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United States Patent Office Patiented Aug 2,951,093 United States Patent Office Patiented Aug. 30, 1960 2 higher than the lowest temperature at which the corre sponding alkyl aluminium halides will react with boric 2,951,093 oxide or the metal borate to produce the corresponding MANUEFACTURE OF TRALKYL BORANES trialkyl boranes, before they decompose to yield the appropriate alkyl aluminium halide and alkali metal Robert Craig Anderson, Stevension, Scotland, assignor 5 halide. to Imperial Chemical industries Limited, London, Eng According to another modification which is in some land, a corporation of Great Britain cases preferred, the alkyl aluminium halide may be formed No Drawing. Filed Aug. 4, 1958, Ser. No. 753,142 in situ in the presence of the boric oxide or anhydrous metal borate, from the corresponding alkyl halide or alkyl . Claims priority, application Great Britain Aug. 30, 1957 O halides and aluminium. In this case it is preferred that 4 Claims. (C. 260-606.5) the boric oxide or metal borate and the aluminium should be dispersed by admixture with an inert diluent, for example, a finely divided solid inorganic material such The present invention relates to a new and improved as crystalline silica. This facilitates the passage of the process for the preparation of normal alkyl boranes of 15 vapours of the alkyl halide through the mixture of alu the kind wherein the alkyl group contains from 1 to 3 minium and boric oxide or metal borate at the elevated carbon atoms. temperature required for reaction. In the absence of The methods hitherto described for the preparation of such a diluent the boric oxide or metal borate may begin trialkyl boranes have in general been technically ineffi to sinter and thereby offer resistance to the passage of cient or inconvenient or have necessitated the use of 20 the vapour. In the case where trimethylborane is being reagents which are relatively expensive or not readily prepared this embodiment is not preferred since it is not available. These methods have included, for example, easy to separate the trimethyl borane from the excess the reaction between boron trifluoride and dimethyl zinc; methyl chloride. Thus it is preferred in this case to use the reaction between trimethyl borate or the diethyl ether preformed alkyl aluminium sesquichloride. addition compound of boron trifluoride and Grignard 25 When boric oxide is employed, it is preferably finely reagents; the reaction between trimethyl borate and powdered. When an anhydrous metal borate is to be methyl aluminium sesquiodide; the reaction between used it is preferred to use the finely powdered product trialkyl borates and aluminium triethyl; the reaction be obtained by dehydrating borax by heating it, allowing tween boron hydrides, or sodium borohydrides in the it to cool and grinding. presence of aluminium chloride, and various olefines; 30 and the reaction between boric oxide and aluminium The reaction leading to the formation of the trialkyl trimethyl or methyl aluminium sesquiiodide. borane is normally carried out at atmospheric pressure. According to the present invention a process for the If desired, however, it may be carried out under reduced production of normal trialkyl boranes of the kind pressure. It is also unnecessary to use a solvent but a wherein the alkyl groups contain from 1 to 3 carbon 35 solvent may be used if desired. No advantages accrue, atoms comprises heating in an inert atmosphere a mix however, from the use of a solvent. ture containing boric oxide as such or in the form of The tralkyl boranes and the alkyl aluminium halides an anhydrous metal borate and one or more normal are spontaneously inflammable and the latter also react alkyl aluminium halides wherein the alkyl groups con violently with water. It is essential, therefore, that the tain from 1 to 3 carbon atoms and the halide is a chlo 40 reaction should be carried out in the absence of moisture ride or bromide when the alkyl groups are methyl groups and in an inert atmosphere, and also that the condensation and a chloride when the alkyl groups are ethyl or of the trialkyl boranes should be carried out in an inert n-propyl groups and condensing the vapour of the result atmosphere, for example, one of nitrogen. ing trialkyl borane. The reaction between the alkyl aluminium halides and 45 the boric oxide or metal borate takes place satisfactorily The alkyl aluminium halide is preferably a chloride. at temperatures above 100° C., and it is preferred to The bromides alone are ineffective when the alkyl groups operate at temperatures within the range 150 to 250 C. are ethyl or n-propyl groups but they may be made When using the alkyl aluminium halide itself it is fre effective by including in the reaction mixture metal chlo quently convenient to operate at the temperature at rides capable of reacting with the alkyl aluminium 50 which the most volatile of the alkyl aluminium halides bromide to give compounds having both alkyl groups present boils, and when the alkyl aluminium halide is and chlorine atoms attached to aluminium. Suitable used as such it is convenient to carry out the reaction in chlorides include aluminium chloride, organoaluminium a vessel fitted with means whereby any unreacted alkyl chlorides, alkali and alkaline earth metal chlorides. aluminium halide in the vapour phase may be condensed lh The halide may be either a dialkyl aluminium mono 55 and returned to the reaction vessel. If necessary, a halide or the monoalkyl aluminium dihalide, or it may packed fractionation column may be employed to assist be a mixture of these. It is, however, preferred to em in separation of the desired product. As a rule, this is ploy the materials known as alkyl aluminium sesqui not necessary in the case where the alkyl aluminium halides which result from the reaction between alumin halide is used in the form of its complex with an alkali ium and the corresponding alkyl halide. 60 or alkaline earth metal halide since the reaction may then According to one preferred modification of the inven be carried out at a temperature such that the complex tion, the alkyl aluminium halide is used in the form of is molten. In this case the reaction occurs so rapidly a complex with an alkali or alkaline earth metal halide. that substantially the only vapour encountered is that This may be prepared prior to use or may conveniently of the trialkyl borane. be produced in presence of the boric oxide or metal 65 In the case where the invention is carried out by in borate by the reaction of an alkali metal halide and troducing the vapour of methyl chloride into a mixture the appropriate monoalkyl aluminium dihalide. These containing aluminium and boric oxide or a metal borate, alkali metal alkyl aluminium trihalides have the advan which as already stated preferably includes an inert tage that the reaction can be carried out at a higher diluent, it is difficult to separate the vapours of the meth temperature and hence at a higher rate than with the 70 yl chloride and the trimethyl borane even with the aid corresponding alkyl aluminium halide since they are of a fractionation column. In this case an advantageous solids which can be heated to temperatures substantially method of isolation consists in chilling the vapours con 2,951,098. 3 . 4. taining the methyl chloride and the trimethyl borane to ..., had a temperature of about 220 to 265. C. The tri about -70 C. to condense them, adding an excess of methyl borane commenced to appear in the condensation triethylamine and distilling the resulting mixture at a tem trap shortly after the heating had been commenced. perature above 0 C., but substantially below the boiling After about 40 minutes the reaction was completed, at point of triethylamine. Under these conditions the tri one stage being so vigorous that the trap cooled to -70° ethylmethylammonium chloride formed remains unde C. was unable completely to condense the product. The composed but the equimolecular co-ordination compound product was isolated by addition of an excess of tri of trimethylborane and triethylamine also formed breaks methylamine and the resulting product purified by sub up into its progenitors, and the trimethyl borane may be limation. The amount of the sublimate corresponded to condensed by cooling the vapour to a temperature below O 60% of the theoretical yield based on the raw materials -22 C. These operations are conducted in an inert used. atmosphere. Example 5 The invention is illustrated by the following examples, The reactor used was the same as in Example 3 and in which all parts and percentages are by weight except was first flushed out with nitrogen. 381 parts ethyl where otherwise indicated. aluminium dichloride and a mixture of 176 parts sodium Example 1 chloride and 35 parts boric oxide were introduced into A suspension of 7 parts of boric oxide in 41 parts of the still. An exothermic reaction took place and after methyl aluminium sesquichloride was heated to boiling in further heating for 2.5 hours, there had collected 51 a reactor provided with a calcium chloride moisture trap 20 parts of a fraction distilling at 92 to 98°C. which con and having a short fractionating column and a distilla sisted substantially of triethylborane. tion head leading to condensation trap cooled to -70 Example 6 C. and which had been flushed out with nitrogen before The reactor used was the same as in Example 1 and introducing the methyl aluminium sesquichloride. The was flushed out with nitrogen before use. 340 parts temperature at the zone of reflux rose gradually from 25 methyl aluminium dichloride and a mixture of 176 parts 128°C.
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