- A telechelic fluorinated diol from 1,6-diiodoperfluorohexane
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The radical addition of 1-iodoperfluorohexane (1) to allyl alcohol (2-propen-1-ol) (2) was investigated in the presence of various initiating systems (photochemically or in the presence of redox catalysts or organic initiators), leading to C6F13CH2CHICH2OH (3) in various yields. A scale of efficiency of the involved radical system was proposed, triphenylphosphine and AIBN yielding the best conversions of 1. Interestingly, AIBN, when added three times in the course of the reaction was the most suitable for an almost quantitative consumption of 1. Then, 3 was reduced to C6F13C3H6OH (4) in high yields by tributylstannane. Such a two-step procedure was extrapolated to the preparation of the fluorinated telechelic diol from 1,6-diiodoperfluorohexane (5). First, the formations of both the 1-to-1 monoadduct (6) and 1-to-2 α,ω-diadduct (7) were noted and discussed: optimised conditions enabled production of 7 in 81% yield with a complete conversion of 5. Then, telechelic diol HOC3H6C6F12 C3H6OH (8) was synthesised selectively in 88% yield, from the reduction of the iodine atoms of 7 by tributylstannane. 1H, 19F and 13C NMR spectroscopies allowed characterisation of all the intermediates and products without ambiguity.
- Lahiouhel,Ameduri,Boutevin
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Read Online
- A fluorous ethylenediamine promoted direct C-H arylation of unactivated arenes with aryl halides
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A novel and recyclable fluorous ethylenediamine was prepared. Together with potassium tert-butoxide, the fluorous ethylenediamine showed a good activity in promoting the coupling of aryl halides with benzene derivatives without the aid of transition-metal catalysts. Furthermore, a chain homolytic aromatic substitution mechanism was proposed in this paper.
- Zhu, Yi-Wei,Shi, Yi-Xin
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supporting information
p. 10 - 13
(2016/07/06)
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- Probing the limitations of the fluorous content for tag-mediated microarray formation
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The synthesis of a di-perfluorohexyl tag is reported for use in a fluorous-based carbohydrate microarray. A comparative microarray study with this di-perfluorohexyl tag and a mono-perfluorooctyl and mono-perfluorohexyl tag found the increased fluorous content conducive to better spot morphology and easier washing protocols without precluding reuse of the fluorous slide.
- Edwards, Heather D.,Nagappayya, Sahana K.,Pohl, Nicola L. B.
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supporting information; experimental part
p. 510 - 512
(2012/02/01)
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- Mesophase structure of low-wetting liquid crystalline polyacrylates with new perfluoroalkyl benzoate side groups
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The synthesis, thermal behavior, bulk microstructure, and wettability of new polyacrylates carrying spaced 4-perfluorohexylpropyl benzoate and 4-perfluorooctylpropyl benzoate units in the side groups were Investigated. X-ray diffraction analysis proved the formation of different smectic mesophases (SmI2, SmF2, and SmC2) and the evolution of their structures and lattice parameters with temperature. The mesophase polymorphic behavior depended on the length of the perfluorinated chain segment in the repeat unit. The electron density profiles along the smectic layer normal were drawn and provided a deeper insight into the packing of the side chains in a tilted, double layer structure. Thin polymer films were cast from solution, and their low wettability was established by measurements of contact angles with different probing liquids. We suggest that the hydrophobicity and lipophobicity of the films are enhanced by the mesophase surface structure which is mediated by the high-order, mesophase bulk structure.
- Martinelli, Elisa,Paoli, Francesca,Gallot, Bernard,Galli, Giancarlo
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experimental part
p. 4128 - 4139
(2011/10/30)
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- Cyclic peptide facial amphiphile preprogrammed to self-assemble into bioactive peptide capsules
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(Figure Presented) Programmed assembly: A unique supramolecular building block, a cyclic peptide facial amphiphile, predestined to self-assemble into a nanocapsule structure, has been developed (see figure). This general strategy will allow the easy construction of a variety of bioactive nanocapsules.
- Chung, Eun Kyung,Lee, Eunji,Lim, Yong-Beom,Lee, Myongsoo
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supporting information; experimental part
p. 5305 - 5309
(2010/09/10)
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- 3-(Perfluoroalkyl)propanols: Valuable building blocks for fluorous chemistry
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2-Iodo-3-(perfluoroalkyl)propanols are obtained in excellent yields and several-hundred-gram quantities by the controlled radical addition of commercially available n-perfluoroalkyl and perfluoroisoalkyl iodides to allyl alcohol. Their consecutive reduction with hydrazine hydrate and Raney nickel catalyst in methanol afforded the corresponding 3-(perfluoroalkyl)propanols in high yields and purity. Georg Thieme Verlag Stuttgart.
- Rabai, Jozsef,Szijjarto, Csongor,Ivanko, Peter,Szabo, Denes
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p. 2581 - 2584
(2008/03/13)
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- Fluorous dimethylthiocarbamate (FDMTC) protecting groups for alcohols
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N,N-Bis(perfluoroalkyl)thiocarbamoyl chlorides (FDMTC-Cls) were synthesized as reagent for the protection of alcohols. Using the crystalline FDMTC-Cls, the FDMTC groups were introduced into the alcohol molecules in excellent yields in the presence of sodium hydride in THF at room temperature. The products were separated from the excess alcohols by solid-phase extraction with a fluorous reverse-phase silica gel column (Fluorous Solid Phase Extraction; FSPE). The FDMTC groups were readily removed by oxidation with m-chloroperbenzoic acid (m-CPBA) and subsequent hydrolysis with KHCO3.
- Kojima, Masaru,Nakamura, Yutaka,Ishikawa, Takuma,Takeuchi, Seiji
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p. 6309 - 6314
(2007/10/03)
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- Process for producing a polyfluoroalkyl (meth)acrylate
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A process for producing a polyfluoroalkyl (meth)acrylate, which comprises isolating, from a reaction mixture containing a polyfluoroalkyl (meth)acrylate obtained by reacting a polyfluoroalkyl iodide of the formula CnF2n+1(CH2)mI (wherein n is an integer of from 2 to 7, and m is an integer of from 1 to 4) with a metal (meth)acrylate in tert-butanol, said polyfluoroalkyl (meth)acrylate by the following steps (1) to (3):(1) a step of taking out a crude liquid from the reaction mixture by solid-liquid separation;(2) a step of distilling the crude liquid to separate it into compound group A of compounds having a lower boiling point than the polyfluoroalkyl (meth)acrylate and compound group B of the polyfluoroalkyl (meth)acrylate and compounds having a higher boiling point than the polyfluoroalkyl (meth)acrylate; and(3) a step of distilling and purifying the polyfluoroalkyl (meth)acrylate from the compound group B in the presence of a polymerization inhibitor.
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- Synthesis and 19F NMR study of RF-oleic acid-F13
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A seven-step synthesis of Z-13,13,14,14,15,15,16,16,17,17,18,18, 18-tridecafluoro-octadec-9-enoic acid (oleic acid-F13) is reported. The key step is a Wittig reaction to form the C9-C10 double bond with a Z:E isomeric ratio greater than 20:1. The 19F nuclear magnetic resonance (NMR) spectrum is included and unambiguous assignments have been made with the aid of 19F-19F correlation NMR spectroscopy (COSY spectra).
- Buchanan, Gerald W.,Smits, Rufus,Munteanu, Elena
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p. 255 - 259
(2007/10/03)
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- Selective mono- and di{(perfluoroalkyl)acylation} of ferrocene
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The selective synthesis of mono- and 1,1′-di{(perfluoroalkyl)acylated} ferrocenes by Friedel-Crafts acylation with (perfluoroalkyl)acyl halides is described. The acyl derivatives were further converted to the corresponding (perfluoroalkyl)alkyl ferrocenes by reduction of the carbonyl group with LiAlH4/AlCl3. Electrochemical studies of all the obtained substituted ferrocenes were carried out to assess the influence of the perfluoroalkyl ponytails on their redox behavior.
- Hazafy, David,Sobociková, Marie,?těpni?ka, Petr,Ludvík, Ji?í,Kotora, Martin
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p. 177 - 181
(2007/10/03)
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- Investigation of the factors controlling the regioselectivity of the hydroboration of fluoroolefins
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Either Markovnikov or anti-Markovnikov regioselectivity can be achieved at will during the hydroboration-oxidation of perfluoroalkyl(aryl)ethylenes by varying the hydroborating agent.
- Ramachandran, P. Veeraraghavan,Jennings, Michael P.
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p. 386 - 387
(2007/10/03)
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- Synthesis of 3-perfluoroalkyl-propyl esters of L-(+)-tartaric acid
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A convenient and effective method for the preparation of perfluoroalkyl-propanols (F-(CF2)n-(CH2)3-OH, n = 6,8,10) via boric acid esters is described. The radical addition of F-alkyl iodides to the C=C double bonds of triallyl borate is followed by the reduction step using tributylstannane hydride under one-pot conditions. Finally, the mild aqueous deprotection of the alcoholic function completes the reaction with an overall yield of 75-79%. The fluorophilicity (f) values of these and some other fluoroalcohols, which describe their phase preference, were determined by gas chromatography. F-alkyl-propanols are useful synthetic precursors of fluorinated esters of L-tartaric acid - potential chelating agents in fluorous biphase transformations.
- Szlavik, Zoltan,Tarkanyi, Gabor,Tarczay, Gyoergy,Goemoery, Agnes,Rabai, Jozsef
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- Copper-catalyzed addition of perfluoroalkyl iodides to unsaturated alcohols and transformation of the addition products
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Iodoperfluoroalkyl alcohols RFCH2CHI(CR2)nOH (RF = C6F13; R = H, CH3; n = 1-3, 9) have been readily prepared in high yield by the addition of perfluoroalkyl iodides RFI to allylic and other unsaturated alcohols at 120 deg C in the presence of a catalytic amount (10percent mol) of metallic copper powder.The dibenzoyl peroxide-induced reaction gave lower yields of the addition products in most cases.The chemical changes of iodoperfluoroalkylated alcohols to epoxides and alcohols are described.A discussion of the by-products obtained and of the reaction mechanism is provided.
- Kotora, M.,Hajek, M.,Ameduri, B.,Boutevin, B.
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- Effect of a Perfluoroalkyl Group on the Elimination and Substitution Reactions of Two Homologous Series of Perfluoroalkyl-Substituted Iodoalkanes
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Substitution and elimination reactions of two homologous series of compounds, induced by strong bases, were studied in aqueous alcohol and anhydrous methanol solution.Series I compounds, RF(CH2)nI having n = 2 (RF = a perfluoroalkyl group, also named an F-alkyl group), gave only RFCH=CH2 under all conditions.By contrast, RF(CH2)3Igave 4-10 times as much substitution as elimination products.Isomerization of RFCH2CH=CH2 (6) to RFCH=CHCH3 (7) occurred; this result may account, in part, for the extremely high 7/6 alkene ratios (37-81/1) obtained from elimination reactions of RFCH2CHICH3.All series II compounds, RFCH2CHI(CH2) nCH3 (n = 0-5), gave entirely elimination, and principally toward the RF group.E/Z isomer ratios varied from 2.65 to 5.These results were compared to those obtained from 1- and 2-iodooctane under the same conditions.A practical synthesis of CF3(CF2)5CH2CH2CH2I is described; the isomeric (F-alkyl)propenes 6 and 7 were also separately prepared.Rates of reactions under standard conditions for both series I and II compounds were measured.Kinetically, only second-order processes were observed, but a sharp break occurred in rate as the RF group was separated more than two carbons from the departing iodine atom, in series I compounds.Series II compounds reacted about one-tenth as fast as series I compounds.These results are discussed in the context of previous work with F-alkyl-substituted compounds.
- Brace, Neal O.,Marshall, Lawrence W.,Pinson, Carol J.,Wingerden, Gail van
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p. 2361 - 2368
(2007/10/02)
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- SOME APPROACHES TO THE SYNTHESIS OF FLUORINATED ALCOHOLS AND ESTERS. II. USE OF F-ALKYL IODIDES FOR THE SYNTHESIS OF F-ALKYL ALKANOLS
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Free radical addition of an F-alkyl iodide (RFI) to an alkenol or ester, followed by appropriate reduction is an efficient method for preparating the corresponding F-alkyl-alkanols of the homologous series, RF(CH2)nOH.When n=2, 4 or higher, the two steps take place smoothly.The 1,2,3-substituted systems RFCH2CHYCH2Z, however, are susceptible to surprising difficulties.Reduction of RFCH2CHICH2OH to RF(CH2)3OH by hydrogen and catalyst (strong base acid acceptor), can be done either in one step or via RFCH=CHCH2OH; however, dehydrohalogenation may also give the epoxide, and reduction in this case leads to the secondary alcohol, RFCH2CH(CH3)OH.By contrast, reduction of RFCH2CHICH2OAc by tributyltin hydride or with hydrogen over palladium (diethylamine acid acceptor) goes smoothly.Zinc and acid reduction of RFCH2CHICH2OAc gives elimination to RFCH2CH=CH2; even RFCH=CICH2OH gives RFCH=C=CH2 besides RFCH=CHCH2OH.RFCH=CICH2CH2OH, however, with zinc and acid is reduced cleanly to RFCH=CHCH2CH2OH.
- Brace, Neal O.
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p. 313 - 328
(2007/10/02)
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