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(12) United States Patent (10) Patent No.: US 7,501,075 B2 Emmel Et Al

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(12) United States Patent (10) Patent No.: US 7,501,075 B2 Emmel Et Al US00750 1075B2 (12) United States Patent (10) Patent No.: US 7,501,075 B2 Emmel et al. (45) Date of Patent: Mar. 10, 2009 (54) SYNTHESIS AGENT CONTAINING 5,002,689 A 3, 1991 Mehta et al. METHYLLITHIUM/LITHIUM BROMIDE, 5,100,575 A * 3/1992 Hatch et al. .............. 252, 1823 AND PROCESS FOR THE PREPARATION 5,141,667 A 8, 1992 Morrison et al. THEREOF 5,171.467 A * 12/1992 Mehta et al. ............. 252, 1823 5,320,774 A 6/1994 Mehta et al. 5,677,543 A 10, 1997 Weiss et al. (75) Inventors: Ute Emmel, Frankfurt am Main (DE), 6,495,064 B2 * 12/2002 Weiss et al. ............ 252/182.14 Peter Rittmeyer, Sulzbach Taunus (DE), 6,770,763 B2 * 8/2004 Magnus et al. .............. 548,550 Ulrich Wietelmann, Friedrichsdorf 2003/0236401 A1* 12/2003 Magnus et al. .............. 540/363 (DE); Rainer Aul, Rodgau (DE) 2006/0241299 A1 * 10, 2006 Volante et al. ................ 546, 16 2007/0276.163 A1* 11/2007 Evans et al. ................. 568,558 (73) Assignee: streal GmbH, Frankfurt am Main FOREIGN PATENT DOCUMENTS DE 39 O5857 C2 9, 1989 (*) Notice: Subject to any disclaimer, the term of this DE 39 O5857 C3 9, 1989 patent is extended or adjusted under 35 DE 39 43841 C2 9, 1989 U.S.C. 154(b) by 588 days DE 44 24 222 C1 9, 1995 M YW- y yS. DE 3856 437 T2 6, 2001 EP O753 52O 1, 1997 (22) Filed: Aug. 23, 2005 * cited by examiner O O Primary Examiner Joseph D Anthony (65) Prior Publication Data (74) Attorney, Agent, or Firm Fulbright & Jaworski L.L.P. US 2006/OO493.79 A1 Mar. 9, 2006 (57) 57 ABSTRACT (30) Foreign Application Priority Data A synthesis agent containing methyllithium and lithium bro Sep. 6, 2004 (DE) ....................... 10 2004 O43 5O1 mide is described, in which MeLi and LiBrare dissolved in a solvent of the general formula (I) (51) Int. Cl. C09K 3/00 (2006.01) C07F I/02 (2006.01) RN-OR (52) U.S. Cl. .............................. 252/1823; 252/182.12: R21 Nors 252/182.16; 252/182.29; 502/152: 502/169 (58) Field of Classification Search .............. 252/182.3, :- 1 2 252/182.16 wherein R" and R independently of pne another are H, See application file for complete search history. methyl (Me) or ethyl (Et), and RandR are Me or Et, the molar ratio of LiBr to Melibeing at least 0.7 and not more (56) References Cited than 1.5 and the methyllithium concentration being at least 4 U.S. PATENT DOCUMENTS 4,976,886 A 12/1990 Morrison et al. 29 Claims, No Drawings US 7,501,075 B2 1. 2 SYNTHESIS AGENT CONTAINING EP 753 520 further provides for the addition of up to 10% METHYLLITHIUM/LITHIUM BROMIDE, lithium bromide or lithium iodide in order to obtain a special AND PROCESS FOR THE PREPARATION synthesis agent Suitable for Stereochemical reactions. In THEREOF Example 3, a solution containing 7.2% Melli and 8.25% lithium bromide is described. This composition corresponds This application claims priority from DE 102004.043501.4 to a molar ratio LiBr:MeLi of approximately 0.29:1. filed Sep.6.2004, herein incorporated by reference in its It is known that the selectivity of some organic reactions is entirety. greatly affected by the salt content, more precisely the molar The invention relates to a synthesis agent containing meth ratio of lithium organyl to lithium salt. yllithium/lithium bromide, and to a process for the prepara 10 tion thereof. Such effects are summarised by A. Loupy and B. Tchoubar Methyllithium is used as a reagent in the production of (“Salt Effects in Organic and Organometallic Chemistry', pharmaceutical products, such as vitamins or steroids, and in VCH, Weinheim 1992) or C. Fehr (Angew. Chem. 1996, 108, special synthesis steps, such as reactions of the carbene type 2726-2748). For example, the enantiomeric excess (ee) in the for the preparation of allenes and alkoxycyclopropanes, asymmetric protonation of prochiral enolates is affected by methylating reactions for the preparation of alkenyllithium lithium salt additives (A. Yanagisawa et al., Synlett 1998, and steroidal alkenyl compounds, reduction reactions of vari 174-176): ous transition metal halides, such as PdCl to Pd(0), the preparation of methyllithium cuprates for 1.4-conjugated additions or for the preparation of other organometallic com pounds, such as MeMg, MeTi(NEt), Me Al, Me-Al. OSiMe3 OLi Me. As or Me,Ga. n-C5H1 n-BuLi, MX n-C5H11 He Methyllithium is available commercially in the form of an solvent, 0°C. approximately 5% solution in diethyl ether or in the form of 25 an approximately 6% solution in diethyl ether, which con tains approximately 10% lithium bromide as complex-form Ph ing stabiliser. These commercial forms of methyllithium in H wPh O diethyl ether have only limited usability owing to the low N flash point of diethyl ether. Other ethereal solutions of meth 30 O N N O He-1 THF Y wn-C5H1 yllithium have no commercial importance because on the one O -78° C., 2h hand the concentration of methyllithium therein is very low (approximately 3 wt.%) and on the other hand their stability is inadequate (e.g. in THF or glycol ethers). In hydrocarbons and aromatic compounds, on the other hand, methyllithium is 35 insoluble. A certain degree of solubility in aromatic com 1 pounds is achieved if the methyllithium-THF complex is used (max.3.74 wt.%). Accordingly, documents EP-A 02285 374 MX, (equiv) Solvent % ee. and U.S. Pat. No. 5,171.467 disclose alkyllithium compounds THF 63 EtO 74 in aromatic hydrocarbons which have been stabilised by a 40 LiBr (1) THF 79 content of a Lewis base, such as tetrahydrofuran, and lithium LiBr (1) EtO 83 halides. However, because these solutions tend to decompose LiBr (2) THF 79 by metallation of the aromatic hydrocarbon, dialkylmagne LiBr (2) EtO 85 LiBr (5) THF 77 sium compounds are added. The content of active lithium LiBr (5) EtO 90 compounds falls as a result to 2.6 wt.%, and the reactivity is 45 LiBr (10) THF 78 affected by the presence of dialkylmagnesium compounds. LiBr (10) EtO 88 From EP 753 520 there are also known synthesis agents a Small amount of hexane (Ca. 6%) was contained in each solvent; containing dissolved methyllithium, which synthesis agents determined by GC analysis with chiral column (Chiraldex TMB-TA, astec). contain methyllithium in a solvent of the general formula: (R)-Enriched ketone 6 was obtained in each case 50 The object of the present invention is to overcome the (I) disadvantages of the prior art and, in particular, to provide RN1 OR3 synthesis mixtures containing methyllithium in a solvent that R21 YoR4 is better to handle than diethyl ether, which synthesis mix 55 tures have a highly selective action. The object is achieved by a synthesis agent containing wherein R' and R independently of one another are H. methyllithium and lithium bromide, in which Melli and LiBr methyl (Me) or ethyl (Et) and RandR are methyl or ethyl. are dissolved in a solvent of the general formula (I) These synthesis agents are prepared by a) dispersing lithium powder or lithium granules in a solvent 60 of the general formula I and adding methyl halide in RN1 OR3 metered amounts, R21 YOR4 b) maintaining the reaction temperature in the range from 0 to 60° C. and 65 c) separating the resulting lithium halide from the methyl wherein R' and R independently of one another are H. lithium solution. methyl (Me) or ethyl (Et), and RandR are Me or Et, US 7,501,075 B2 3 4 the molar ratio of LiBr to Melibeing at least 0.7 and not more Instead, it can be used, for example, for a Subsequent batch than 1.5 and the methyllithium concentration being at least 4 for the preparation of further methyllithium. In this manner, wt.%. methyllithium-lithium bromide-containing Solutions (syn In a preferred embodiment, the molar ratio of LiBr to Meli thesis agents) having a very high LiBr concentration can be is at least 0.8, particularly preferably at least 1.0. 5 obtained in a particularly simple and economical manner. The synthesis agent may comprise from 1 to 40 wt.% of The Subject-matter of the invention is explained in greater one or more aromatic solvents, preference being given to detail by means of the following examples: benzene, toluene, ethylbenzene, Xylene or cumene. However, it is also possible for the synthesis agent to contain no aro EXAMPLE 1. matic solvent. 10 The synthesis agent containing methyllithium and lithium Preparation of a 5.5% methyllithium Solution bromide can be prepared by reaction of a methyl halide Having a LiBr:MeLi Ratio of 0.78:1 (M-Hal, where Hal=Clor Br) with lithium metal, the reaction being carried out in a solvent of formula (I) and the lithium In an argon-filled glovebox. 29.6 g of anhydrous lithium bromide being added to the resulting reaction mixture and/or 15 bromide were introduced into a 250 ml ISO threaded bottle. being added to the solvent before the reaction. This means that, in the case where the amount of LiBr necessary to 93 g of a lithium-bromide-free 8.0% methyllithium solution achieve a LiBr:MeLi stoichiometry has not already been in 1,1-diethoxymethane (DEM) were then added. The mix introduced with the reaction solvent, the required amount of ture was stirred magnetically for 3 hours; the majority of the LiBr is added after the reaction and before or after separation lithium bromide had then gone into Solution.
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