- Halogen-exchange reactions between alkyl fluorides and boron trihalides or tetrahalides. A convenient synthesis of alkyl halides from alkyl fluorides
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A simple and effective method for converting fluoroalkanes to their corresponding chloro-, bromo- and iodo-alkanes using commercially available boron trihalides and titanium tetrahalides is described. - Keywords: Halogen-exchange reactions; Alkyl fluorides; Boron trihalides; Titanium tetrahalides; NMR spectroscopy; Mass spectrometry
- Namavari, Mohammad,Satyamurthy, N.,Barrio, Jorge R.
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- The first example of tungsten-based carbene generation from WCl6 and atomic carbon and its use in olefin metathesis
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We describe a new route for the synthesis of tungsten-based carbenes generated by the reaction of WCl6 with atomic carbon in a carbon arc reactor. The active species formed under these conditions, [W] = CCl2, was found to catalyze olefin metathesis reactions of 1-octene, 2-octene and 1-heptene. We also evaluated the mechanism of formation of [W] = CCl2 within the WCl6/C system at the DFT level.
- Düz, Bülent,Yüksel, Dilek,Ece, Abdulilah,Sevin, Fatma
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- Carbon-13 Nuclear Magnetic Resonance of Mono- and Di-chloro-hexanes and Mono- and Di-chloro-heptanes. Assignment of Configurations
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Carbon-13 NMR spectra of mono- and dichloro-hexanes and mono- and dichloro-heptanes are reported.Substituent effects for α, β and γ positions are presented.Differences between the 13C chemical shifts of diastereoisomers are observed in the cases of 2,4- and 2,5-dichlorohexanes and 2,4-, 2,5- and 3,5-dichloroheptanes.
- Nouguier, R.,Surzur, J.-M.,Virgili, A.
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- Symmetric and asymmetric proton transfer from heptane and octane radical cations to heptane molecules in γ-irradiated n-C7H16-n-C8H18-2-C6H 13CL crystals: Structural disorder in mixed alkan
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A study has been made of the isomeric composition of secondary chloroheptanes formed upon γ-irradiation at 77 K and subsequent melting of heptane containing 1 mol% 2-chlorohexane and various concentrations of octane. It is observed that the relative impor
- Demeyer, Adelheid,Ceulemans, Jan
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- Ferric chloride–catalyzed deoxygenative chlorination of carbonyl compounds: A comparison of chlorodimethylsilane and dichloromethylsilane system
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Deoxygenative chlorination of carbonyl compounds using the HMe2SiCl/FeCl3/EtOAc and HMeSiCl2/FeCl3/EtOAc systems has been systemically investigated. The HMe2SiCl-FeCl3 system showed the advantages of good substrate applicability, mild reaction conditions, simple operation, low cost, and easy availability of raw materials. Also, it provided a simple and efficient synthesis route for carbonyl deoxychlorination via a one-pot method. Using the HMeSiCl2/FeCl3/EtOAc system, the β-methylchalcone derivative could be obtained in good yields in addition to obtaining the chlorinated compound. Finally, two plausible reaction routes were proposed to describe the formation of the chlorinated compound and the β-methylchalcone derivative.
- Xing, Bing-Han,Zhao, Xuan-Xuan,Qin, Yu-Jun,Zhang, Pu,Guo, Zhi-Xin
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p. 667 - 675
(2020/05/22)
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- Photoinduced, Copper-Catalyzed Carbon-Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature
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We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C-N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C-C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2]- may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.
- Ratani, Tanvi S.,Bachman, Shoshana,Fu, Gregory C.,Peters, Jonas C.
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supporting information
p. 13902 - 13907
(2016/01/15)
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- Cobalt(II)-Porphyrin Catalyzed Selective Functionalization of Alkanes with sulfurylchloride: A Remarkable Substituent Effect
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Cobalt(II)-porphyrin complex 1 and 2 catalyses the chlorination and sulfochlorination respectively of n-alkanes and cycloalkanes with sulfuryl chloride in benzene.The p-substituent of the benzene ring in the porphyrin complex 1 and 2 shows a remarkable chemoselectivity in these reactions.
- Khanna, Vibha,Tamilselvan, Pitchiah,Kalra, Swinder Jeet Singh,Iqbal, Javed
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p. 5935 - 5938
(2007/10/02)
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- Intramolecular H-Transfer Reactions During the Decomposition of Alkylhydroperoxides in Hydrocarbons as the Solvents
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Eight defined primary and secondary alkylhydroperoxides were decomposed in n-alkanes as the solvent, mostly in the presence of manganese stearate.In all cases the corresponding alcohols and carbonyl compounds were formed as the main products with yields of 60-90percent.Besides, difunctional products were formed by an intramolecular H-transfer in the alkoxy radicals corresponding to the starting hydroperoxides.Products possibly formed by an intramolecular H-transfer in the corresponding alkylperoxy radical could be found only in the case of 4-methyl-2-hydroperoxy pentane.The amount of products formed by intramolecular H-transfer depended on the nature of the C-H bond in δ-position to the original hydroperoxy group and lay between 4percent (primary C-H in the case of 4-hydroperoxy heptane) and 13percent (tertiary C-H in the case of 2-hydroperoxy-5-methyl hexane) with respect to the starting hydroperoxide.The amount of products formed by oxidative attack of the alkoxy and alkylperoxy radicals at the normal paraffins used as the solvents was unexpectedly low (always less than 10percent with respect to the starting hydroperoxide).An increment system is proposed for the calculation of 13C-nmr shifts in alkyl hydroperoxides.
- Jinsheng, Li,Pritzkow, Wilhelm,Voerckel, Volkmar
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- Triphase Catalytic Conversion of Alkenes to Organic Halides
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Reactions of alkenes with hydrohalogenic acids (HCl and HBr) have been studied in the presence of polystyrylmethylenehexadecylbutylphosphonium bromide (1) and polystyrylmethylenehexadecyldiphenylphosphonium bromides (2) as triphase catalysts to yield organic halides by a simple product isolation.The catalysts could be recovered and recycled without loss of activity
- Khurana, Jitender M.,Tetenyi, Peter,Kodomari, Mitsuo,Regen, Steven L.
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p. 1129 - 1130
(2007/10/02)
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