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(12) United States Patent (10) Patent No.: US 6,251,057 B1 Jung Et Al

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(12) United States Patent (10) Patent No.: US 6,251,057 B1 Jung Et Al USOO6251.057B1 (12) United States Patent (10) Patent No.: US 6,251,057 B1 Jung et al. (45) Date of Patent: Jun. 26, 2001 (54) DEHYDROHALOGENATIVE COUPLING R.A. Benkeser, et al, Sillylation of Organic Halides. A New REACTION OF ORGANIC HALIDES WITH Method of Forming the Carbon-SiliconBond; Journal of the SILANES American Chemical Society, 91:13, pp. 3666-3667, Jun. 18, 1969. (75) Inventors: Il Nam Jung, Seoul; Bok Ryul Yoo, R.A. Benkeser, et al, Trichlorosilane-Tertiary Amine Com Koyang; Joon Soo Han, Seoul, binations as Reducing agents for Polyhalo Compounds. Seung-Hyun Kang, Seoul, Yeon Seok Potential Analogies with Phosphorus Chemistry; Journal of Cho, Seoul, all of (KR) the American Chemical Society, 90:10, Sep. 11, 1968. (73) Assignee: Korea Institute of Science and * cited by examiner Technology, Seoul (KR) Primary Examiner Paul F. Shaver (*) Notice: Subject to any disclaimer, the term of this (74) Attorney, Agent, or Firm-Oblon, Spivak, McClelland, patent is extended or adjusted under 35 Maier & Neustadt, P.C. U.S.C. 154(b) by 0 days. (57) ABSTRACT The present invention relates to methods for making the (21) Appl. No.: 09/543,546 compounds of formula I which is a dehydrohalogenative (22) Filed: Apr. 5, 2000 coupling of hydrochlorosilanes of formula II with organic halides of formula III in the presence of a Lewis base (30) Foreign Application Priority Data catalyst. Apr. 13, 1999 (KR) ................................................. 99-13006 Mar. 15, 2000 (KR) ................................................. 00-13090 R°CHSR'Cl, (I) (51) Int. Cl." .................................................... C07F 7/08 HSR'Cl, (II) (52) U.S. Cl. .............................................................. 572/481 R°CHX (III) (58) Field of Search ............................................... 556/481 In formulas I and II, R' represents a hydrogen, chloro, or (56) References Cited methyl; in formula III, X represents a chloro or bromo; in formula III, R can be selected from the group consisting of U.S. PATENT DOCUMENTS a C-, alkyl, a Co fluorinated alkyl with partial or full 3,699,143 * 10/1972 Benkeser et al. .................... 556/481 fluorination, a Cls alkenyl groups, a silyl group containing 4,985,580 * 1/1991 Chadwicket al..... ... 556/481 alkyls, (CH), SiMe-Cl wherein n is 0 to 2 and m is 0 to 5,118.829 * 6/1992 Gohndrone ........ ... 556/481 3, aromatic groups, Ar(R) wherein Ar is C aromatic 5,508.460 * 4/1996 Berry et al........................... 556/481 hydrocarbon, R is a C- alkyl, halogen, alkoxy, or vinyl, and q is 0 to 5, a haloalkyl group, (CH),X wherein p is 1 OTHER PUBLICATIONS to 9 and X is a chloro or bromo; or an aromatic hydrocarbon, N. Furuya, et al. The Condensation Reaction of Trichlorosi Ar CHX wherein Aris Caromatic hydrocarbon and X lane with Allylic Chlorides Catalyzed by Copper Salts in the is a chloro or bromo. in formula I, R is the same as R in Presence of a Tertiary Amine; Journal of Organometallic formula III and further, R can also be (CH2)SiRC1 or Chemistry, 96 (1975) C1-C3. ArCH-SiRC1, when R in formula III is (CH),X or Robert J.P. Corriu, et al., Synthesis and reactivity of bis(tri ArCHX, because of the coupling reaction of X with the ethoxysilyl)methane, tris(triethoxysilyl)methane and Some compound of formula II. derivatives'; Journal of Organometallic Chemistry 562 (1988) 79–88. 17 Claims, No Drawings US 6,251,057 B1 1 2 DEHYDROHALOGENATIVE COUPLNG Synthesis of organosilicon compounds. Although the dehy REACTION OF ORGANIC HALIDES WITH drochlorinative coupling reaction of activated alkyl chlo SILANES rides such as benzyl chloride or allyl chloride have been reported, the coupling reaction of unactivated alkyl chlo BACKGROUND OF THE INVENTION rides with trichlorosilane has never been reported. In the 1. Field of the Invention previously reports, tertiary amine was used in excess, more than the Stoichiometric amount respect to alkyl chloride. The The present invention relates to processes for making the tertiary amine used is a hydrogen chloride Scavenger rather compounds of formula I which comprise a dehydrohaloge than a catalyst. Since the ammonium Salt obtained from the native coupling of hydrochlorosilanes of formula II with tertiary amine and hydrogen chloride have to be neutralized organic halides of formula III in the presence of Lewis base to recycle the amine, it would be too costly to be utilized on catalyst. an industry Scale. It is necessary to find a way to reduce the usage of the amine or find another effective catalyst to apply the coupling reaction for industrial purposes. (II) The present inventors have discovered that a coupling 15 reaction of alkyl halides and hydrochlorosilanes in the (III) presence of various tertiary amines or tertiary phosphines as In formulas I and II, R' represents a hydrogen, chloro, or a catalyst proceeded to give the corresponding coupled methyl; in formula III, X represents a chloro or bromo; in products by liberating hydrogen halide as a gas. The dehy formula III, R can be selected from the group consisting of drohalogenative coupling reaction can be applied to not only a C-7alkyl, a Co fluorinated alkyl with partial or full the activated alkyl halides such as benzyl chloride or allyl fluorination, a Cls alkenyl groups, a silyl group containing chloride, but also to the unactivated alkyl halides Such as alkyls, (CH),SiMes, Cl, wherein n is 0 to 2 and m is 0 to n-alkylhexyl chloride or haloalkyl Substituted organosilicon 3, aromatic groups, Ar(R), wherein Ar is C. aromatic compound. Suitable amine catalysts include, but are not hydrocarbon, R is a C alkyl, halogen, alkoxy, or Vinyl, limited to triethylamine, tri-n-propylamine, tri-n- and q is 0 to 5, a haloalkyl group, (CH2).X wherein p is 1 25 butylamine, N,N,N',N'-tetramethylethylene diamine, to 9 and X is a chloro or bromo; or an aromatic hydrocarbon pyridine, N,N-dimethyltoluidine, N-alkylpyrrolidine. Suit able phosphine catalysts include, but are not limited to ArCH2X wherein Aris Caromatic hydrocarbon and X is tributyl phosphine, trie thyl phosphine, a chloro or bromo. in formula I, R is the same as R in tricyclohexylphosphine, triphenylphosphine, bis formula III and further, R can also be (CH2)SiRC1 or (diphenylphosphine)methane, 1,2-bis(diphenylphosphine) ArCH-SiRC1, when R in formula III is (CH),X or ethane, and phosphine coordinated transition metallic com ArCHX, because of the coupling reaction of X with the pounds Such as tetrakis(triphenylphosphine)palladium, tris compound of formula II. (triphenylphosphine)rhodium chloride, or tetrakis 2. Description of the Prior Art (triphenylphosphine)platinum. In 1968, Benkeser and Smith reported the reduction of carbon tetrachloride to chloroform by using a 1:1 mixture of 35 SUMMARY OF THE INVENTION trichlorosilane and tertiary amine as reducing agents The present invention relates to processes for making (Benkeser, R. A.; Smith, W. E. J. Am. Chem. Soc. 1968,90, compounds of formula I which comprises a dehydrohalo 5307). They proposed that the amine-catalyzed reduction of genative coupling between hydrochlorosilanes of formula II carbon tetrachloride to chloroform proceeded via the for and organic halides of formula III in the presence of a Lewis mation of (trichloromethyl)trichlorosilane by the dehydro 40 base catalyst. chlorinative coupling reaction between the carbon tetrachlo The reaction can be illustrated as follows: ride and trichlorosilane, and Subsequent cleavage of the carbon-Silicon bonded Species by ammonium chloride to HSiRCl2 + ROH2X -- RCHSIRC1 + HX give chloroform and tetrachlorosilane. In 1969, Benkeser and co-workers also reported that benzyl chloride and ben 45 (II) (III) (I) Zyl chlorides could be silylated with trichlorosilane-tertiary amine 1:1 mixture to give the corresponding trichlorosilyl In formulas I and II, R' represents a hydrogen, chloro, or Substituted products by the dehydrochlorinative coupling methyl; in formula III, X represents a chloro or bromo; in reaction (Benkeser, R. A., Gaul, J. M.; Smith, W. E. J. Am. formula III, R can be selected from the group consisting of Chem. Soc. 1969, 91, 3666). 50 a C-17 alkyl, a Co fluorinated alkyl with partial or full In 1975, Furuya and Sukawa reported allytrichlorosilane fluorination, a Cls alkenyl groups, a silyl group containing could be prepared in high yield by a coupling reaction of alkyls, (CH), SiMe-Cl wherein n is 0 to 2 and m is 0 to allyl chloride with a 1:1 mixture of trichlorosilane and 3, aromatic groups, Ar(R), wherein Ar is C. aromatic tertiary amine in the presence of copper chloride as a catalyst hydrocarbon, R is a C- alkyl, halogen, alkoxy, or vinyl, (Furuya, N.; Sukawa, T. J. Organometal. Chem. 1975, 96, 55 and q is 0 to 5, a haloalkyl group, (CH),X wherein p is 1 C1). to 9 and X is a chloro or bromo; or an aromatic hydrocarbon, Recently, Corriu and co-workers reported that the reaction Ar CH2X wherein Ar is C. aromatic hydrocarbon and X of chloroform with trichlorosilane in the presence of exceSS is a chloro or bromo. in formula I, R is the same as R in tributylamine gave bis(trichlorosily)methane and tris formula III and further, R can also be (CH2)SiRC1 or (trichlorosilyl)methane (Corriu, R. J. P.; Granier, M.: 60 ArCHSiRC1, when R in formula III is (CH),X or Lanneau, G. F.J. Organometal. Chem. 1998,562, 79). These ArCHX, because of the coupling reaction of X with the reports Suggest that a chloroalkyl group containing organic compound of formula II. compounds and organosilanes having Si-H bonds could undergo the dehydrochlorinative coupling reaction with DETAILED DESCRIPTION OF THE trichlorosilane in the presence of an organic base. 65 INVENTION The dehydrochlorinative coupling reaction is a novel In a Sealed StainleSS Steel tube, hydrochlorosilane repre method of forming silicon-carbon bonds useful for the sented by formula II, organic halide of formula III, solvent, US 6,251,057 B1 3 4 and catalyst are placed all together under inert atmosphere.
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