DOCSLIB.ORG

Highly Asymmetric-Selective and Stereoselective Polymerization Of

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Highly Asymmetric-Selective and Stereoselective Polymerization Of Polymer Journal, Vol. 19, No.9, pp 1047-1065 (1987) Highly Asymmetric-selective and Stereoselective Polymerization of (RS)-rx-Methylbenzyl Methacrylate with Cyclohexyl­ magnesium Bromide-Axially Dissymmetric 2,2'­ Diamino-6,6' -dimethylbiphenyl System Shigeyoshi KANOH, Sakae GOKA, Nobutsugu MUROSE, Hideo KUBO, Masao KONDO, Tomoaki SUGINO, Masatoshi MOTOI, and Hiroshi SUDA Department of Chemistry and Chemical Engineering, Faculty of Engineering, Kanazawa University, 2-40-20 Kodatsuno, Kanazawa 920, Japan (Received February 13, 1987) ABSTRACT: Enantiomer-selective polymerization of (RS)-IX-methylbenzyl methacrylate [(RS)-MBMA] was investigated in toluene at -30oc. Reaction products between cyclohexylmag­ nesium bromide (cHexMgBr) and axially dissymmetric 2,2 '-diamino-6,6' -dimethylbiphenyl (AMB) in the mole ratio of 1.5: I were used as a chiral initiating system. The polymer produced a biphenyl group from the catalyst fragment. The polymerization proceeded in an anionic coordi­ nation mechanism and the racemic monomer was kinetically resolved during the course of the reaction. The enantiomer selectivity ratio when using (R)-AMB was estimated to be r<sl= 18.0 according to the integrated composition equation for an "ideal" copolymerization of the enantiomeric monomers. Most parts of the polymer were found to be of full isotacticity from inspection of the 13C NMR spectrum. Some physical properties of the polymer strongly suggested that it is a mixture of (R)- and (S)-homopolymers. This may be an example of an asymmetric­ selective (stereoelective) and stereoselective polymerization of vinyl monomer. In the copolymer­ izations between (RS)-MBMA and achiral methacrylates, the catalyst also showed high selectivity toward (RS)-MBMA. Each of the copolymers from methacrylates of methyl, benzyl, and diphenylmethyl alcohols was coisotactic, and the enantiomer selections were consistent with that observed for the homopolymerization. On the other hand, both the isotacticity of copolymer and the selection greatly decreased in the copolymerization with IX,IX-dimethylbenzyl methacrylate which has no hydrogen at the IX-carbon of the ester group. KEY WORDS Asymmetric-selective and Stereoselective Polymerization I (RS)-IX-Methylbenzyl Methacrylate I Axially Dissymmetric I 2,2'-Diamino- 6,6'-dimethylbiphenyl I Cyclohexylmagnesium Bromide I Anionic Coordination I Isotactic I Polymer Racemate I Ideal Copolymerization Equation I Enantiomer Selectivity Ratio I Since binaphthyl-substituted crowns by recognized as "chiral seeds" possessing the Cram1 and BINAL-H reagents by NoyorF salient chiral discrimination ability for asym­ appeared, axially dissymmetric biaryl units metric polymerization.3 -s have now become very common in the design Optically pure 2,2 '-diamino-6,6 '-dimethyl­ and synthesis of chiral auxiliaries for many biphenyl (AMB) or 2,2'-diamino-1,1'-bi­ asymmetric reactions. 3 Recently special atten­ naphthyl (ABN) has been used for the for­ tion is drawn increasingly to the construction mation of a chiral LiAlH4 complex.9 •10 Each of chiral polymerization initiators by the use of reagent provided moderate or rather low selec­ such compounds. These compounds have been tivity in the enantioface-differentiating reduc- 1047 S. KANOH et a/. tion of phenyl alkyl ketones. We have found showed the highest selectivity. On the other recently that products of reactions between hand, the same polymerization was success­ Grignard reagent and each of the two diamines fully achieved by· Okamoto's catalyst, are excellent catalysts for the enantiomer­ Grignard reagent-(-)-sparteine system. 11 selective polymerization of racemic oc-methyl­ This polymerization system may be regarded benzyl methacrylate [(RS)-(MBMA)]. 3•4 as the so-called asymmetric-selective or Among these catalysts, the cyclohexylmag­ stereoelective polymerization according to the nesium bromide (cHexMgBr)-AMB system classification by Tsuruta.12 CH H C=C I ·J 2 ) C=O 0 "6'"'I* (R)-AMB (R)-ABN (RS)-MBMA In this paper, we wish to describe a detailed [methy/-14C]toluidine hydrochloride were investigation on the enantiomer-selective available from The Radiochemical Center, polymerization of (RS)-MBMA with the Amersham. cHexMgBr-optically pure AMB system in toluene at - 30°C. In addition, the reaction Grignard Reagents between cHexMgBr and AMB is described After the dilution of [1- 14C]ethanol with also. ordinary ethanol, this was converted into the corresponding bromide with PBr3 •14 An EXPERIMENTAL ethereal solution of the ethyl bromide (0.13 J.LCi mmol- 1) was refluxed with mag­ Materiah nesium turnings for 0.5 h to afford [1- 14C]­ Diethyl ether and tetrahydrofuran (THF) as ethylmagnesium bromide ([1- 14C]EtMgBr). polymerization media were distilled over Ethylmagnesium bromide (EtMgBr) and LiAlH4 in vacuo just before use. Toluene was cHexMgBr were prepared according to the refluxed and distilled over CaH2 , and then method described previously.4 All the Grig­ redistilled under vacuum from butyllithium nard reagents were used as ethereal solutions just before use. Methacrylic esters of methyl after determining the concentrations. (MMA) and benzyl alcohol (BzMA) were obtained from commercial sources. (RS)­ Axially Dissymmetric Biphenyl Diamines MBMA and oc,oc-dimethylbenzyl methacrylate AMB was prepared according to Scheme 1, (DMBMA) and diphenylmethyl methacrylate with some modification of the procedures de­ (DPMMA) were prepared from methacryloyl scribed in the literature. 15 - 19 The synthetic chloride and the corresponding alcohols in routes of the brominated derivatives of AMB benzene or diethyl ether in the presence of are also shown in Scheme 1. triethylamineY The monomers were dried 2,2'-Diamino-6,6'-dimethylbiphenyl (AMB) over CaH2 , and distilled repeatedly over 2-Amino-3-nitrotoluene (2). To acetic an­ Cu2Cl2 in vacuo. [1-14C]ehtanol and o- hydride (1.21) was added a-toluidine (214 g, 1048 Polymer J., Vol. 19, No. 9, 1987 Enantiomer-selective Polymerization of (RS)-MBMA 11 Ac 20 21 cHN03 Cu 31 cHCI DMF cV NBS --DM_F_.._ Br 2 NaOAc Scheme 1. Synthetic routes of AMB, AMBBr, and AMB2Br. 2 mol) with stirring at 50°C. After 0.5 h, the amount of Na2 S03 . After the solvent was solution was cooled to 10°C. Concentrated removed, the residue was recrystallized from HN03 (61%, 220ml) was added dropwise ethanol to afford 318 g (91 %) of 3: mp 66- over a period of 2 h with maintaining the tem­ 6rC (lit. 16 67-68°C). perature exactly at 11 ± 1oc, and the reaction 2,2'-Dimethyl-6,6'-dinitrobiphenyl (4). A so­ was continued for an additional 30 min­ lution of 3 (320 g, 1.2 mol) in N,N-di­ utes at this temperature. The reaction mix­ methylformamide (DMF) (200 ml) was warm­ ture was poured onto ice water (3 1). The re­ ed at 140°C. Copper powder (150 g) that was sulting precipitates were separated, added to treated with iodine in acetone17 was added by cHCl (500 ml), and refluxed for 2 h. The hot portions with caution against exothermic re­ solution was poured into water (750 ml). The action. Stirring and gentle reflux were con­ dark red precipitates were separated, and tinued for 1 h. The copper was separated and recrystallized from ethanol (130 ml). The first thoroughly washed with hot benzene. The crop obtained was 84 g (55%) of practically filtrate was washed with water and then with pure 2: mp 94-96°C (lit. 15 95-96°C). dil. HCI. After the removal of the solvent, the 2-Iodo-3-nitrotoluene (3). Powdered 2 (228 g, residue was recrystallized from ethanol to yield 1.5 mol) was added portion by portion to 150g (91%) of 4: mp 109-ll0°C (lit. 18 107- cH2 S04 (500ml) with stirring below 50°C. To 1080C). this were added crushed ice ( 500 g) and then 2,2' -Diamino-6,6'-dimethylbiphenyl (AMB). water (500ml) with cooling. The finely sus­ The reduction of 4 (30 g, 0.11 mol) was carried pended precipitates were diazotized with a out using hydrazine hydrate (50 ml) and a saturated aqueous solution of NaN02 (120 g, catalytic amount of W-2 Raney nickel in 1.9 mol) at 5-10°C. After excess nitrite was ethanol (11). 19 After the color of the inter­ decomposed with urea, a saturated aqueous mediates disappeared, the catalyst was sepa­ solution of KI (257 g, 1.55 mol) was added at rated through celite. The filtrate was con­ 15°C. The mixture was allowed to stand over­ centrated to give quantitatively colorless crys­ night at room temperature. The brownish pre­ tals of AMB (23 g): mp 135-136°C (lit. 20 cipitates were separated, dissolved in benzene, 136°C); IR (KBr) 3440, 3420, 3340, 1620, 1300, 1 1 and washed with water containing a small 790, and 745cm- ; H NMR (CDC13) fJ 1.97 Polymer J., Vol. 19, No. 9, 1987 1049 S. KANOH et a/. (s, 6H, CH3), 3.37 (br s, 4H, NH2), and 6.6- Similarly (S)-AMB was converted to (S)­ 7.3 ppm (m, 6H, ArH); 13C NMR [CDC13- AMB2Br: mp 200-201 oc; [a]55 -54.4° (c, 1.0 dimethylsulfoxide-d6 2: 1 (vjv)] b 19.4 (q), g dl-1, ethanol). 112.4 (d), 119.0 (d), 121.7 (s), 127.9 (d), 137.1 3-Bromo-6 ,2' -Diamino-2 ,6' -Dimethyl­ (s), and 144.7 ppm (s). Found: C, 79.16%; H, biphenyl (AMBEr) 7.63%; N, 13.60%. Calcd for C14H16 N2: C, 2-Nitro-2' -amino-6,6' -dimethylbiphenyl (5). 79.20%; H, 7.60%; N, 13.20%. The partial reduction of 4 was carried out Resolution of (RS)-AMB. The optical re­ using Na2S in ethanol in the presence of ethyl solution of AMB via D 5 -( +)-tartrate was acetate according to the reported method. 23 achieved following the method of Mislow et Dilution of the reaction mixture with water a/. 21 (R)-( + )-AMB: yield, 33%; mp 160- gave yellow crystals of5: yield, 87%; mp 122- 1610C (lit. 21 156-158°C); [a]55 + 50.SO (c, 1.0 1230C (lit.
Load more

Recommended publications
  • Addition of a Grignard Reagent to an Ester: Formation of a Tertiary Alcohol
    Addition of a Grignard Reagent to an Ester: Formation of a Tertiary Alcohol Introduction: Grignard reagents are important and versatile reagents in organic chemistry. In this experiment, you will prepare a Grignard reagent and react it with an ester to prepare a tertiary alcohol. Specifically, in this reaction you will prepare phenyl magnesium bromide from bromobenzene and magnesium metal and then react it with methyl benzoate to prepare triphenylmethanol (Figure 1). In this reaction, two equivalents of phenylmagnesium bromide add to methyl benzoate. Note: Grignard reagents are sensitive to water. ALL glassware must be completely clean and dry. Reagents have been stored over molecular sieves to keep them dry in storage, but you should also keep containers closed as much as possible. Finally, water in the air can also react with the Grignard reagents over time. To successfully prepare triphenylmethanol in this experiment, you will need to be well organized and not take too much time between steps. Figure 1. O 1) Me O OH Br Mg MgBr THF + 2) H3O triphenylmethanol Mechanism: The formation of Grignard reagents from aryl halides is a complex mechanism, which takes place on the surface of the magnesium metal. You do not need to concern yourself with the details of this step of the mechanism. Figure 2. MgBr O Bu MgBr Bu MgBr O + OH O Bu MgBr O H3O Me OEt Bu Me OEt Me Bu Me Bu Me –EtOMgBr Bu Bu The mechanism of the reaction of a Grignard reagent with an ester is shown in Figure 2 (using methyl propionate and butylmagnesium bromide).
    [Show full text]
  • WO 2015/025175 Al 26 February 2015 (26.02.2015) P O P C T
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2015/025175 Al 26 February 2015 (26.02.2015) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C09K 5/06 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/GB2014/052580 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 22 August 2014 (22.08.2014) KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, (25) Filing Language: English OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, (26) Publication Language: English SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, (30) Priority Data: ZW. 13 15098.2 23 August 2013 (23.08.2013) GB (84) Designated States (unless otherwise indicated, for every (71) Applicant: SUNAMP LIMITED [GB/GB]; Unit 1, Satel kind of regional protection available): ARIPO (BW, GH, lite Place, Macmerry, Edinburgh EH33 1RY (GB). GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, (72) Inventors: BISSELL, Andrew John; C/o SunAmp, Unit TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, 1, Satellite Place, Macmerry, Edinburgh EH33 1RY (GB).
    [Show full text]
  • Grignard Reaction: Synthesis of Triphenylmethanol
    *NOTE: Grignard reactions are very moisture sensitive, so all the glassware in the reaction (excluding the work-up) should be dried in an oven with a temperature of > 100oC overnight. The following items require oven drying. They should be placed in a 150mL beaker, all labeled with a permanent marker. 1. 5mL conical vial (AKA: Distillation receiver). 2. Magnetic spin vane. 3. Claisen head. 4. Three Pasteur pipettes. 5. Two 1-dram vials (Caps EXCLUDED). 6. One 2-dram vial (Caps EXCLUDED). 7. Glass stirring rod 8. Adaptor (19/22.14/20) Grignard Reaction: Synthesis of Triphenylmethanol Pre-Lab: In the “equations” section, besides the main equations, also: 1) draw the equation for the production of the byproduct, Biphenyl. 2) what other byproduct might occur in the reaction? Why? In the “observation” section, draw data tables in the corresponding places, each with 2 columns -- one for “prediction” (by answering the following questions) and one for actual drops or observation. 1) How many drops of bromobenzene should you add? 2) How many drops of ether will you add to flask 2? 3) 100 µL is approximately how many drops? 4) What are the four signs of a chemical reaction? (Think back to Chem. 110) 5) How do the signs of a chemical reaction apply to this lab? The Grignard reaction is a useful synthetic procedure for forming new carbon- carbon bonds. This organometallic chemical reaction involves alkyl- or aryl-magnesium halides, known as Grignard 1 reagents. Grignard reagents are formed via the action of an alkyl or aryl halide on magnesium metal.
    [Show full text]
  • Proceedings of the Indiana Academy of Science
    The Solubility of Magnesium Bromide in Di-n-Butyl Ether John A. Ricketts and Paul Brown, DePauw University Rowley (1) has extensively investigated the solubility of magnesium bromide in diethyl ether, Et2 0, and has found that magnesium bromide forms a solid mono-, di-, and tri-etherate with transition temperatures of 12° C. (tri-etherate to di-etherate) and 22.6° C. (di-etherate to mono- etherate). This investigation measures the solubility of magnesium bro- 5° mide in di-n-butyl ether, Bu 2 0, in the temperature range of C. to 56° C. and also determines the chemical nature of the solid phase in equilibrium with the saturated solution of magnesium bromide in Bu 2 0. Experimental Solubility measurements were taken at approximately 5° C. inter- vals. Any of the fixed temperature points that were used were controlled to ± 0.02°C. Excess solid was added to 50 ml. of pure Bu 2 contained in a 100 ml. round-bottomed flask. All Bu 2 used in the experiments was purified by fractional distillation from sodium on to sodium and only the fraction which distilled in the temperature range 141-2° C. was used. The refractive index of the Bu>0 was measured as 1.3990 at 20° C. (lit. 1.3992). The vapor phase chromatogram of the liquid contained only a single peak. The flask was mounted in the constant temperature bath and the closed system stirred mechanically for a period of time ranging from 4 to 12 hours. Samples of the liquid phase were withdrawn, weighed, and analyzed, one sample for magnesium ion using EDTA with Erichrome Black T as indicator and another sample from the same flask for bromide ion by the Vohlhard method.
    [Show full text]
  • The Effects of Stoichiometry and Starting Material on the Product Identity and Yield in Grignard Addition Reactions
    Supplementary information for Comprehensive Organic Chemistry Experiments for the Laboratory Classroom © The Royal Society of Chemistry 2017 The effects of stoichiometry and starting material on the product identity and yield in Grignard addition reactions Supplementary Material This experiment has been performed both in the 150 person standard introductory organic chemistry laboratory (taught primarily by undergraduate teaching assistants in five sections of 30-40 students) and in a special introductory organic chemistry laboratory for freshman, taught to 23 students in sections of 7 and 16. This course is the first organic laboratory for these students but has been taught in the spring semester along with the second semester of organic lecture. The lab periods for this course are five hours long, and this experiment is typically performed in the latter half of the semester. This experiment is used to illustrate to students the importance of planning their time in lab; they must be out of the lab in the 5 hours allotted. While many students finish the experiment in this time, others plan to finish the following week along with a shorter experiment. Those who were running behind were encouraged to finish through the drying of their organic layer with MgSO4 and set up the distillation the following week. When doing this they should make sure that their organic layer is in a closed container to prevent evaporation of their product. Moisture Sensitive Conditions There are many diverse protocols for maintaining the anhydrous conditions required to successfully prepare and utilize Grignard reagents. We typically open a fresh can of anhydrous ether and dispense it directly, without additional drying in a still or air sensitive techniques for solvent transfers.
    [Show full text]
  • The Reaction of Ethylene Oxide with Various Grignard
    THE REACTION OF ETHYLENE OXIDE WITH VARIOUS GRIGNARD REAGENTS by Albert Henry Agett A THESIS Submitted to the Graduate School of Michigan State College of Agriculture and Applied Science in partial fulfilment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry. 1940 ProQuest Number: 10008482 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10008482 Published by ProQuest LLC (2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 ACKNOVfLEDGEMEM? To Dr. S. C. Huston I wish to express my gratitude for the many suggestions and the helpful understanding that have made possible this work. A. H. Agett c o m a s Introduction Historical Experimental I. Preparation of "bromides and materials used. IX. Preparation of Grignard reagents. III.Beactions of Grignard reagents with ethylene oxide. A. One mole ethylene oxide. B. !Two moles ethylene oxide. C. Dialkyl magnesium compounds. 17. Preparation, analysis, and identification of intermediate compounds formed. A. One mole ethylene oxide with one mole of Grignard reagent. B. One mole Grignard reagent with one mole ethylene hronohydrin. C. One mole n-arnyl magnesium "bromide with one mole ethylene oxide, D.
    [Show full text]
  • Standard X-Ray Diffraction Powder Patterns
    NBS MONOGRAPH 25—SECTION 4 Standard X-ray Diffraction Powder Patterns U.S. DEPARTMENT OF COMMERCE NATIONAL BUREAU OF STANDARDS THE NATIONAL BUREAU OF STANDARDS The National Bureau of Standards is a principal focal point in the Federal Government for assuring maximum application of the physical and engineering sciences to the advancement of technology in industry and commerce. Its responsibilities include development and mainte- nance of the national standards of measurement, and the provisions of means for making measurements consistent with those standards; determination of physical constants and properties of materials; development of methods for testing materials, mechanisms, and structures, and making such tests as may be necessary, particularly for government agencies; cooperation in the establishment of standard practices for incorporation in codes and specifi- cations advisory service to government agencies on scientific and technical problems ; invention ; and development of devices to serve special needs of the Government; assistance to industry, business, and consumers m the development and acceptance of commercial standards and simplified trade practice recommendations; administration of programs in cooperation with United States business groups and standards organizations for the development of international standards of practice; and maintenance of a clearinghouse for the collection and dissemination of scientific, technical, and engineering information. The scope of the Bureau's activities is suggested in the following listing of its three Institutes and their organizatonal units. Institute for Basic Standards. Applied Mathematics. Electricity. Metrology. Mechanics. Heat. Atomic Physics. Physical Chemistry. Laboratory Astrophysics.* Radiation Phys- ics. Radio Standards Laboratory:* Radio Standards Physics; Radio Standards Engineering. Office of Standard Reference Data. Institute for Materials Research.
    [Show full text]
  • Chemical Names and CAS Numbers Final
    Chemical Abstract Chemical Formula Chemical Name Service (CAS) Number C3H8O 1‐propanol C4H7BrO2 2‐bromobutyric acid 80‐58‐0 GeH3COOH 2‐germaacetic acid C4H10 2‐methylpropane 75‐28‐5 C3H8O 2‐propanol 67‐63‐0 C6H10O3 4‐acetylbutyric acid 448671 C4H7BrO2 4‐bromobutyric acid 2623‐87‐2 CH3CHO acetaldehyde CH3CONH2 acetamide C8H9NO2 acetaminophen 103‐90‐2 − C2H3O2 acetate ion − CH3COO acetate ion C2H4O2 acetic acid 64‐19‐7 CH3COOH acetic acid (CH3)2CO acetone CH3COCl acetyl chloride C2H2 acetylene 74‐86‐2 HCCH acetylene C9H8O4 acetylsalicylic acid 50‐78‐2 H2C(CH)CN acrylonitrile C3H7NO2 Ala C3H7NO2 alanine 56‐41‐7 NaAlSi3O3 albite AlSb aluminium antimonide 25152‐52‐7 AlAs aluminium arsenide 22831‐42‐1 AlBO2 aluminium borate 61279‐70‐7 AlBO aluminium boron oxide 12041‐48‐4 AlBr3 aluminium bromide 7727‐15‐3 AlBr3•6H2O aluminium bromide hexahydrate 2149397 AlCl4Cs aluminium caesium tetrachloride 17992‐03‐9 AlCl3 aluminium chloride (anhydrous) 7446‐70‐0 AlCl3•6H2O aluminium chloride hexahydrate 7784‐13‐6 AlClO aluminium chloride oxide 13596‐11‐7 AlB2 aluminium diboride 12041‐50‐8 AlF2 aluminium difluoride 13569‐23‐8 AlF2O aluminium difluoride oxide 38344‐66‐0 AlB12 aluminium dodecaboride 12041‐54‐2 Al2F6 aluminium fluoride 17949‐86‐9 AlF3 aluminium fluoride 7784‐18‐1 Al(CHO2)3 aluminium formate 7360‐53‐4 1 of 75 Chemical Abstract Chemical Formula Chemical Name Service (CAS) Number Al(OH)3 aluminium hydroxide 21645‐51‐2 Al2I6 aluminium iodide 18898‐35‐6 AlI3 aluminium iodide 7784‐23‐8 AlBr aluminium monobromide 22359‐97‐3 AlCl aluminium monochloride
    [Show full text]
  • Methylmagnesium-Bromide-Solution
    SIGMA-ALDRICH sigma-aldrich.com SAFETY DATA SHEET Version 5.3 Revision Date 06/24/2014 Print Date 10/21/2014 1. PRODUCT AND COMPANY IDENTIFICATION 1.1 Product identifiers Product name : Methylmagnesium bromide solution Product Number : 189898 Brand : Aldrich 1.2 Relevant identified uses of the substance or mixture and uses advised against Identified uses : Laboratory chemicals, Manufacture of substances 1.3 Details of the supplier of the safety data sheet Company : Sigma-Aldrich 3050 Spruce Street SAINT LOUIS MO 63103 USA Telephone : +1 800-325-5832 Fax : +1 800-325-5052 1.4 Emergency telephone number Emergency Phone # : (314) 776-6555 2. HAZARDS IDENTIFICATION 2.1 Classification of the substance or mixture GHS Classification in accordance with 29 CFR 1910 (OSHA HCS) Flammable liquids (Category 2), H225 Substances and mixtures, which in contact with water, emit flammable gases (Category 1), H260 Acute toxicity, Oral (Category 4), H302 Skin corrosion (Category 1B), H314 Serious eye damage (Category 1), H318 Specific target organ toxicity - single exposure (Category 3), Central nervous system, H336 For the full text of the H-Statements mentioned in this Section, see Section 16. 2.2 GHS Label elements, including precautionary statements Pictogram Signal word Danger Hazard statement(s) H225 Highly flammable liquid and vapour. H260 In contact with water releases flammable gases which may ignite spontaneously. H302 Harmful if swallowed. H314 Causes severe skin burns and eye damage. H336 May cause drowsiness or dizziness. Precautionary statement(s) P210 Keep away from heat/sparks/open flames/hot surfaces. - No smoking. P223 Keep away from any possible contact with water, because of violent reaction and possible flash fire.
    [Show full text]
  • Synthesis and Properties of Diorganomagnesium Compounds
    University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 12-1967 Synthesis and Properties of Diorganomagnesium Compounds Conrad William Kamienski University of Tennessee - Knoxville Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Chemistry Commons Recommended Citation Kamienski, Conrad William, "Synthesis and Properties of Diorganomagnesium Compounds. " PhD diss., University of Tennessee, 1967. https://trace.tennessee.edu/utk_graddiss/3077 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Conrad William Kamienski entitled "Synthesis and Properties of Diorganomagnesium Compounds." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. Jerome F. Eastham, Major Professor We have read this dissertation and recommend its acceptance: Bruce M. Anderson, George K. Schwitzer, David A. Shirley Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) Novemb er 27, 1967 To the Graduate Council: I am submitting herewith a dissertation written by Conrad Wiliiam Kamienski entitled "Synthesis and Properties of Diorgano­ magnesium Compounds." I recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a maj or in Chemistry .
    [Show full text]
  • Data Sheet According to 1907/2006/EC, Article 31 Printing Date 20.07.2021 Revision: 20.07.2021
    Page 1/8 Safety data sheet according to 1907/2006/EC, Article 31 Printing date 20.07.2021 Revision: 20.07.2021 SECTION 1: Identification of the substance/mixture and of the company/undertaking · 1.1 Product identifier · Trade name: Methylmagnesium bromide, 3M in ether · Item number: 93-1265 · 1.2 Relevant identified uses of the substance or mixture and uses advised against No further relevant information available. · 1.3 Details of the supplier of the safety data sheet · Manufacturer/Supplier: Strem Chemicals, Inc. 7 Mulliken Way NEWBURYPORT, MA 01950 USA [email protected] · Further information obtainable from: Technical Department · 1.4 Emergency telephone number: EMERGENCY: CHEMTREC: + 1 (800) 424-9300 During normal opening times: +1 (978) 499-1600 SECTION 2: Hazards identification · 2.1 Classification of the substance or mixture · Classification according to Regulation (EC) No 1272/2008 d~ GHS02 flame Water-react. 1 H260 In contact with water releases flammable gases which may ignite spontaneously. d~ GHS07 Acute Tox. 4 H302 Harmful if swallowed. STOT SE 3 H336 May cause drowsiness or dizziness. · 2.2 Label elements · Labelling according to Regulation (EC) No 1272/2008 The product is classified and labelled according to the CLP regulation. · Hazard pictograms d~d~ GHS02 GHS07 · Signal word Danger · Hazard-determining components of labelling: Diethyl ether, anhydrous · Hazard statements H260 In contact with water releases flammable gases which may ignite spontaneously. H302 Harmful if swallowed. H336 May cause drowsiness or dizziness. · Precautionary statements P101 If medical advice is needed, have product container or label at hand. (Contd. on page 2) GB 44.1.1 Page 2/8 Safety data sheet according to 1907/2006/EC, Article 31 Printing date 20.07.2021 Revision: 20.07.2021 Trade name: Methylmagnesium bromide, 3M in ether (Contd.
    [Show full text]
  • Magnesium Bromide (Mgbr2) As a Catalyst for Living Cationic Polymerization and Ring-Expansion Cationic Polymerization
    Electronic Supplementary Material (ESI) for Polymer Chemistry. This journal is © The Royal Society of Chemistry 2020 Supporting Information Magnesium Bromide (MgBr2) as a Catalyst for Living Cationic Polymerization and Ring-Expansion Cationic Polymerization Yuji Daito,a Reina Kojima,a Naoyuki Kusuyama,a Yasuhiro Kohsaka,b,c and Makoto Ouchia* a Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan. b Research Initiative for Supra-Materials (RISM), Shinshu University, Japan c Faculty of Textile Science and Technology, Shinshu University, 3-15-1 Tokida, Ueda, Nagano 386-8567, Japan *Correspondence to: [email protected] 1 Materials For Polymerization Isobutyl vinyl ether (IBVE, TCI; >99%) was washed with 10% aqueous sodium hydroxide and then with water, dried overnight over potassium hydroxide, and distilled twice from calcium hydride before use. 2,6-di-tert-butyl-4-methylpyridine (DTBMP, Aldrich; 98%) and CCl4 (Wako; >99.5%) were distilled from calcium hydride once before use. Toluene (Kishida Kagaku, Osaka; 99.5%) were dried and purified by passing through purification columns (Solvent Dispensing System, SG Water USA, Nashua, NH; Glass Contour), kept over molecular sieves 4A for more than one day. Et2O (Wako; >99.5%, super dehydrated) were kept over molecular sieves 4A for more than one day. MgBr2 (Strem Chemicals, Inc.; anhydrous, 98%), MgBr2×OEt2 (Aldrich; 99%), MgCl2 (Toho Catalyst Co., Ltd; D grade), MgI2 (Aldrich; 98%), Mg(OTf)2 (TCI; >98.0%) and SnBr4 (Aldrich; 99%) were used as received. For Acidolysis trifluoroacetic acid (TFA, TCI; >99.0%) and THF (Wako; >99.5%, with stabilizer) were used as received.
    [Show full text]