A method has been developed for effecting rearrangements of allylacetoacetates to γ,δ-unsaturated ketones (Carroll rearrangement) and allylaryl ethers to the corresponding allylphenols (Claisen rearrangement) under conditions of adsorption on aluminum oxide and silica gel. The method provides a sharp reduction of the temperature of these reactions and improvement of their efficiency.

The x-ray crystal structures of two adducts of intramolecular cyclization are studied. These are tetracyclo[10.3.0.0 1.9 .0 3.8 ]pentadeca-3, (8),9-diene-2,11-dione (III) and 7-methoxytetracyclo [9.3.0.0 1.8 .0 3.7 ]tetradeca-8-ene-2,10-dione (IV). For III: a = 13.427(2), b = 10.639(2), c = 8.258(1) A, space group P2 1 2 1 2 1 , Z = 4. For IV: a = 15.834(2), b = 13.344(2), c = 6.524(04) A, γ = 71.50(1)°, space group P2 1 /a, Z = 4

The x-ray crystal structures of two adducts of intramolecular cyclization are studied. These are tetracyclo[10.3.0.0 1.9 .0 3.8 ]pentadeca-3, (8),9-diene-2,11-dione (III) and 7-methoxytetracyclo [9.3.0.0 1.8 .0 3.7 ]tetradeca-8-ene-2,10-dione (IV). For III: a = 13.427(2), b = 10.639(2), c = 8.258(1) A, space group P2 1 2 1 2 1 , Z = 4. For IV: a = 15.834(2), b = 13.344(2), c = 6.524(04) A, γ = 71.50(1)°, space group P2 1 /a, Z = 4

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

AbstractStarting with isobutyraldehyde (I), the methylpentenynecobalt carbonyl complex (VI) is prepared via the intermediates (III) and (V).

AbstractThe dienes (I) and (VI) are coupled with the dienophiles (II) or (IV) in the presence of silica to give the cycloadducts (III), (V), and (VII) respectively.

An essentially new method was developed for carrying out [4 + 2]cycloaddition on the surface of Chromatographie adsorbents in the absence of solvent. This method permits the use of much milder reaction conditions and to increase the reaction's selectivity.

Reaction of methoxyallene with arylsulphenyl chlorides proceeds nonselectively with formation of mixtures of 1,2- and 2,3-arylthiochloro adducts, the composition of which depends on the nature of the reagent and solvent. π-Donating compounds of various types in the presence of Lewis acids are alkylated by adducts of methoxyallene with arylsulphenyl chlorides and primarily products are formed by attack at the C3 atom of the reagent.

ChemInformVolume 21, Issue 38 Isocyclic Compounds ChemInform Abstract: Alkylation of π-Donor Compounds with Methoxyallene - Arenesulfenyl Chloride Adducts. I. P. SMOLYAKOVA, I. P. SMOLYAKOVA Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorV. A. SMIT, V. A. SMIT Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorA. I. LUTSENKO, A. I. LUTSENKO Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorE. D. DAEVA, E. D. DAEVA Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this author I. P. SMOLYAKOVA, I. P. SMOLYAKOVA Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorV. A. SMIT, V. A. SMIT Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorA. I. LUTSENKO, A. I. LUTSENKO Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorE. D. DAEVA, E. D. DAEVA Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this author First published: September 18, 1990 https://doi.org/10.1002/chin.199038188Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. References I. P. SMOLYAKOVA, V. A. SMIT, A. I. LUTSENKO, E. D. DAEVA, Alkylation of π-Donor Compounds with Methoxyallene - Arenesulfenyl Chloride Adducts., Izv. Akad. Nauk SSSR, Ser. Khim., 1990, 114–121. Google Scholar Volume21, Issue38September 18, 1990 ReferencesRelatedInformation

AbstractThe dicobalt hexacarbonyl complexes (I) of conjugated enynes are coupled with alkenoyl tetrafluoroborates, generated in situ from the alkenoyl fluorides (II) and boron trifluoride, to give the alkenynone complexes (IV).

AbstractAcylation of the cobalt carbonyl complex (I) with acryloyl tetrafluoroborate, prepared in situ from acryloyl fluoride (II) and boron trifluoride, and subsequent reaction with the nucleophiles methanol (III) or H2O produce the undecadiyne complex (IV) or the dihydropyran complex (V).

The β-arylthioalkylation of 2-methoxy-1,3-butadiene is regiospecific at the alkoxy-substituted C=C bond, giving 6-arylthioalk-1-en-3-ones.

A two-step synthesis was proposed for the tetracyclic triquinane bis-enone from two monocyclic precursors. The bis-enone obtained is a structural fragment of retigeranic acid.

ChemInformVolume 20, Issue 38 Isocyclic Compounds ChemInform Abstract: Intramolecular Khand-Pauson Reaction with Participation of an Electron Deficient Double Bond. A. L. VERETENOV, A. L. VERETENOV Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorA. S. GYBIN, A. S. GYBIN Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorV. A. SMIT, V. A. SMIT Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this author A. L. VERETENOV, A. L. VERETENOV Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorA. S. GYBIN, A. S. GYBIN Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorV. A. SMIT, V. A. SMIT Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this author First published: September 19, 1989 https://doi.org/10.1002/chin.198938189Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume20, Issue38September 19, 1989 RelatedInformation

Acylation of the dicobaltohexacarbonyl complex of 4-methylpenten-3-yne-1 with acryloyl tetrafluoroborate in a medium containing nitromethane with subsequent addition of a nucleophile (methanol or water) leads to anomalous products that are made up of two molecules of starting enyne and one fragment of acryloyl cation. On methanolysis a product of linear structure is formed — a functionally substituted undecane, and on hydrolysis a cyclic product is formed — a functionally substituted dihydropyran.

Dicobaltohexacarbonyl 4-methyl-pent-3-en-1-yne complexes have been acylated with acryloyl and crotonoyl tetrafluoroborates followed by methanolysis to make acylmethoxy adducts containing hem-dimethyl moieties. Conditions have been defined under which such adducts containing enone systems are selectively reduced to allyl acohols with retention of the cobaltocarbonyl moieties. The latter can be converted by Quand-Poson reaction to the inaccessible polyfunctional derivatives of 7,7-dimethylbicyclo[3.3.0]octane.

1,4-Adducts of 1-alkoxybutadiene with arylsulfenyl chlorides were obtained. It was shown that these adducts can be used as C-electrophiles to transfer 1-alkoxy-4-arylthiobuten-2-al groups in reactions with π-donors.