DOCSLIB.ORG

Efficient Asymmetric Simmons-Smith Cyclopropanation and Diethylzinc

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Efficient Asymmetric Simmons-Smith Cyclopropanation and Diethylzinc catalysts Article Efficient Asymmetric Simmons-Smith Cyclopropanation and Diethylzinc Addition to Aldehydes Promoted by Enantiomeric Aziridine-Phosphines Aleksandra Buchcic-Szychowska 1, Justyna Adamczyk 1, Lena Marciniak 2, Adam Marek Pieczonka 1 , Anna Zawisza 1, Stanisław Le´sniak 1 and Michał Rachwalski 1,* 1 Department of Organic and Applied Chemistry, University of Lodz, Tamka 12, 91-403 Lodz, Poland; [email protected] (A.B.-S.); [email protected] (J.A.); [email protected] (A.M.P.); [email protected] (A.Z.); [email protected] (S.L.) 2 The Bio-Med-Chem Doctoral School of the University of Lodz and Lodz Institutes of the Polish Academy of Sciences, University of Lodz, 91-403 Lodz, Poland; [email protected] * Correspondence: [email protected]; Tel.: +48-42-635-5767 Abstract: During an implementation of current research, a set of optically pure chiral aziridines and aziridine imines bearing a phosphine moiety was prepared with high values of chemical yield. The above chiral heteroorganic derivatives were tested for catalytic utility as chiral ligands in asymmetric Simmons-Smith cyclopropanation and asymmetric diethylzinc addition to various aldehydes. Most of the desired products were formed in high chemical yields, with satisfactory Citation: Buchcic-Szychowska, A.; values of enantiomeric excess (sometimes more than 90%) and diastereomeric ratios (in case of Adamczyk, J.; Marciniak, L.; cyclopropanation reaction). Pieczonka, A.M.; Zawisza, A.; Le´sniak,S.; Rachwalski, M. Efficient Keywords: asymmetric synthesis; aziridines; chiral ligands; cyclopropanation; diethylzinc addition Asymmetric Simmons-Smith Cyclopropanation and Diethylzinc Addition to Aldehydes Promoted by Enantiomeric Aziridine-Phosphines. 1. Introduction Catalysts 2021, 11, 968. https:// The asymmetric construction of chiral non-racemic organic compounds is still an doi.org/10.3390/catal11080968 extremely important issue for many research teams around the world. Both the chemical yield and optical purity of the desired products of stereocontrolled synthesis depend on the Academic Editor: Filippo Perna selection of an appropriate promoter for such a reaction. This role can be played by a chiral Received: 31 July 2021 ligand [1,2], an organocatalyst [3,4], a chiral auxiliary [5], bifunctional catalysts (molecule Accepted: 12 August 2021 possessing two distinct functional groups) [6,7] or another cooperative catalytic system [8]. Published: 13 August 2021 The asymmetric Simmons-Smith reaction is one of the approaches in the synthesis of cyclopropane derivatives [9]. A cyclopropane ring with unusual electronic and steric Publisher’s Note: MDPI stays neutral properties is present in many natural products [10] and drugs [11–15]. Molecules containing with regard to jurisdictional claims in this three-membered motif can be constructed in transformations with or without transition published maps and institutional affil- metals [16] in the presence of, e.g., complexes of porphyrin [17], proline derivatives [18,19], iations. chiral phase-transfer catalysts [20] or as demonstrated in our laboratory, using chiral aziridinyl ligands containing sulfinyl moiety [21]. In turn, asymmetric diethylzinc addition to carbonyl compounds (especially aromatic aldehydes) is one of the most exploited test reactions in the chemical literature [22,23]; Copyright: © 2021 by the authors. however, it is still a very simple and effective tool for studying the catalytic activity of Licensee MDPI, Basel, Switzerland. chiral ligands. Based on our experience, ligands containing an aziridine fragment show This article is an open access article very high efficiency in reactions of this type [23–28]. distributed under the terms and Chiral systems containing a phosphine group and an aziridine ring within one conditions of the Creative Commons molecule are not the subject of many reports in the chemical literature [29]. Enriching the Attribution (CC BY) license (https:// current state of knowledge about such chiral junctions, we recently published a successful creativecommons.org/licenses/by/ application of aziridine phosphines in the asymmetric Friedel-Crafts reaction [30]. 4.0/). Catalysts 2021, 11, 968. https://doi.org/10.3390/catal11080968 https://www.mdpi.com/journal/catalysts Catalysts 2021,, 11,, xx FORFOR PEERPEER REVIEWREVIEW 2 of 11 Catalysts 2021, 11, 968 2 of 11 current state of knowledge about such chiral junctions,junctions, wewe recentlyrecently published a successful application of aziridine phosphines in the asymmetric Friedel–Crafts reaction [30]. Taking into consideration all of the aforementioned circumstances, we decided to TakingTaking into consideration all of the aforementionedaforementioned circumstances, we decided to synthesize a series of optically pure aziridines and aziridine imines possessing phosphine synthesizesynthesize a a series series of of optically optically pure pure aziridines aziridines and and aziridine aziridine imines imines possessing possessing phosphine phosphine motif in order to check their catalytic activities in the asymmetric Simmons–Smith cyclo- motifmotif in in order order to to check check their their catalytic catalytic activities activities in inthe the asymmetric asymmetric Simmons–Smith Simmons-Smith cyclo- cy- propanationclopropanation and and asymmetric asymmetric diethylzinc diethylzinc addition addition to aldehydes. to aldehydes. Thus, Thus, we wanted we wanted to show to thatshow chiral that chiralaziridine-phosphines aziridine-phosphines are universal are universal catalysts catalysts operating operating in in various various types types of asymmetricasymmetric transformations. transformations. 2.2. Results Results and and Discussion Discussion 2.1.2.1. Preparation Preparation of of the the Aziridine-Phosphines Aziridine-Phosphines 11––88 TheThe chiral chiral enantiomeric enantiomeric aziridine-phosphines aziridine-phosphines 1–18– 8(Figure(Figure 1)1 )were were prepared prepared as as previ- pre- ouslyviously described described [30], [30 ],through through triethoxysilan triethoxysilane-mediatede-mediated reduction reduction of of the the corresponding phosphinephosphine oxides oxides [30]. [30]. N N N N PPh PPh PPh PPh2 PPh2 PPh2 PPh2 2 (R)-1 (S)-2 (S)-3 (S)-4 N N N N PPh PPh PPh PPh PPh2 PPh2 PPh2 PPh2 (R)-5 (S)-6 (S)-7 (S)-8 (S)- (S)-7 (S)- Figure 1. TheThe structures structures of chiral aziridine-phosphines 1–8.. 2.2.2.2. Synthesis Synthesis of of Imine-Phosphines Imine-Phosphines 99––1212 ChiralChiral imine-phosphines imine-phosphines 99––1212 (Scheme(Scheme 1)1 )were were obtained obtained starting starting from from appropriate appropriate 1- (2-aminoalkyl)aziridines,1-(2-aminoalkyl)aziridines, which which were were formed asas a a result result of of the the zinc zinc bromide-mediated bromide-mediated self- self-ringring opening opening reaction reaction of NH-aziridines, of NH-aziridines, as previouslyas previously described described [31 [31].]. The The corresponding correspond- ing1-(2-aminoalkyl)aziridines 1-(2-aminoalkyl)aziridines were were then reactedthen reacted with 2-(diphenylphosphino)benzaldehydewith 2-(diphenylphosphino)benzalde- af- hydefording affording 1-(2-iminealkyl)aziridine 1-(2-iminealkyl)aziridine catalysts catalysts functionalized functionalized by a phosphine by a phosphine group in group excellent in excellentyields (Scheme yields1 (Scheme). 1). Scheme 1. SynthesisSynthesis of chiral imine-phosphines 9–12.. Catalysts 20212021,, 1111,, 968x FOR PEER REVIEW 33 of of 11 2.3. Asymmetric Simmons–Smith Simmons-Smith CyclopropanationCyclopropanation PromotedPromoted byby Aziridine-PhosphinesAziridine-Phosphines1 1––88and and Imine-Phosphines 9–12 Equipped with all optically pure ph phosphorus-functionalizedosphorus-functionalized aziridines 11––1212,, we we de- de- cided to check their utility asas chiralchiral ligandsligands catalyzingcatalyzing anan asymmetricasymmetric cyclopropanationcyclopropanation reaction of cinnamyl alcohol (13) as aa modelmodel substrate.substrate. The transformationstransformations werewere carriedcarried out in DCM with 22 equiv.equiv. ofof diethylzincdiethylzinc and and 3 3 equiv. equiv. of of diiodomethane diiodomethane in in the the presence presence of of a aligand ligand (10 (10 mol%) mol%) (Scheme (Scheme2). 2). All All the the results results are are presented presented in in Table Table1. 1. Scheme 2. Asymmetric cyclopropanation cyclopropanation of of alcohol alcohol 1313 inin the the presence presence of of catalysts catalysts 11––1212 leadingleading to to cyclopropane derivative 14. Table 1. Asymmetric Simmons–Smith Simmons-Smith cyclopropanationcyclopropanation ofof cinnamylcinnamyl alcoholalcohol catalyzed by aziridines 1–12. EntryEntry Ligand Ligand Product Product 14 14 Yield (%) ee (%) a Dr b Abs. Conf. c Yield (%) ee (%) a Drb Abs. Conf. c 1 1 70 62 5:1 1R,2R 1 1 70 62 5:1 1R,2R 2 2 72 65 5:1 1S,2S 2 2 72 65 5:1 1S,2S 3 3 3 3 63 6354 54 5:1 5:1 1 1SS,2,2SS 4 4 4 4 65 6558 58 5:1 5:1 1 1SS,2,2SS 5 5 5 5 90 9092 92 12:1 12:1 1 1RR,2,2RR 6 6 6 6 93 9398 98 15:1 15:1 1 1SS,2,2SS 7 7 90 82 10:1 1S,2S 7 8 7 8 90 9182 85 10:1 10:1 1 1SS,2,2SS 8 9 8 9 91 8585 72 10:1 10:1 1 1SS,2,2SS 910 9 10 85 8372 70 10:1 10:1 1 1SR,2,2SR 1011 10 11 83 7970 68 10:1 10:1 1R 1S,2,2RS 12 12 80 70 10:1 1S,2S 11 11 79 68 10:1 1S,2S a Determined by chiral HPLC using Chiralcel OD-H column (for major product). b Determined by 1H NMR of the crude12 mixture.12c According to the80 literature data [21,32].70 Conditions: 10 mol%10:1 of the ligand, cinnamyl1S,2S alcohol (0.5a Determined mmol), diethylzinc by chiral (1.0 HPLC M in hexanes,using Chir 1 mmol),alcel OD-H diiodomethane column (0.6(for mmol), major DCMproduct). (5 mL), b Determined 0 ◦C, 4 h. by 1H NMR of the crude mixture. c According to the literature data [21,32]. Conditions: 10 mol% of the ligand,Theanalysis cinnamyl ofalcohol the results (0.5 mmol), collected diethylz ininc Table (1.01 M leads in hexanes, to the 1 followingmmol), diiodomethane conclusions.
Load more

Recommended publications
  • Efficient Asymmetric Addition of Diethylzinc to Ketones Using Tartaric Acid Derivative As Chiral Ligand
    General Papers ARKIVOC 2008 (ii) 25-32 Efficient asymmetric addition of diethylzinc to ketones using tartaric acid derivative as chiral ligand Ailing Hui,a Jintang Zhang,b Huayin Sun,b and Zhiyong Wangb* aEngineering Research Center of Bio-process (Hefei University of Techonology), Ministry of Education, 193 Tunxi Road, Hefei, Anhui 230009, PRC bDepartment of Chemistry, University of Science & Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026, PRC E-mail: [email protected] Abstract A new chiral ligand derived from natural tartaric acid was synthesized and was applied to the asymmetric addition of diethylzinc to aldehyde and ketones. Moderate to good enantioselectivities were obtained in the asymmetric addition of diethylzinc to ketones with 10% mol catalyst loading at room temperature. Keywords: Tartaric acid, asymmetric addition, diethylzinc, aldehyde, ketone Introduction Chiral alcohols are ubiquitous in the structure of natural products and drug compounds, and are also important precursors for many other functional organic molecules. One of the most useful methods for the asymmetric preparation of sec-alcohols and tert-alcohols is the enantioselective addition of dialkylzinc reagents to carbonyl compounds with chiral ligands 1. Recent studies 2 showed the ligands with C2-symmetrical axes could catalyze dialkylzinc to aldehydes or ketones 3. Taking the advantage of the chirality of L-tartaric acid, we4 designed and synthesized a series of ligands with C2-symmetric axe, two of them were successfully applied to the asymmetric addition of diethylzinc to ketones. Recently, another new chiral ligands derived from L-tartaric acid were synthesized, as showed in Scheme 1. Furthermore, these ligands were employed as promoters in the addition of diethylzinc to aldehyde and ketones.
    [Show full text]
  • Chemical Name Federal P Code CAS Registry Number Acutely
    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 Extremely Hazardous 1,1,1-Trichloro-2, -bis(p-methoxyphenyl)ethane Extremely Hazardous 1,1a,2,2,3,3a,4,5,5,5a,5b,6-Dodecachlorooctahydro-1,3,4-metheno-1H-cyclobuta (cd) pentalene, Dechlorane Extremely Hazardous 1,1a,3,3a,4,5,5,5a,5b,6-Decachloro--octahydro-1,2,4-metheno-2H-cyclobuta (cd) pentalen-2- one, chlorecone Extremely Hazardous 1,1-Dimethylhydrazine 57-14-7 Extremely 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 Extremely Hazardous 1,2,3-Propanetriol, trinitrate P081 55-63-0 Acutely Hazardous 1,2,3-Propanetriol, trinitrate 55-63-0 Extremely Hazardous 1,2,4,5,6,7,8,8-Octachloro-4,7-methano-3a,4,7,7a-tetra- hydro- indane Extremely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]- 51-43-4 Extremely Hazardous 1,2-Benzenediol, 4-[1-hydroxy-2-(methylamino)ethyl]-, P042 51-43-4 Acutely Hazardous 1,2-Dibromo-3-chloropropane 96-12-8 Extremely Hazardous 1,2-Propylenimine P067 75-55-8 Acutely Hazardous 1,2-Propylenimine 75-55-8 Extremely Hazardous 1,3,4,5,6,7,8,8-Octachloro-1,3,3a,4,7,7a-hexahydro-4,7-methanoisobenzofuran Extremely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime 26419-73-8 Extremely Hazardous 1,3-Dithiolane-2-carboxaldehyde, 2,4-dimethyl-, O- [(methylamino)-carbonyl]oxime.
    [Show full text]
  • Chem 115 Myers
    Myers Organozinc Reagents: Asymmetric Additions to Carbonyl Compounds Chem 115 Recent Reviews: • In 1984, Oguni and Omi found that a small amount of (S)-leucinol catalyzed the enantioselective addition (49% ee) of diethylzinc to benzaldehyde. Pu, L.; Yu, H.-B. Chem. Rev. 2001, 101, 757–824. Lemire, A.; Cote, A.; Janes, M. K.; Charette, A. B. Aldrichimica Acta 2009, 42, 71–83. Lumbroso, A.; Cooke, M. L.; Breit, B. Angew. Chem. Int. Ed. 2013, 52, 1890–1932. H3C O OH OH 2 mol % NH CH3 2 CH3 H + (C2H5)2Zn Background: toluene, 20 °C, 43 h 96% yield, 49% ee • The reactivity of dialkylzinc reagents towards ketones and aldehydes is low; the rate of addition of Et2Zn to benzaldehyde is negligible at room temperature. Oguni, N.; Omi, T. Tetrahedron Lett. 1984, 25, 2823–2824. • The addition of a catalytic amount of TMEDA will promote the addition of diethylzinc at room temperature to 4-benzoylbenzaldehyde in 93% yield. • In 1986, Noyori et al. published the first highly selective procedure for the asymmetric addition of diethyl- and dimethylzinc to aldehydes employing (–)-3-exo-(dimethylamino)isoborneol (DAIB) as a chiral catalyst. O OH 5 mol % TMEDA CH3 H3C CH3 H + (C2H5)2Zn toluene, 23°C, 14 h N(CH3)3 Bz Bz 93% OH racemic H3C (–)-DAIB Soai, K.; Watanabe, M.; Koyano, M. Bull. Chem. Soc. Jpn. 1989, 25, 2124–2125. O 2 mol % (–)-DAIB OH + R' Zn • X-Ray structures of dimethylzinc and its adduct with 1,3,5-trimethylhexahydro-1,3,5-triazine 2 R H toluene, 0 °C R R' show that upon bis-complexation, dimethylzinc shifts from a linear geometry to a tetrahedral geometry and that the carbon-zinc bond length increases from 1.95 Å to 1.98 Å.
    [Show full text]
  • Atomic Layer Deposition of Zno on Mesoporous Silica: Insights Into Growth Behavior of Zno Via In-Situ Thermogravimetric Analysis
    nanomaterials Article Atomic Layer Deposition of ZnO on Mesoporous Silica: Insights into Growth Behavior of ZnO via In-Situ Thermogravimetric Analysis Piyush Ingale 1 , Kristian Knemeyer 1, Mar Piernavieja Hermida 1, Raoul Naumann d’Alnoncourt 1,* , Arne Thomas 2 and Frank Rosowski 1,3 1 BasCat—UniCat BASF JointLab, Technische Universität Berlin, Hardenbergstraße 36, 10623 Berlin, Germany; [email protected] (P.I.); [email protected] (K.K.); [email protected] (M.P.H.); [email protected] (F.R.) 2 Institut für Chemie, Technische Universität Berlin, 10623 Berlin, Germany; [email protected] 3 Process Research and Chemical Engineering, BASF SE, 67056 Ludwigshafen, Germany * Correspondence: [email protected] Received: 28 April 2020; Accepted: 19 May 2020; Published: 20 May 2020 Abstract: ZnO is a remarkable material with many applications in electronics and catalysis. Atomic layer deposition (ALD) of ZnO on flat substrates is an industrially applied and well-known process. Various studies describe the growth of ZnO layers on flat substrates. However, the growth characteristics and reaction mechanisms of atomic layer deposition of ZnO on mesoporous powders have not been well studied. This study investigates the ZnO ALD process based on diethylzinc (DEZn) and water with silica powder as substrate. In-situ thermogravimetric analysis gives direct access to the growth rates and reaction mechanisms of this process. Ex-situ analytics, e.g., N2 sorption analysis, XRD, XRF, HRTEM, and STEM-EDX mapping, confirm deposition of homogenous and thin films of ZnO on SiO2. In summary, this study offers new insights into the fundamentals of an ALD process on high surface area powders.
    [Show full text]
  • A New Look at the Reactivity of TEMPO Toward Diethylzinc Krzysztof Budny-Godlewski,† Dominik Kubicki,† Iwona Justyniak,‡ and Janusz Lewinskí *,†,‡
    Communication pubs.acs.org/Organometallics A New Look at the Reactivity of TEMPO toward Diethylzinc Krzysztof Budny-Godlewski,† Dominik Kubicki,† Iwona Justyniak,‡ and Janusz Lewinskí *,†,‡ † Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland ‡ Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland *S Supporting Information ABSTRACT: Reactions of diethylzinc with TEMPO were investigated. − ° Dropwise addition of 1 equiv of TEMPO to Et2Zn at 10 C leads to the nitroxide complex EtZn(TEMPO) in high yield, whereas upon addition of 2 equiv of TEMPO the corresponding homoleptic nitroxide ff compound Zn(TEMPO)2 is formed. Di usion ordered NMR spectros- copy experiments revealed that both zinc nitroxide compounds exist in monomeric forms in solution, while single-crystal X-ray diffraction confirmed their dimeric structure in the solid state. he stable nitroxyl radical TEMPO (2,2,6,6-tetramethylpi- to confirm the radical mechanism of this process. Incidentally, peridinyl oxide) was first synthesized in 19591 and since the formation of a small amount of the isolable dimeric T μ that time has attracted widespread interest. It has been widely complex [EtZn( 2-TEMPO)]2 was observed. The authors also 2 used in polymer synthesis and catalytic organic reactions. noted that the reaction of TEMPO with Et2Zn does not occur η5 6 Much attention has also been paid to its application as a ligand unless ( -C5Me5)2Zn is present in the reaction system. or radical trapping agent in reactions with metal complexes.3,4 Recently, TEMPO has also been used as a reagent in various The latter studies have demonstrated that TEMPO is a very other transformations involving group 2 organometallics.
    [Show full text]
  • 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.
    [Show full text]
  • Material Safety Data Sheet
    MATERIAL SAFETY DATA SHEET Manufacturer: Strem Chemicals, Inc Strem Customer Service (978) 499-1600 7 Mulliken Way CHEMTREC (Emergency Only) (800) 424-9300 Newburyport, MA 01950-4098 U.S.A. Poison Center (800) 562-8236 www.strem.com Section 1: Product Identification Chemical Name: Diethylzinc, min. 95% (Material sold in non-returnable cylinder) Product Number: 93-3030 CAS Registry Number: 557-20-0 Formula: Zn(C2H5)2 EINECS Number: 209-161-3 Chemical Family: metal alkyl Synonym: zinc, diethyl Section 2: Composition and Information on Ingredients Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL) Title Compound 557-20-0 100% 5 mg/m3 (fume) 5 mg/m3 (fume) Section 3: Hazards Identification Inhalation of zinc oxide fume produced from this compound in a fire may cause metal fume fever or zinc Emergency Overview: shakes consisting of chills, fever, muscular pain, nausea, and vomiting. May cause thermal burns. Primary Routes of Exposure: Eyes, skin, and inhalation of combustion products. Eye Contact: Direct contact of liquid with the eyes will cause thermal burns and possible blindness. Skin Contact: Liquid bursts in to flame in air, causing thermal burns to skin. Fume causes burns to the nose, mucous membranes and respiratory tract causing metallic taste, dry throat, Inhalation: and chills. Ingestion: Ingestion is an unlikely mode of entry as the material is pyrophoric. Acute Health Affects: Causes burns to skin, eyes and respiratory tract. Inhalation may cause chills and nausea. No serious long-term chronic effects associated with zinc compounds. Prolonged inhalation may cause Chronic Health Affects: laryngitis. Prolonged ingestion may cause constipation.
    [Show full text]
  • University of Groningen Acetals of 1-Aryl-2,2-Dimethyl-1,3
    University of Groningen Acetals of 1-aryl-2,2-dimethyl-1,3-propanediols synthesis and use as chiral auxiliary Ebens, Rijko Hendrik Ebe IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 1993 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Ebens, R. H. E. (1993). Acetals of 1-aryl-2,2-dimethyl-1,3-propanediols synthesis and use as chiral auxiliary. s.n. Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license. More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne- amendment. Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 06-10-2021 Chapter 4 ASYMMETRIC CYCLOPROPANATION 4.1 INTRODUCTION This chapter deals with asymmetric cyclopropanations of Zalkenyl acetals 2.19.
    [Show full text]
  • Chemical Reaction-Transport Model of Oxidized Diethylzinc Based on Quantum Mechanics and Cite This: RSC Adv.,2018,8, 1116 Computational fluid Dynamics Approaches†
    RSC Advances PAPER View Article Online View Journal | View Issue Chemical reaction-transport model of oxidized diethylzinc based on quantum mechanics and Cite this: RSC Adv.,2018,8, 1116 computational fluid dynamics approaches† Jian Li,a Hanlin Gan, b Yifeng Xu,a Chaoyang Wang,b Feng Long Gu *b and Gang Wang *ac We developed and studied a chemical reaction-transport model for the production of zinc oxide (ZnO) with diethylzinc (DEZn) and oxygen (O2). It was confirmed that a large number of ZnO particles were generated during the growth process by testing the internal particles of the cavity by X-ray diffraction. The formation of Zn3O3 in the gas phase reaction was simulated using density functional theory, and the effect of nucleation and formation of nanoparticles on the growth of the films was revealed. We also speculate that the adsorption of Zn-containing gas on the wall is the main route by which a ZnO film is formed. The mechanism calculated by quantum chemistry was applied in computational fluid dynamics (CFD) Creative Commons Attribution 3.0 Unported Licence. simulations using Fluent14.0 software, and the concentration distribution and gas reaction path of the reaction chamber were calculated and analyzed. Finally, a 9 gas phase reaction model and an 8 surface reaction model were established. Together with the transport model, a complete chemical reaction- transport reaction model was constructed for the ZnO–MOCVD cavity. The validity of the model was Received 19th October 2017 verified, and the optimum temperature range of DEZn and oxygen-stabilized growth of ZnO films was Accepted 15th December 2017 determined to be 673–873 K.
    [Show full text]
  • Synthesis of Poly(Hydroxyalkanoates
    SYNTHESIS OF POLY(HYDROXYALKANOATES): ROUTES TO POLY(3- HYDROXYBUTYRATE) AND POLY(3-HYDROXYPROPIONATE) FROM THE CARBONYLATION AND RING-OPENING POLYMERIZATION OF EPOXIDES A Dissertation Presented to the Faculty of the Graduate School of Cornell University In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy by Erin Whitfield Dunn August 2012 © 2012 Erin Whitfield Dunn SYNTHESIS OF POLY(HYDROXYALKANOATES): ROUTES TO POLY(3- HYDROXYBUTYRATE) AND POLY(3-HYDROXYPROPIONATE) FROM THE CARBONYLATION AND RING-OPENING POLYMERIZATION OF EPOXIDES Erin Whitfield Dunn, Ph.D. Cornell University 2012 New methods for the syntheses of poly(3-hydroxybutyrate) (P3HB) and poly(3-hydroxypropionate) (P3HP) from epoxides are reported. Epoxides are readily available, inexpensive starting materials that can be transformed into valuable biodegradable and biocompatible polyesters. We successfully developed a one-pot synthesis of P3HB from propylene oxide and carbon monoxide using a multicatalytic transformation. The intermediate !-butyrolactone was formed and subsequently polymerized in situ. The carbonylation of propylene oxide to !-butyrolactone was + - accomplished using a catalyst of the form [Lewis acid] [Co(CO)4] , and the lactone monomer was then polymerized by a (BDI)ZnOAc (BDI = !-diiminate) catalyst. The two catalysts were found to have orthogonal reactivity, and were compatible with each other as well as with the solvent, substrate, and any reaction side-products. The reaction proceeded with high activity and selectivity to synthesize P3HB with high molecular weights. Furthermore, this dual-catalyst approach eliminated exposure to the toxic !-butyrolactone monomer. We also report the synthesis of P3HP from ethylene oxide and carbon monoxide. The carbonylation of ethylene oxide proceeded in greater than 99% yield + - and high selectivity with the bimetallic catalyst [(ClTPP)Al(THF)2] [Co(CO)4] (ClTPP = meso-tetra(4-chlorophenyl)porphyrinato; THF = tetrahydrofuran).
    [Show full text]
  • Diethylzinc (Dez) 1
    Akzo Nobel Polymer Chemicals LLC MATERIAL SAFETY DATA SHEET DIETHYLZINC (DEZ) 1. CHEMICAL PRODUCT AND COMPANY INFORMATION Product name Chemical description DIETHYLZINC (DEZ) Diethylzinc Synonym Chemical formula DEZ C4 H10 Zn CAS number Chemical family 557-20-0 Zinc alkyls Supplier Akzo Nobel Polymer Chemicals LLC 300 South Riverside Plaza Chicago, IL 60606 USA Medical/Handling Emergency Transportation Emergency + 1-914-693-6946 CHEMTREC - USA: 1-800-424-9300 Dobbs Ferry, NY USA CANUTEC - CANADA: 1-613-996-6666 Product use Product/technical Information Semiconductors 1-800-828-7929 Date of first issue Date of last issue / Revision # 03-02-1995 08-26-1999 / 8.00 2. COMPOSITION/INFORMATION ON INGREDIENTS Ingredient Percentage(s) CAS number Diethylzinc 99.00 - 100.00 557-20-0 3. HAZARDS IDENTIFICATION Emergency overview Clear, colorless liquid. DANGER! EXTREMELY FLAMMABLE. CATCHES FIRE IF EXPOSED TO AIR. CAUSES SKIN AND EYE BURNS. REACTS VIOLENTLY WITH WATER. Metal alkyls are pyrophoric. The metal alkyl reacts spontaneously with air and/or moisture resulting in ignition. In case of fire, reignition of the metal alkyl may occur after the fire has been extinguished. Health effects Skin and eye contact are the primary routes of exposure to this product. Inhalation of the metal alkyl in this product is unlikely due to the highly reactive nature of the metal alkyl with air and its low vapor pressure. This material will react with moisture in or on the skin to produce thermal and chemical burns. This product will react with moisture in the eyes to produce severe chemical and thermal burns. Ingestion will result in burning of the mouth, throat and any part of the gastrointestinal system with which the material comes in contact.
    [Show full text]
  • OMZN018 GHS US English US
    OMZN018 - DIETHYLZINC, 1M in heptane DIETHYLZINC, 1M in heptane Safety Data Sheet OMZN018 Date of issue: 11/20/2017 Revision date: 03/14/2018 Version: 1.1 SECTION 1: Identification 1.1. Identification Product name : DIETHYLZINC, 1M in heptane Product code : OMZN018 Product form : Mixture Physical state : Liquid Formula : C4H10Zn Synonyms : ZINC ETHYL Chemical family : METAL ALKYL IN SOLVENT 1.2. Recommended use and restrictions on use Recommended use : Chemical intermediate 1.3. Supplier GELEST, INC. 11 East Steel Road Morrisville, PA 19067 USA T 215-547-1015 - F 215-547-2484 - (M-F): 8:00 AM - 5:30 PM EST [email protected] - www.gelest.com 1.4. Emergency telephone number Emergency number : CHEMTREC: 1-800-424-9300 (USA); +1 703-527-3887 (International) SECTION 2: Hazard(s) identification 2.1. Classification of the substance or mixture GHS-US classification Flammable liquids Category 2 H225 Highly flammable liquid and vapor Substances and mixtures which in contact with water emit flammable H260 In contact with water releases flammable gases which may ignite gases Category 1 spontaneously Skin corrosion/irritation Category 1B H314 Causes severe skin burns and eye damage Serious eye damage/eye irritation Category 1 H318 Causes serious eye damage Specific target organ toxicity (single exposure) Category 3 H336 May cause drowsiness or dizziness Hazardous to the aquatic environment - Acute Hazard Category 1 H400 Very toxic to aquatic life Hazardous to the aquatic environment - Chronic Hazard Category 1 H410 Very toxic to aquatic life with long
    [Show full text]