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United States Patent (19) 11) Patent Number: 4,510,327 Peet Et Al

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United States Patent (19) 11) Patent Number: 4,510,327 Peet Et Al United States Patent (19) 11) Patent Number: 4,510,327 Peet et al. 45 Date of Patent: Apr. 9, 1985 54) PROCESS FOR MAKING ALKALI-METAL 4,082,81 4/1978 Shook ..................................... 568/1 TETRAORGANYLBORATES 4, 134,923 1/1979 Reiner .................................... 568/1 4, 177.215 12/1979 Seidel ...................................... 568/ (75) Inventors: William G. Peet, Elkton, Md., 4,251,468 2/1981 Nazarenko et al. .................... 568/ Frederick N. Tebbe, Hockessin, Del. OTHER PUBLICATIONS 73) Assignee: E. I. Du Pont de Nemours and Company, Wilmington, Del. Hough et al., J. Am. Chem. Soc. 80; 1828, (1958). Schlesinger et al., J. Am. Chem. Soc. 75: 199, (1952). (21) Appl. No.: 482,597 Grassberger et al., Angew. Chem. Int. Ed. 8: 275, 22 Filed: Apr. 6, 1983 (1969). (51) Int. Cl. ................................................ C07F 5/02 Primary Examiner-Helen M. S. Sneed 52) U.S. Cl. ........................................................ 568/1 Attorney, Agent, or Firm-Scott G. Hallquist (58) Field of Search ........................ 260/462 R 568/1 57) ABSTRACT (56) References Cited Alkali-metal tetraorganylborate compounds of formula U.S. PATENT DOCUMENTS MBR4 are prepared by reacting triorganylboranes R3B 2,853.525 9/1958 Wittig et al. with alkali-metal hydroxide or alkoxide compounds of 331,662 3/1967 Washburn et al. the formula MOR1. 4,045,495 8/1977 Nazarenko et al. .................... 568/1 4,046,815 9/1977 Nazarenko et al. .................... 568/1 4.076.756 2/1978 Nazarenko et al. .................... 568/1 18 Claims, No Drawings 4,510,327 1. 2 tetraorganylborates by reacting alkali-metal tetraethyl PROCESS FOR MAKING ALKALI. METAL borates and triorganylboranes at 130°-180° C., e.g., TETRAORGANYLBORATES BACKGROUND OF THE INVENTION 5 The present invention relates to a process for halide M in the foregoing formula is Na or Li; R is a butyloxy, free synthesis of alkali-metal tetraorganylborate com allyloxy, carbyl, methallyl, phenyl, benzyl or pyrrolyl pounds. grOup. Tetraorganylborate compounds have a broad spec The availability of certain tetraorganyl compounds trun of utility. Tetraalkylborate compounds are used as O has been limited by the lack of a direct, efficient, conve alkylating agents, polymerization catalysts, and poly nient process for their synthesis. Certain methods repre mer stabilizers. The most widely-reported tetrarylbo sentative of the prior art are complex, requiring use of rate, sodium tetraphenylborate, is an important analyti gaseous reactants or extensive purification procedures cal reagent, as well as an NMR chemical shift reagent, to make tetraorganylborate compounds of a grade suit a photographic reagent, and a catalyst in several poly 15 able for quantitative analysis. merization reactions. Gmelin, Handbuch der Anor SUMMARY OF THE INVENTION ganischen Chemie, 33/8, Boron Compounds, (1976) dis According to the present invention, a process is pro closes a number of uses for sodium tetraphenylborate, vided for making alkali-metal tetraorganylborates of the including use as a quantitative precipitant of radioactive 20 cesium from reactor waste effluents. formula MBR4, comprising reacting a triorganylborane Wittig et al., U.S. Pat. No. 2,853,525, disclose a pro of the formula R3B with a compound of the formula cess for producing sodium tetraphenylborate by react MOR. In the foregoing formulas, R is a linear or ing a Grignard reagent with a boron trihalide in accor branched-chain alkyl group of 1 to 6 carbon atoms, an aryl or substituted aryl group of 6 to 12 carbon atoms, dance with the following two-step reaction: 25 or an aralkyl group of 7 to 9 carbon atoms. R is hydro gen or an alkyl group having from 1 to 6 carbons, and M is Li, Na, K or Cs. DETALED DESCRIPTION OF THE 30 INVENTION The present invention provides a process for making alkali metal tetraorganylborates of the formula MBR4, X in the foregoing formulas is a halide ion. comprising reacting a triorganylborane R3B with an Washburn et al., U.S. Pat. No. 3,311,662, describe a alkali metal alkoxide or hydroxide MORI. As previ method of making sodium tetraarylborate compounds, 35 ously stated, R can be a linear or branched-chain alkyl including sodium tetraphenylborate (NaB(Ph)4), by group of from 1 to 6 carbon atoms, an aryl or substi reacting aryl sodium compounds with triarylborons, tuted aryl group of 6 to 12 carbon atons, or an aralkyl C.S., group of 7 to 9 carbons. Aryl substituents can be any group which does not itself take part in the reaction, for ArNa-i-B(Ar)3-NaB(Ar)4, 40 example, alkyl, aryl, amine, or alkoxide. Preferably, Ris methyl, ethyl, phenyl, napthyl or benzyl. Most prefera or by reacting aryl sodium compounds with boron bly, R is phenyl. M can be Li, Na, Kor Cs, of which Na trihalides, e.g., is preferred. R can be hydrogen or an alkyl group, linear or branched, of up to 6 carbons. For cost and 4ArNa-BCl3-NaB(Ar)4-3NaCl. 45 availability considerations, preferably R is hydrogen, methyl or isopropyl. For yield considerations, R is Ar in the foregoing formulas can be aryl, alkaryl, preferably t-butyl. haloary, aryloxyaryl or alkoxyaryl. The synthesis of tetraorganylborates according to the Hough et al., J. Am. Chem. Soc. 80: 1828 (1958), dis present invention is believed to proceed by one or more close the following reaction of gaseous diborane with 50 sodium metal to provide sodium borohydride: of the following stoichiometries: Schlesinger et al., J. Am. Chem. Soc. 75: 199 (1952), 55 disclose a method of preparing sodium borohydride by reacting sodium methoxide or sodium tetramethox yborohydride with gaseous diborane, e.g.: Examples of tetraalkylborate compounds which can be made by the process of the invention include alkali 60 metal salts of tetramethylborate, tetraethylborate, tet ra(i-propyl)borate, tetra(i-butyl)borate and tetra(n- In addition, Schlesinger et al. report that lithium ethox butyl)borate. A preferred process is one in which trie ide (LiOC2H5) reacted with diborane to provide lithium thylborane is reacted with sodium methoxide to pro borohydride. However, this reference also reports that duce sodium tetraethylborate, a useful alkylating agent. potassium methoxide "did not react" with diborane to 65 Examples of tetraarylborate compounds accessible by produce potassium borohydrides. the process of the present invention include alkali metal Grassberger et al., Angew, Chem. Int. Ed. 8: 275 salts of tetraphenylborate, tetratolylborate, tetrafluoro (1969), disclose a process for preparing alkali-metal phenylborate, tetraethylphenylborate, tetramethoxy 4,510,327 3 4. phenylborate, tetraphenoxyphenylborate, and tet ranaphthylborate. Processes for making sodium tetra EXAMPLES phenylberate and sodium tetranaphthylborate are pre Example 1 ferred, considering the utility of these compounds as analytical reagents for determination of potassium, ce Preparation of NaB(Ph)4 by Reaction of NaOCH3 and sium and rubidium. B(Ph)3 Tetraaralkylborate compounds which can be pro ' A reaction mixture was formed by mixing triphenyl duced according to the process of the invention include boron (B(Ph)3) (1.0 g, 4.1 mmol) and sodium methoxide alkali metal salts of tetrabenzylborate and tetraphene (NaOCH3) (0.1 g, 1.8 mmol), and heating the resulting thylborate. A process for producing Sodium tetraben 10 mixture, with stirring, above the melting point of BPh3 zylborate, a useful reducing agent, is preferred. Suitable (>200). After about 15 minutes, the resulting slurry molar ratios of R3B to MORI reactants range from was cooled to about 23, and toluene added to extract about 0.3 to about 3.0, but the optimal ratio is dependent by-products. Undissolved product, NaBPh4, was sepa upon the values of M, R and R. In a particular synthe rated from the toluene extract by filtration, dissolved in sis, optimal ratios can be determined empirically to 5 water, and contacted with a molar excess of cesium increase yield. Where R is phenyl, M is Na, and R is fluoride (CsF) in aqueous solution. The resulting white isopropyl, a ratio about 1.3 to about 1.5 is preferred. precipitate was filtered, washed with water and ethyl In the method of the invention a solvent can be used ether, and dried under vacuum. The final product (0.05 but is not required. Inert solvents, particularly hydro g, 0.11 mmol) was analyzed by infrared spectroscopy. carbon solvents such as toluene, decahydronaphthal 20 The spectrum obtained was identical to that observed in ene, xylene, benzene or cyclohexane, can increase prod an analysis of a sample of cesium tetraphenylboron uct yield and are therefore preferred. Cyclohexane is an (CsBPh4) prepared by reacting CsF and NaBPh4 ob especially preferred solvent. The process of the inven tained from commercial sources. tion can be conducted in an autoclave. Alternatively, 25 Example 2 the process of the invention can be conducted in an Preparation of NaBPh4 by Reaction of NaOCH3 and open system, in which by-products are distilled from BPh3 in Decahydronaphthalene the reaction mixture at reaction temperature. A reaction mixture was formed by adding 0.21 g (3.9 The process of the invention is typically conducted at mmol) NaOCH3 to 3 ml decahydronaphthalene. The temperatures from about 100° C. to about 400° C., pref 30 mixture was boiled, reducing the total volume to about erably from about 180° C. to about 200 C. The process 1 ml by azeotropic removal of CH3OH and H2O. The of the invention can be conducted below 100 C. and resulting slurry was cooled to about 23 and 1.0 g (4.1 above 400 C. However, below 100 C., reaction rates minol) BPh3 added. This mixture was heated to about are quite slow, and above 400 C., a decomposition side 200, and held at this temperature for about 7 minutes, reaction can result. 35 with stirring. The mixture was cooled, 20 ml toluene Due to the possibility of reaction of alkoxide and added, and the resulting mixture filtered.
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