1117-79-9Relevant academic research and scientific papers
A facile synthesis of racemic 4-ethyl fatty acids
Liu, Yu-Ping,Guan, Wei,Yin, De-Cai,Tian, Hong-Yu,Sun, Bao-Guo
, p. 492 - 494 (2012)
The synthesis of racemic 4-ethyl fatty acids is reported. A Grignard reagent was first prepared by 3-chloroalkane reacting with magnesium and then 4-ethyl fatty acid methyl esters were synthesised by coupling the Grignard reagent with methyl 3-bromopropionate in the presence of the catalyst Li 2CuCl4. The 4-ethyl fatty acid methyl esters were saponified and then acidified to give the 4-ethyl fatty acids. The syntheses of 4-ethylhexanoic acid, 4-ethylheptanoic acid, 4-ethyloctanoic acid, 4-ethylnonaoic acid and 4-ethyl decanoic acid are described. The structures of the 4-ethyl fatty acid methyl esters and 4-ethyl fatty acids were confirmed by 1H NMR, 13C NMR and HRMS.
Stereoretentive chlorination of cyclic alcohols catalyzed by titanium(IV) tetrachloride: Evidence for a front side attack mechanism
Mondal, Deboprosad,Li, Song Ye,Bellucci, Luca,Laino, Teodoro,Tafi, Andrea,Guccione, Salvatore,Lepore, Salvatore D.
, p. 2118 - 2127 (2013/04/10)
A mild chlorination reaction of alcohols was developed using the classical thionyl chloride reagent but with added catalytic titanium(IV) chloride. These reactions proceeded rapidly to afford chlorination products in excellent yields and with preference for retention of configuration. Stereoselectivities were high for a variety of chiral cyclic secondary substrates including sterically hindered systems. Chlorosulfites were first generated in situ and converted to alkyl chlorides by the action of titanium tetrachloride which is thought to chelate the chlorosulfite leaving group and deliver the halogen nucleophile from the front face. To better understand this novel reaction pathway, an ab initio study was undertaken at the DFT level of theory using two different computational approaches. This computational evidence suggests that while the reaction proceeds through a carbocation intermediate, this charged species likely retains pyramidal geometry existing as a conformational isomer stabilized through hyperconjugation (hyperconjomers). These carbocations are then essentially "frozen" in their original configurations at the time of nucleophilic capture.
A facile and green protocol for nucleophilic substitution reactions of sulfonate esters by recyclable ionic liquids [bmim][X]
Liu, Yajun,Xu, Yongnan,Jung, Sun Ho,Chae, Junghyun
supporting information, p. 2692 - 2698,7 (2012/12/12)
Ionic liquids [bmim][X] (X = Cl, Br, I, OAc, SCN) are highly efficient reagents for nucleophilic substitution reactions of sulfonate esters derived from primary and secondary alcohols. The counter anions (X-) of the ionic liquids, [bmim][X], effectively replace the sufonates affording the corresponding substitution products such as alkyl halides, acetates, and thiocyanides in excellent yields. The newly developed protocol is very environmentally attractive because the reactions use stoichiometric amounts of ionic liquids as sole reagents in most cases and do not require additional solvents, any other activating reagents, non-conventional equipment, or special precautions. Moreover, these ionic liquids can be readily recycled without loss of reactivity, making the whole process greener.
A facile and green protocol for nucleophilic substitution reactions of sulfonate esters by recyclable ionic liquids [bmim][X]
Liu, Yajun,Xu, Yongnan,Jung, Sun Ho,Chae, Junghyun
supporting information, p. 2692 - 2698 (2013/01/15)
Ionic liquids [bmim][X] (X = Cl, Br, I, OAc, SCN) are highly efficient reagents for nucleophilic substitution reactions of sulfonate esters derived from primary and secondary alcohols. The counter anions (X-) of the ionic liquids, [bmim][X], effectively replace the sufonates affording the corresponding substitution products such as alkyl halides, acetates, and thiocyanides in excellent yields. The newly developed protocol is very environmentally attractive because the reactions use stoichiometric amounts of ionic liquids as sole reagents in most cases and do not require additional solvents, any other activating reagents, non-conventional equipment, or special precautions. Moreover, these ionic liquids can be readily recycled without loss of reactivity, making the whole process greener. Georg Thieme Verlag KG Stuttgart · New York.
Iron(III)-catalyzed halogenations by substitution of sulfonate esters
Ortega, Nuria,Feher-Voelger, Andres,Brovetto, Margarita,Padron, Juan I.,Martin, Victor S.,Martin, Tomas
experimental part, p. 963 - 972 (2011/06/20)
A novel halogenation reaction from sulfonates catalyzed by iron(III) is described. The reaction can be performed as a stoichiometric or a catalytic version. This reaction provides a convenient strategy for the efficient access to structurally diverse secondary chlorides, bromides and iodides. The stereochemical course of the reaction is governed by the substrate and the experimental conditions. Secondary alcohols modified as quisylates or pysylates are substantially more reactive. Aliphatic quisylates proceed with overall inversion of configuration under catalytic conditions. Chemoselectivity in bismesylates was observed in favour of the secondary mesylate. Additionally, based on the experimental results, a possible catalytic cycle for the halogenation has been proposed.
Clarification of the stereochemical course of nucleophilic substitution of arylsulfonate-based nucleophile assisting leaving groups
Braddock, D. Christopher,Pouwer, Rebecca H.,Burton, Jonathan W.,Broadwith, Phillip
experimental part, p. 6042 - 6049 (2009/12/24)
(Chemical Equation Presented) Secondary alcohols modified as tosylates, PEG-sulfonates, or quisylates undergo inversion of configuration at the reacting center when treated with lithium halide in acetone at reflux, where the PEG-sulfonates and quisylates are substantially more reactive. In sterically hindered cases, elimination is a competing process. In contrast, when treated with TiCl4, simple secondary sulfonates give chloride products with partial inversion of configuration. Any observed retention of configuration in a given alkyl sulfonate substrate under these conditions is likely due to neighboring group participation or diastereoselective attack on a carbocation (or ion pair) rather than an SNi mechanism.
Process for preparing monochlorinated hydrocarbons having a high isomeric purity
-
, (2008/06/13)
Monochlorinated hydrocarbons of high isomeric purity are prepared by a process, which comprises: reacting a monoalcohol having an alkyl radical having from 3 to 20 carbon atoms with cyanuric chloride; and purifying the resulting monochlorinated hydrocarbon by distillation after separation of salts and washing the monochlorinated hydrocarbon with alkali. The invention relates to a process for preparing monochlorinated hydrocarbons which contain an alkyl radical having from 3 to 20 carbon atoms and have a high isomeric purity by reacting a monoalcohol having a hydrocarbon radical containing an alkyl radical having from 3 to 20 carbon atoms to which additional cycloaliphatic radicals, aryl radicals, aralkyl radicals and alkylaryl radicals may be bound with cyanuric chloride, separating off salts, washing the reaction mixture with alkali and purifying the resulting monochlorinated hydrocarbons by distillation.
Reactivity of bismuth(III) halides towards alcohols. A tentative to mechanistic investigation
Keramane, El Mehdi,Boyer, Bernard,Roque, Jean-Pierre
, p. 1909 - 1916 (2007/10/03)
The reactivity of bismuth(III) halides (BiX3; X=Cl, Br and I) towards a series of alcohols has been investigated. Three different reactions have been studied, namely: halogenation, dehydration and etherification. The behaviour of these bismuth derivatives was found to depend on the nature of the halide bonded to the bismuth atom. Their reactivities can be interpreted on the basis of the Hard and Soft Acids and Bases (HSAB) principle. A mechanism is proposed which involves the formation of a complex of the alcohol with Bi(III).
Activation of the silicon-halogen bond by bismuth (III) halides. Halogenation of alcohols: prospective and mechanism
Labrouillere, Mireille,Roux, Christophe Le,Oussaid, Abdelouahad,Gaspard-Iloughmane, Hafida,Dubac, Jacques
, p. 522 - 530 (2007/10/02)
In the presence of catalytic amount of BiCl3, chloromethylsylanes can be used as chlorinating agents for alcohols, and as chloro-dealkylating agents for silyl ethers and carboxylic and sulfonic esters.The chlorination of (R)-(-)-octan-2-ol and the (R)-(-)-2-mesyloctane by TMSCl gave predominantly the (S)-(+)-2-chlorooctane with inversion of configuration at secondary carbon.According to the class of alcohol, the mechanism involves SN2, SN2' or SN1 processes.This new activation of the Si-Cl bond, probably trough a Si-Cl...BiCl3 interaction gives a hard-soft reagent that can generate a silicenium cation, was also observed with Me3SiBr, BiBr3 and Me3SiI, BiI3 systems.The reaction is also presented as a possible alcoholysis of chlorosilanes, which can lead to siloxanes in non-aqueous conditions. catalysis / halogenation / alcohol / ester / silyl ether / chlorosilane / chlorotrimethylsilane / bromotrimethylsilane / iodotrimethylsilane / siloxane / bismuth (III) halide
CHLORIERENDE METHYLIERUNG VON ALDEHYD- UND KETOGRUPPEN MIT NIOB-REAGENZIEN SOWIE AUFKLAERUNG DES MECHANISMUS
Kauffmann, Thomas,Abel, Thomas,Neiteler, Gabriele,Schreer, Martin
, p. 503 - 506 (2007/10/02)
The reagents MeNbCl4 and Me2NbCl3, applied as isolated pure compounds, react with ketones in preparatively useful yields according to RR'CO -> RR'C(Cl)CH3.Whereas benzaldehyde reacts with MeNbCl4 analogously, the aliphatic aldehyde heptanal forms beside the expected product two cinechlorination products, indicating a mechanism via radicals.MeNbCl4 is highly aldehyde-vs.-ketone selective.Conversely, high ketone-vs.-aldehyde selectivity is achievable by application of MeNbCl4*PPh3 or NbCl5*PPh3 + 1.5 Me2Zn.
