- Supported complexes of cupric chloride with DMF as catalysts in the reaction of CCl4 with n-decane
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The complex of cupric chloride with DMF immobilized on the surface of silica gel exhibits high catalytic activity in the reaction of tetrachloromethane with n-decane. The fact that the reaction is inhibited by phenols and oxygen implies that it occurs by
- Golubeva,Nevskaya,Vorontsov,Abdrashitov
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- Continuous flow synthesis of n-alkyl chlorides in a high-temperature microreactor environment
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Applying continuous flow processing in a high-temperature/high-pressure regime, n-alkyl chlorides can be prepared in high yields and selectivity by direct uncatalyzed chlorodehydroxylation of the corresponding n-alcohols with 30% aqueous hydrochloric acid. Optimum conditions for the preparation of n-butyl and n-hexyl chloride involve the use of a glass microreactor chip, a reaction temperature of 160-180 C (20 bar backpressure) and a residence time of 15 min.
- Reichart, Benedikt,Tekautz, Guenter,Kappe, C. Oliver
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- Ionic liquids as reagents and solvents in conjunction with microwave heating: Rapid synthesis of alkyl halides from alcohols and nitriles from aryl halides
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We show that using ionic liquids as reagents in conjunction with microwave heating it is possible to prepare primary alkyl halides from the corresponding alcohols rapidly. Using ionic liquids as solvents in conjunction with microwave heating it is possible to prepare aryl nitriles from the corresponding aryl bromides or iodides. The scope and limitations of using microwave-promotion as a tool in these reactions is discussed.
- Leadbeater, Nicholas E.,Torenius, Hanna M.,Tye, Heather
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- Electrochemical deoxygenation of primary alcohols
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Direct electrolysis of primary alcohols, in the presence of methyl toluate, leads smoothly to the formation of the corresponding deoxygenated product in high yield. Georg Thieme Verlag Stuttgart · New York.
- Lam, Kevin,Mark, István E.
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- Organic Synthesis in Micellar Media. Oxidation of Alcohols and Their Conversion into Alkyl Chlorides
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The use of micelles was investigated for various organic reactions: oxidation of alcohols with sodium hypochlorite in micelles, oxidation of alcohols with hexadecyltrimethylammonium chromate as micelle, and conversion of primary alcohols to 1-chloroalkanes by aqueous hydrogen chloride in the presence of micelles.In all cases, product isolation was simple and satisfactory yields were obtained.
- Jursic, Branko
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- The Use of Silica Gel-Supported Ionenes as Reagents and Catalysts for Several Substitution Reactions in Toluene
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Several ionene bromides were used as reagents for the displacement of decyl methanesulfonate into 1-bromodecane.They were reactive when adsorbed by silica gel.The enhanced activities of the ionenes were hardly dependent on their structures and molecular weights but decreased gradually with increasing the amount of ionene adsorbed by silica gel.Ionene chlorides exhibited a similar enhancement of reactivity when adsorbed by silica gel.However, unlike the ionenes, a large increase in activity due to adsorption was not observed with pendant-type polycations such as poly(4-vinylpyridinium bromide) and poly.The silica gel-supported ionenes also exhibited excellent catalytic activities for solid-liquid-solid triphase substitution reactions, particularly for the reactions between 1-bromodecane and such inorganic salts as consisted of relatively hard-basic nucleophilic anions.
- Ohtani, Noritaka,Chida, Kosaku,Serita, Hajime,Matsunaga, Toshiaki,Kimura, Chikai
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- Cross-coupling reaction of alkyl halides with alkyl grignard reagents catalyzed by cp-iron complexes in the presence of 1,3-butadiene
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Iron-catalyzed cross-coupling reaction of alkyl halides with alkyl Grignard reagents by the combined use of cyclopentadienyl ligand and 1,3-butadiene additive is described. The reaction smoothly proceeds at room temperature using unactivated alkyl bromides and fluorides via non-radical mechanism, which is in sharp contrast with hitherto known Fe-catalyzed cross-coupling reactions of alkyl halides.
- Iwasaki, Takanori,Shimizu, Ryohei,Imanishi, Reiko,Kuniyasu, Hitoshi,Kambe, Nobuaki
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- Cu-catalyzed alkylation of Grignard reagents: A new efficient procedure
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The presence of NMP (4-9 equiv.) clearly improves the yield and the chemoselectivity of the Cu-catalyzed alkylation of organomagnesium reagents. Thus, secondary and tertiary alkylmagnesium chlorides were used successfully for the first time in such a reaction and ester, amide, nitrile or keto groups are tolerated. The procedure is cheap, environmentally friendly and very easy to carry out (1-3% Li2CuCl4 or CuCl, THF, 20°C). It is an interesting alternative to the classical alkylation of organocuprates reagents. (C) 2000 Published by Elsevier Science Ltd.
- Cahiez, Gérard,Chaboche, Christophe,Jézéquel, Michelle
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- Conversion of alcohols into alkyl chlorides using trichloroisocyanuric acid with triphenylphosphine
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Trichloroisocyanuric acid with triphenylphosphine in anhydrous acetonitrile will convert alcohols into alkyl halides.
- Hiegel, Gene A.,Rubino, Mark
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- The versatile behavior of the PdCl2/Et3SiH system. Conversion of alcohols to the corresponding halides and alkanes
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The versatility of the palladium(II) chloride/triethylsilane system has been tested in the transformation of alcohols. The conversion to the corresponding halides and alkanes has been achieved in good yields and in the absence of solvent for a variety of substrates.
- Ferreri,Costantino,Chatgilialoglu,Boukherroub,Manuel
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- The complexes of copper with grafted ionic liquids in the environmentally important processes
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The complexes of copper (II) chloride with quaternary ammonium salts grafted on various mineral supports (the modifications of SiO2 - KSK, silochrome, Perlkat) are highly active in two environmentally important processes: the reaction of carbon tetrachloride with alkanes and the oxidative coupling of thiols. The effectiveness of the catalysts depends on the transition metal, the ionic liquid, and the support nature. In CCl4 transformations, the highest activity is shown by the complexes with alkylamines derivatives grafted on silica with wide pores. In case of thiol oxidation, complexes with heterocycles derivatives grafted on Perlkat with narrow pores are most active. The effectiveness of the CCl4 transformations catalysts increases upon the addition of alcohol to the reaction mixture.
- Tarkhanova, Irina,Zelikman, Vladimir,Gantman, Mikhail
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- A procedure for Appel halogenations and dehydrations using a polystyrene supported phosphine oxide
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The conversion of a commercially available polystyrene supported phosphine oxide into synthetically useful polymeric halophosphonium salts using oxalyl chloride/bromide takes place at room temperature in 5 min and generates only CO and CO2 as by-products. The polymeric halophosphonium salts so obtained are useful reagents for Appel halogenations and other dehydrative coupling reactions. This gives rise to a simple three-step synthesis cycle for Appel and related reactions using a commercially available polymeric phosphine oxide with very simple purification and no phosphorus waste.
- Tang, Xiaoping,An, Jie,Denton, Ross M.
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- Catalytic remote hydrohalogenation of internal alkenes
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Primary alkyl halides have broad utility as fine chemicals in organic synthesis. The direct halogenation of alkenes is one of the most efficient approaches for the synthesis of these halides. Internal alkenes, in particular mixtures of isomers from refine
- Li, Xiang,Jin, Jianbo,Chen, Pinhong,Liu, Guosheng
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p. 425 - 432
(2022/02/07)
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- A New Protocol for Catalytic Reduction of Alkyl Chlorides Using an Iridium/Bis(benzimidazol-2′-yl)pyridine Catalyst and Triethylsilane
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The reduction of alkyl chlorides using triethylsilane is investigated. Primary, secondary, tertiary, and benzylic C-Cl bonds are effectively converted into C-H bonds using an [IrCl(cod)] 2/2,6-bis(benzimidazol-2′-yl)pyridine catalyst system. This catalyst system is quite simple since the tridentate N-ligand can be easily prepared in one step from commercially available reagents.
- Fukuyama, Takahide,Hamada, Yuki,Ryu, Ilhyong
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supporting information
p. 3404 - 3408
(2021/07/14)
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- Method for hydrogenolysis of halides
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The invention discloses a method for hydrogenolysis of halides. The invention discloses a preparation method of a compound represented by a formula I. The preparation method comprises the following step: in a polar aprotic solvent, zinc, H2O and a compound represented by a formula II are subjected to a reaction as shown in the specification, wherein X is halogen; Y is -CHRR or R; hydrogenin H2O exists in the form of natural abundance or non-natural abundance. According to the preparation method, halide hydrogenolysis can be simply, conveniently and efficiently achieved through a simple and mild reaction system, and good functional group compatibility and substrate universality are achieved.
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- Dehalogenative Deuteration of Unactivated Alkyl Halides Using D2O as the Deuterium Source
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The general dehalogenation of alkyl halides with zinc using D2O or H2O as a deuterium or hydrogen donor has been developed. The method provides an efficient and economic protocol for deuterium-labeled derivatives with a wide substrate scope under mild reaction conditions. Mechanistic studies indicated that a radical process is involved for the formation of organozinc intermediates. The facile hydrolysis of the organozinc intermediates provides the driving force for this transformation.
- Xia, Aiyou,Xie, Xin,Hu, Xiaoping,Xu, Wei,Liu, Yuanhong
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p. 13841 - 13857
(2019/10/17)
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- Transfer Hydrogenation of Alkenes Using Ethanol Catalyzed by a NCP Pincer Iridium Complex: Scope and Mechanism
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The first general catalytic approach to effecting transfer hydrogenation (TH) of unactivated alkenes using ethanol as the hydrogen source is described. A new NCP-type pincer iridium complex (BQ-NCOP)IrHCl containing a rigid benzoquinoline backbone has been developed for efficient, mild TH of unactivated C-C multiple bonds with ethanol, forming ethyl acetate as the sole byproduct. A wide variety of alkenes, including multisubstituted alkyl alkenes, aryl alkenes, and heteroatom-substituted alkenes, as well as O- or N-containing heteroarenes and internal alkynes, are suitable substrates. Importantly, the (BQ-NCOP)Ir/EtOH system exhibits high chemoselectivity for alkene hydrogenation in the presence of reactive functional groups, such as ketones and carboxylic acids. Furthermore, the reaction with C2D5OD provides a convenient route to deuterium-labeled compounds. Detailed kinetic and mechanistic studies have revealed that monosubstituted alkenes (e.g., 1-octene, styrene) and multisubstituted alkenes (e.g., cyclooctene (COE)) exhibit fundamental mechanistic difference. The OH group of ethanol displays a normal kinetic isotope effect (KIE) in the reaction of styrene, but a substantial inverse KIE in the case of COE. The catalysis of styrene or 1-octene with relatively strong binding affinity to the Ir(I) center has (BQ-NCOP)IrI(alkene) adduct as an off-cycle catalyst resting state, and the rate law shows a positive order in EtOH, inverse first-order in styrene, and first-order in the catalyst. In contrast, the catalysis of COE has an off-cycle catalyst resting state of (BQ-NCOP)IrIII(H)[O(Et)···HO(Et)···HOEt] that features a six-membered iridacycle consisting of two hydrogen-bonds between one EtO ligand and two EtOH molecules, one of which is coordinated to the Ir(III) center. The rate law shows a negative order in EtOH, zeroth-order in COE, and first-order in the catalyst. The observed inverse KIE corresponds to an inverse equilibrium isotope effect for the pre-equilibrium formation of (BQ-NCOP)IrIII(H)(OEt) from the catalyst resting state via ethanol dissociation. Regardless of the substrate, ethanol dehydrogenation is the slow segment of the catalytic cycle, while alkene hydrogenation occurs readily following the rate-determining step, that is, β-hydride elimination of (BQ-NCOP)Ir(H)(OEt) to form (BQ-NCOP)Ir(H)2 and acetaldehyde. The latter is effectively converted to innocent ethyl acetate under the catalytic conditions, thus avoiding the catalyst poisoning via iridium-mediated decarbonylation of acetaldehyde.
- Wang, Yulei,Huang, Zhidao,Leng, Xuebing,Zhu, Huping,Liu, Guixia,Huang, Zheng
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supporting information
p. 4417 - 4429
(2018/04/05)
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- Ni-Catalyzed Carboxylation of Unactivated Alkyl Chlorides with CO2
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A catalytic carboxylation of unactivated primary, secondary, and tertiary alkyl chlorides with CO2 at atmospheric pressure is described. This protocol represents the first intermolecular cross-electrophile coupling of unactivated alkyl chlorides, thus leading to new knowledge in the cross-coupling arena.
- B?rjesson, Marino,Moragas, Toni,Martin, Ruben
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supporting information
p. 7504 - 7507
(2016/07/06)
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- Copper-catalyzed alkyl-alkyl cross-coupling reactions using hydrocarbon additives: Efficiency of catalyst and roles of additives
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Cross-coupling of alkyl halides with alkyl Grignard reagents proceeds with extremely high TONs of up to 1230000 using a Cu/unsaturated hydrocarbon catalytic system. Alkyl fluorides, chlorides, bromides, and tosylates are all suitable electrophiles, and a TOF as high as 31200 h-1 was attained using an alkyl iodide. Side reactions of this catalytic system, i.e., reduction, dehydrohalogenation (elimination), and the homocoupling of alkyl halides, occur in the absence of additives. It appears that the reaction involves the β-hydrogen elimination of alkylcopper intermediates, giving rise to olefins and Cu-H species, and that this process triggers both side reactions and the degradation of the Cu catalyst. The formed Cu-H promotes the reduction of alkyl halides to give alkanes and Cu-X or the generation of Cu(0), probably by disproportionation, which can oxidatively add to alkyl halides to yield olefins and, in some cases, homocoupling products. Unsaturated hydrocarbon additives such as 1,3-butadiene and phenylpropyne play important roles in achieving highly efficient cross-coupling by suppressing β-hydrogen elimination, which inhibits both the degradation of the Cu catalyst and undesirable side reactions.
- Iwasaki, Takanori,Imanishi, Reiko,Shimizu, Ryohei,Kuniyasu, Hitoshi,Terao, Jun,Kambe, Nobuaki
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p. 8522 - 8532
(2015/01/08)
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- Chlorination of hydrocarbons with CCl4 catalyzed by complexes of Mn, Mo, V, Fe
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Catalytic chlorination of alkanes, cycloalkanes, and adamantane utilizing tetrachloromethane as the source of chlorine and applying catalysts containing manganese, molybdenum, vanadium, and iron activated with nitrile ligands, alcohols, and water was fulfilled. The optimum ratios of catalysts and reagents and the best reaction conditions were found for selective synthesis of chlorine-substituted hydrocarbons derivatives. Pleiades Publishing, Ltd., 2013.
- Khusnutdinov,Shchadneva,Bayguzina,Oshnyakova,Mayakova,Dzhemilev
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p. 1557 - 1566
(2014/02/14)
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- Catalytic phosphorus(V)-mediated nucleophilic substitution reactions: Development of a catalytic appel reaction
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Catalytic phosphorus(V)-mediated chlorination and bromination reactions of alcohols have been developed. The new reactions constitute a catalytic version of the classical Appel halogenation reaction. In these new reactions oxalyl chloride is used as a consumable stoichiometric reagent to generate the halophosphonium salts responsible for halogenation from catalytic phosphine oxides. Thus, phosphine oxides have been transformed from stoichiometric waste products into catalysts and a new concept for catalytic phosphorus-based activation and nucleophilic substitution of alcohols has been validated. The present study has focused on a full exploration of the scope and limitations of phosphine oxide catalyzed chlorination reactions as well as the development of the analogous bromination reactions. Further mechanistic studies, including density functional theory calculations on proposed intermediates of the catalytic cycle, are consistent with a catalytic cycle involving halo- and alkoxyphosphonium salts as intermediates.
- Denton, Ross M.,An, Jie,Adeniran, Beatrice,Blake, Alexander J.,Lewis, William,Poulton, Andrew M.
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experimental part
p. 6749 - 6767
(2011/10/02)
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- Phosphine oxide-catalysed chlorination reactions of alcohols under Appel conditions
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A phosphine oxide-catalysed chlorination reaction of primary and secondary alcohols has been developed. This process represents the first triphenylphosphine oxide-catalysed alcohol chlorination under Appel conditions. The Royal Society of Chemistry 2010.
- Denton, Ross M.,An, Jie,Adeniran, Beatrice
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supporting information; experimental part
p. 3025 - 3027
(2010/08/04)
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- Safe, facile radical-based reduction and hydrosilylation reactions in a microreactor using tris(trimethylsilyl)silane
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A highly efficient system for tris(trimethylsilyl)silane (TTMSS) mediated deoxygenation, dehalogenation and hydrosilylation reactions is described in a microstructured device; this convenient platform enables the scale up of radical-based processes. The Royal Society of Chemistry.
- Odedra, Arjan,Geyer, Karolin,Gustafsson, Tomas,Gilmour, Ryan,Seeberger, Peter H.
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scheme or table
p. 3025 - 3027
(2009/02/04)
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- Characterization of polychlorinated alkane mixtures - A Monte Carlo modeling approach
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A Monte Carlo model was developed to characterize the molecular composition of polychlorinated alkane mixtures. The model is based upon a simulation of the free-radical chlorination process by which polychlorinated alkane mixtures are produced industrially from n-alkanes. In the model, the free-radical chlorination reaction was simulated by randomly selecting a position on a partially converted alkane molecule for target by chlorine free-radical attack. The relative reactivities of the hydrogen atoms on the alkane chain towards chlorine free-radical substitution were either determined experimentally or extrapolated from experimental results and incorporated into the model. The result of the simulation is the prediction of the detailed molecular composition of any PCA mixture. Good agreement was found when comparing the distribution of molecules predicted by the model to analytically determined distributions of real PCA mixtures. Results from the model were then coupled with rules describing the action of biological enzymes to estimate the upper limit possible for the aerobic biodegradation of PCA mixtures.
- Jensen, Soren R.,Brown, Wayne A.,Heath, Ester,Cooper, David G.
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p. 703 - 717
(2008/02/13)
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- Proton acceptor site selectivity in the proton transfer from heptane radical cations to decane molecules in γ-irradiated heptane/decane/ 1-chloroheptane crystals at 77 K
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A study is made of the yield and isomeric composition of chlorodecanes formed by γ-irradiation of heptane/decane/ 1-chloroheptane crystals at 77 K and subsequent warming. It is observed that in such systems 2-chlorodecane is predominantly formed with smaller yields of the other chlorodecane isomers, in isomers, in analogy with observations of γ-irradiated CCl3F/decane. The selective formation of 2-chlorodecane is attributed to proton transfer from heptane radical cations to decane molecules, (n-C7H16·+ + n-C10H22→ 1-C7H15· + n-C10H23+), followed by neutralization of the so-formed protonated decanes by chloride ions upon warming. The results confirm that, when different secondary C-H bonds in neutral n-alkane molecules are directly accessible to the planar chain-end C-H bonds in n-alkane radical cations from which proton donation takes place, proton transfer occurs preferentially to the penultimate position (intrinsic acceptor site selectivity). Comparison of the isomeric composition of the chlorodecanes in heptane/decane/1-chloroheptane and CCl3/decane, on the other hand, clearly points to structurally-determined acceptor site selectivity with respect to the inner C-H bonds of decane in the heptane system.
- Slabbinck, Lutgart,Demeyer, Adelheid,Ceulemans, Jan
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p. 2241 - 2247
(2007/10/03)
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- Thiocyanation of alkyl halides with alkyl thiocyanates in the presence of quaternary phosphonium halides
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Alkyl thiocyanates undergo simple SN2 reactions with the counter ions of quaternary phosphonium salts in nonpolar solvents and thiocyanate ions are liberated as the leaving ion. Depending on the nucleophile, the reaction proceeded irreversibly or reversibly. The reaction of benzyl thiocyanate with azide ions afforded a quantitative yield of benzyl azide. The reactions of alkyl thiocyanates with halide ions gave an equilibrium mixture where the reverse reaction of the alkyl halides produced with the liberated thiocyanate ions took place simultaneously. Thus, thiocyanate-halide exchange reactions between an alkyl thiocyanate and an alkyl halide were possible in the presence of a catalytic amount of a quaternary salt.
- Ohtani, Noritaka,Murakawa, Shigeki,Watanabe, Kohji,Tsuchimoto, Daisuke,Sato, Daiki
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p. 1851 - 1856
(2007/10/03)
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- REGIOSPECIFIC AND STEREOSPECIFIC SUBSTITUTION OF HYDROXYL IN ALIPHATIC ALCOHOLS BY HALOGEN
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A new system containing triphenylphosphine and trichloro- and tribromoacetic ester makes it possible to substitute the hydroxyl group in alcohols by halogen.Regiospecific and stereospecific substitution of the hydroxyl by the halogen takes place as a result of the reaction of primary and secondary aliphatic alcohols and of 2-alkenols, susceptible to isomerization processes, with this system.
- Matveeva, E. D.,Kurts, A. L.,Yalovskaya, A. I.,Nikishova, N. G.,Bundel', Yu. G.
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p. 642 - 646
(2007/10/02)
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- Preparation of aliphatic chlorine compounds
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Aliphatic chlorine compounds of the formula where R1 is alkylene which may be interrupted by one or more oxygen atoms and which may be substituted by halogen, alkyl or aryl, and X is hydrogen, chlorine or OR2, where R2
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- HOMOLOGATION DES DERIVES HALOGENES
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The halide R-X is converted, in two steps, to its homologous R-CH2-X.
- Yankep, Emmanuel,Charles, Georges
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p. 427 - 430
(2007/10/02)
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- Novel Functional Group Transformations involving Alkyl Phenyl Selenones
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Alkyl phenyl selenones readily undergo substitution reactions, and are valuable precursors of epoxides on reaction with aldehydes inthe presence of bases.
- Krief, Alain,Dumont, Willy,Denis, Jean-Noel
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p. 571 - 572
(2007/10/02)
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