- Technological method for preparation of allyl ether compounds
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The invention discloses a technological method for preparation of allyl ether compounds; the technological method can obtain the high-purity allyl ether compounds in low cost and high yield, has the advantages of high selectivity of the allyl ether compounds, less side reaction, easy separation and purification of the products, friendly technological process environment and the like, and is suitable for large-scale industrialized production.
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Paragraph 0053-0055
(2017/02/17)
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- Hydrogen-bond-activated palladium-catalyzed allylic alkylation via allylic alkyl ethers: Challenging leaving groups
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C-O bond cleavage of allylic alkyl ether was realized in a Pd-catalyzed hydrogen-bond-activated allylic alkylation using only alcohol solvents. This procedure does not require any additives and proceeds with high regioselectivity. The applicability of this transformation to a variety of functionalized allylic ether substrates was also investigated. Furthermore, this methodology can be easily extended to the asymmetric synthesis of enantiopure products (99% ee).
- Huo, Xiaohong,Quan, Mao,Yang, Guoqiang,Zhao, Xiaohu,Liu, Delong,Liu, Yangang,Zhang, Wanbin
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supporting information
p. 1570 - 1573
(2014/04/17)
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- Catalytic alkylation of alcohols to liquid ethers and organic compounds to alkylated products
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A catalytic process is taught for non-oxidative alkylation of organic compounds, comprising alcohols, alkanes, glycols, ethers, aldehydes, ketones, carboxylic acids, esters, amines, thiols or phosphines, by alkyl groups produced from alcohols or glycols, forming products comprising ethers and other higher molecular weight alkylated compounds. The process is conducted at a reflux temperature below 200° C. in the presence of an acid, alkali or neutral salt dehydrating agent comprising sulfuric acid, phosphoric acid or their salts, lime or anhydrous calcium sulfate in the absence of zero valent metals and air. Specifically, this catalytic process converts ethanol to ethyl butyl ethers, ethyl hexyl ethers and dibutyl ethers or oxygenated gasoline as well as amines comprising n-butyl amine plus butanol to dibutyl amine and butyl hexyl amines at ambient pressure. This same catalytic alkylation chemistry, which does not constitute a condensation reaction, alkylates 4-hydroxybenzoic acid using ethanol to 4-ethoxyethylbenzoic acid products.
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Paragraph 0031
(2013/08/15)
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- Rate and product studies on the solvolyses of allyl chloroformate
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The solvolysis rate constants of allyl chloroformate (CH 2=CHCH2OCOCl, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with the sensitivity values of 0.93 ± 0.05 and 0.41 ± 0.02 for l and m, respectively. These l and m values can be considered to support a S N2 reaction pathway. The activation enthalpies (ΔH≠) were 12.5 to 13.4 kcal·mol-1 and the activation entropies (ΔS≠) were -34.4 to -37.3 cal·mol-1·K -1, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, kMeOH/k MeOD) of 2.16 was also in accord with the SN2 mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.
- Koh, Han Joong,Kang, Suk Jin
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p. 4117 - 4121
(2013/08/23)
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- Scope of the allylation reaction with [RuCp(PP)]+ catalysts: Changing the nucleophile or allylic alcohol
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The scope of the dehydrative allylation reaction using allyl alcohol as allyl donor with [RuCp(PP)]+ complexes as catalysts is explored. Aliphatic alcohols are successfully allylated with allyl alcohol or diallyl ether, obtaining high selectivity for the alkyl allyl ether. The reactivity of aliphatic alcohols is in the order of primary > secondary tertiary. The tertiary alcohol 1-adamantanol reacts extremely slowly in the absence of strong acid, but when HOTs is added, reasonable yields of 1-adamantyl allyl ether are obtained. The alkyl allyl ether is found to be the thermodynamically favored product over diallyl ether. Apart from alcohols, thiols and indole are also efficiently allylated, while aniline acts as a catalyst inhibitor. Allylation reactions with various substituted allylic alcohols give products with retention of the substitution pattern. It is proposed that a Ru(IV) σ-allyl species plays a key role in the mechanism of these allylation reactions.
- Van Rijn, Jimmy A.,Guijt, Marieke C.,De Vries, Dwight,Bouwman, Elisabeth,Drent, Eite
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experimental part
p. 212 - 219
(2012/04/17)
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- Copper(I)-olefin complexes: The effect of the trispyrazolylborate ancillary ligand in structure and reactivity
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The spectroscopic and structural characteristics and the relative reactivity of several TpMsCu(olefin) (olefin = ethylene, 1, 1-hexene, 2, allyl ethyl ether, aee, 3, cyclohexene, 4, and styrene, 5) complexes bearing the bulky hydrotris(3-mesitylpyrazolyl)borate ligand have been examined. Experimental data, including an unusual high-field chemical shift in the 1H and 13C NMR spectra, and DFT theoretical calculations support the proposal that the copper-olefin linkage is mainly sustained by σ-donation, lacking a substantial degree of π-back-donation.
- Martin, Carmen,Munoz-Molina, Jose Maria,Locati, Abel,Alvarez, Eleuterio,Maseras, Feliu,Belderrain, Tomas R.,Perez, Pedro J.
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experimental part
p. 3481 - 3489
(2010/10/04)
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- Catalytic conversion of liquid alcohols and other reactants to products
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Catalyst based reactions are taught for non-oxidative chemical conversion of liquid alcohols to higher boiling alcohols, ethers, glycol ethers and related products, comprising ethanol to butanol, propanols to hexanols, butanols to octanols, and others at ambient pressure. This same catalytic chemistry also converts substituted organic compounds comprising amines, ketones, ethers and other substituted organic compounds possessing at least one active hydrogen to related higher molecular weight products in the absence of air. The catalysts are based on selected transition metal complexes possessing a degree of symmetry. Laboratory results have demonstrated [chromium(II)]2, [cobalt(II)]2, [vanadium(II)]2 and similar families of catalysts to be effective for non-oxidative catalytic conversion of substituted organic compounds to products comprising related higher molecular weight compounds in good yields in the absence of air, at modest temperatures and ambient pressure.
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Page/Page column 4-5
(2008/06/13)
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- The tris(trimethylsilyl)silane/thiol reducing system: A tool for measuring rate constants for reactions of carbon-centered radicals with thiols
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An extension of the well-known 'free-radical-clock' methodology is described that allows one to determine the rate constants of carbon-centered radicals with a variety of thiols by using the tris(trime-thylsilyl)silane/thiol couple as a reducing system. A
- Chatgilialoglu, Chryssostomos
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p. 2387 - 2398
(2007/10/03)
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- Reaction network of aldehyde hydrogenation over sulfided Ni-Mo/Al 2O3 catalysts
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A reaction network of aldehyde hydrogenation over NiMoS/Al 2O3 catalysts was studied with aldehydes with straight and branched carbon chains and different chain lengths as feed materials. The reactions in the gas phase and the liquid phase were compared. The main reaction in the aldehyde hydrogenation process is the hydrogenation of the CO double bond, which takes place over the coordinatively unsaturated sites. The major side reactions are self-condensation of aldehydes and condensation of aldehydes with alcohols. Both reactions involve α-hydrogen and are primarily catalyzed by acid-base bifunctional sites over the exposed Al2O 3 surfaces.
- Wang, Xueqin,Saleh, Ramzi Y.,Ozkan, Umit S.
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- Halide-Free Dehydrative Allylation Using Allylic Alcohols Promoted by a Palladium-Triphenyl Phosphite Catalyst
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The triphenyl phosphite-palladium complex was found to effect catalytic substitution reactions of allylic alcohols via a direct C-O bond cleavage. The dehydrative etherification proceeded efficiently without any cocatalysts and bases to give allylic ethers in good to excellent yields.
- Kayaki, Yoshihito,Koda, Takashi,Ikariya, Takao
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p. 2595 - 2597
(2007/10/03)
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- The carbonylation of allylic halides and prop-2-en-1-ol catalysed by triethylphosphine complexes of rhodium
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In ethanol, [RhX(CO)(PEt3)2] added directly or formed in situ from [Rh2(OAc)4]·2MeOH (OAc = O2CMe) and PEt3 or [Rh(OAc)(CO)(PEt3)2] catalysed the carbonylation of CH2=CHCH2X (X = Cl, Br or I) to ethyl but-3-enoate with CH2=CHCH2OEt as a side product. Small amounts of the isomerisation product, ethyl but-2-enoate were produced but no base was required for the reaction. The selectivity of the reaction is in the order Cl > Br > I and prop-2-en-1-ol can be successfully carbonylated to prop-2-enyl but-3-enoate by the same system using 3-chloroprop-1-ene as a promoter. 3-Fluoropropene was not carbonylated, but in the presence of H2 underwent hydroformylation to produce acetals. 3-Chlorobut-1-ene and 1-chlorobut-2-ene both produced ethyl pent-3-enoate and 3-ethoxybut-1-ene. In situ and ex situ NMR and IR spectroscopic studies have been used to show that the first step of the reaction is oxidative addition to give [Rh(CH2CH=CH2)Cl2(CO)(PEt3) 2] for which thermodynamic parameters have been obtained. Both 3-chlorobut-1-ene and 1-chlorobut-2-ene give [Rh(CH2CH=CHMe)Cl2-(CO)(PEt3)2] but with different E:Z ratios. The detailed mechanism of the oxidative addition is discussed. The CO inserts into the Rh-C bond to give [Rh(COCH2CH=CH2)Cl2(CO)(PEt3) 2], from which but-3-enoyl chloride reductively eliminates to react with ethanol to give the observed products. High-pressure IR and high-pressure NMR studies reveal that [RhX(CO)(PEt3)2] (X = Cl or Br) reacts with CO to give [RhX(CO)2(PEt3)2], which exists as two isomeric forms. The compound [Rh(OAc)(CO)(PEt3)2] catalyses the formation of prop-2-enyl ethanoate from 1-chloroprop-2-ene and sodium ethanoate. A mechanism is proposed.
- Payne, Marc J.,Cole-Hamilton, David J.
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p. 3167 - 3175
(2007/10/03)
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- Hydrolysis and Alcoholysis of Esters of o-Nitrobenzenesulfonic Acid
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The rate of solvolysis of esters of o-nitrobenzenesulfonic acid with water and C1-C4 alcohols is satisfactorily described by two-parametric Hammett-Taft equation with predominating effect of the electronic factor σ*. The effect of the structure of the hydrocarbon rest in the sulfonic ester group does not fit to this relationship.
- Sendega,Makitra,Pirig
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p. 1438 - 1446
(2007/10/03)
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- Synthesis of benzyl/allyl alkyl ethers from corresponding magnesium alkoxides
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In the presence of iodine, alcohols react with magnesium to produce magnesium alkoxides which are then treated with benzyl chloride or allyl bromide to produce benzyl alkyl ethers or allyl alkyl ethers.
- Lin, Ji-Mao,Li, Hui-Hui,Zhou, Ai-Min
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p. 5159 - 5160
(2007/10/03)
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- Carbonylation of Organic Halides catalysed by Rhodium Triethylphosphine Complexes
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Allyl and benzyl halides but not phenyl or propyl halides have been carbonylated in ethanol in the presence of rhodium triethylphosphine complexes to their respective butenoic or benzylic esters; no added base was required.
- Simpson, Michael C.,Payne, Marc J.,Cole-Hamilton, David J.
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p. 2899 - 2900
(2007/10/02)
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- Unimolecular Reactions of Isolated Organic Ions: Loss of Carbon Monoxide from the Oxonium Ion CH2=CHCH2+O=CH2 via Double Hydrogen Transfer
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The reactions of the metastable oxonium ion CH2=CHCH2+O=CH2 have been investigated.This C4H7O+ species was generated by ionisation and alkyl radical loss from allyl ethyl or allyl propyl ether.CH2=CHCH2+O=CH2 is apparently ideally suited to fragmentation via simple cleavage to form the favourable products CH2=CHCH2+ and CH2O.However, at low internal energies, expulsion of a neutral species having a mass of 28 amu takes place essentially to the exclusion of CH2O loss. 2H- and 13C-labelling experiments reveal that it is carbon monoxide which is eliminated, via double hydrogen transfer between the developing products accessible to C-O bond fission.The role of ion-neutral complexes in these hydrogen transfer steps is discussed.
- Bowen, Richard D.,Wright, Andrew D.,Derrick, Peter J.
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p. 501 - 507
(2007/10/02)
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- Relative Thermodynamic Stabilities of Isomeric Alkyl Allyl and Alkyl (Z)-Propenyl Ethers
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The relative thermodynamic stabilities of ten allyl ethers (ROCH2CH=CH2) and the corresponding isomeric (Z)-propenyl ethers (where R is an alkyl group, or a methoxysubstituted alkyl group) have been determined by chemical equilibration in DMSO solution with t-BuOK as catalyst.From the variation of the equilibrium constant with temperature, the values of the thermodynamic parameters ΔG, ΔH and ΔS of isomerization at 298.15 K were evaluated.The propenyl ethers are highly favored at equilibrium, the values of both ΔG and ΔH for the allyl -> propenyl reaction being ca. -18 to 25 kJ mol-1.The favor of the propenyl ethers is increased by bulky alkyl substituents, and decreased by methoxysubstituted alkyl groups.In most cases the entropy contribution is negligible; however, for R=(MeO)2CH and R=(MeO)3C the values of ΔS are ca. -5 J K-1 mol1-.
- Taskinen, Esko
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p. 11389 - 11394
(2007/10/02)
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- CHEMISTRY OF SYSTEMS OF THE ALLYL TYPE I. SYNTHESIS OF ALLYL AND 2-PROPYNYL ETHERS UNDER PHASE-TRANSFER CATALYSIS CONDITIONS
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A convenient method was developed for the synthesis of allyl and 2-propynyl ethers under phase-transfer catalysis conditions, which make it possible to dispense with the use of an inert organic solvent and to ensure the practically complete conversion of the alkylating agent.
- Ibragimov, I. I.,Tarasov, V. A.,Aliev, A. G.,Belyaeva, V. I.
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p. 1398 - 1402
(2007/10/02)
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- γ-Ray-induced reduction of sterically hindered alkyl carboxylates with trichlorosilane in the presence of hydrogen chloride. Two-step mechanism for the formation of alkanes via the alkyl chloride
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γ-Irradiation of a mixture of 1-adamantyl acetate and trichlorosilane (TCS) in the presence of hydrogen chloride yields adamantane. The first step of this reaction entails cleavage of the alkyloxygen bond by the action of HCl and TCS to give the alkyl chloride. The chloride, in the second step, is dechlorinated by TCS by a known, free-radical mechanism. t-Amyl and benzyl acetates react analogously to 1-adamantyl acetate in this system to give isopentane and toluene, whereas other primary and secondary alkyl derivatives produce the corresponding dialkyl ethers by a known, free-radical mechanism.
- Oka, Kunio,Nakao, Ren
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- Carbonylation of allylic ethers to esters
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A method is disclosed for the production of esters by reaction of an allylic ether with carbon monoxide in the presence of a catalytically effective amount of a Group VIII noble metal catalyst and halide compound to obtain esters. The halide compound is present in an amount sufficient to prevent the catalyst from being converted into a Group VIII metal during the reaction. When the reaction is conducted in the presence of a quaternary ammonium salt the ester may be extracted by solvent extraction to minimize catalyst decomposition caused when extractive distillation is used to separate the ester.
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- SYNTHESE D'ETHERS ET DE THIOETHERS ALLYLIQUES FLUORES PAR CATALYSE PAR TRANSFERT DE PHASE
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Several fluorinated allylic ethers, thioethers and diethers have been prepared in excellent yields by phase transfer catalysis (CTP).The used halogenated compounds are allyl chloride and bromide, p-chloromethylstyrene.The used fluorinated alcohols are aromatic pentafluorophenol and various aliphatics: CF3-CH2OH, CF2H-CF2-CH2-OH, ClCF2-CF2-CH2OH, C6F13C2H4OH, HO-CH2-CF2-CFCl-CF2-CH2OH and HO-C6H4-C(CF3)2-C6H4-OH.All these new compounds have been characterized by 1H and 13C NMR.We conclude that CTP is the best method to obtain allylic and diallylic compounds.
- Boutevin, B.,Youssef, B.,Boileau, S.,Garnault, A. M.
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p. 399 - 410
(2007/10/02)
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- Iodine(III)-Mediated Allylaton of Aromatic Compounds and Alcohols Using Allylmetal (Group IVb) Compounds
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The reaction of allylmetal (group IVb) compounds with aromatic compounds and iodosylbenzene in the presence of BF3-Et2O afforded the corresponding allylation products.Allylation of alcohols was also carried out to give allyl ethers.The activation of iodosylbenzene by the coordination of BF3-Et2O was assumed to be one of the most important factors for the reaction.The involvement of the reactive allyliodine(III) compounds in these reactions is discussed.Keywords - hypervalent organoiodine compound, iodosylbenzene; allylsilane; allylgermane; allylstannane; allyliodine(III) compound
- Ochiai, Masahito,Fujita, Eiichi,Arimoto, Masao,Yamaguchi, Hideo
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- Solvolysis of Allyl Arenesulfonates. Cautionary Comments concerning the NOTs Scale of Solvent Nucleophilicities
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The rates of solvolysis of five allyl arenesulfonates are analysed in terms of the extended Grunwald-Winstein equation.The l values are constant but the m values decrease slightly as the nucleofugality of the leaving group increases.The solvent nucleophilicity (NOTs) values presently available in the literature are based upon a m value for methyl p-toluenesulfonate (tosylate) solvolysis of 0.3; it is demonstrated that a value of 0.55 is more appropriate.The previously reported l values and correlation coefficients for tosylate ester solvolyses are accurate and the "ap parent" sensitivities to solvent ionizing power (m values) are easily corrected.However, for use in conjunction with solvent ionizing power scales for other leaving groups, NTs values based on the appropriate m value or, alternatively, NEt3O+%& values (based on triethyloxonium ion solvolysis) are required.
- Kevill, Dennis N.,Rissmann, Thomas J.
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p. 3062 - 3064
(2007/10/02)
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- Thallium(III)-Mediated Allylation of Alcohols and Carboxylic Acids: Umpolung of Reactivity of Allylmetal (Group IVb) Compounds
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A new general method for the synthesis of allyl ethers and allyl acetates is described.Allylmetal (group IVb) compounds, on treatment with thallium(III) salts in alcohols or acetic acid, gave the corresponding allyl ethers or allyl acetates in good yields.The reaction was successfully applied to the synthesis of the 6-membered cyclic ether 20 via the intramolecular, thallium(III)-mediated allylation reaction of the allylsilane 18.Keywords - allyl ether; allyl acetate; thallium(III) salt; allylsilane; allylstannane; intramolecular cyclization; umpolung
- Ochiai, Masahito,Fujita, Eiichi,Arimoto, Masao,Yamaguchi, Hideo
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p. 5027 - 5030
(2007/10/02)
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- CORRELATION OF THE RATES OF SOLVOLYSIS OF ALLYL AND BENZYL ARENESULPHONATES
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Analysis of the specific rates of solvolysis of allyl arenesulphonates in terms of the extended Grunwald-Winstein equation indicates a marked dependence on both the solvent nucleophilicity (high/value) and the solvent ionizing power (high m value).As the charge delocalization in the leaving group increases, both l and m values fall.For allyl toluene-p-sulphonate solvolysis in 28 solvents at 50.0 deg C, values for l(0.83) and for m (0.63), based on the use of NKL and Y values, are very similar to the equivalent values of 0.90 and 0.67 previously reported for benzyl toluene-p-sulphonate solvolysis.Related extended Grunwald-Winstein analyses are considered and the need for variety in the choice of solvents is emphasized.
- Kevill, Dennis N.,Rissmann, Thomas J.
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p. 717 - 720
(2007/10/02)
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- Organic Tellurium and Selenium Chemistry. Reduction of Tellurides, Selenides, and Selenoacetals with Triphenyltin Hydride
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Preparative and mechanistic details are described for the conversion of selenides into hydrocarbons RH> by heating with triphenyltin hydride at about 120 deg C.The process has been extended to selenoacetals in a form that constitutes a reduction methods for carbonyl compounds RR'C(SePh)2 -> RR'CH2>.Selective reduction of selenoacetals in the presence of thioacetals is possible.Cold-labeled species can be prepared by using triphenyltin deuteride.Tellurides are available easily without problems arising from exposure to air provided that the work is done in a photographic darkroom equipped with a red safety light.These tellurides, as well as the corresponding dichlorides , are reduced under very mild conditions (25-80 deg C) by triphenyltin hydride.The selenium- and tellurium-based chemistry has been used for the unusual process of reducing an epoxide in the presence of a ketone carbonyl.
- Clive, Derrick L. J.,Chittattu, Gim J.,Farina, Vittorio,Kiel, William A.,Menchen, Steven M.,et al.
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p. 4438 - 4447
(2007/10/02)
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