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Ep 0694549 A2 Europaisches Patentamt (19) European Patent Office Office europeenpeen des brevets EP 0 694 549 A2 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) |nt CIA C07F 5/02, C07F 5/04 31.01.1996 Bulletin 1996/05 (21) Application number: 95304096.1 (22) Date of filing: 14.06.1995 (84) Designated Contracting States: (72) Inventor: Burkhardt, Elizabeth R. CH DE FR GB IE LI Bridgeville, Pennsylvania 15017 (US) (30) Priority: 30.06.1994 US 268304 (74) Representative: Bull, Michael Alan et al London WC2A 1 AT (GB) (71) Applicant: Mine Safety Appliances Company Pittsburgh, Pennsylvania 15238 (US) (54) Synthesis of organohaloboranes and alkoxyorganoboranes (57) A one-step process is provided for the synthesis are synthesized in a single reactor by reacting olefin(s) of organohaloboranes, including diisopinocamphey- and/or alkyne(s) with boron trihalide and diborane. Ichloroborane, and alkoxyorganoboranes. The present Alkoxyorganoboranes are synthesized in a single reac- process does not utilize a thermally unstable ether ad- tor by reacting olefin(s) and/or alkyne(s) with alkylborate duct or a malodorous dimethyl sulfide adduct as required and diborane. in prior processes. In general, the organohaloboranes CM < O) ^> io ^> O) CO o a. LU Printed by Jouve (FR), 18, rue Saint-Denis, 75001 PARIS EP 0 694 549 A2 Description Field of the Invention 5 The present invention relates to a novel process for the synthesis of organohaloboranes and alkoxyorganoboranes, and especially to the synthesis of diorganomonohaloboranes and organodihaloboranes. Background of the Invention 10 Chloroborane complexes, the precursors to organohaloboranes, have been prepared by a variety of methods. See H.C. Brown, S. U. Kulkarni, J. Organomet. Chem. 1 982, 239, 23-41 . For example, lithium or sodium borohydride and boron trichloride give chloroborane-ether adduct according to the following reaction: ether 15 MBH4 + BC13 > 2 H2BC1-Et20 + MCI where M = Na, Li. See H.C. Brown, P. A. Tierney, J.Am. Chem. Soc. 1958, 80, 1552; H. Noth, H. Beyer, Ber. 1960, 93, 225; U.S. Patent No. 3,026,329. A mixture of borane-tetrahydrof uran adduct and boron trichloride form chloroborane-tetrahydrofuran adduct accord- 20 ing to the following reaction: THF 2 THF - BH3 + BCI3 » 3 H2BC1 • THF See D.J. Pasto and P. Balasubramaniyan, J. Am. Chem. Soc. 1967, 89,295; D.J. Pasto and S. Kang, J. Am. Chem. 25 Soc. 1 968, 90, 3797. Borane-dimethylsulfide adduct (DMSB) and dimethylsulfide boron trichloride give dimethylsulfide chloroborane ac- cording to the following reaction: 2 Me2S- BH3 + Me2S- BCI3 -> 3 H2BCI-Me2S 30 See K. Kinbergerand W. Sierbert, Z. Naturforsch., B 1975, 30, 55; H.C. Brown and N. Ravindran, J. Org. Chem. 1977, 42, 2533; H.C. Brown, Inorg. Chem. 1977, 16, 2938. These chloroborane ether and sulfide adducts have been used in hydroboration reactions as described in detail below. Finally, gas phase reaction of diborane and boron trichloride gives dichloroborane according to the following reac- tions: 35 B2H6 +4 BCI3 -> 6 HBCI2 2BCI3 +5 B2H6 -> 6 B2H5CI See J. Cueilleron, J. Bonix, Bull. Soc. Chim., France 1967, 2945. Although these gas phase reactions were not conducted 40 for subsequent hydroboration reactions, they demonstrate that chloroboranes can be prepared in the absence of coor- dinating ether or sulfide ligands. Diisopinocampheylchloroborane (hereafter referred to as DPC) is a very useful chiral reducing agent for prochiral ketones and imines. DPC can be prepared from a-pinene and chloroborane diethyl etherate. H.C. Brown, PK. Jadhav. J. Am. Chem. Soc. 1983, 105, 2092. A variation of this process using dimethyl sulfide chloroborane has been elaborated 45 by G. Birand A.O. King. G. Bir, D. Kaufmann, Tetr. Letters 1987, 28, 777; and A.O. King et al., J. Org. Chem. 1993, 58, 3731-3735. Brown purports to obtain high optical purity DPC through a two-step procedure. See U.S. Patent Nos. 4,772,752 and 5,043,479. In this procedure, diisopinocampheylborane, a moisture and thermally sensitive intermediate is isolated from the reaction of a-pinene and DMSB. Subsequent addition of hydrogen chloride gives the final product, DPC, as a so moisture sensitive solid, which is isolated from the solution. On an industrial scale this complicated process presents several technical difficulties including the handling of thermally-sensitive solids as well as the handling of moisture sen- sitive product. A.S. Thompson, in J. Org. Chem. 1992, 57, 7044-7052, and A.O. King, supra, have shown that solutions of DPC made from >70% ee a-pinene and DMSB or dimethyl sulfide chloroborane can be used in excess to achieve high optical 55 purity reduction products, without the need for the handling of the moisture sensitive DPC solid. Allot these processes for making DPC involve use of chloroborane-diethyl ether adduct, which is thermally unstable, or dimethyl sulfide chloroborane adduct, which is notoriously malodorous. Some of the ether and sulfide ligands cause problems in the formation and use of the organochloroboranes. For example, diorganochloroborane formed from a 2 EP 0 694 549 A2 haloborane-tetrahydrof uran adduct can cleave tetrahydrofuran rendering the borane compound unusable. Furthermore, the sulfide adducts leave a sulfur smell on the final product. Development of a method for hydroboration of a-pinene by chloroborane to form DPC without the use of ether chloroborane adduct or sulfide chloroborane adduct is, therefore, very desirable. 5 Summary of the Invention Accordingly, the present invention provides a process for the generation of diorganohaloboranes and organodihalo- boranes without the use of ether chloroborane adduct or sulfide chloroborane adduct. Diorganohaloboranes are useful 10 precursors to borinic acids and esters by methods known in the art. See D.S. Matteson et al., Organometallics 1984, 7, 1284-1288; H.C. Brown ibid. 1983, 2, 1311-1316; ibid. 1986, 5, 994-997. Organodihaloboranes are precursors to boronic acids and esters See H.C. Brown, Organometallics 1982, 1, 212. Generally, the present invention provides a novel process for the preparation of organohaloboranes of the formula, R2R3BX (a diorganohaloborane) and RBX2 (an organodihaloborane), comprising the step of reacting in a single reactor is an olefin(s) and/or alkyne(s) with boron trihalide and diborane according to the following general reactions: 3R + 3R1 + B2H6 + BX3 -> 3R2R3BX 6R + B2H6 + 4BX3 -> 6R2BX2 20 wherein X is a fluoro, a chloro, a bromo, or an iodo group, R is an olefin or an alkyne and R1 is an olefin or an alkyne. R1 can be the same as or different from R. In the above reactions, if R is an olefin, R2 is the corresponding alkyl group. If R is an alkyne, R2 is the corresponding alkenyl group. Likewise, if R1 is an olefin, R3 is the corresponding alkyl group. If R1 is an alkyne, R3 is the corresponding alkenyl group. In the case of R2R3BX, R2 and R3 can be linked together to form a ring or bicyclic system, such as B-chloro-9-borabicyclo[3.3.1]nonane. The reaction can be run neat or in any 25 solvent compatible with the reagents and product. Examples of suitable solvents for a number of reactions under the present invention include the following hydrocarbon solvents: pentane, hexane, heptane, cyclohexane, methylcyclohex- ane toluene or benzene. Moreover, alkoxydiorganoboranes and dialkoxyorganoboranes can be prepared under the above general reactions wherein X is an alkoxy group. In the synthesis of such alkoxyorganoboranes, a dialkylborane (or tetraalkyldiborane) 30 may be added to the reaction mixture as a catalyst. Olefins for use in the above reactions have the general formula: 35 wherein R4, R5, R6 and R7 are any combination of hydrogen, an aryl group, an aralkyl, a branched alkyl group, an unbranched alkyl group or a cyclic group, such groups containing from one to ten carbon atoms. Alternatively, R4 and R5 can be linked by a Cn chain wherein n=2-10 or R4 and R6 are linked by a Cn chain wherein n=2-10. The aryl and 45 alkyl groups may comprise functionalities such as ester groups, ether groups, halo groups, silyl groups or nitro groups. The olefin group may also be a terpene from a naturally derived source. Alkynes for use in the present reaction have the general formula: R8C -s- CRCR9 50 wherein R8 and R9 are any combination of hydrogen, an aryl group, an aralkyl group, a branched alkyl group, an un- branched alkyl group or a cyclic group, such groups containing from one to ten carbon atoms. Alternatively, R8 and R9 can be linked by a Cn chain where n=8-15. The aryl and alkyl groups may comprise functionalities such as ester groups, ether groups, halo groups, silyl groups or nitro groups. 55 The present single reactor or "one-pot" process eliminates the need for coordinating ligands such as ethers or sulfides. The process generates substantially no waste by-products and can easily be run on a large scale. Particularly useful compounds for preparation using the present process are DPC, diisocampheylchloroborane and dicyclohexylchloroborane. Dicyclohexylchloroborane is useful for the preparation of boron enolates. 3 EP 0 694 549 A2 Detailed Description of the Invention As used in connection with the present invention, the term "alkyl" means a branched, an unbranched, or a cyclic saturated hydrocarbon group containing one to twenty carbon atoms; the term "aralkyl" means an co-aryl-alkyl group, 5 wherein the aryl group may be a phenyl group, a substituted phenyl group or any other aromatic ring system; the terms "halo" or "halide" mean a fluoro, a chloro, a bromo, or an iodo group; the term "alkyne" means a compound containing a carbon-carbon triple bond; the term "olefin" means a compound containing a carbon-carbon double bond; "enantio- meric excess" (or e.e.) is defined as the excess of one of a pair of enantiomers, usually expressed as a percentage derived from the formula: [(R-S)/(R+S)] x 100; the term "prochiral" describes an sp2 hybridized atom which upon con- 10 version to sp3 hybridization yields a chiral centre at that atom.
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