Hexachlorocyclopentadiene in diels—alder asymmetric reaction

Ахмедов, И. М.; Peynircioglu, B.; Mamedov, E. G.; Tanyeli, Cihangir; Demir, Ayhan S.

doi:10.1016/s0040-4020(01)85072-9

Cited by 9 publications

(2 citation statements)

References 8 publications

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“…The derivatives of the Diels-Alder adduct of HCC can be used as building blocks for the synthesis of antibiotics, phytotoxins and functionalized carbocyclic nucleoside analogues (Berger, Rabiller, K6nigsberger, Faber & Griengl, 1990;Duke & Wells, 1987). It was also reported that the asymmetric thermal Diels-Alder reactions with chiral dienophiles L-menthyl acrylate and L-menthyl allyl ether gave cycloadducts of HCC up to 15% optical yield of predominant enantiomer (Akhmedov, Peynircio~lu, Mamedov, Tanyeli & Demir, 1994). Milder reaction conditions achieved by the use of Lewis-acid catalysts (BF3.OEt, BBr3, SnC14, A1CI3) increased the optical yields up to 2.8-fold.…”

Section: Commentmentioning

confidence: 96%

“…That the (-)-isomer of the product has an (R) configuration is shown for the first time as a result of this study. Previously, the (R) product was obtained only by thermal Diels-Alder reactions (Akhmedov et al, 1994). The TiCI4 catalyzed reaction seems to be proceeding through completely different transition states compared with the other Lewis-acid-catalyzed reactions.…”

Section: Commentmentioning

confidence: 98%

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Configuration of the Diels–Alder Adduct of Hexachlorocyclopentadiene withL-Menthyl Acrylate

Ülkü¹,

Tahir²,

Demir³

et al. 1997

Acta Crystallogr C

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Section: Commentmentioning

confidence: 96%

Section: Commentmentioning

confidence: 98%

Configuration of the Diels–Alder Adduct of Hexachlorocyclopentadiene withL-Menthyl Acrylate

Ülkü¹,

Tahir²,

Demir³

et al. 1997

Acta Crystallogr C

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ChemInform Abstract: Hexachlorocyclopentadiene in Diels‐Alder Asymmetric Reaction.

et al. 1994

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Acetylenic Esters of Polychlorobicyclo[2.2.1]hept-2-ene-5-carboxylic Acids

Mamedov

2005

Russ J Appl Chem

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Acetylenic esters of polychlorobicyclo[2.2.1]hept-2-ene-5-carboxylic acids were prepared from the corresponding acid chlorides and acetylenic alcohols.Polyhalonorbornenes are widely used in production of synthetic polyester resins with enhanced heat and flame resistance, epoxy resins, and additives to lubricating oils, and also as starting compounds in organic synthesis [133]. They exhibit fungicide, insecticide, and hebricide power and other kinds of biological activity. Modification with reactive acetylenic fragments enhances these properties. Interest in polyhalonorbornene derivatives is steadily growing, and new compounds of this class are being synthesized [4,5]. The presence of heavy halogen atoms extends the possibilities of structural studies of these compounds by IR and NMR spectroscopy and X-ray diffraction analysis [6 38].Acetylenic esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acids were studied in [9311]. In this study we developed preparation procedures and examined the structures of acetylenic esters of polychlorinated norbornenecarboxylic acids. These esters are prepared by the reactions of polychlorobicyclo[2.2.1]hept-2-ene-5-carboxylic acid chlorides with acetylenic alcohols. The starting chlorides V!VII were prepared by [4+2]-cycloaddition of chlorinated cyclopentadienes I!III to acryloyl chloride IV: I3III IV V3VII, where X = Cl (I, V), H (II, VI), OCH 3 (III, VII).The condensation of I!III with IV was performed at 100 3150oC for 10 315 h. The best results were obtained at 140oC, reaction time 10 h. Replacement of the geminal chlorine atoms by methoxy groups and hydrogen atoms favorably affects the reaction course; the yield of V!VII increases (see table).The 1 H NMR spectra show that compounds V!VII prepared under these conditions are exclusively endo isomers.Reactions of acid chlorides V!VII with alkynes VIII!X yielded the corresponding acetylenic esters of polychlorinated norbornenecarboxylic acids, XI!XIX: V3VII VIII3X XI3XIX , where R 1 = R 2 = H (VIII); R 1 = CH 3 , R 2 = H (IX); R 1 = CH 3 , R 2 = CH=CH 2 (X); R 1 = R 2 = H, X = Cl (XI); R 1 = CH 3 , R 2 = H, X = Cl (XII); R 1 = CH 3 , R 2 = CH=CH 2 , X = Cl (XIII); R 1 = R 2 = X = H (XIV); R 1 = CH 3 , R 2 = X = H (XV); R 1 = CH 3 , R 2 = CH=CH 2 , X = H (XVI); R 1 = R 2 = H, X = OCH 3 (XVII); R 1 = CH 3 , R 2 = H, X = OCH 3 (XVIII); R 1 = CH 3 , R 2 = CH=CH 2 , X = OCH 3 (XIX).The reaction was performed in organic solvents (diethyl ether, benzene) in the presence of tertiary amines (triethylamine, pyridine).The use of chlorides V!VII as starting compounds allows preparation of esters XI!XIX of high purity

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Hexachlorocyclopentadiene in diels—alder asymmetric reaction

Cited by 9 publications

References 8 publications

Configuration of the Diels–Alder Adduct of Hexachlorocyclopentadiene withL-Menthyl Acrylate

Configuration of the Diels–Alder Adduct of Hexachlorocyclopentadiene withL-Menthyl Acrylate

ChemInform Abstract: Hexachlorocyclopentadiene in Diels‐Alder Asymmetric Reaction.

Acetylenic Esters of Polychlorobicyclo[2.2.1]hept-2-ene-5-carboxylic Acids

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