US007847 126B2 (12) United States Patent (10) Patent No.: US 7,847,126 B2 Rampf et al. (45) Date of Patent: Dec. 7, 2010 (54) PROCESS FOR PREPARING TERTIARY (56) References Cited PHOSPHINES U.S. PATENT DOCUMENTS 3,499,039 A 3/1970 Lorenz et al. ............ 260/606.5 (75) Inventors: Florian Rampf, Köln (DE), 4,668,823. A 5/1987 Murray ....................... 567/424 Hans-Christian Militzer, Odenthal 6,335,471 B1 1/2002 Eastham et al. ............... 568, 17 (DE) OTHER PUBLICATIONS Tomori, H. etal: "An Improved Synthesis 11-19.21, of Functionalized (73) Assignee: LANXESS Deutschland GmbH, Biphenyl-Based Phosphine 23 Ligands' Journal of Organic Chem Leverkusen (DE) istry (2000), 65(17), 5334-5341, 2000, XPO02248873 Tabelle 1. Kaye, S. et al: “The use of catalytic amounts of CuCl and other (*) Notice: Subject to any disclaimer, the term of this improvements in the benzyne route to biphenyl-based phosphine patent is extended or adjusted under 35 ligands' Advanced Synthesis & Catalysis (2001), 343(8), 789-794, U.S.C. 154(b) by 854 days. 2001, XPOOI161250 das gauze Dokument. Schmidbauer H. et al.: “Extreme sterische Hinderung: Synthese and (21) Appl. No.: 11/810,374 Strunktur des Tetra (tert-butyl) phosphonium Kations—ein Fall von T-Symmetrie” Chemische Berichte. Bod. 113, Nr. 4, 1980, Seiten (22) Filed: Jun. 5, 2007 1612-1622, XPO02248874 Verlag Chemie GMBH. Weinheim., DE ISSN: 0009-2940 Seite 1613, unten; Seite 1614, Verbindung 5. Dumont W.W. et al.: IIZinn(II)-halogenidKomplexe mit Tri-tert (65) Prior Publication Data butylphosphin und Tris(dimethylamino)phosphin Zeitschrift fur US 2007/0299273 A1 Dec. 27, 2007 Anorganischeund Allgemeine Chemie. Bd. 441, 1978, Seiten 86-92. XPOO1 160738 Verlag Johann Ambrosius Barth. Leipzig., DDISSN: Related U.S. Application Data 0044-2313 Verbindung der Formel VII. Adv. Synth. Catal., (month unavailable) 2001, 343 (8), 789-794, (62) Division of application No. 10/417.989, filed on Apr. Kaye et all “The Use of Catalytic Amounts of CuCl and Other Improvements in the Benzyne Route to Biphenyl-Based Phosphine 17, 2003, now Pat. No. 7,230,136. Ligands'. J. Am. Chem. Soc., (month unavailable) 2001, 123 (11), 2677-2678, (30) Foreign Application Priority Data Stambuli et al., “Screening of Homogeneous Catalysts by Fluores Apr. 19, 2002 (DE) ................................ 102 17 517 cence Resonance Energy Transfer. Identification of Catalysts for May 17, 2002 (DE) ................................ 102 22 O33 Room-Temperature Heck Reations”. Primary Examiner Elvis O Price (51) Int. Cl. (74) Attorney, Agent, or Firm Michael A. Miller C07F 9/54 (2006.01) C07F 5/02 (2006.01) (57) ABSTRACT C07F 7/28 (2006.01) The invention relates to a process for synthesizing tertiary (52) U.S. Cl. ..................... 568/2:568/9:556/7:556/23; phosphines by reacting halophosphines with organomagne 556/51 sium compounds in the presence of copper compounds and (58) Field of Classification Search ..................... 568/2, optionally of salts. 568/9: 556/7, 23,51 See application file for complete search history. 1 Claim, No Drawings US 7,847,126 B2 1. 2 PROCESS FOR PREPARING TERTARY SUMMARY OF THE INVENTION PHOSPHINES A process has now been found for preparing compounds of This application is a divisional of U.S. patent application the formulae (Ia) and (Ib) Ser. No. 10/417,989 filed Apr. 17, 2003 now U.S. Pat. No. PR'Ars. (Ia) 7,230,136, entitled “Process for Preparing Tertiary Phos phines, the contents of which are hereby incorporated by RP B PR, (Ib) reference in their entirety. where 10 BACKGROUND OF THE INVENTION R" is in each case C-C2-alkyl, SiRs, (C-Cs-alkylene)- SiRs, C-C2-fluoroalkyl, Ca-Ca-aryl or Cs-Cls-aryla 1. Field of the Invention lkyl where the radicals The invention relates to a process for synthesizing tertiary Rare in each case independently C-C2-alkyl phosphines by reacting halophosphines with organomagne 15 and where, in formula (Ia). sium compounds in the presence of copper compounds and n is one, two or three and optionally of salts. Ar is a substituted or unsubstituted aryl radical 2. Brief Description of the Prior Art Tertiary phosphines, and methods of using and preparing and where, in formula (Ib), the same are generally known in the art. Many tertiary phos B is an unsubstituted or substituted radical from the group of phines have a high industrial significance, for example as C-C2-alkylene, C-C2-alkenylene, Ca-Co-arylene, ligands for metal atoms for forming metal complexes, as Cs-Cao-bisarylene, Co-Cao-ferrocenylene, reducing agents or, in the form of their oxides, as flame characterized in that halophosphines of the formula (IIa) or retardants or extractants. Metal complexes with tertiary phos 25 (IIb) phines are frequently used as catalysts in chemical reactions. PX, Arg, (IIa) Tertiary phosphines may also be used for absorbing metals, for example from liquid media. XP-B-PX (IIb) Tertiary phosphines may typically be synthesized by react ing organometallic compounds with halophosphines. The 30 where organometallic compounds used are predominantly organo n is one, two or three magnesium and organolithium compounds. However, with X is in each case independently chlorine, bromine or iodine increasing steric demands of the organic radicals to be intro and duced or already present in the molecule, it becomes very 35 Ar informula (IIa) has the same definition as specified under difficult to obtain tertiary phosphines. the formula (Ia) and B in formula (IIb) has the same defi For example, phosphorus trichloride reacts with an excess nition as specified under the formula (Ib) of tert-butylmagnesium chloride to only give di(tert-butyl) are reacted with organomagnesium compounds of the formu chlorophosphine (see Hoffmann, Schellenbeck, Chemische Berichte, 1967, 100 (2), 692-693), or dichlorophenylphos 40 lae (IIIa) phine reacts with an excess of tert-butylmagnesium chloride (R'),Mg(Y)(2) (IIIa) to only give tert-butylchlorophenylphosphine (see Hoff mann, Schellenbeck, Chemische Berichte, 1966, 99, 1134 where 1142). R" have the definitions specified under the formula (Ia) and In the synthesis of tricyclohexylphosphine from phospho 45 m is one or two and rus trichloride and cyclo-hexylmagnesium compounds, the Y is chlorine, bromine or iodine desired product is obtained only at high temperature and in low yields (see Issleib, Brack; Zeitschr, allg. anorg. Chem. or halophosphines of the formula (Ic) 1954, 277,258-270). 50 RPX (IIc) Stambuliet al. were able to demonstrate that when copper (I) iodide is added in the presence of lithium bromide, it is also where possible to use organomagnesium compounds to obtain Sub R" has the definition given under the formulae (Ia) and (Ib) stitutions on bulky arylalkylchlorophosphines and tert-butyl chlorophosphine (J. Am. Chem. Soc., 2001, 123 (11), 2677 55 are reacted with organomagnesium compounds of the for 2678). The high copper and salt requirements, and likewise mula (IIIb) the required reaction temperatures of -78°C., make the pro B—(MgY) (IIIb) cess industrially impracticable. where Kaye et al. (Adv. Synth. Catal., 2001, 343 (8), 789-794) 60 describes the reaction of bis(aryl Grignard) compounds with Y is chlorine, bromine or iodine chlorophosphines in the presence of copper(I) chloride, requiring large amounts of copper compounds, which com and plicates the industrial realization. where the reaction is in each case carried out There was therefore the need to provide a process which 65 in the presence of one or more copper compounds and makes it possible to synthesize tertiary phosphines in an optionally in the presence of Salt and efficient and industrially acceptable manner. optionally in the presence of Solvent. US 7,847,126 B2 3 4 It is pointed out at this juncture that the scope of the inven C-C2-alkenylene is, for example, 1.2-ethenylene, 1,4- tion also encompasses any desired combinations of areas of but-2-enylene, 1.2-cyclopentenylene and 1.2-cyclohex preference. enylene. C-C-alkoxy is, for example, methoxy, ethoxy, isopro DETAILED DESCRIPTION OF THE INVENTION 5 poxy, n-propoxy, n-butoxy and tert-butoxy. The general term aryl as a further substituent encompasses In the scope of the invention, Aris, for example and with carbocyclic radicals and heteroaromatic radicals in which no, preference, a carbocyclic aromatic radical having 6 to 24 one, two or three framework atoms per cycle, but at least one framework carbonatoms or a heteroaromatic radical having 4 framework atom in the entire radical, are heteroatoms to 24 framework atoms where no, one, two or three frame 10 selected from the group of nitrogen, Sulphur or oxygen. work atoms per cycle, but at least one framework atom in the Ca-Ca-Aryl is, for example and with preference, phenyl, entire molecule, are heteroatoms which are selected from the pyridyl, o-, m-, or p-tolyl, naphthyl or anthracenyl. group of nitrogen, Sulphur or oxygen. The carbocyclic aro The same applies to the aryl moiety of an arylalkyl radical. matic radical or heteroaromatic radical may also be substi Cs-Cs-Arylalkyl is, for example and with preference, ben tuted by up to five identical or different substituents per cycle 15 Zyl. which are selected from the group of fluorine, chlorine, bro For the purposes of the invention, fluoroalkyl is in each mine, nitro, cyano, protected formyl, C-C2-alkyl, C-C2 case independently a straight-chain, cyclic, branched or fluoroalkyl, Ca-Ca-aryl, Cs-C-arylalkyl, -PO—(C- unbranched alkyl radical which may be singly, multiply or Cs)-alkyl, —PO (C-C)-aryl —PO—(C-Cs)- fully substituted by fluorine atoms. alkyl)(C-C)-aryl), tri(C-C-alkyl)siloxyl or radicals of For example and with preference, C-C-fluoroalkyl is tri the general formula (IV) fluoromethyl, 2.2.2-trifluoroethyl, pentafluoroethyl and non A-D-R (IV) afluorobutyl, C-C-fluoroalkyl is additionally perfluorocy clohexyl, perfluorohexyl and perfluorooctyl, and C-C2 where, independently, fluoroalkyl is further additionally perfluorodecyl and A is absent or is a C-Cs-alkylene radical and 25 perfluorododecyl.