aryl radical contains 6 to 8 carbon atoms.

Under certain circumstances it is advantageous if during the implementation instead Trisodium aluminum hexahydride sodium aluminum tetrahydride is used in the reaction mixture add NaH or AlCl3.

The organically substituted, complex sodium aluminum hydrides can in non-polar media, e.g. B. in benzene, derivatives of organic acids, ketones and Reduce aldehydes to alcohols in the same way and to the same extent as this with not substituted, complex aluminum hydrides in ether is possible. In contrast to the unsubstituted, complex aluminum hydrides such as sodium ethoxyhydride, -methoxyhydride and -aryloxyhydrides also dehalogenize alkyl and aryl halides and Reduce nitro compounds to azo compounds, but are different from the ones mentioned Compounds also soluble in aromatic hydrocarbons. All of the above Reactions can thus both in ethers and just as well in non-polar media be made.

As already stated, those produced according to the invention are Sodium aluminum hydrides not only in ethers but also in aromatic hydrocarbons, like benzene, toluene and xylene soluble in highly concentrated solutions. So z. B. prepared a 70% solution of the product according to the invention in benzene and put on the market. The product prepared according to the invention dissolves also found in ethers such as diethyl ether, tetrahydrofuran, monoglyme, diglyme and the like. very good.

Compared to LiAlH4 and the one in the article in Liebig's Annalen der Chemie, Vol. 607, described sodium ethoxy-aluminum hydride is the invention Sodium aluminum hydride produced is much more widely applicable because there are also such Can reduce substances that are insoluble in ethers, such as tetrahydrofuran, but in aromatic Hydrocarbons are soluble.

Another benefit of using aromatic hydrocarbons as a solvent instead of ethers lies in the preparation of anhydrous Solvents which are indispensable when working with the hydrides mentioned.

If you namely the maximum water content of the commercial solvents examined, it is found that the maximum water content in diethyl ether is 20 times is as large as in benzene or toluene. From the calculation of the amount of hydride which would be required to remove the water content of the solvent, as well as the corresponding amount of the evolved hydrogen shows that it is in use of benzene or toluene - as is the case with the sodium aluminum hydrides produced according to the invention is possible - it is no longer necessary to pre-dry these solvents.

The relationships are shown in the table below: Diethyl ether Benzene Toluene Tetrahydro furan Water solubility in grams per 100 kg of the solution by means of. . . . .................... . . . . . . . . . 1.20 0.057 0.045 miscible Amount of hydride required for removal in grams 13.45 0.64 0.505 The amount of hydrogen developed in Ncm3 2985 142 112 From this list it can be seen that the losses of the 200% solution of the product according to the invention in benzene or toluene amount to a maximum of 2.5 to 10% of the reducing agent, which is still in the usual use of a 10% excess of the reducing agent acceptable limits.

On the other hand, the loss caused by the water content can decrease No reducing agents due to the more than 20 times higher water content of the ethers be tolerated more. Another disadvantage of ethers is that they are solvents still contain alcohols and explosive peroxides, which are also eliminated have to.

The main advantage of using an about 70% solution of the invention product manufactured in toluene or benzene is its perfect safety and Ease of use. The product according to the invention is in fact neither pure State, still self-igniting in a 70% solution. Even when in contact with Water does not cause spontaneous combustion.

A 70% solution of the product produced according to the invention can thus be used easily poured, pumped and dosed, d. H. exactly the same as a usual one Liquid to be handled.

This behavior compares to the use of lithium aluminum hydride a significant improvement.

The following examples illustrate the invention.

Example 1 In an apparatus which is described in more detail in Example 2 2.1 g of 80% solid Na3AlH6 (0.0164 mol) and 50 ml of benzene were charged. The remaining 20% is silicon. The mixture was refluxed and added dropwise 8.27 g of Al (OCH2CH2 OCH3) 3 (0.0328 mol), dissolved in 10 ml of benzene, were added. The reaction mixture was boiled for a further 30 minutes with stirring. After filtration and Evaporation of the solvent gave 9.36 g of NaAlH2 (OCH2CH2 OCH3) 2 that is 94.1% the theory.

The starting compound Al [OCH2CH2 OCH3] 3 was obtained by the following reaction Shown: Al (OCH3) 3 + 3CH3OCH2CH2OH AlLOCH2CH2OCH3] 3 + 3CH3OH This reaction was carried out with a 160% own excess of CH3 OCH2CH2OH. (Instead of a To use excess CH3 OCH2CH2 OH, the theoretical amount can also be used and the excess of this compound by another solvent, preferably Benzene or toluene, to be replaced,) The resulting methyl alcohol was from the reaction mixture distilled off during the reaction using a rectification column. After the methyl alcohol had been removed, the excess CH3 OCH2CH2 OH was im Eliminated vacuum. The reaction product is a liquid, highly viscous substance of of the formula Al (OCH2CH2 OCH3) 3 with benzene, toluene and ethers in any ratio can be mixed.

Example 2 In a three-necked round-bottomed flask with a capacity of 100 ml a stirrer, a reflux condenser and a dropping funnel were provided 1.7 g of 85% Na3AlH6 (the remainder of 15% contained aluminum and silicon) were introduced and 35 ml of tetrahydrofuran added. The mixture was heated to the boil and a Solution of 8.26 g of Al [OCH2CH2N (CH3) 2] 3 in 15 ml of tetrahydrofuran dropwise with stirring added. Heating was continued for 43 minutes and then the mixture Chilled to 15 "C.

After filtration, the tetrahydrofuran was removed from the filtrate and thus a residue is obtained, which is dried at 1000 C under a pressure of 0.1 mm Hg became; 9.1 g of a compound of the formula NaAlH2 [OCH2CH2N (CH3) 2] 2 were obtained obtained, that is 93.5% of theory according to equation (8). The (CH3) 2NCH2CH2OH, which is necessary for the production of AlrOCH2CH2N (CH3) 2] 3, was made by a Reaction made common for the conversion of primary amines to tertiary Amines is known, starting from H2NCH2CH2OH, formaldehyde and formic acid.

The starting compound Al [OCH2CH2N9CH3) 2] 3 was obtained from aluminum methylate prepared in a manner similar to that in Example 1 for the production of Al (OCH2CH2 OCH3) 3 is described.

Example 3 In a 250 ml flask fitted with a reflux condenser, With a stirrer and dropping funnel, 7.35 g of Na3AlH6 and 1.86 g of AlFOCH2CH2N (CH3) 2] 3 introduced and added 85 ml of tetrahydrofuran.

The mixture was heated to reflux and a solution of 2.72 g AlCl3 in 25 ml tetrahydrofuran was added dropwise over 30 minutes. That The mixture was then heated for a further 45 minutes and then cooled to 20 ° C and filtered. The tetrahydrofuran was removed from the filtrate and the distillation residue dried at 100 ° C below 0.1 mm Hg; 15.84 g of NaAIH3 OCH2CH2N (CH3) 2 were obtained, that's 91.6% of theory.

Example 4 a) Preparation of the starting compounds Na3AlH6 and NaAlH4 46 g of sodium (2 mol) and 32.9 g of aluminum powder were placed in a pressure vessel with a capacity of 2.5 l 82% (the remainder was alumina), 50.5 g NaAlH2 (OCH2CH2OCH3) 2 (0.25 mol) according to Example 1, introduced and 500 ml of benzene added; was in the pressure vessel the stirrer for stirring the reaction mixture.

Then hydrogen was introduced into the vessel until a pressure of 100 atm has been reached. The reaction was carried out at a temperature of 170 ° C Carried out for 3 hours. The reaction mixture was filtered and the solid residue extracted with benzene; 55.4 g of solid Na3AIH6 with a purity of 88.5% were obtained obtained, that is 96.1% of theory. The benzene filtrate contained dissolved sodium aluminum alkoxyhydride which was used as a catalyst in the following syntheses.

The direct synthesis of the two hydrides NaAlH4 and Na3AIH6 goes into similar way in front of you, too if other connections of the type NaAIHxz4-x z. B.

NaAlH [O (CH2) 2 OCH3] 3 NaAlH3 [O (CH2) 2 O (CH2) 2 OCH3] or NaAlH2 [O (CH2) 2N (CH3) 2] 2 were used as catalysts. Hydrogen pressure can be applied over a wide range from 2 to 200 atmospheres. At a pressure below 2 atmospheres, however, the reaction is too slow; increasing the pressure above 200 atmospheres has no substantial effect on the reaction, so that increasing the pressure above 200 atmospheres is of no practical value. The amount of catalyst used can vary in the range 0.5 to 100% based on the amount of sodium and aluminum used. In the present example 50% catalyst was used. Amounts of catalyst smaller than 0.5% cause the reaction rate to decrease.

If a larger amount of catalyst is used, this is not disadvantageous because it can be used again.

It is advantageous to carefully grind the reaction mixture before the actual synthesis. b) Implementation According to the Invention 2.75 g of NaAlH4 (98%), 200 ml of benzene and 8 g were placed in a II three-necked flask equipped with a stirrer, water cooler and dropping funnel brought in. The reaction mixture was refluxed and a solution of 21.9 g was added dropwise benzene was added in 50 times over the course of 30 minutes, after which the reaction mixture was refluxed for a further 4 hours. The mixture was then cooled to 15 ° C. and filtered. The filter cake was washed with benzene, the benzene was removed from the collected filtrates and the distillation residue was dried at 1000 ° C. below 0.1 mm Hg. It resulted in 32g which corresponds to 98.16% of theory.

The starting product of the formula was made in toluene by the well-known reactions: The starting product was prepared from aluminum methylate by a reaction similar to that described in Example 1. The alcoholate was refluxed from a mixture of toluene, sodium hydride and shown in 20% excess. The toluene and the excess ether alcohol were removed in vacuo and the remaining amount of the two components was distilled off under a pressure of 0.05 mm Hg at 160.degree.

Example 5 The same apparatus as in Example 4b was used with 5.6 g of Na3AlHs (91.1%), 500 ml of benzene and 26.1 g filled. The reaction mixture was refluxed with a solution of 120 g added dropwise boiled in 200 ml of benzene for 30 minutes. The reaction mixture, treated in the same way as in Example 4b, gave 147.2 g that is 97.36% of theory.

For the production of the same methods were used as described in Example 4b).

Example 6 The same apparatus as in Example 4b was used with 2.75 g NaAlH4 (98.2%), 2.5 g NaH (96.0%) and 150 ml toluene. The reaction mixture became under reflux dropwise a solution of 29.4 g A1EOCH2CH2CH20CH3] 3 in 50 ml of toluene added over 45 minutes. The reaction mixture contained in the Treatment in the same manner as in Example 4b gave 34.0 g of NaAlH2 [OCH2CH2CH2 OCH3] 2 that is 98.57% of theory.

CH3 OCH2CH2CH2OH, which is used for the production of Al [OCH2CH2CH2OCH3] 3 needed was made by methylation of a hydroxyl group in 1,3-propanediol under Made using sodium hydride and (CH3 O) 2SO2.

This reaction was carried out in boiling toluene. The starting material A1EOCH2CH2CH2 OCH3] 3 was made from aluminum methylate in the same way as in the example 1 manufactured.

Example 7 In the same apparatus as described in Example 4b, 2.75 g of NaAlH4 (98.2%), 26.1 g and filled with 500 ml of benzene. A solution of 72 g was added dropwise to the reaction mixture under reflux added in 150 ml of benzene over 45 minutes. The reaction mixture was treated in the same manner as in Example 4b to give 99.51 g that is 98.72% of theory.

The same method was used in the manufacture of the starting material as used in example 4b.

Example 8 The apparatus described in Example 4b was charged with 2.75 g of NaAlH4 (98.2%), 2.07 g and filled with 100 ml of tetrahydrofuran.

The reaction mixture was refluxed with dropwise addition of a solution of 5.5 g boiled in 20 ml of tetrahydrofuran for 45 minutes. After the same treatment as in example 5 wuruen 9, 6t g NaAlH3 OCH, ~ O j obtained, that is 96.01% of theory. The two starting alcoholates for this example were made from with that in example 4b for and in example 1 for given method.

Example 9 The same apparatus as in Example 4b) was used with 5.6 g Na3AIH6 (91%) and 250 ml benzene charged.

The reaction mixture was refluxed with dropwise addition a solution of 38.4 g of Al [OCH2CH2OCH2CH2OCH3] 3 in 80 ml of benzene. The other Treatment of the reaction mixture as described in Example 4 b) gave 42 g NaAlH2 [OCH2CH2OCH2CHWOCH3] 2 which corresponds to 96.56% of theory.

The alcoholate Al [OCH2CH2OCH2CH2OCH3] 3 was converted from CH3 OCH2CH2 OCH2CH2 OH prepared according to the method described in Example 1.

Example 10 2.75 g of NaAlH4 and 100 ml of benzene were introduced into the same apparatus as described in Example 4b). The reaction mixture was added dropwise with a solution of 41.5 g boiled in 150ml benzene in the reflux condenser. The reaction mixture was treated in the same way as in Example 4b) and gave 43.2 g that is 97.74% of theory. that for the production of is required was prepared in the following way: the sodium phenolate was alkylated in boiling toluene with HOCH2CH2CH2Cl; that obtained by this reaction was isolated and converted to the alcoholate by reaction with sodium hydride in boiling toluene; this was alkylated with HOCH, CH, Cl to give the compound of formula was obtained. The starting product, the complex alcoholate, was prepared in the apparatus described in Example 4b) according to the following equation: NaAlH4 + 4 # -OCH2CH2CH2OCH2CH2OH The alcohol was added dropwise to a 5% solution of sodium aluminum tetrahydride in tetrahydrofuran in the required stoichiometric amount. The reaction proceeds quantitatively with considerable evolution of heat and formation of hydrogen. After the evolution of hydrogen had ceased, the tetrahydrofuran was distilled off and the product was freed from the remainder of the tetrahydrofuran under a pressure of 0.1 mm Hg at 1000.degree.

Example 11 The same apparatus as described in Example 4b) was, with 5.6 g Na3AlH6 (91.1%), 27.6 g Na [O (CH2) 2 O (CH2) 4OCH2CH3] and 600 ml of benzene charged. The reaction mixture was refluxed at dropwise Addition of a solution of 127.6 g of Al [O (CH2) 2 O (CH2) 4OCH2CH3] 3 in 250 ml of benzene during Cooked for 45 minutes. After the same treatment of the reaction mixture as in Example 4b) described, 154.0 g of NaAlH [O (CH2) 2O (CH2) 4OCH2 OCH3] 3 were obtained, which corresponds to 96.13% of theory.

The alcohol of the formula C2H5 O (CH2) 4O (CH2) 2 OH used for the manufacture of the starting alcoholate is required, 1,4-butanediol was converted into a Hydroxyl group with sodium hydride in boiling toluene and subsequent alkylation made with C2HsBr. The obtained product QHO (CH2) 40H was obtained by reaction converted into the alcoholate with sodium hydride in boiling toluene and the C2H5O (CH2) 4ONa then alkylated with ClCH2CH2OH to give. C2H5 O (CH2) 4O (CH2) 2 OH That The starting alcoholate of the formula Al [O (CH2) O (CH2) 4OC2H5] 3 was made from aluminum methylate and C2H5 O (CH2) 4O (CH2) 2 OH in the same way as described in example 4b), shown. The compound of the formula NaO (CH2) 2 O (CH2) 4OC2H5 was obtained by reaction of sodium hydride with C2H5 O (CH2) 4O (CH2) 2 OH in the same way as in example 4b) shown.

Example 12 The same apparatus as described in Example 4b) was charged with 2.75 g of NaAlH4 (98.2% 0, 2.5 g of NaH (96.0%) and 300 ml of toluene Reflux with a solution of 46.25 g added dropwise boiled in 100 ml of toluene. After the same treatment as in Example 4b), 50 g obtained, that is 97.4% of theory.

That that for the production of needed has been made out and NaOCH2CH2OH in boiling toluene using the method described in Example 4b). The starting product was prepared according to the method described in Example 1.

Example 13 The same apparatus as described in Example 4b), was charged with 5.6 g Na3AlH6 (91.1%) and 250 ml tetrahydrofuran. The reaction mixture was refluxed by adding dropwise a solution of 22.3 g of Al [OC2H4N (C2H5) 2] 3 boiled in 80ml tetrahydrofuran for 45 minutes. After treating the reaction mixture according to the method described in Example 4b) became 26.71 g NaAlH2 [OC2H4N (C2H5) 2] 2 obtained, that is 97.3% of theory.

The starting alcoholate Al [OCH2CH2N (C2H5) 2] 3 was made from aluminum alcoholate and (C2H5) 2NCH2CH2 OH according to the method described in Example 1.

Example 14 5.6 g of trisodium aluminum hexahydride (91.1%) in 250 ml of benzene were introduced into the apparatus as described in Example 4b). The suspension was heated to a boil and a solution of 37.2 g in 80 ml of benzene. added dropwise over 30 minutes. According to the method in Example 4 b), 39.8 g obtained, which corresponds to 94% of theory.

The starting compound was obtained by reacting aluminum methylate with a solution of in toluene as a solvent in the ratio of toluene to as solved 1: 1. That was added in an excess of 150% of theory. In accordance with equation (1), the methyl alcohol was removed from the reaction mixture in a rectification column. The toluene was at atmospheric pressure and eventually the excess removed in partial vacuum at a temperature of up to 150 ° C. The product was a non-distillable, highly viscous substance that can be mixed with benzene, toluene and ethers in any ratio.

Example 15 In the same apparatus as in Example 4b) was a Suspension of 5.6 g of trisodium aluminum hexahydride (91.1%) was introduced in 250 ml of benzene. The suspension was refluxed with the addition of a solution of 33.3 g of Al [OCH2CH2CH2N (CH3) 2] 3 boiled in 80ml benzene for 30 minutes. The reaction product was prepared according to Method in Example 4b) processed further and gave 36.7 g of NaAlH2 [OCH2CH2N (CH3) 2] 2 To produce the starting product, (CH3) 2NCH2CH2CH2OH was first made from HOCH2CH2CH2NH2 represented by the conventional reaction with formaldehyde and formic acid; Al [OCH2CH2CH2N (CH3) 2] 3 was then made from (CH3) 2NCH2CH2CH2OH in the same manner as shown in example 14. The compound obtained is a highly viscous one, not Distillable liquid, miscible with benzene, toluene and ethers in all proportions.

Example 16 In the apparatus described in Example 4 b) was a Suspension of 5.6 g of trisodium aluminum hexanhydride (91.2%) in 250 ml of benzene prepared.

The suspension was refluxed with dropwise addition a solution of 55.5 g of Al [OCH2CH2N (CH2CH2 OCH3) 2] 3 in 80 ml of benzene for 30 Minutes cooked. In the same way as described in Example 4b), 59.4 g NaAlH2 [OCH2CH2N (CH2CH2 OCH3) 2] 2 obtained, that is 91.7% of theory.

To represent the starting compound, (CH3 OCH2CH2) 2NCH2CH2 OH can be prepared according to the following equations: N (CH2CH2OH) 3 + NaH -> NaOCH2CH2N (CH2CH2OH) 2 + H2 NaOCH2CH2N (CH2CH2OH) 2 + NaH + 2 (CH3O) 2SO2 (CH3 OCH2CH2) 2NCH2CH2CH + H2 + 2CH3OSO2ONa A refluxing suspension of sodium hydride in xylene (200 ml xylene per 1 gram mole of sodium hydride) N (CH2CH2 OH) 3 was added dropwise with stirring and heating continued until the evolution of hydrogen ceased. Then (CH3 O) 2SO2 was added under the same conditions, refluxing resumed and continued until the evolution of hydrogen ceased. The mixture was cooled and 100 ml of a 60% solution of potassium hydroxide per 1 gram mol (CH3 O) 2SO2 added. The reaction mixture was then filtered, the solid phase washed with xylene and the xylene solution of HOCH2CH2N (CH2CH2 OCH3) 2 extracted with water, neutralized and then acidified with hydrochloric acid. The received The hydrochloride was isolated by evaporating the water in vacuo and the base was removed Addition of a 70% solution of potassium hydroxide in water is released with a small excess, but not more than 10% of the theoretical amount.

The mixture was then stirred with diethyl ether and the precipitated Potassium chloride filtered off. The product (CH3 OCH2CH2) 2NCH2CH2OH was derived from the ethereal Solution obtained by distillation and converted into the aluminate in the same way as converted in Examples 1 and 14.

Example 17 In the same apparatus as in Example 4b) was a Prepare a suspension of 5.6 g Na3AlH6 (91.1%) in 250 ml benzene. The suspension was Boiled in the reflux condenser and a solution of 72.3 g of Al [OCH2CH2N (CH2CH2CH2CH2 OCH3) 2] 3 in 120 ml of benzene added dropwise over 30 minutes. It was in the same Worked as in Example 4b) and 72.1 g of NaAlH2 [OCH2CH2N (CH2CH2CH2CH2 OCH3) 2] 2 obtained, corresponding to 93.2% of theory.

The amino alcohol required as the starting product was made from HOCH2CH2NH2 obtained by alkylation of CH3 OCH2CH2CH2CH2C1. The latter connection was made obtained by methylation of a hydroxyl group of 1,4 butanediol and then this converted into chloride with thionyl chloride. The necessary [(CH3OCH2CH2CH2CH2) 2NCH2CH2O] 3Al was prepared in the same manner as described in Example 1.

Example 18 In the same apparatus as in Example 4b) was a Suspension of 5.6 g (0.05 mol) of trisodium aluminum hexahydride (91.1%) in 250 ml Benzene prepares. The suspension was refluxed and a solution of 38.4 g of Al [OCH (CH2 OCH3) 2] 3 in 80 ml of benzene were added over 30 minutes. It was continue in the same way as in example 4b) worked and 55.6 g NaAlH2EOCHCH2OCH3) 2] 2 obtained, which corresponds to 95% of theory.

The starting product (CH3OCH2) 2CHOH was made from glycerine by methylation of the two hydroxyl groups with the help of sodium hydride and (CH3 O) 2SO2 in a similar way Way as shown in example 16. The obtained ether alcohol was used for the reaction with aluminum methoxide to produce the starting product Al [OCH (CH2OCH3) 2] 3 in used in the same way as in Example 4b).

Example 19 In the same apparatus as in Example 4b) was a Suspension of 5.6 g of trisodium aluminum hexahydride (91.1%) in 200 ml of tetrahydrofuran manufactured. A solution was obtained under the same conditions as in Example 4b) of 20.4 g of (n-C3H7O) 5Al in 200 ml of tetrahydrofuran were added. The representation, in same way as in Example 4b), resulted in 24.1 g of NaAlH2 [O (n-C3H7)] 2, that is 94.3% the theory.

Examples 20 to 30 In the apparatus described in Example 4b) and under the same conditions, compounds of the formula NaAIHQ3 synthesized according to the equation NaAlH4 + 3NaQ + 3AlQ3 # 4NaAlHQ3 (20), whose various radicals Q are defined in Table 1 below.

A suspension was produced in the apparatus described in Example 4b) of 2.75 g (0.05 mol) sodium aluminum tetrahydride (98.2%) and 0.15 mol alcoholate of the NaQ type, where Q again has the same meanings as in the following table Has.

The reaction medium was 200 ml of benzene. The reaction mixture was Boiled at normal pressure under the reflux condenser and a solution of 1.15 mol AlQ3 in 100 ml of benzene was added dropwise over 30 minutes. The reaction mixture was then refluxed for a further 4 hours.

After cooling to 15 ° C., the clear solution was filtered off; the solid residue mainly contained the starting materials and impurities and was freed from the filtrate by washing with benzene. The benzene was distilled off from the clear solution obtained and the collected product was dried in a vacuum of 0.1 mm Hg at 100.degree. The yields obtained in grams and in percent taking into account the various reactants of Examples 20 to 30 are given in Table 1. Table 1 Starting compounds yield Example NaAlH4 NaQ AlQ3 NaAlHQ3 g Q g% 20 2.75 CH3O (CH2) 2O- 14.7 37.8 52.1 96.5 21 2.75 C2H5O (CH2) 3O- 16.8 44.1 59.8 94.1 22 2.75 CH3O (CH2) 3O- 16.8 44.1 60.4 95.0 continuation Starting compounds yield Example NaAIEf4 | NaQ AlQ, NaMHQ, g QQ 23 2.75 C, H, O (CH,), 0-18.9 50.4 68.5 95.1 24 2.75 (o) - CH2O - 18.6 49.5 67.6 95.5 O 25 2.75)) \ OCH2O 20.7 55.8 74.4 94.4 26 2.75 (CH3) 2N (CH2) 2O- 16.7 43.7 60.5 96.1 27 2.75 (C2H5) 2N (CH3) 2O- 20.9 56.3 64.9 95.7 28 2.75 (CH3OCH2CH2) 2N (CH2) 2O- 22.4 60.8 61.2 94.6 29 2.75 (CH3OCH,) 2CHO- 21.3 57.6 78.3 96.1 30 2.75 CH3O (CH2) 2O (CH2) 2O- 21.3 57.6 76.1 93.2 Examples 31 to 33 In the apparatus described in Example 4b) and under the same conditions as are described in Examples 20 to 30, further compounds of the formula NaAlH2 Q2 were synthesized according to the following equations: The various radicals Q are shown in Table 2 below.

The starting material in all examples was 5.6 g (0.05 mol) Na3AlH6 (91.1%) in 250 ml of benzene and 0.1 mol of A1Q3 in 100 ml of benzene are used.

Taking into account the yields obtained in grams and percent the various specific reactants are given in Table 2.

Table 2 Starting compounds Yield of NaAlH2Qz Example Na3AIE36 AlQ, g Q gg 31 5.6 c2H, O (CH2) 20-29.4 32.7 94.7 32 5.6 C2H5O (CH2) 3O- 33.6 36.9 95.3 33 5.6 -CH2O- 33.0 33.0 35.4 93p Examples 34 to 42 In the same apparatus as in Example 4b) and under the same conditions as in Examples 4b) and 30, further compounds of the formula NaAlH3Q were synthesized according to the following equation: 3NaAlH4 + NaQ + AlQ3 # 4NaAlH3Q (22) The starting suspension in all examples contained 8.25 g (0.15 mol) NaAlH4 (98.2%) and 0.05 mol NaQ in 150 mol tetrahydrofuran. In all examples, a solution of 0.05 mol of AlQ3 in 100 ml of tetrahydrofuran was added. After isolation, as described in Example 4b), the compounds listed in Table 3 below were obtained.

Taking into account the yields obtained in grams and percent the various specific reactants are listed in Table 3.

Table 3 Starting compound yield of NaAlH3Q Example NaAlH4 NaQ AlQ3 g Q ggg 34 8.25 CH3O (CH2) 2O- 4.9 12.6 25.1 98.1 35 8.25 C2H5O (CH2) 2O- 5.6 14.7 27.1 95.4 36 8.25 CH3O (CH2) 3O- 5.6: 14.7 26.8 8 94.2 continuation Starting compound 0 yield of NaAlH Example NaAlH4 NaQ AlQ, g Q ggg 37 8.25 C, H, O (CH,), 0-5.2 16.8 29.0 93.0 38 8.25% y0CH2O 6.9 18.6 31.9 95.1 39 8.25 (C2H5) 2N (CH2) 2O- 6.9 18.8 32.4 95.9 40 8.25 (CH3OCH, CH2) 2N (CH,) 2O- 7.5 20.2 34.0 95.1 41 8.25 (CH3OCH,) 2CHO- 7.1 19.2 33.0 96.0 42 8.25 (CH3OCH3) 2O (CH3) 2O- 7.1 19.2 32.3 93.8 Application examples Example 43 23 g (1 mol) sodium, 33 g aluminum powder (95% purity, 5% aluminum oxide), 400 ml toluene and 9.2 g NaAlH2 [O (CH2) 2N (CH3) 2] 2 that is equal to 16 percent by weight, based on the amount of sodium and aluminum used. The hydrogen was introduced into the pressure vessel to a pressure of 150 atm. The pressure vessel was heated to a temperature of 160 to 1700 ° C. while maintaining the pressure at 150 atm. The reaction was over after 4 hours, after which the pressure vessel was cooled and emptied.

The solid phase was extracted with tetrahydrofuran, with a lot of 200ml per 10g of NaAlH4 obtained was applied. From the tetrahydrofuran extract 50.1 g of NaAlH4 were obtained after evaporation, that is 92.6% of theory.

Regarding the catalyst used and its amount the conditions described in Example 4 a) met. The optimal temperature limit lies between 150 and 170 "C. At temperatures below 150 ° C. the reaction is too slow or does not progress at all. At temperatures above 170 ° C, trisodium aluminum hexahydride is formed as a by-product.

It is also possible to use stoichiometric amounts of sodium and Aluminum work; but an excess of aluminum (10 to 50%) is more advantageous, to avoid excessive formation of trisodium hexahydride.

Example 44 The same apparatus as in Example 4b) was used with 63g NaAlH [OC2H4N (CH3) 233 and 250 ml of benzene charged. The reaction mixture was taking Reflux with the dropwise addition of 14 g of benzoyl chloride boiled for 30 minutes; then 50 ml of benzene were added and the reaction mixture took a further 2 hours Refluxed. After cooling and hydrolyzing with the addition of HCl, 9.75 g of benzyl alcohol isolated, that is 90.16% of theory.

Example 45 The. the same apparatus as in Example 4b) was with 55.2 g NaAlH [OCH2CH, OCH3] 3 and 200 ml of benzene charged.

The reaction mixture was refluxed with the addition of 15 g of ethyl benzoate boiled with 50 ml of benzene for 30 minutes and this under reflux for a further 2 hours continued. The reaction mixture was cooled, hydrolyzed to give 8.76 g of benzyl alcohol, this is 81% of theory.

Similarly, the following compounds were reduced under essentially the same conditions with the same molar concentration of solvents and molar amount of reactants. Reaction off Starting product Product time in loot hours (CH3CO) 20 C2H5OH 2 91.2 n -C3H7COOC2H5 C4HgOH 2-89, 89.0 C2HsCOON (CH3) 2 C3H70H4 62.8 However, the method is not limited to the use of the compounds given above. Any other compound of the NaAlHxZ4 type can be used under the same conditions, e.g. B.

NaAlH2 (OCH2CH2 OCH3) 2 or NaAlH3 (OCH, OCH2 OCH3).

Around 1 gramol of a compound containing only one carbonyl group (-CH = O or - CO -), reducing into the associated alcohol, is a theoretical one Amount of NaAlHxZ4 -necessary, which equals x gramol x NaAlHIZ4-x.

Around 1 gramol of a compound, only one carboxyl group in the molecule containing, to reduce, is a lot of the connection NäAlHxZ4 -necessary that equals 2 / x gramolof NaAlHxZ4-x.

Example 46 In the apparatus described in Example 4b), a solution of 13.4 g of p-CH3C6H4NO2 in 100 ml of benzene was added dropwise over 30 minutes to a refluxing solution of 40.4 g (0.2 mol) of NaAlH2 [O (CH2 ) 2OCH3] 2 in 200 ml of benzene was added. The solution was refluxed for a further hour and then cooled to 20 ° C. After adding 200 ml of water, the mixture was neutralized with the theoretical amount of sulfuric or hydrochloric acid. The solution was filtered, the benzene layer stripped off and the benzene evaporated. There were 9.4 g of the compound that's 92% of theory.

Any compound of the formula NaAlH, Z4 -z. B.

NaAlH2 [O (CH2) 2N (CH3) 2] 2 NaAlH3 [O (CH,) 2 O (CH2) OCH3] be applied.

Example 47 A solution of 67 g (0.33 mol) of NaAlH2 [O (CH2) 2 OCH3] 2 were introduced into 500 ml of benzene and one was melted shut Glass ampoule containing 27.11 g (0.2 mol) SiHCL3 and five steel balls of 30 mm Diameter, inserted into the vessel. The pressure vessel was closed three times flushed with nitrogen under a pressure of 20 atm and the nitrogen again drained.

A sudden movement of the pressure vessel opened the ampoule smashed. A spontaneous reaction occurred and the pressure rose to 5 at. Der The contents of the pressure vessel were emptied into a gas container and determined by analysis, that 4.8 l (20 ° C.) silicon hydride, SiH4, was obtained, that is 96% of theory. The other compounds listed in Example 46 of the general formula NaAlHxZ4 -can also be used and give similar results.

Example 48 Under the same conditions as described in Example 47, the reaction of 34 g (0.2 mol) Silicon tetrachloride with 90 g (0.44 mol) NaAlH2 [O (CH2) 2 OCH3] 2 in 500 ml of benzene set in motion. The reaction gave 4.61 (20 ° C) Silicon hydride, SiH4, that is 92% of theory. Other compounds of the formula NaAlHxZ4-x can be used in the same way and with the same result.

Example 49 Under identical conditions as in Example 47 was the reaction of 21 g (0.2 mol) SiH4 with 90 g (0.44 mol) NaAlH2 [O (CH2) 2 OCH3] 2 in 500 ml of benzene carried out and 4.85 ml of silicon hydride, SiH4, with a yield received by 97%.

Other compounds of the formula NaAlhxZ4-x can be similar Way to be used with the same result.

Example 50 Under identical conditions as in Example 47, the reaction of 30 g (0.2 mol) of CH3SiC13 with 90 g (0.33 mol) carried out in 500ml benzene. The reaction yielded 4,441 CH3SiH3, that is 89% of theory. Other compounds of the formula NaAlHxZ4 -can be used in the same way and with the same result.

Example 51 In the apparatus described in Example 4b) containing a solution of 33.3 g (0.165 mol) of NaAlH2 LOCH2CH2 OCH3] 2 in 200 ml of benzene the reaction was carried out with 21.1 g (0.1 mol) of C6HsSiCl3 in 150 ml of benzene.

The two solutions were combined over the course of 30 minutes, whereupon Was refluxed for 30 minutes. The compound of the formula C6HsSiH3 was isolated in the usual way and 9.3 g of the product, that is 86% of theory, obtain. Other compounds of the formula NaAlHxZ4 can be used in the same way can be used with equal success.

Examples 52 to 54 In. a rotating pressure vessel with a capacity of 1.5 liters a solution of NaAlH2 [OCH2CH2N (CH3) 2] 2 in 500 ml of benzene was introduced, in a in the following Table 4 indicated amount. Five steel balls with a diameter of 30 mm and a sealed glass ampoule containing the halide, the formula and amount of which are given in Table 4 were placed in the pressure vessel brought in. The pressure vessel was flushed through with hydrogen and so was the ampoule in broken in the manner given in Example 47.

The pressure vessel rotated at a temperature of 1000 C for 2 hours through. After cooling to 200 C, the glass was drained into a gas container, the volume measured and its composition determined by gas chromatography.

Table 4 Starting materials product NaAlH2 = [OCH2CH2N (CH3) 21 alkyl halide Example hydrocarbon g mole g mole 1 (20 "C) 1 (20 ° C) 52 141 0.5 CH3Cl 50.5 1 CH4 23.5 94 53 282 1 c2H4Br2 188 1 C2H6 23.1 92 54 141-0X5 C2H4J 156 1 C2H, 23.8 95 Examples 55 to 57 A solution of placed in 300 ml of p-xylene. (The amount of the compounds used in Examples 55 to 57 is shown in Table 5.) The mixture was then refluxed at atmospheric pressure. A solution of the aryl halide in 100 ml of p-xylene was then added dropwise to the boiling liquid over 30 minutes. The aryl halides and their amounts are given in Table 5. The mixture was then refluxed for a further 2 hours. After cooling to 20 ° C., 100 times water and then 100 ml of 20% hydrochloric acid were added. The organic layer was quantitatively separated and neutralized by shaking with 5 ml of 40% aqueous potassium hydroxide; the solution was then placed in a one-liter volumetric flask and xylene filled up to the mark.

The product was identified and the yield using gas chromatography established.

Table 5 Starting product r Starting product Experiment NaAIH, rOCH, - 6. Aryl halide product yield L / 2 hydrocarbon g mole g mole g% 55 30.5 0.12 J 50.6 0.2 naphthalene 24.8 96.8 Br 56 30.5 0.1 12 23.6 0.1 - Benzene 7.3 93.5 Br Br 57 45.7 0.18 31.5 0.1 benzene 7.2 92.2 Br-BJL Br EXAMPLE 58 69 g (3 mol) of sodium metal, 28.4 g (1 mol) of aluminum powder (90.1%), 114 g (1 mol) of Na3AlH6 (89.8%) were placed in a pressure vessel with a capacity of 2.5 liters. , 11 of a xylene solution of 95 g of NaAlH2 [OCH2CH2N (CH3) 2] 2 and 1.5 liters of steel balls with a diameter of 5 mm were introduced. The pressure vessel was closed, flushed through with water, evacuated and brought to a temperature of 185 to 190 ° C. At this temperature, hydrogen was discharged and the partial pressure of the hydrogen was kept at 0.45 to 0.55 atm. After the end of the reaction and the hydrogen uptake, the vessel was cooled, emptied and the steel balls removed; the suspension obtained was treated as in Example 4. The synthesis gave 205 g of a light-gray mass; containing 191 g of trisodium aluminum hexahydride, which corresponds to a yield of 94% Example 4 can be used.

The addition of trisodium aluminum hexahydride to the reaction mixture before the actual synthesis is only relevant for the grinding of the aluminum, the otherwise would not be possible. Other material can also be used for this purpose be used, e.g. B. alumina gives the same results.

The end product is then, however, with the added inert material contaminated.

Claims (6)

Claims: 1. Process for the production of complex, organic Sodium aluminum hydrides of the general formula NäAlHxZ4 -in which x is an integer from 1 to 3 and Z has the meaning given below, by reacting a Sodium hydride with an aluminum trialcoholate at elevated temperature in the presence an inert organic solvent, characterized in that trisodium aluminum hexahydride or sodium aluminum tetrahydride with a compound of the general formula AlZ3 or NaAlZ4 or with a mixture of compounds corresponding to the last formula of the general formula NaZ and AlZ3, in which Z is the remainder of one of the following Alcohols is: (1) tetrahydrofurfuryl alcohols, (2) tetrahydropyranyl alcohols, (3) Ether alcohols obtained by alkylating a hydroxyl group in diols are, (4) polyether alcohols obtained by condensation of ether alcohols and diols, however, each with elimination of a water molecule have been obtained, (5) amino alcohols of general formula R2N (CH2) y OH in which R is an identical or different alkyl; Aryl or alkoxyalkyl, where the alkyl radical has 1 to 4 carbon atoms and the Aryl radical contains 6 to 8 carbon atoms and y is an integer from 2 to 4, means. 2. The method according to claim 1, characterized in that as inert organic solvent an aromatic hydrocarbon or a Ether used, whose boiling point at atmospheric pressure is lower than the decomposition temperature of the process products. 3. The method according to claim 2, characterized in that benzene, Ethylbenzene, toluene or xylene are used. 4. The method according to any one of claims 1 to 3, characterized in that that the reaction is refluxed at the boiling point of the reaction mixture performs. 5. The method according to any one of claims 1 to 4, characterized in, that the starting alcoholate used is one in which the radical Z is a (CH3 OCH2CH2O) group. 6. The method according to any one of claims 1 to 4, characterized in that that the starting alcoholate used is one in which the radical Z is a (CH3) 2N-CH2CH2O group is. The present invention relates to a method of manufacture complex, organic sodium aluminum hydrides of the general formula NaAlHxZ4 -in which x is an integer from 1 to 3 and Z has the meaning given below, by reacting a sodium hydride with an aluminum trial alcoholate at increased Temperature in the presence of an inert organic solvent. Certain organically substituted sodium aluminum hydrides, e.g. B. sodium aluminum ethoxyhydride, -methoxyhydride and -aryloxyhydrides are known and are used as specific reducing agents used in organic chemistry. It is Z. B. possible when using this Compounds as reducing agents aldehydes, ketones, organic acid esters and chlorides to reduce alcohols, nitro compounds to amines and nitriles to aldehydes. These compounds can also be used advantageously as dehalogenizing agents Find.