557-20-0Relevant articles and documents
ZINC ENOLATES: C- OR O-METALLATION?
Dekker, Jan,Schouten, Abraham,Budzelaar, Peter H. M.,Boersma, Jaap,Van Der Kerk, Gerrit J. M.,et al.
, p. 1 - 12 (1987)
Two methods have been used for the generation of zinc enolates: the reaction of EtZnOMe with enol acetates, and that of lithium enolates with zinc chloride.Most of the zinc compounds prepared proved to be very reactive towards carbonyl functions, and so they cannot be isolated from the EtZnOMe/enol acetate system.The final products of these reactions are polymerisation and self-condensation products and β-diketonates, the latter being formed by condensation reactions of the zinc enolates with an acetate molecule.The structure of 2 HPac=pivaloylacetone, (CH3)3CCOCH2COCH3), isolated in 20percent yield from the reaction of EtZnOMe with CH3COOC(t-Bu)=CH2, was determined by X-ray diffraction analysis.The compound forms monoclinic crystals, space group P21/c, with two dimers in a cell of dimensions a 11.677(4), b 18.299(9) and c 12.719(5) Angstroem and β 117.26(3) deg.The structure closely resembles that of the known complex 2.The complications involving reactions of zinc enolates with enol acetates were avoided by treating lithium enolates with zinc chloride.Polimeryzation and self-condensation could be prevented by using the very bulky enolate LiOC(t-Bu)=CMe2.In this way, the corresponding stable zinc enolate RZnCl*THF was obtained as a dissociating dimer.No replacement of the second chlorine atom by an enolate group occurred even when a large excess of lithium enolate was used.The reactivity of the zinc enolates suggest that they contain both zinc-carbon and zinc-oxygen bonds.They are assumed to have a cyclic structure which resembles that of the Reformatsky reagent.
ULTRASONIC IRRADIATION IN ONE-POT SYNTHESIS OF TRIETHYLALUMINUM ETHERATE AND ITS CONVERSION INTO OTHER ORGANOMETALLIC COMPOUNDS
Lin, Yih-tsung
, p. 277 - 284 (1986)
A mixture of ethyl bromide, aluminum and magnesium powders was irradiated with ultrasound and ethylaluminum sesquibromide(I) formed at room temperature.As soon as diethyl ether was introduced into the reaction medium, ethylmagnesium bromide(II) was formed in situ and subsequently treated with I to give the etherate of triethylaluminum (III, TEA * OEt2) in satisfactory yield (82percent) and purity (98percent).III, thus obtained, could react with triethyl borate or zinc chloride to give triethylborane (90percent) and diethylzinc (82percent) respectively.
Novel hexanuclear and octanuclear zinc alkyl cages derived from a bis-oxamidate ligand
Rufino-Felipe, Ernesto,Caballero-Jiménez, Judith,Guerrero-Ramírez, Luis-Guillermo,Flores-álamo, Marcos,Mu?oz-Hernández, Miguel-ángel
, p. 107 - 110 (2016)
1 and 2 were prepared by coordination self-assembly from reacting N,N′-bis(3,5-di-tert-buthyl-2-phenol)oxamide (L-H4) with ZnEt2 in toluene and THF, respectively. The molecular X-ray structures show 1 as an octanuclear Zn8 cage and 2 as a hexanuclear Zn6 cage. The nuclearity of these cages is driven by the solvent, in fact 1 gives 2 upon addition of THF. Good polymer conversions for the ROP of rac-lactide were achieved by using 1 and 2 with alcohols as co-catalysts.
Dinuclear Zinc-AzePhenol Catalyzed Asymmetric Aza-Henry Reaction of N-Boc Imines and Nitroalkanes under Ambient Conditions
Liu, Shanshan,Gao, Wen-Chao,Miao, Yu-Hang,Wang, Min-Can
, p. 2652 - 2659 (2019/02/26)
The asymmetric aza-Henry reaction of N-Boc imines and nitroalkanes was realized in the presence of 10 mol % dinuclear zinc-AzePhenol catalysts under ambient conditions. A variety of nitroamines were obtained in good yields (up to 97%) with excellent enantioselectivities (up to 99% ee) and high diasteroselectivity (up to 14:1 dr). Our protocol combined the operational simplicity and mild reaction conditions, thus making the process amenable for technical applications.
Iron-catalyzed chain growth of ethylene: In situ regeneration of ZnEt2 by tandem catalysis
Cariou, Renan,Shabaker, John W.
, p. 4363 - 4367 (2015/11/11)
A dual catalyst system to implement in situ regeneration of ZnEt2, the Chain Transfer Agent (CTA) in Catalyzed Chain Growth of ethylene (CCG), has been demonstrated. As in typical CCG systems, an Fe homogeneous catalyst is used to grow oligomeric chains that transfer rapidly to ZnEt2. However, rather than liberating alkane products and destroying the expensive chain transfer agent via acid hydrolysis workup, a second Fe-alkyl catalyst, (BiPy)2FeEt2, has been introduced to regenerate ZnEt2 via ethyl/alkyl exchange and liberate the oligomer chains as α-olefins via ss-hydride elimination. This improvement reduces the ZnEt2 loading and leaves the chain growth catalyst competent, in contrast to Ni(acac)2 shown to be unsuitable for in situ tandem catalysis. These findings greatly enhance the industrial viability of the chemistry.
The continuous reaction device and method of using the continuous composite (by machine translation)
-
Paragraph 0184, (2017/01/02)
PROBLEM TO BE SOLVED: compounds with high productivity can be generated. SOLUTION: 1 the raw material supply section 12 and a first, a second and 2 the raw material supply section 14, and a reaction part 18, the first reaction part 1 from the raw material supply section 1 and a second quantity of raw material, the raw material supply section 2 from the first reaction part 2 and a second quantity of raw material, the raw material supply section 1 from the first reaction part 1 and a second temperature of the raw material, the raw material supply section 2 from the first reaction part 2 and supplied to the temperature of the raw material, and having a control part 22, a continuous reaction device as shown in the drawing. Selected drawing: fig. 1 (by machine translation)
Efficient access to 3-substituted-γ-hydroxylactams: The uncatalyzed addition of diorganozinc reagents to cyclic imides with heterocyclic substitution
Deglopper, Kimberly S.,Dennis, Joseph M.,Johnson, Jeffrey B.
supporting information, p. 1843 - 1845 (2014/03/21)
A range of 3-substituted-γ-hydroxylactams have been prepared via the uncatalyzed addition of organozinc nucleophiles to cyclic imides. This reactivity is primarily limited to imides containing heterocyclic N-substitution, but proceeds efficiently with a variety of diorganozinc reagents, including those prepared and utilized without purification, as well as organozinc halides. It is hypothesized that the presence of a Lewis basic directing group is required for optimum reactivity.
Solvent dependence of the structure of ethylzinc acetate and its application in CO2/epoxide copolymerization
Orchard, Katherine L.,Harris, Jonathan E.,White, Andrew J. P.,Shaffer, Milo S. P.,Williams, Charlotte K.
, p. 2223 - 2229 (2011/05/11)
NMR and single-crystal X-ray diffraction experiments indicate that the ligand stoichiometry of the complexes formed from the reaction between zinc bis(acetate) and diethylzinc depends on the nature of the solvent (coordinating vs noncoordinating) and that the strength of the donor interaction of a coordinating solvent (THF vs pyridine) affects the nuclearity of the complex's repeat unit in the solid state. The complexes are active catalysts for the copolymerization of cyclohexene oxide and CO2, under mild conditions.
METHOD FOR MANUFACTURING DIALKYL ZINC AND DIALKYL ALUMINUM MONOHALIDE
-
Page/Page column 8, (2011/02/25)
Disclosed is a manufacturing method for dialkyl zinc and dialkyl aluminum monohalide that makes it possible to efficiently manufacture both dialkyl zinc and dialkyl aluminum monohalide of high purity and at a high yield on an industrial scale with a single reaction from zinc chloride and trialkyl aluminum starting materials, while suppressing the production of precipitates in the reaction process and suppressing the adhesion of precipitates to the equipment and the admixture thereof into the product. The manufacturing method for dialkyl zinc and dialkyl aluminum monohalide is a dialkyl zinc and dialkyl aluminum monohalide manufacturing method that causes a reaction between zinc chloride and trialkyl aluminum, and uses trialkyl aluminum with a hydride concentration of 0.01 mass% to 0.10 mass%. Dialkyl zinc that contains essentially no aluminum is separated from the reactants, and then dialkyl aluminum monohalide that contains essentially no zinc is separated.
METHODS FOR PREPARING DIORGANOZINC COMPOUNDS
-
Page/Page column 15-16; 17; 18-21; 23, (2009/01/20)
There are provided methods for preparing the diorganozmc compounds of formula R2Zn (I or Ia), where R is a defined organic radical, and the two R groups can be the same or different The starting material is the zinc compound ZnX2 (II) or R2ZnX (IIa), where X is a defined anion and R2 is a defined organic radical. The zinc reagent of type II is combined with a Grignard reagent and also, when X is Cl or Br, with an alkali metal reagent (VI) to form the diorganozinc product (I or Ia). Also provided are methods for preparing the zinc alcoholates of formula Zn(OR1)2 by reaction of ZnX2, where X = Cl or Br, with an alkali metal reagent of the formula MOR1, where M = Na or K, and where R1 is a defined organic radical.
