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United States Patent (19) (11) 4,045,495 Nazarenko Et Al

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United States Patent (19) (11) 4,045,495 Nazarenko Et Al United States Patent (19) (11) 4,045,495 Nazarenko et al. (45) Aug. 30, 1977 (54) PROCESS FOR THE PRE PARATION OF TRARYLBORANES FOREIGN PATENT DOCUMENTS (75) Inventors: Nicholas Nazarenko; William Carl 583,006 9/1959 Canada Seidel, both of Orange, Tex. 814,647 6/1959 United Kingdom (73) Assignee: E. I. Du Pont de Nemours and Primary Examiner-Helen M. S. Sneed Company, Wilmington, Del. (57) ABSTRACT 21 Appl. No.: 630,995 Preparation of triarylboranes, e.g. triphenylborane by 22 Filed: Nov. 12, 1975 reacting an alkali metal, e.g. sodium; an organohalide, e.g. chlorobenzene and an orthoborate ester, e.g. triiso (51) Int. Cl’................................................ COTF 5/04 propylorthoborate in an inert organic solvent, recover 52 U.S. C. .............................................. 260/606.5 B ing the borane by contacting the reaction product with (58) Field of Search .................................. 260/606.5 B water while maintaining the ratio of borane to hydroly (56) References Cited sis products (e.g. borinic acid) at at least 13/1, distilling U.S. PATENT DOCUMENTS volatiles from the aqueous mixture and contacting the resultant material with acid to a pH not less than about 2,884,441 4/1959 Groszas ........... - - - - 260/606.5 B X 6 to form the borane. 3,030,406 4/1962 Washburn et al. ... 260/606. SB X 3,090,801 5A963 Washburn et al. ..... ... 260/606.5 B X 3, 19,857 A1964 Yates et al. ...................... 260/462 C 7 Claims, 1 Drawing Figure U.S. Patent Aug. 30, 1977 4,045,495 4,045,495 1 2 1-5 with chlorobenzene and isopropyl orthoborate PROCESS FOR THE PREPARATION OF using cyclohexane as an inert organic solvent in one or TRARYLBORANES two steps under anhydrous conditions and at a tempera ture in the range 15-120' C., contacting the product BACKGROUND OF THE INVENTION with water to obtain an aqueous solution of the sodium Field of the Invention isopropoxide salt of triphenylborane and acidifying the The present invention is directed to an improved salt to a pH in the range 7.1-7.4 to obtain the borane process for preparing triarylboranes by reacting an while maintaining the ratio of borane to borane hydro alkali metal, a haloaromatic compound, and an orthobo lysis products greater than 13/1. rate ester for the recovery of the borane. O Description of the Prior Art THE DRAWING Organoboranes, i.e. compounds having one or more A schematic representation of a typical method for carbons bonded to boron, have been prepared by a practicing the process of the present invention is shown variety of methods including the Grignard reaction in the drawing. using reagents of RmgX type in ether solutions of boron 15 halides. U.S. Pat. No. 2,880,242 discloses an improved DETALED DESCRIPTION OF THE process for preparing trisubstituted boranes by the di INVENTION rect action of an organic halide and boron halide in dry The preferred triarylboranes contemplated by the ethereal solutions with an alkali metal. present invention include those of the formula Rs-B U.S. Pat. No. 3,119,857 discloses the preparation of 20 wherein R is an aryl or substituted aryl group having 6 organoboron compounds by reacting an organo-alkali to 12 carbon atoms, e.g. phenyl, orthotolyl, paratolyl, metal with a boron trihalide or an ester of boric acid in naphthyl, methoxy paraphenyl, para-aminophenyl, bi an inert liquid reaction medium to produce the corre phenyl, chlorophenyl and bromophenyl. Triphenylbo sponding organoboron halide or organo boric acid es rane and the sodium isopropoxide adduct thereof are of ter. 25 particular interest. Another process for the preparation of organoboron Alkali metals which are operable in the present pro compounds is disclosed in U.S. Pat. No. 3,187,054 cess include lithium, potassium, etc. with sodium being which method involves reacting a boron trihalide, preferred. The rate and efficiency of the reaction with boron ester or boron-carbon compound with an or alkali metal depends at least in part upon the surface ganosodium compound in an inert hydrocarbon solvent. 30 area of the alkali metal. Preferably, the metal is in a The preparation of a variety of aryl polyboronic acids suspension of particles of 1-5 in the reaction solvent, and esters by reacting an aromatic halide with finely but particles up to and exceeding 100 may be utilized dispersed metallic sodium in the presence of a borate along with certain activators including the lower alkyl ester preferably at atmospheric pressure and at tempera alcohols, i.e. those having 1 to 6 carbon atoms, e.g. tures below about 50 C. is disclosed in U.S. Pat. No. 35 methanol, ethanol and isopropanol. The activator is 3,090,801. The preparation of the sodium hydroxide salt preferably employed when the reaction is conducted at of triphenylborane by reacting triphenylborane with lower temperatures and may be introduced directly into sodium hydroxide is disclosed by Wittig and Raffin an the reaction mixture or as a solution in the reaction article entitled Uber Komplexibildung mit Triphenyl-bor, solvent. If the reaction is conducted at temperatures of Ann. 573 208 (1951). The preparation of related com 100' C. or higher, e.g. in a methylcyclohexane solvent pounds, e.g. alkyl phosphines, is disclosed in U.S. Pat. the sodium can be introduced in the molten state di No. 3,223,736. rectly to the reaction medium. Since the instant reaction is highly exothermic, the cooling requirements can rep SUMMARY OF THE INVENTION resent an excessive economic penalty if the reaction is The present invention provides a process for the prep 45 conducted too rapidly. Therefore, it is desirable to con aration of triarylborane, e.g. triphenylborane by react trol the reaction rate at the desired operating conditions ing a finely-divided alkali metal, e.g. sodium metal, to reduce the cooling requirements. This object can be having a particle size in the range 1-100, with an or accomplished without adversely affecting the yield by ganohalide such as a haloaromatic, e.g. chlorobenzene continuously metering the sodium dispersion to the and an orthoborate ester derived from secondary alkyl 50 reaction or by staged addition of the sodium dispersion. alcohols, e.g. isopropanol and sectoutanol in an inert A wide variety of compounds may be employed as organic hydrocarbon solvent which can be maintained the inert organic solvent in the present process. The as a liquid at reaction conditions. Optionally, promoters reactants should be relatively soluble in the solvent at such as benzene to increase electron transfer and isopro reaction temperature and should not react with the panol to activate the alkali metal may be added. The solvent. Compounds such as benzene which increase reaction is conducted in the absence of significant electron transfer (transfer agents) can be included in the amounts of water, i.e. under substantial anhydrous con medium especially at lower reaction temperatures. The ditions. The reaction products are contacted with water suitability of certain solvents can vary depending upon to form the sodium hydroxide salt of triarylborane. the method of conducting the process. For example, in Subsequently the salt is acidified to a pH not less about a process wherein the arylating agent is prepared and 6 with an acid, e.g. hydrochloric acid to recover the then reacted with the orthoester, solvents such as tolu triarylborane. The alkali metal alkoxide salt of triaryl ene, xylene, and cumene tend to be less desirable be borane can be prepared in one step or in two steps by cause they react with the arylating agent. However, initially preparing the organosodium compound and when the orthoborate ester is present the arylating subsequently reacting that material with the orthobo 65 agent preferentially reacts with the ester thereby ren rate ester. More particularly, one embodiment of the dering solvents such as toluene essentially inert. Prefer present process involves the preparation of triphenylbo ably the solvent has a boiling point at atmospheric pres rane by reacting finely divided sodium, i.e. particles of sure near the desired reaction temperature to facilitate 4,045,495 3 4. heat removal via reflux of the solvent. Suitable solvents desired products when employed in the manner speci include singly or in mixture branched or unbranched fied herein. alkanes, having 5-8 carbon atoms, e.g. pentane, hexane, When the process of the present invention is con heptane, octane and 3-methylpentane; cycloalkanes ducted in the preferred manner set forth hereinabove having 5-8 carbon atoms, e.g. cyclohexane, methylcy boron containing by-products are less than 6% and clohexane, cyclooctane, cyclopentane; alkenes having preferably less than 3% by weight based upon the 5-8 carbon atoms and cycloalkanes having 5-8 carbon weight of triarylborane and the sodium salt adduct of atoms wherein unsaturation does not react with the the triarylborane is stable in the aqueous solution. alkali metal, the organohalide or the orthoester. Exam The present process provides the alkali metal alkoxide ples of the foregoing include hexene and octene. Other O salt of triarylborane in sufficient purity so that a subse suitable inert organic solvents will be apparent to one quent treatment with water yields an aqueous solution skilled in the art in view of the foregoing consideration. wherein the alkali metal hydroxide salt of the triarylbo Cyclohexane is preferred because it boils at a preferred rane is stable for extended periods. Although previously reaction temperature and thus permits effective heat disclosed method involved the treatment of reaction removal and because it provides high yield to the de products with water, copious amounts of impurities sired products when certain esters are employed as is such as borinic acid and precursors present reacted with discussed hereinbelow, the minor amount of triarylborane produced when the The organohalide can be any halogen substituted mixture containing the alkali metal hydroxide salt was organic which is compatible in the system and wherein acidified resulting in poor recovery of the borane.
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