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Patent No.: US 9399.650 B2 (71) Applicant US0093.9965OB2 (12) United States Patent (10) Patent No.: US 9,399.650 B2 Ignatyev et al. (45) Date of Patent: Jul. 26, 2016 (54) METHOD FOR PRODUCING SALTS HAVING (51) Int. Cl. MONOFLUORO-TRCYANOBORATE C07F 5/02 (2006.01) ANONS (52) U.S. Cl. (71) Applicant:licant: MERCK PATENTGMB. Darmstadtd (58) CPCField ........................................of classification search C07F 5/02 (2013.01) CPC ......................................................... CO7F 5/02 (72) Inventors: Nikolai (Mykola) Ignatyev, Duisburg See application file for complete search history. (DE); Jan Arke Peter Spenger, Rommerskirchen (DE); Johannes (56) References Cited Landmann, Amorbach (DE); Maik Finze, Kleinrinderfeld (DE) PUBLICATIONS (73) Assignee: Merck Patent GmbH, Darmstadt (DE) Bernhardt etal. The reactions of MIBF4(M = Li, K) and (C2H4)2O. BF3 with (CH3)3SiCN. Formation of MBFx(CN)4-x (M = Li, (*) Notice: Subject to any disclaimer, the term of this K: x = 1, 2) and (CH3)3SNCBEx(CN)3-x, (x = 0, 1), Zeitschrift fuer patent is extended or adjusted under 35 Anorganische and Allgemeine Chemie, 2003, vol. 629, pp. 677-685.* U.S.C. 154(b) by 0 days. International Search Report for PCT/EP2014/001551 dated Sep. 9, 2014. (21) Appl. No.: 14/898,410 Bernahardt, E. et al., The reactions of MIBF4 (M-Li, K) and (C2H5)2O.BF3 with (CH3)3SiCN. Formation of M BFx(CN)4-x (22) PCT Filed: Jun. 6, 2014 (M=Li, K: x=1,2) and CH3)3SiNCBFx(CN)3-x, x= 0, 1). (86). PCT No.: PCT/EP2014/OO1551 * cited by examiner S371 (c)(1), (2) Date: Dec. 14, 2015 Primary Examiner — Joseph Kosack (74) Attorney, Agent, or Firm — Millen, White, Zelano & (87) PCT Pub. No.: WO2014/1984.01 Branigan, P.C. PCT Pub. Date: Dec. 18, 2014 (57) ABSTRACT (65) Prior Publication Data The invention relates to a method for producing alkali metal US 2016/O 130286 A1 May 12, 2016 salts having monofluoro-tricyanoborate anions from alkali (30) Foreign Application Priority Data CalaTOOOLStal tetrafil borates. Jun. 14, 2013 (DE) ......................... 10 2013 OO9959 10 Claims, No Drawings US 9,399.650 B2 1. 2 METHOD FOR PRODUCING SALTS HAVING where MONOFLUORO-TRICYANOBORATE Me denotes an alkali metal, ANIONS by reaction of a compound of the formula II The invention relates to a process for the preparation of 5 Me"I'BF (CN), II, alkali metal salts having monofluorotricyanoborate anions from alkali metal tetrafluoroborates. where Me' denotes an alkali metal, which may be identical to Alkali metal salts having monofluorotricyanoborate anions or different from Me, and are Suitable starting materials for the preparation of ionic in denotes 2, 3 or 4. liquids having monofluorotricyanoborate anions. The use of with a trialkylsilyl cyanide in the presence of a trialkylsilyl ionic liquids of this type is manifold, as described, for chloride, trialkylsilyl bromide and/or trialkylsilyl iodide, example, in WO 2004/072089 or in WO 2012/041437. They where the alkyl groups of the trialkylsilyl cyanide or trialkyl are suitable, for example, as electrolyte component for elec silyl halide in each case, independently of one another, denote trochemical cells, in particular for dye Solar cells. a linear or branched alkyl group having 1 to 10 C atoms, The preparation of alkali metal monofluorotricyanoborates where the conditions of the reaction are selected in such away can be carried out, for example, by reaction of an alkali metal that both the water content and also the oxygen content are a cyanide with boron trifluoride etherate, as described in WO maximum of 1,000 ppm, and Subsequent metal cation 2004/O72089. exchange in the case where Me" does not correspond to Me. Alternatively, alkali metal monofluorotricyanoborates can Alkali metals are the metals lithium, Sodium, potassium, be prepared by reaction of an alkali metal tetrafluoroborate caesium or rubidium. with a trialkylsilyl cyanide. The reaction of a tetrafluorobo In compounds of the formula I, Me is preferably sodium or rate with trimethylsilyl cyanide is described, for example, in potassium, particularly preferably potassium. B. H. Hamilton et al., Chem. Commun., 2002, 842-843 or in Accordingly, the process according to the invention is pref E. Bernhardt et al., Z. Anorg. Allg. Chem. 2003, 629, 677 erably suitable for the synthesis of sodium monofluorotricy 685. 25 anoborate or potassium monofluorotricyanoborate. The trialkylsilyl cyanide can also be prepared in situ for the The compounds of the formula II are commercially avail preparation of the alkali metal monofluorotricyanoborates. able, in particular for compounds of the formula II where n=4. Many preparation methods have been described for the syn or they are accessible by known synthetic processes. thesis of trialkylsilyl cyanide. The preparation of the compounds of the formula II where Trialkylsilyl cyanide can be prepared, for example, from an 30 n=2 and n=3, as described above or preferably described, can alkali metal cyanide and a trialkylsilyl chloride. EP 76413 be carried out, for example, by reaction of an alkali metal describes that this reaction was carried out in the presence of cyanide with borontrifluoride etherate, as described in WO an alkali metal iodide and in the presence of N-methylpyr 2004/O72089. rolidone. In the compounds of the formula II, Me' can be an alkali EP40356 describes that this reaction was carried out in the 35 metal selected from the group lithium, Sodium, potassium, presence of a heavy-metal cyanide. caesium or rubidium, which is selected independently of the WO 2008/102661 describes that this reaction was carried alkali metal of the end product of the formula I. Me' in out in the presence of iodine and Zinc iodide. formula II may be identical to or different from Me informula WO 2011/085966 describes that this reaction can be car I. ried out in the presence of an alkali metal iodide or fluoride 40 In compounds of the formula II, Me' is preferably sodium and optionally iodine. Preference is given here to the use of or potassium. In compounds of the formula II, Me' is particu Sodium cyanide and sodium iodide or potassium cyanide and larly preferably sodium. potassium iodide, where the alkali metal iodide is preferably A linear or branched alkyl group having 1 to 10C atoms is, added in a molar amount of 0.1 mol, based on 1 mol of alkali for example, methyl, ethyl, n-propyl, isopropyl. n-butyl, sec metal cyanide and trialkylsilyl chloride. In general, this pro 45 butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, ethyl cess for the preparation is based on the description by M. T. hexyl, n-nonyl or n-decyl. Reetz, I. Chatziosifidis, Synthesis, 1982, p. 330; J. K. Ras Trialkylsilyl cyanides are commercially available or are mussen, S.M. Heilmann and L. R. Krepski. The Chemistry of accessible by known synthetic processes. Cyanotrimethylsilane in G. L. Larson (Ed.) "Advances in The alkyl groups of the trialkylsilyl cyanide may be iden Silicon Chemistry”, Vol. 1, p. 65-187, JAI Press Inc., 1991 or 50 tical or different. The alkyl groups of the trialkylsilyl cyanide WO 2008/102661. have 1 to 10 C atoms, preferably 1 to 8C atoms, particularly However, there continues to be a need for economical preferably 1 to 4C atoms. The alkyl groups of the trialkylsilyl improved alternative synthetic methods for the preparation of cyanide are preferably identical in the case of alkyl groups alkali metal monofluorotricyanoborates. having 1 to 4 C atoms. An alkyl group of the trialkylsilyl The object of the present invention is therefore to develop an improved preparation process which starts from readily 55 cyanide is preferably different if it is an alkyl group of 5 to 10 accessible and comparatively cheap starting materials, where C atoms or of 5 to 8 C atoms. Suitable examples of trialkyl at the same time the reaction time is reduced and/or the purity silyl cyanides are trimethylsilyl cyanide, triethylsilyl cya of the end products is increased. nide, triisopropylsilyl cyanide, tripropylsilyl cyanide, Surprisingly, it has been found that the purity of the end octyldimethylsilyl cyanide, butyldimethylsilyl cyanide, t-bu product can be increased and/or the reaction time can be 60 tyldimethylsilyl cyanide or tributylsilyl cyanide. reduced if the reaction with a trialkylsilyl cyanide takes place Particular preference is given to the use of trimethylsilyl in the presence of a trialkylchlorosilane, trialkylbromosilane cyanide, which is commercially available or can also be pre and/or trialkyliodosilane. pared in situ. The invention therefore relates to a process for the prepa In the process according to the invention, the trialkylsilyl ration of compounds of the formula I 65 cyanide, as described above or described as preferred or selected from the group trimethylsilyl cyanide, triethylsilyl Me)"BF(CN). I, cyanide, triisopropylsilyl cyanide, tripropylsilyl cyanide, US 9,399.650 B2 3 4 octyldimethylsilyl cyanide, butyldimethylsilyl cyanide, t-bu preferred if the water content of the reagents and of the tyldimethylsilyl cyanide or tributylsilyl cyanide, is not pre atmosphere is less than 500 ppm, very particularly preferably pared in situ. a maximum of 100 ppm. The trialkylchlorosilane, trialkylbromosilane or trialkylio The conditions with respect to the water content and oxy dosilane is commercially available or can be prepared by gen content do not apply to the work-up after Successful standard processes. Trialkylbromosilane or trialkyliodosilane reaction of the compound of the formula II with the trialkyl can be prepared in situ from a trialkylchlorosilane and an silyl cyanide. alkali metal bromide or alkali metal iodide. The invention therefore furthermore relates to the process, Trialkylsilyl chlorides (or synonymously trialkylchlorosi as described above, where the trialkylsilyl halide or a mixture 10 of trialkylsilyl halides is employed in a total amount of 1 to 20 lanes), trialkylsilyl bromides (synonymously trialkylbro mol %, based on the amount of trialkylsilyl cyanide mosilanes) and/or trialkylsilyl iodides (synonymously tri employed.
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