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2007 VOLUME 7 NUMBER 4 Product Directory Grignard and Organozinc Reagents RIEKE® HIGHLY REACTIVE METALS GRIGNARD REAGENTS ORGANOZINC HALIDES DIALKYLMAGNESIUM AND DIALKYZINC REAGENTS 2-Pyridylzinc bromide: a shelf-stable 2-pyridyl anion equivalent; an important motif in many pharmacologically active molecules. sigma-aldrich.com 2 Table of Contents Sigma-Aldrich is committed to providing the most extensive portfolio of high-quality Grignard, organozinc, and other organometallic reagents, and we continually expand our product listing. Within each section of this directory, products are listed by increasing carbon content. Rieke® Highly Reactive Metals If viewing the electronic version simply select Grignard Reagents a category to jump to that section or activate Alkyl Alkenyl Alkynyl Aryl Heteroaryl your Adobe Bookmarks. You may also search by name, product number, molecular formula, Organozinc Halides or CAS registry number simply by using the “find” feature in Adobe (Ctrl+F in Windows or Alkyl Alkenyl Aryl Heteroaryl Introduction Command+F in a Mac environment). Dialkylmagnesium and Dialkylzinc Reagents If you are unable to find a reagent for your research “Please Bother Us” at [email protected], or contact your local Sigma-Aldrich office (see back cover). Foreword Reuben D. Rieke President and CEO, Rieke Metals, Inc. Professor Emeritus, University of Nebraska Lincoln, NE In the last 35 years, considerable research has been done in the area of generating reactive metals that can be used to synthesize novel organometallic reagents. In 1972, we reported a general approach for preparing highly reactive metal powders, relying on the reduction of metal salts with alkali metals in ethereal or hydrocarbon solvents. These useful metal powders were eventually named “Rieke metals” and they have greatly expanded the number of organometallic reagents that can be made. Grignard reagents are some of the most widely employed organometallic reagents and a wealth of information is known about their reactivity. Although the formation of these reagents is commonly thought to be completely general, there are many organic halides that do not react with ordinary magnesium turnings. The use of Rieke® Magnesium dramatically increases the range of Grignard reagents that are possible by allowing reactions at lower temperatures and thus avoiding decomposition and side reactions. Rieke® Magnesium, as well as an abundant portfolio of pre-formed Grignard reagents, are conveniently available through Sigma-Aldrich. Prior to the discovery of Rieke® Zinc, it was not possible to react alkyl, aryl, and vinyl bromides or chlorides directly with zinc metal. The preparation of these reagents was only possible by a metathesis reaction of a zinc halide with an organolithium or Grignard reagent. Unfortunately, this approach was of limited utility since the process was not compatible with many types of functional groups. Rieke® Zinc, on the other hand, will react directly with the bromides or chlorides and will tolerate a variety of sensitive groups such as nitriles, esters, amides, ethers, sulfides, and ketones to give functionalized organozinc reagents. Organozinc reagents are powerful C–C bond-forming tools, participating in Cu(I)-promoted reactions (developed at Rieke Metals, Inc.) or in Pd-catalyzed cross-coupling reactions, i.e. the Negishi coupling. Sigma-Aldrich offers Rieke® Zinc, as well as numerous pre-formed Rieke® organozinc reagents for use in these and other important reactions. R R O OH ROH R Ar R X O O R O O2 O RCO H 2 CuX CuX Ar Cl CuX X CO2 Br O O Br X O R'CN R' R' RMgX R' MgX R RZnX R R' R' R O CuX CuX R' SnCl R' Y 3 O X Ar X O R' Sn R R' R R'X 3 [Pd] or R' R" CuX OH R' R R R Ar R OH RR' R' R" R sigma-aldrich.com 3 Rieke® Highly Reactive Metals Reactive Rieke® Mg metal R Reactive Rieke® Zn metal R Mg Zn MW: 24.31 Mg* MW: 65.39 Zn* [7439-95-4] [7440-66-6] 2.5 g/dL suspension in tetrahydrofuran: 499579 5 g/dL suspension in tetrahydrofuran: 499552 Rieke Grignard Reagents Reactive Metals Alkyl ® Methylmagnesium chloride solution Isopropylmagnesium chloride 8 tert-Butylmagnesium chloride solution Highly CH ClMg C H ClMg 3 lithium chloride complex solution 4 9 H3C MW: 74.79 H3C MgCl C3H7Cl2LiMg MW: 116.87 H3C MgCl CH3 [676-58-4] MW: 145.24 ·LiCl [677-22-5] H3C H3C MgCl 3.0 M in tetrahydrofuran: 189901, 257095 [807329-97-1] 2.0 M in diethyl ether: 224499 1.0 M in tetrahydrofuran: 656984 1.0 M in tetrahydrofuran: 364649, 364657 Methylmagnesium bromide solution CH3BrMg Cyclopropylmagnesium 1-Methyl-2-propenylmagnesium MW: 119.24 H3C MgBr bromide solution chloride solution [75-16-1] C3H5BrMg C H ClMg 4 7 MgCl 1.0 M in butyl ether: 302430 MW: 145.28 MgBr MW: 114.86 [23719-80-4] [21969-32-4] CH3 3.0 M in diethyl ether: 189898, 257087 1.4 M in toluene/tetrahydrofuran 0.5 M in tetrahydrofuran: 526797 0.5 M in tetrahydrofuran: 420042 (75:25): 282235 Allylmagnesium chloride solution 2-Methylallylmagnesium Methylmagnesium iodide solution C3H5ClMg chloride solution MW: 100.83 CH3IMg MgCl C4H7ClMg [2622-05-1] MgCl MW: 166.24 H3C MgI MW: 114.86 CH3 [917-64-6] 2.0 M in tetrahydrofuran: 225908, 256617 [5674-01-1] 3.0 M in diethyl ether: 254363, 257109 0.5 M in tetrahydrofuran: 419532 Allylmagnesium bromide solution C H BrMg Methyl-d3-magnesium iodide solution 3 5 2-Butenylmagnesium chloride solution MW: 145.28 CD3IMg MgBr C4H7ClMg D C MgI [1730-25-2] MW: 114.86 MW: 169.26 3 H3C MgCl [41251-37-0] 1.0 M in diethyl ether: 225754, 256609 [22649-70-3] 1.0 M in diethyl ether: 293091 0.5 M in tetrahydrofuran: 419583 Butylmagnesium chloride solution Ethylmagnesium chloride solution C4H9ClMg 3-Butenylmagnesium bromide solution MW: 116.87 CH3 MgCl C2H5ClMg C4H7BrMg [693-04-9] MW: 159.31 MW: 88.82 H3C MgCl MgBr [2386-64-3] 1.45 M in butyl diglyme: 529923 [7103-09-5] 2.0 M in diethyl ether: 300330 2.0 M in diethyl ether: 224375 0.5 M in tetrahydrofuran: 419591 2.0 M in tetrahydrofuran: 303828 2.0 M in tetrahydrofuran: 291005 (Trimethylsilyl)methylmagnesium Ethylmagnesium bromide solution Isobutylmagnesium chloride solution chloride solution C H ClMg C4H11ClMgSi C2H5BrMg 4 9 CH H C 3 MW: 146.97 3 Si MgCl MW: 133.27 H C MgBr MW: 116.87 MgCl H3C 3 H C CH [925-90-6] [5674-02-2] 3 [13170-43-9] 3 3.0 M in diethyl ether: 189871, 256978 2.0 M in diethyl ether: 225746 1.0 M in diethyl ether: 256021 1.0 M in tert-butyl methyl ether: 345105 2.0 M in tetrahydrofuran: 479683 1.0 M in tetrahydrofuran: 364665, 364673 (1,3-Dioxolan-2-ylmethyl)magnesium Isobutylmagnesium bromide solution bromide solution C H BrMg C4H7BrMgO2 Propylmagnesium chloride solution 4 9 CH O MW: 161.32 3 MW: 191.31 C3H7ClMg MgBr H3C O MgBr H C [926-62-5] [180675-22-3] MW: 102.85 3 MgCl [2234-82-4] 2.0 M in diethyl ether: 338257 0.5 M in tetrahydrofuran: 472611 2.0 M in diethyl ether: 224391 sec-Butylmagnesium chloride solution Pentylmagnesium chloride solution C H ClMg Isopropylmagnesium chloride solution C4H9ClMg 5 11 CH3 MW: 116.87 MW: 130.90 MgCl C3H7ClMg H3C CH3 H3C MgCl [6393-56-2] MW: 102.85 MgCl [15366-08-2] [1068-55-9] H3C 2.0 M in diethyl ether: 224421 2.0 M in tetrahydrofuran: 469033 2.0 M in diethyl ether: 224383, 257028 2.0 M in tetrahydrofuran: 230111, 257036 R: Product of Rieke® Metals, Inc. ®Registered trademark of Rieke Metals, Inc. To discuss how our expertise can benefit your next scale-up project or to obtain a quote, contact your local Sigma-Aldrich office or visit www.safcglobal.com 4 Pentylmagnesium bromide solution Heptylmagnesium bromide solution 3-Methylbenzylmagnesium C5H11BrMg C7H15BrMg chloride solution R MW: 175.35 MgBr MW: 203.40 MgBr C8H9ClMg MgCl H C H3C [693-25-4] 3 [13125-66-1] MW: 164.92 [29875-06-7] 2.0 M in diethyl ether: 290998 1.0 M in diethyl ether: 550655 CH3 0.5 M in tetrahydrofuran: 562157 Pentamethylenebis- Benzylmagnesium chloride solution (magnesium bromide) solution C7H7ClMg 4-Methylbenzylmagnesium MgCl C5H10Br2Mg2 MW: 150.89 chloride solution R MW: 278.55 BrMg MgBr [6921-34-2] C8H9ClMg MgCl [23708-48-7] 1.0 M in diethyl ether: 302759 MW: 164.92 H3C 0.5 M in tetrahydrofuran: 310018 2.0 M in tetrahydrofuran: 225916 [29875-07-8] 0.5 M in tetrahydrofuran: 563773 1,1-Dimethylpropylmagnesium 2-Bromobenzylmagnesium chloride solution bromide solution R 2-Methoxybenzylmagnesium C5H11ClMg C7H6Br2Mg chloride solution R MgCl H C MgBr MW: 130.90 3 MW: 274.24 C8H9ClMgO H C CH MgCl [28276-08-6] 3 3 [56812-60-3] Br MW: 180.91 OCH3 1.0 M in diethyl ether: 277282 0.25 M in diethyl ether: 562149 [480438-46-8] 0.25 M in tetrahydrofuran: 562092 2,2-Dimethylpropylmagnesium 3-Bromobenzylmagnesium chloride solution R bromide solution R 3-Methoxybenzylmagnesium C5H11ClMg C7H6Br2Mg MgBr chloride solution R H3C Grignard Reagents Grignard MgCl MW: 130.90 MW: 274.24 C8H9ClMgO H3C CH3 MgCl [13132-23-5] [107549-22-4] Br MW: 180.91 [26905-40-8] 1.0 M in diethyl ether: 550213 0.25 M in diethyl ether: 562130 OCH3 0.25 M in tetrahydrofuran: 562084 Cyclopentylmagnesium 4-Fluorobenzylmagnesium chloride solution chloride solution R 4-Methoxybenzylmagnesium C5H9ClMg C7H6ClFMg MgCl chloride solution R MW: 128.88 MgCl MW: 168.88 [32916-51-1] [1643-73-8] F C8H9ClMgO MW: 180.91 MgCl 2.0 M in diethyl ether: 224405 0.25 M in tetrahydrofuran: 563927 [38769-92-5] H3CO 0.25 M in tetrahydrofuran: 562033 Cyclopentylmagnesium Octylmagnesium chloride solution bromide solution C8H17ClMg 4-(Trifluoromethoxy)benzyl- 8 C5H9BrMg MW: 172.98 H3C MgCl MW: 173.33 MgBr [38841-98-4] magnesium bromide solution [33240-34-5] C8H6BrF3MgO 2.0 M in tetrahydrofuran: 324566 MW: 279.34 MgBr 2.0 M in diethyl ether: 428337 F3CO Octylmagnesium
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  • Schlenk Equilibrium in Toluene Solutions of Grignard Reagents

    Schlenk Equilibrium in Toluene Solutions of Grignard Reagents

    SCHLENK EQUILIBRIUM IN TOLUENE SOLUTIONS OF GRIGNARD REAGENTS Ants Tuulmets*, Marvi Mikk and Dmitri Panov Institute of Organic Chemistry, University of Tartu, Tartu, EE2400 Estonia Abstract Grignard reagents were prepared from η-butyl chloride, η-butyl bromide and bromobenzene in toluene in the presence of small amounts of diethyl ether. The reagents disproportionate according to the Schlenk equilibrium with the formation of a precipitate rich in magnesium halide. The supernatant solution comprises higly soluble complexes of the stoichiometry xR2Mg.yMgX2.zEt20 (x>y). The extent of side-reactions during the formation of these Grignard reagents increases in the order nBuCI<nBuBr<PhBr. Introduction Organomagnesium compounds can be prepared not only in conventional ethers but also in hydrocarbon media or without any solvent at all [1-5]. For many purposes the replacement of ethers by hydrocarbons of higher boiling point is expedient. The process in hydrocarbons is preferable, since the reaction medium is cheap, nonhygroscopic, and fire hazards are low. The use of unsolvated organomagnesium halides is limited to primary alkyl and aryl compounds. Branched chain primary, secondary, and tertiary alkyl halides, vinyl, allyl, and benzyl halides do not react under these conditions or produce Wurtz-type coupling products [2,6]. In the presence of one molar equivalent of complexing agents, e.g. ethers and tertiary amines, several organomagnesium compounds have been obtained in hydrocarbon media [5,7,8], Furthermore, alkylmagnesium bromide and chloride reagents in toluene containing less than one equivalent of diethyl ether have also been prepared [9-12]. Because the Grignard reagents in donor solvents are complexed at least with two solvent molecules per atom of magnesium, the reagents obtained in the presence of smaller amounts of donors should be considered as partially solvated.
  • UNITED STATES PATENT OFFICE 2,677,686 PYRAZINEDERVATIVES and METHO) of PREPARING the SAME Victor K

    UNITED STATES PATENT OFFICE 2,677,686 PYRAZINEDERVATIVES and METHO) of PREPARING the SAME Victor K

    Patented May 4, 1954 2,677,686 UNITED STATES PATENT OFFICE 2,677,686 PYRAZINEDERVATIVES AND METHO) OF PREPARING THE SAME Victor K. Smith, Jr., Feari River, and Samuel Kushner, Nanuet, N. Y., assignors to American Cyanamid Company, New York, N. Y., a corpo ration of Maine No Drawing. Application 5uly 22, 1952, Serial No. 300,336 8 Claims. (C. 260-250) 2 This invention relates to mono-substituted ous layer is extracted with a solvent, such as di pyrazine. More particularly, it relates to substi ethyl ether. The ether can be concentrated and tuted-2-carbonyl pyrazine. the desired compound crystallized out Or the The role of vitamins in nutrition is well known ether can be removed and the product distilled. i and assumes greater importance as new informa 5, The reaction of the present invention may be tion is made available concerning the particular carried out at a temperature of -10° to 15° C. function of each. Recently it has been found The reaction is complete in from about a few that folic acid was effective in curing macrocytic ininutes up to about tWO hours. anemias and other blood conditions. Also, Com The process of the present invention is de pounds which are folic acid antagonistS, Such as scribed in greater particularity by the following aninopterin, have been found useful in treating specific examples which are given by way of ill abnormal blood conditions such as leukemia. lustration and not limitation. it is well established that nicotinamide is an im Eacample 1 portant, vitamin of the B complex group and its deficiency is the specific cause of pelagira.
  • Acutely / Extremely Hazardous Waste List

    Acutely / Extremely Hazardous Waste List

    Acutely / Extremely Hazardous Waste List Federal P CAS Registry Acutely / Extremely Chemical Name Code Number Hazardous 4,7-Methano-1H-indene, 1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro- P059 76-44-8 Acutely Hazardous 6,9-Methano-2,4,3-benzodioxathiepin, 6,7,8,9,10,10- hexachloro-1,5,5a,6,9,9a-hexahydro-, 3-oxide P050 115-29-7 Acutely Hazardous Methanimidamide, N,N-dimethyl-N'-[2-methyl-4-[[(methylamino)carbonyl]oxy]phenyl]- P197 17702-57-7 Acutely Hazardous 1-(o-Chlorophenyl)thiourea P026 5344-82-1 Acutely Hazardous 1-(o-Chlorophenyl)thiourea 5344-82-1 Extemely Hazardous 1,1,1-Trichloro-2, -bis(p-methoxyphenyl)ethane Extemely Hazardous 1,1a,2,2,3,3a,4,5,5,5a,5b,6-Dodecachlorooctahydro-1,3,4-metheno-1H-cyclobuta (cd) pentalene, Dechlorane Extemely Hazardous 1,1a,3,3a,4,5,5,5a,5b,6-Decachloro--octahydro-1,2,4-metheno-2H-cyclobuta (cd) pentalen-2- one, chlorecone Extemely Hazardous 1,1-Dimethylhydrazine 57-14-7 Extemely Hazardous 1,2,3,4,10,10-Hexachloro-6,7-epoxy-1,4,4,4a,5,6,7,8,8a-octahydro-1,4-endo-endo-5,8- dimethanonaph-thalene Extemely Hazardous 1,2,3-Propanetriol, trinitrate P081 55-63-0 Acutely Hazardous 1,2,3-Propanetriol, trinitrate 55-63-0 Extemely Hazardous 1,2,4,5,6,7,8,8-Octachloro-4,7-methano-3a,4,7,7a-tetra- hydro- indane Extemely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]- 51-43-4 Extemely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]-, P042 51-43-4 Acutely Hazardous 1,2-Dibromo-3-chloropropane 96-12-8 Extemely Hazardous 1,2-Propylenimine P067 75-55-8 Acutely Hazardous 1,2-Propylenimine 75-55-8 Extemely Hazardous 1,3,4,5,6,7,8,8-Octachloro-1,3,3a,4,7,7a-hexahydro-4,7-methanoisobenzofuran Extemely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime 26419-73-8 Extemely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime.