Patent GB-956256-A (GB)
Title: Boron compounds
Inventor: MILLER HENRY CHARLES
IPC: C22B3/26
Filed: 1961-06-06
Abstract: The invention comprises polyborates of the formula Ma(B12H12-yXy)b, wherein M is a cation of valence 1 to 4, (B12H12-yXy) is an anion of valence 2, X is a monovalent group capable of bonding to carbon of a benzene nucleus by replacement of hydrogen bonded to said carbon, a and b are each positive whole numbers of 1 to 3 whose respective values are determined by the valence of M, and y is an integer from 1 to 12.  M may be hydrogen, H3O+, a metal, ammonium, hydrazonium, N-substituted ammonium, N-substituted hydrazonium, aryldiazonium, P-substituted phosphonium, or a metal-ammine complex; the substituent in these cations may be a saturated or unsaturated or substituted hydrocarbon group or may contain a heterocyclic ring, a list of suitable substituents being given.  X may be halogen, hydrocarbon, carboxyl, N,N-disubstituted amide, acyl halide, halomethyl, hydroxymethyl, hydrocarbyloxymethyl, dihydrocarbylaminomehtyl, cyano, trihalomethyl, acyl, aldehyde, nitro, nitroso, azo, sulpho, sulphonyl, or acetoxymercury.  The X groups may be all the same or may differ.  Many specific polyborates are listed in the Specification.  Most of the compounds are crystalline salt-like solids which dissolve in water or hydroxylated solvents and may contain water or solvent of crystallization. The compounds show absorption bands in the infra-red spectrum characteristic of dodecaborate anions.  To prepare the compounds, a dodecahydrododecarborate of the formula Ma(B12H12)b is treated with an electrophilic reagent to introduce the substituent X; the substituent may be subsequently modified by reduction, esterification, hydrolysis, or amidation to form amino, amido, carboxy, ester, sulphonyl halide, and sulphonamide groups.  A list of suitable electrophilic reagents is given. Reaction may take place in a glass, platinum, or stainless steel vessel in the presence of an inert solvent, e.g. water, an alcohol, or 1,2-dimethoxyethane, preferably at a temperature of 0-75 DEG C. under atmospheric pressure.  A catalyst, e.g. aluminium trichloride, boron trifluoride, or polyphosphoric acid, is sometimes used.  Free acids may be formed by contacting an aqueous solution of the salt with an acidic cation exchange resin and evaporating the solution obtained under reduced pressure.  The dodecahydrododecaborate reactants are prepared by reaction of an alkali metal or alkaline earth metal hydroborate with diborane under 3 to 500 atmospheres absolute pressure in the substantial absence of moisture; an inert solvent, e.g. an ether or a tertiary amine, may be present, and preferably the diborane is in molar excess. Examples include the preparation of Na2-B12H12.H2O, K2B12H12, H2B12H12, [(CH3)4N]2-B12H12, and Cs2B12H12.  The preparation of compounds according to the invention is illustrated in examples which describe the preparation of Cs2B12H2Cl10, Na2B12H6Br6, a mixture of [(CH3)4N]2B12H6Br6 and [(CH3)4N]2B12H7-Br5, Cs2B12H10I2, [(CH3)4N]2B12H11NO2, Na2-B12H11NO2, Cs2B12H11NO, Cs2B12H11CH2OH, CsHB12H11C(CH3)3, H2B12H11C6H11, Cs2B12-H11C6H11, H2B12H10(CH=CH2)2 and its caesium salt, H2B12H11CH=CHC6H5 and its caesium salt, and <FORM:0956256/C1/1> and its caesium salt.  Some of these compounds are associated with water, dioxane, or 1,2-dimethoxyethane of crystallization.  The preparation of many other compounds is described in general terms.  The compounds are useful as sequestering agents for removing metals (e.g. Cu, Ni, Co, Zn, Cd, Ag, Hg) from gasoline or from aqueous solutions. Compounds having azo substituents may be used in dyeing compositions, and highly halogenated compounds as impregnating agents to retard combustion of cellulosic products. The salts are also useful as wetting agents.ALSO:The invention comprises polyborates of the formula Ma(B12H12-yXy)b wherein M is a cation of valence 1 to 4, (B12H12-yXy) is an anion of valence 2, X is a monovalent group capable of bonding to carbon of a benzene nucleus by replacement of hydrogen bonded to said carbon, a and b are each positive whole numbers of 1 to 3 whose respective values are determined by the valence of M, and y is an integer from 1 to 12. M may be hydrogen, H3O+, a metal, ammonium, hydrazonium, N-substituted ammonium or hydrazonium, aryldiazonium, P-substituted phosphonium, or a metal-amine complex; the substituent in these cations may be a saturated or unsaturated or substituted hydrocarbon group or may contain a heterocyclic ring, a list of suitable substituents being given. X may be halogen, hydrocarbon, carboxyl, N,N-disubstituted amide, acyl halide, halomethyl, hydroxymethyl, hydrocarbyloxymethyl, dihydrocarbylaminomethyl, cyano, trihalomethyl, acyl, aldehyde, nitro, nitroso, azo, sulpho, sulphonyl, or acetoxy-mercury. The X groups may be all the same or may differ. Many specific polyborates are listed in the Specification. Most of the compounds are salt-like solids which dissolve in water or hydroxylated solvents and may contain water or solvent of crystallisation. The compounds show absorption bands in the infra-red spectrum characteristic of dodecaborate anions. To prepare the compounds, a dodecahydrododecaborate of the formula Ma(B12H12)b is treated with an electrophilic reagent to introduce the substituent X; the substituent may be subsequently modified by reduction, esterification, hydrolysis, or amidation to form amino, amido, carboxy, ester, sulphonyl halide, or sulphonamide groups. A list of suitable electrophilic reagents is given. Reaction may take place in a glass, platinum, or stainless steel vessel in the presence of an inert solvent, e.g. water, an alcohol, or 1,2-dimethoxyethane, preferably at a temperature of 0 DEG -75 DEG C. under atmospheric pressure. A catalyst, e.g. aluminium trichloride, boron trifluoride, or polyphosphoric acid, is sometimes used.  Free acids may be formed by contacting an aqueous solution of the salt with an acidic cation exchange resin and evaporating the solution obtained under reduced pressure.  Examples describe the preparation of a mixture of [(CH3)4N]2B12H6Br6 and [(CH3)4N]2B12H1Br5, [(CH3)4N]2B12H11NO2, Cs2B12H11CH2OH, CsHB12H11C(CH3)3, H2B12H11C6H11, Cs2B12H11C6H11, H2B12H10(CH=CH2)2 and its caesium salt, H2B12H11CH=CHC6H5 and its caesium salt, and <FORM:0956256/C2/1> and its caesium salt.  The preparation of many other compounds is described in general terms. The compounds are useful as sequestering agents for removing metals (e.g. Cu, Ni, Co, Zn, Cd, Ag, Hg) from gasoline or from aqueous solutions. Compounds having azo substituents may be used in dyeing compositions, and highly halogenated compounds as impregnating agents to retard combustion of cellulosic products.  The salts are aso useful as wetting agents.ALSO:Dyes.-Arylazo - substituted dodecahydrododecaborates (see Division C2) are used for imparting colour to fabrics.  Specific compounds referred to are:- <FORM:0956256/C3/1> and its caesium salt, <FORM:0956256/C3/2> , <FORM:0956256/C3/3> , <FORM:0956256/C3/4> , and K2B12H11(N=NC6H5). Purifying hydrocarbons.- A gasoline containing dissolved copper stearate is purified by treatment with an aqueous ammoniaxal solution of Na2B12H2Cl10, which acts as a sequestering agent for the copper.ALSO:Highly halogenated polyborates of the formula Ma(B12H12-y Xy)b wherein M is a cation, X is chlorine or bromine, y is 7 to 12, and a and b are 1 to 3 depending on the valence of M (see Division C1), are useful as impregnating agents to retard combustion of cellulose products.