DOCSLIB.ORG

Lecular Cross-Electrophile Coupling Reaction of Sulfonamides with Al- Kyl Chlorides Erika L

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Lecular Cross-Electrophile Coupling Reaction of Sulfonamides with Al- Kyl Chlorides Erika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a. Strained sulfonamides (Doyle and Sigman) MeO Ts NiCl2·glyme (,!.+0$!0$%)*(1$!%,/!)+..+,'>!3*('(=$/!$'$)*0+&#('$2F!23)#! N I OMe chiral bioxazoline %2! %'?>'! #%'(/$29! C30*#$0.+0$F! *#$! %.(/+! '$%1(,4! 40+3&2! + NaI, Mn0, TMSCl NHTs 4$,$0%*$/!)%,!2$01$!%2!2*0+,4!'(4%,/2F!0$23'*(,4!(,!)%*%'>2*! 3 73% yield, 94% ee /$%)*(1%*(+,9 !!"#$! /(2)+1$0>! +-! ,$;! )%*%'>2*2! )%&%8'$! +-! b. Ammonium salts (Martin) $,4%4(,4! 567! 8+,/2! ;+3'/! (.&0+1$! +30! %8('(*>! *+! /$2(4,! Me I CO H 0$%)*(+,2!*#%*!$A&'+(*!0$*()$,*!$'$)*0+&#('$2F!%2!;$''!%2!(,< NiCl2 2 NMe phenanthroline ligand 3 Me -+0.!-3*30$!)%*%'>2*!/$2(4,9!! + CO2 Ph Mn0 50+22<$'$)*0+&#('$! )+3&'(,4! MDE5N! 0$%)*(+,24! +-! %.(,$! Ph 81% yield /$0(1%*(1$2! %0$! 0%0$F! %,/! )300$,*! $A%.&'$2! 0$L3(0$! 238< c. Katritzky salts (Watson) NiCl ·dme 5!6!7!8 Me Me N 2 2*0%*$2!;#$0$!*#$!567!8+,/!#%2!8$$,!%)*(1%*$/F !$(*#$0! bipyridine ligand N + 8>!(,)+0&+0%*(+,!(,*+!%!2*0%(,$/!0(,4!+0!8>!-+0.%*(+,!+-!%,! N 0 Ph Br MgCl2, Mn %..+,(3.!2%'*99!10!11!12!C+0!$A%.&'$F!*#$!B+>'$!%,/!O(4.%,! BF4 Ph Me 85% yield '%8+0%*+0($2! 0$&+0*$/! *#$! ,()?$'<)%*%'>=$/! )0+22< d. Sulfonamides (This work) $'$)*0+&#('$!)+3&'(,4!0$%)*(+,!+-!2*0%(,$/F!8$,=>'()!23'-+,>'! Ts Me Ni Ts Ni %=(0(/(,$2!;(*#!%0>'!(+/(/$2!*+!4$,$0%*$!$,%,*(+$,0()#$/!P< N catalyst Ar N catalyst Ar NHTs " MeMgI MeMgI %0>'&#$,$*#>'23'-+,%.(/$2! MO)#$.$! Q%N9 ! @%0*(,! %,/! )+< Ar Cl Ar Cl ;+0?$02!/$1$'+&$/!*#$!,()?$'<)%*%'>=$/!)0+22<$'$)*0+&#('$! > 20:1 dr > 20:1 dr )+3&'(,4!0$%)*(+,!+-!8$,=>'()!%..+,(3.!2%'*2!;(*#!)%08+,! /(+A(/$!*+!%--+0/!8$,=>'()!)%08+A>'()!%)(/2!MO)#$.$!Q8N9#$! G,! *#(2! .%,32)0(&*F! ;$! /$2)0(8$! *#$! -(02*! )0+22< H$)$,*'>F! *#$! R%*2+,! '%8+0%*+0>! 0$&+0*$/! *#$! ,()?$'< $'$)*0+&#('$! )+3&'(,4! 0$%)*(+,! +-! 8$,=>'()! 23'-+,%.(/$2! )%*%'>=$/!)0+22<$'$)*0+&#('$!)+3&'(,4!0$%)*(+,!+-!S%*0(*=?>! MO)#$.$! Q/N913! K'?>'! )#'+0(/$2! %,/! 8$,=>'()! 23'-+,%.(/$2! 2%'*2! ;(*#! %0>'! 80+.(/$2! MO)#$.$! Q)N9#%! "#$2$! (.&+0*%,*! %0$! $,4%4$/! (,! %,! (,*0%.+'$)3'%0! ,()?$'<)%*%'>=$/! DE5! /$1$'+&.$,*2!#%1$!/$.+,2*0%*$/!*#$!-$%2(8('(*>!+-!%&&'>< 0$%)*(+,! *+! %--+0/! .+,+2382*(*3*$/! )>)'+&0+&%,$29! K//(< (,4!%.(,$!/$0(1%*(1$2!%2!$'$)*0+&#('$2!(,!)0+22<$'$)*0+&#('$! *(+,%''>F! !<*+2>'<T<)#'+0+&(&$0(/(,$2! 3,/$04+! %! 2*$0$+2$< '$)*(1$! 0(,4! )+,*0%)*(+,! *+! %--+0/! *0%,2<2382*(*3*$/! )>)'+< Ni Source (5 mol %) Me Ts Ligand (5 mol %) &0+&%,$2!;(*#!#(4#!/(%2*$0$+2$'$)*(1(*>9!"#$2$!0$23'*2!%0$! N Additive (1 equiv) F C O F3C ,+*$;+0*#>! 8$)%32$! *#$! %8('(*>! *+! .%,(&3'%*$! *#$! 2*03)< 3 Cl MeMgI (2 equiv) O *30$2!+-!23'-+,%.(/$2!(2!1%'3%8'$!/3$!*+!*#$(0!&0$1%'$,)$!(,! 1 PhMe, rt, 24 h 2 *#$! &#%0.%)$3*()%'! (,/32*0>914! C+0! $A%.&'$F! 23'-+,%.(/$< Entry Ni Source Ligand Additive Yield (%)a )+,*%(,(,4!)+.&+3,/2!%0$!?,+;,!*+!&+22$22!%!;(/$!1%0($< *>! +-! 8(+'+4()%'! &0+&$0*($2F! (,)'3/(,4! %,*(<(,-'%..%*+0>F! 1 ((R)-BINAP)NiCl2 none MgI2 77 %,*(<#>&$0*$,2(1$! %,/! %,*(<)+,13'2%,*! %)*(1(*>9! H$)$,*! 2 ((R)-BINAP)NiCl2 none none 63 b 2*3/($2!#%1$!/$.+,2*0%*$/!*#%*!23'-+,%.(/$2!)%,!.$/(%*$! 3 ((R)-BINAP)NiCl2 none MgI2 40 c &0+*$(,<&0+*$(,! (,*$0%)*(+,2! (,1+'1$/! (,! )%,)$0! &0+40$2< 4 ((R)-BINAP)NiCl2 none MgI2 77 2(+,! %,/! (,#(8(*! ,$30+*0%,2.(**$0! 8(+2>,*#$2(2915! G,! *#(2! 5 Ni(cod)2 rac-BINAP MgI2 27 .%,32)0(&*F! ;$! 0$&+0*! *#$! 2*03)*30%'! 0$%00%,4$.$,*! +-! 6d Ni(cod) rac-BINAP MgI 23 23'-+,%.(/$2U*#$!*0%,2-+0.%*(+,!+-!!<*+2>'&(&$0(/(,$2!*+! 2 2 !<*+2>'M%.(,+$*#>'N)>)'+&0+&%,$2U%2! ;$''! %2! 2$**(,4! *#$! 7 NiCl2(dme) rac-BINAP MgI2 29 -+3,/%*(+,! -+0! -30*#$0! /$1$'+&.$,*! +-! ,()?$'<)%*%'>=$/! 8 NiCl2(dme) rac-BINAP none 8 DE5!0$%)*(+,2!+-!3,2*0%(,$/!%,/!,$3*0%'!%.(,$!/$0(1%*(1$29! 9 NiCl2(dme) XantPhos none 0 HEOJV"O!K7B!BGO5JOOGI7! 10 NiCl2(dme) DPEPhos none 16 11 NiCl (dme) BPhen none 11 =*>*406+*95, 0<, #84<09;+7?*, &/011234*(5/06)74*, 2 &086479:,%*;(5709.!R$!8$4%,!8>!$1%'3%*(,4!*#$!(,*0%.+< 12 NiCl2(dme) SiMes·HBF4 none 15 '$)3'%0!)0+22<$'$)*0+&#('$!)+3&'(,4!0$%)*(+,!+-!23'-+,%.(/$! 13 NiCl2(dme) PCy3 none 28 -9! "#$! +&*(.%'! DE5! 0$%)*(+,! )+,/(*(+,2! $.&'+>$/! %(0< 14 NiCl2(PCy3)2 none none 7 15 none none none 0 2*%8'$! MM"N<WG7KXN7(5'%! %2! *#$! )%*%'>2*F! @$@4G! %2! *#$! 0$< 16e ((R)-BINAP)NiCl none Mg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e Ts ((R)-BINAP)NiCl (5 mol%) R N 2 Ar N ((R)-BINAP)NiCl2 (5 mol%) MeMgI (2 equiv) Ar Cl X NHR PhMe, rt, 24 h MgI2 (1 equiv) MeMgI (2 equiv) 8a–d PhMe, rt, 24 h 9a–d > 20:1 dr > 20:1 dr S Entry R X SM Yield 9 (%)a Recovered 8 (%)a Me O N O 1 Ts Cl 8a 96 < 2 3 4 5 2 Ns Cl 8b < 5 < 5 82%b 59%a (73%)b 53%a,c (80%)b,c Me 3 Tf Cl 8c > 99 < 2 b F N 4 Ts Cl 8d 32 34 5 Ts F 8e < 2 < 2 S N 6 Ts Br 8f < 12 < 2 6 7 a,d 64% 65%b,c &"#$%&! &$'$()#*$&! +,! #-! ./0! +12$&! 3*! 43)51(#23*! '3! &D23%1'$&! "#$%&:! '"#$%&! &$'$()#*$&! +,! #-! ./0! +12$&! 3*! 678/9! 12! #*'$(*1%! 2'1*&1(&:! '82,! I! JH 43)51(#23*!'3!678/9!12!#*'$(*1%!2'1*&1(&:!)@!$EF#G!/CD%!1&&H K'(#?%F3(3)$'7,%L+$*M$*$2F%?3*,%:! * $&:! @:;!$EF#G!/CD%!1&&$&:! R(*#!!<*+2>'!%,/!!<*0(-'>'&(&$0(/(,$2!23))$22-3''>!$,4%4< =*>*406+*95, 0<, L76*/7?79*, %79:, &095/;(5709., R$! (,4!(,!*#$!(,*0%.+'$)3'%0!)0+22<$'$)*0+&#('$!)+3&'(,4!0$%)<
Load more

Recommended publications
  • Structures and Reaction Mechanisms of Organocuprate Clusters in Organic Chemistry
    REVIEWS Wherefore Art Thou Copper? Structures and Reaction Mechanisms of Organocuprate Clusters in Organic Chemistry Eiichi Nakamura* and Seiji Mori Organocopper reagents provide the principles. This review will summarize example of molecular recognition and most general synthetic tools in organic first the general structural features of supramolecular chemistry, which chemistry for nucleophilic delivery of organocopper compounds and the pre- chemists have long exploited without hard carbanions to electrophilic car- vious mechanistic arguments, and then knowing it. Reasoning about the bon centers. A number of structural describe the most recent mechanistic uniqueness of the copper atom among and mechanistic studies have been pictures obtained through high-level neighboring metal elements in the reported and have led to a wide variety quantum mechanical calculations for periodic table will be presented. of mechanistic proposals, some of three typical organocuprate reactions, which might even be contradictory to carbocupration, conjugate addition, Keywords: catalysis ´ conjugate addi- others. With the recent advent of and SN2 alkylation. The unified view tions ´ copper ´ density functional physical and theoretical methodolo- on the nucleophilic reactivities of met- calculations ´ supramolecular chemis- gies, the accumulated knowledge on al organocuprate clusters thus ob- try organocopper chemistry is being put tained has indicated that organocup- together into a few major mechanistic rate chemistry represents an intricate 1. Introduction 1 R Cu X The desire to learn about the nature of elements has been R or R1 R and will remain a main concern of chemists. In this review, we R Cu will consider what properties of copper make organocopper R1 chemistry so useful in organic chemistry.
    [Show full text]
  • Mechanistic Considerations on the Hydrodechlorination Process of Polychloroarenes
    Chapter 3 Mechanistic Considerations on the Hydrodechlorination Process of Polychloroarenes YoshiharuYoshiharu Mitoma, Mitoma, Yumi KatayamaYumi Katayama andand CristianCristian Simion Simion Additional information is available at the end of the chapter http://dx.doi.org/10.5772/intechopen.79083 Abstract Defunctionalization of organochlorines through reductive dechlorination (also known as hydrodechlorination—replacement of chlorine atoms by hydrogen—is one of the main methodologies used in the detoxification of these harmful compounds. Most of the pub- lished papers on this particular matter focused on specific reagents, reaction conditions, and mainly result efficiency. Some of the authors were also concerned with reaction -path ways (e.g., the order in which chlorine atoms were removed from a polychlorinated aro- matic substrate—polychlorinated biphenyls, PCBs; polychlorinated dibenzo-p-dioxins, PCDDs; or polychlorinated dibenzofurans, PCDFs). However, the papers that dealt with the investigation of reaction mechanism were rather scarce. This chapter presents the advances made by researchers in understanding, from a mechanistic point of view, the hydrodechlorination process, along with our own assumptions. In doing so, it would be easier to predict the behavior of such compounds in a specific environment, showing more clearly the scope and limitations of each process, depending on the reaction condi- tions and reagents. Keywords: hydrodechlorination, reaction mechanism, metal/hydrogen donor 1. Introduction Most chlorinated and especially polychlorinated arenes (such as polychloro-dibenzo-p-diox- ins 1, polychloro-dibenzofurans 2, or polychlorobiphenyls 3) are persistent organic pollutants (POPs) that are harmful to both man and the environment [1–5]. © 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons © 2018 The Author(s).
    [Show full text]
  • Neutral, Cationic and Anionic Organonickel and -Palladium Complexes Supported by Cite This: Dalton Trans., 2020, 49, 322 Iminophosphine/Phosphinoenaminato Ligands†‡
    Dalton Transactions View Article Online PAPER View Journal | View Issue Neutral, cationic and anionic organonickel and -palladium complexes supported by Cite this: Dalton Trans., 2020, 49, 322 iminophosphine/phosphinoenaminato ligands†‡ Tomás G. Santiago, Carmen Urbaneja, Eleuterio Álvarez, Elena Ávila, Pilar Palma and Juan Cámpora * We report a series of organometallic nickel and palladium complexes containing iminophosphine ligands R2PCH2C(Ph) = N-Dipp (Dipp = 2,6-diisopropylphenyl; R = iPr, La; R = Ph, Lb; and R = o-C6H4OMe, Lc), synthesized by ligand exchange or oxidative addition reactions, and we investigate the capacity of such ligands to undergo reversible deprotonation to the corresponding phosphinoenaminato species. In the attempted ligand exchange reaction of the nickel bis(trimethylsilyl)methyl precursor [Ni(CH2SiMe3)2Py2] with Lb, the iminophosphine acts as a weak acid rather than a neutral ligand, cleaving one of the Ni–C bonds, to afford the phosphinoenaminato complex [Ni(CH2SiMe3)(L’b)(Py)] (L’b = conjugate base of Lb). Creative Commons Attribution-NonCommercial 3.0 Unported Licence. + We disclose a general method for the syntheses of complexes [Ni(CH2SiMe3)(L)(Py)] (L = La, Lb or Lc), and demonstrate that iminophosphine deprotonation is a general feature and occurs reversibly in the coordination sphere of the metal. By studying proton exchange reactions of the cation [Ni(CH2SiMe3)(Lb) (Py)]+ with bases of different strength we show that the conjugate phosphinoenaminato ligand in Received 17th October 2019, [Ni(CH2SiMe3)(L’b)(Py)] is a base with strength comparable to DBU in THF. The acyl group in the function- Accepted 19th November 2019 alized aryl complex [Ni(p-C6H4COCH3)(Br)(La)] does not interfere in the iminophosphine deprotonation with DOI: 10.1039/c9dt04062e − + NaH.
    [Show full text]
  • Title Investigation of Organoiron Catalysis in Kumada‒Tamao‒Corriu-Type Cross-Coupling Reaction Assisted by Solution-Phase X
    Investigation of Organoiron Catalysis in Title Kumada‒Tamao‒Corriu-Type Cross-Coupling Reaction Assisted by Solution-Phase X-ray Absorption Spectroscopy Takaya, Hikaru; Nakajima, Sho; Nakagawa, Naohisa; Isozaki, Katsuhiro; Iwamoto, Takahiro; Imayoshi, Ryuji; Gower, Nicholas J.; Adak, Laksmikanta; Hatakeyama, Takuji; Honma, Author(s) Tetsuo; Takagaki, Masafumi; Sunada, Yusuke; Nagashima, Hideo; Hashizume, Daisuke; Takahashi, Osamu; Nakamura, Masaharu Bulletin of the Chemical Society of Japan (2015), 88(3): 410- Citation 418 Issue Date 2015 URL http://hdl.handle.net/2433/196165 © 2015 The Chemical Society of Japan.; 本文ファイルは出版 社の許可を得て登録しています.; This is not the published Right version. Please cite only the published version.; この論文は出 版社版でありません。引用の際には出版社版をご確認ご 利用ください。 Type Journal Article Textversion author Kyoto University Bull. Chem. Soc. Jpn. in press (doi:10.1246/bcsj.20140376) Graphical Abstract Investigation of Organoiron Catalysis in Kumada–Tamao–Corriu-Type Cross-Coupling Reaction Assisted by Solution-Phase X-ray Absorption Spectroscopy H. Takaya, S. Nakajima, N. Nakagawa, K. Isozaki, T. Iwamoto, R. Imayoshi, N. J. Gower, L. Adak, T. Hatakeyama, T. Honma, M. Takagaki, Y. Sunada, H. Nagashima, D. Hashizume, O. Takahashi, and M. Nakamura Solution-phase molecular structures of organoiron intermediates of Kumada–Tamao–Corriu-type cross-coupling were illuminated by X-ray absorption spectroscopy. The intermediacy of halomesityl iron complex of II II Fe BrMes(SciOPP) and dimesityl iron complex of Fe Mes2(SciOPP) was adequately elucidated with formal non- redox FeII/FeII catalytic cycle. 1 Investigation of Organoiron Catalysis in Kumada–Tamao–Corriu-Type Cross-Coupling Reaction Assisted by Solution-Phase X-ray Absorption Spectroscopy Hikaru Takaya,*a,b Sho Nakajima,a,b Naohisa Nakagawa,a Katsuhiro Isozaki,a,b,g Takahiro Iwamoto,a,b,g Ryuji Imayoshi,a,b Nicholas J.
    [Show full text]
  • X International Conference “Mechanisms of Catalytic Reactions”
    Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia Lomonosov Moscow State University, Moscow, Russia 2016 X International Conference “Mechanisms of Catalytic Reactions” Svetlogorsk, Kaliningrad Region, Russia October 2 - 6, 2016 ABSTRACTS Novosibirsk-2016 Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia Lomonosov Moscow State University, Moscow, Russia X International Conference “Mechanisms of Catalytic Reactions” Svetlogorsk, Kaliningrad Region, Russia October 2 - 6, 2016 ABSTRACTS Novosibirsk-2016 УДК 544.47+66.09 ББК Г544 M45 Mechanisms of Catalytic Reactions. X International Conference (MCR-X). (October 2 - 6, 2016, Svetlogorsk, Kaliningrad Region, Russia) [Electronic resourse]: Book of abstracts / Boreskov Institute of Catalysis SB RAS ed.: prof. V.I. Bukhtiyarov, - Novosibirsk: BIC, 2016. p.328, – 1 electronic optical disc (CD-R). ISBN 978-5-906376-15-2 В надзаг.: Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia Lomonosov Moscow State University, Moscow, Russia Topics of book: – First-principles approach, theory and simulation in catalysis; – Advanced methods for studies of mechanisms of catalyzed reactions; – In-situ and operando studies of model and real catalysts; – Kinetics and reaction intermediates of catalyzed processes; – From mechanistic studies to design of advanced catalyst systems. The Conference is accompanied
    [Show full text]
  • Mechanistic Aspects of the Kharasch Addition Reaction Catalyzed by Organonickel(II)
    Organometallics 1997, 16, 4985-4994 4985 Mechanistic Aspects of the Kharasch Addition Reaction Catalyzed by Organonickel(II) Complexes Containing the Monoanionic Terdentate Aryldiamine Ligand System -† [C6H2(CH2NMe2)2-2,6-R-4] Lucia A. van de Kuil,‡,§ David M. Grove,‡ Robert A. Gossage,‡ Jan W. Zwikker,§ Leonardus W. Jenneskens,§ Wiendelt Drenth,§ and Gerard van Koten*,‡ Debye Institute, Departments of Metal-Mediated Synthesis and Physical Organic Chemistry, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands Received January 28, 1997X The addition reaction of polyhalogenated alkanes to alkenes (Kharasch addition reaction) is homogeneously catalyzed in the absence of O2 under mild reaction conditions (25 °C) by II the arylnickel complexes [Ni {C6H2(CH2NMe2)2-2,6-R-4}Br] (R ) H, MeC(O), Cl, MeO, NH2) and shows a high selectivity for the 1:1 adduct. Kinetic data on the catalytic system with [Ni{C6H3(CH2NMe2)2-2,6}Br] (R ) H; abbreviated as [Ni(NCN)Br]), methyl methacrylate, and CCl4 reveal a rate of reaction that is first order in nickel complex and in alkene. In our series of para-substituted arylnickel catalysts, the rate of catalysis increases with the electron donating character of the para substituents on the aryl ligand and this rate correlates directly with the NiII/NiIII redox potential. These data, together with separate spectroscopic studies and results from individual experiments employing other solvents, other polyhalogenated alkanes such as CBr4 and CF3CCl3 and other alkene substrates such as styrene, 1-octene, and cyclohexene, lead to the proposal of a catalytic cycle based on a nonchain mechanism with a mononuclear nickel species.
    [Show full text]
  • Pp-03-25-New Dots.Qxd 10/23/02 2:41 PM Page 611
    pp-03-25-new dots.qxd 10/23/02 2:41 PM Page 611 NICKEL CARBONATE 611 NICKEL CARBONATE [3333-67-3] Formula: NiCO3; MW 118.72 Two basic carbonates are known. They are 2NiCO3•3Ni(OH)2•4H2O [29863- 10-3], and NiCO3•2Ni(OH)2 [12607-70-4], MW 304.17. The second form occurs in nature as a tetrahydrate, mineral, zaratite. Commercial nickel car- bonate is usually the basic salt, 2NiCO3•3Ni(OH)2•4H2O. Uses Nickel carbonate is used to prepare nickel catalysts and several specialty compounds of nickel. It also is used as a neutralizing agent in nickel plating solutions. Other applications are in coloring glass and in the manufacture of ceramic pigments. Physical Properties NiCO3: Light green rhombohedral crystals; decomposes on heating; practi- cally insoluble in water, 93 mg/L at 25°C; dissolves in acids. 2NiCO3•3Ni(OH)2•4H2O: Light green crystals or brown powder; decom- poses on heating; insoluble in water; decomposes in hot water; soluble in acids and in ammonium salts solutions. Zaratite: Emerald greed cubic crystals; density 2.6 g/cm3; insoluble in water; soluble in ammonia and dilute acids. Thermochemical Properties ∆Ηƒ° (NiCO3) –140.6 kcal/mol Preparation Anhydrous nickel carbonate is produced as a precipitate when calcium car- bonate is heated with a solution of nickel chloride in a sealed tube at 150°C. Alternatively, treating nickel powder with ammonia and carbon dioxide fol- lowed by boiling off ammonia yields pure carbonate. When sodium carbonate is added to a solution of Ni(II) salts, basic nickel carbonate precipitates out in impure form.
    [Show full text]
  • Modern Organonickel Chemistry
    Modern Organonickel Chemistry Edited by Yoshinao Tamaru Modern Organonickel Chemistry Edited by Yoshinao Tamaru Further Titles of Interest A. de Meijere, F. Diederich (Eds.) Metal-Catalyzed Cross-Coupling Reactions, 2nd Ed., 2 Vols. 2004 ISBN 3-527-30518-1 M. Shibasaki, Y. Yamamoto (Eds.) Multimetallic Catalysts in Organic Synthesis 2004 ISBN 3-527-30828-8 M. Beller, C. Bolm (Eds.) Transition Metals for Organic Synthesis, 2nd Ed., 2 Vols. Building Blocks and Fine Chemicals 2004 ISBN 3-527-30613-7 S.-I. Murahashi (Ed.) Ruthenium in Organic Synthesis 2004 ISBN 3-527-30692-7 J.-E. B€aackvall(Ed.) Modern Oxidation Methods 2004 ISBN 3-527-30642-0 Modern Organonickel Chemistry Edited by Yoshinao Tamaru Editor 9 All books published by Wiley-VCH are carefully produced. Nevertheless, authors, Professor Dr. Yoshinao Tamaru editors, and publisher do not warrant the Department of Applied Chemistry information contained in these books, Faculty of Engineering including this book, to be free of errors. Nagasaki University Readers are advised to keep in mind that 1-14 Bunkyo-machi statements, data, illustrations, procedural Nagasaki 852-8521 details or other items may inadvertently be Japan inaccurate. Library of Congress Card No.: Applied for Cover Picture British Library Cataloging-in-Publication The front cover is showing a Kabuki actor Data: A catalogue record for this book is dressed like a devil, drawn by Sharaku. available from the British Library. Nickel was first isolated in 1751 from an ore referred to as ‘‘devil Nick copper’’. Bibliographic information published by Die Miners named the ore in that way because Deutsche Bibliothek it resembled copper ore, but did not yield Die Deutsche Bibliothek lists this their objective copper.
    [Show full text]
  • REVIEW Methyl Complexes of the Transition Metals
    REVIEW Methyl Complexes of the Transition Metals Jesús Campos,[b] Joaquín López-Serrano,[a] Riccardo Peloso,[a] and Ernesto Carmona*[a] Dedicated to Prof. Pierre Braunstein in recognition of his contributions to inorganic and organometallic chemistry [a] Title(s), Initial(s), Surname(s) of Author(s) including Corresponding Author(s) Department Institution Address 1 E-mail: [b] Title(s), Initial(s), Surname(s) of Author(s) Department Institution Address 2 Supporting information for this article is given via a link at the end of the document.((Please delete this text if not appropriate)) REVIEW Abstract: Organometallic chemistry can be considered as a wide focusing in the last 5 years. It begins with a brief description of area of knowledge that combines concepts of classic organic synthetic methods, followed by a selection of recently reported chemistry, i.e. based essentially on carbon, with molecular inorganic complexes with terminal and bridging methyl ligands from the chemistry, especially with coordination compounds. Transition metal groups 3 to 11 of the periodic table. A specific section is methyl complexes probably represent the simplest and most dedicated to methyl-bridged species with three-centre two- fundamental way to view how these two major areas of chemistry electron bonds. The review concludes highlighting relevant combine and merge into novel species with intriguing features in reactivity of the methyl group in this class of compounds. terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition metal complexes containing Ernesto Carmona (PhD degree, University M—CH3 fragments.
    [Show full text]
  • Provisional Guidance on Use of Chemical Categories
    Nickel compounds – a category approach for metals in EU legislation Jim Hart, Consultant prepared on behalf of the Danish Environmental Protection Agency January 2008 PREFACE: This report was commissioned by the Danish EPA, and describes the use of a categories approach to the classification and labelling of a group of nickel compounds. The Danish EPA is the Rapporteur for the risk assessment of nickel and four nickel compounds (nickel sulphate, nickel dichloride, nickel dinitrate and nickel carbonate) under the EU Existing Chemicals Regulation (EEC) 793/93. Part of this work included data collection and evaluation of a number of other nickel compounds such as the nickel oxides and sulphides. As a result of this work, classification and labelling proposals for the five nickel compounds evaluated under the EU Existing Chemicals Regulation have been prepared by the Danish EPA, and, after discussion in the EU Technical Committee for Classification and Labelling, new and revised entries for the five compounds have been included in Annex I to Directive 67/548/EEC (List of Dangerous Substances), which was adopted by a Technical Progress Committee in February 2007 as part of the 30th Adaptation to Technical Progress of the Directive (ECB, 2007a). In addition, proposals for updating the existing entries for some of the other nickel compounds in Annex I to Directive 67/548/EEC (nickel hydroxide, nickel oxides and nickel sulphides) were also prepared by the Danish EPA, and agreed by the EU Technical Committee for Classification and Labelling for inclusion in the 31st Adaptation to Technical Progress of the Directive. Based on the agreed classification for these individual substances, the Danish EPA then prepared a classification proposal covering more than 100 nickel compounds.
    [Show full text]
  • A Review of Catalytic Approaches to Waste Minimization: Case Study
    Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 80:1211–1222 (2005) DOI: 10.1002/jctb.1325 Review A review of catalytic approaches to waste minimization: case study—liquid-phase catalytic treatment of chlorophenols Mark A Keane∗ Department of Chemical and Materials Engineering, University of Kentucky, Lexington, KY 40506-0046, USA Abstract: Effective waste management must address waste reduction, reuse, recovery/recycle and, as the least progressive option, waste treatment. Catalysis can serve as an integral green processing tool, ensuring lower operating pressures/temperatures with a reduction in energy requirements while providing alternative cleaner synthesis routes and facilitating waste conversion to reusable material. The case study chosen to illustrate the role that catalysis has to play in waste minimization deals with the conversion of toxic chlorophenols in wastewater. The presence of chloro-organic emissions is of increasing concern with mounting evidence of adverse ecological and public health impacts. A critical overview of the existing treatment technologies is provided with an analysis of the available literature on catalytic dechlorination. The efficacy of Pd/Al2O3 to promote the hydrogen-mediated dechlorination of mono- and dichlorophenols is demonstrated, taking account of both the physical and chemical contributions in this three-phase (solid catalyst and liquid/gaseous reactants) system. Hydrodechlorination activity and selectivity trends are discussed in terms of chloro-isomer structure, the influence of temperature is discussed, the role of base (NaOH) addition is examined and the feasibility of catalyst reuse is addressed. 2005 Society of Chemical Industry Keywords: waste minimization; chlorophenols; catalytic hydrodechlorination; palladium on alumina; detoxification; recycle INTRODUCTION: CATALYSIS AND WASTE management—disposal only comes into play when MINIMIZATION all possible reduction/reuse/recycle/treatment options It is now accepted that a progressive approach to have been exhausted.
    [Show full text]
  • Synthesis and Reactivity of Transition Metal Complexes Supported by Oxazolinyl Borato Ligands and the Functionalization of Silica Surface
    Iowa State University Capstones, Theses and Graduate Theses and Dissertations Dissertations 2020 Synthesis and reactivity of transition metal complexes supported by oxazolinyl borato ligands and the functionalization of silica surface Abhranil Biswas Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/etd Recommended Citation Biswas, Abhranil, "Synthesis and reactivity of transition metal complexes supported by oxazolinyl borato ligands and the functionalization of silica surface" (2020). Graduate Theses and Dissertations. 17825. https://lib.dr.iastate.edu/etd/17825 This Thesis is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Synthesis and reactivity of transition metal complexes supported by oxazolinyl borato ligands and the functionalization of silica surface by Abhranil Biswas A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Organic Chemistry Program of Study Committee: Aaron D Sadow, Major Professor Marek Pruski Igor I. Slowing Levi M. Stanley Wenyu Huang The student author, whose presentation of the scholarship herein was approved by the program of study committee, is solely responsible for the content of this dissertation. The Graduate College will ensure this dissertation is globally accessible and will not permit alterations after a degree is conferred. Iowa State University Ames, Iowa 2020 Copyright © Abhranil Biswas, 2020. All rights reserved. ii DEDICATION To my family and friends iii TABLE OF CONTENTS Page DEDICATION ...............................................................................................................................
    [Show full text]