GB959124A - Boron compounds - Google Patents

Abstract

The formulae: M(B12H11NRR1R11)n [RR1R11NH][B12H11NRR1R11], HB12H11 NRR1R11, and M(B12H11-yXy.NRR1R11), [H2B.2N(CH3)3]mZ, and [RR1R11N]2B12H12, where M is a group capable of forming a cation, n is a positive whole number of 1 to 4, the valency of M, R, R1 and R11 represent alphatically saturated groups (i.e. groups containing no acetylenic of ethylenic links) of 1 to 18, preferably 1 to 8 carbon atoms which are directly bonded to the nitrogen atom, or R and R1 may be taken together to form a ring with the N atom to which they are attached, which ring may contain a further heterocyclic nitrogen or oxygen atom, X is a group derived from an electrophilic reagent and y is a number from 1 to 11; Z is a group capable of forming an anion and m is the valency of Z; represent compounds which are useful as sequestering agents for metals, especially heavy metals in aqueous and hydrocarbon media. For example a mixture of hydrocarbons in the boiling range of gasoline, which contains a copper salt (copper stearate) in solution is thoroughly agitated with an ammoniacal aqueous solution of NaB12H11N (C2H5)3. The hydrocarbon layer is separated from the aqueous layer completely free of the deleterious copper salt. Furthermore, copper, nickel, cobalt, zinc and cadmium are removed from aqueous solutions of salts containing these metals by mixing the solutions with an ammoniacal solution of an alkali metal or alkaline earth metal salt of the B12H11NRR1R11 anion, e.g. the Na, K, Li, Cs, Ca or Mg salt of B12H11N (C2H5)3. In addition, the compounds containing the [H2B.2N(CH3)2]+ ion are particularly useful in sequestering gold as its chloride.ALSO:Polyhydrido-dodecaborates (i.e. compounds containing the [B12H12]2-ion and the [B12H11 NRR1R11]ion) are prepared by heating B2H6, B5H9, or B10H14 with a borane-tertiary amine adduct, preferably of general formula H3B-NRR1R11, at a temperature of 75-400 DEG C. and isolating the products. If desired the adduct may be first prepared and purified before using in the reaction, or it may be prepared in situ by mixing B2H6, for example at a temperature of -80 DEG C. to 35 DEG C., with the tertiary amine, and then adding a further quantity of B2H6 or other boronhydride into the reaction vessel and raising the temperature to between 75 DEG C. to 400 DEG C. to produce the desired compounds. R, R1 and R11 are aliphatically saturated groups (i.e. groups which contain no olefinic or acetylenic unsaturation) joined to the N atom by singly bonded carbon atoms, which atoms are otherwise singly bonded to C or H. R, R1 and R11 preferably consist of carbon and hydrogen and contain up to 18, most preferably up to 8 carbon atoms. They may contain at most one ethereal oxygen or tertiary nitrogen atom, and R1 and R11 may be joined to form a ring of which the said oxygen or nitrogen atom is a member, e.g. N-methyl morpholine, N,N1-dimethyl piperazine. R, R1 and R11 may be alike or different and may be alkyl, cycloalkyl, aryl alkyl, oxygen-interrupted alkyl or cyclo-alkyl. Examples of suitable tertiary amines to form adducts are:-triethylamine, methyl diethylamine, tricyclohexylamine, methyldicyclohexylamine, N-butyl morpholine and N-ethyl piperidine; whilst those containing two tertiary N atoms are N,N,N1N1 tetra-methyl diamino ethane, and N,N1diethyl-piperazine; addition compounds derived from the latter amines will have a BH3 bonded to each N atom. Products of the above reaction (see Example I) may be compounds containing the [B12H12]2-ion e.g. [(CH3)3NH]2[B12H12] or the [B2H11NRR1R11]-ion e.g. [(CH3)3NH] [B12H11N(CH3)3] or may also be compounds containing a new cation viz:-[H2B.2N(CH3)3]1+ e.g. [H2B.2N(CH3)3] [B12H11N(CH3)3]. Examples II-X illustrate the preparations of [(C2H5)3NH]2B12H12; [(C2H5)3NH] [B12H11 N(C2H5)3]; [(C4H9)3NH]2B12H12; <FORM:0959124/C2/1> <FORM:0959124/C2/2> Example XI illustrates the formation of the acid H[B12H11N(C2H5)3] by submitting the compound <FORM:0959124/C2/3> to ion exchange on an acid resin. This acid (as shown in Example XII) may be used to produce salts by standard chemical reactions and these exemplify salts of the general formula M[B12H11NRR1R11]n where R, R1 and R11 have their former significance, n in the valency of M, and M can be any group capable of forming a cation e.g. a metal, ammonium, substituted ammonium, sulphonium, substituted sulphonium, phosphonium, substituted phosphonium, hydrogen, hydronium, hydrazonium, substituted hydrazonium and metal amine groups. Examples XIII and XIV exemplify the production of compounds of the general formula: M[B12H11-yXyNRR1R11], where y can be any integer from 1 to 11, M is any cation, and X is a group derived from any electrophilic reagent; by illustrating the formation of <FORM:0959124/C2/4> and <FORM:0959124/C2/5> by the action of Br2 or Cl2 on <FORM:0959124/C2/6> . A similar iodine derivative can also be obtained using ICl. The compound: <FORM:0959124/C2/7> prepared in Example I can be submitted to ion exchange on a resin in its chloride form to give [BH2.2N(CH3)3]Cl. which compound can serve to produce by various metatheses a series of compounds of general formula: [BH2.2N(CH3)3]Z where Z can be, for example, OH, NO3, Br, So4, acetate, or benzoate. The Specification contains long lists of tertiary amines suitable for the compounds of the invention, and long lists of suitable cations M.ALSO:The formula <FORM:0959124/C3/1> where R, R1, R111 are alkyl groups, represents a group of substances which fluoresce under ultra-violet light. These compounds are prepared by heating B2H6, B5H9 or B10H14\t with a tertiary amine-borane adduct, e.g. H3B N(C2H5)3 at a temperature of from 75 DEG to 40o DEG C. and isolating the products. The trialkyl ammonium compounds, e.g. (C2H5)3NHB12 H11N(C2H5)3 which show this fluorescence are useful as components of marking inks employed for identification purposes.