- Engineering active sites on reduced graphene oxide by hydrogen plasma irradiation: Mimicking bifunctional metal/supported catalysts in hydrogenation reactions
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H2 plasma has been used to generate carbon vacancies on reduced graphene oxide to increase its catalytic activity as a hydrogenation catalyst. A relationship between the power of the plasma treatment and the exposure time with the activity of the material was observed for CC double bond hydrogenation. The activity data in the case of 1-octene, showing skeletal isomerization besides hydrogenation, indicate that H2 plasma treatment can introduce hydrogenating and acid sites rendering a bifunctional catalyst that is reminiscent of the activity of noble metals supported on acid supports.
- Primo, Ana,Franconetti, Antonio,Magureanu, Monica,Mandache, Nicolae Bogdan,Bucur, Cristina,Rizescu, Cristina,Cojocaru, Bogdan,Parvulescu, Vasile I.,Garcia, Hermenegildo
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p. 2611 - 2623
(2018/06/18)
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- FRAGRANCE MATERIAL
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Fragrance compounds having a unique chemical structure are provided, including 2-methoxy-2-methylheptane and derivatives thereof. The fragrance compounds can have fruity, radish, and/or herbaceous odor notes with a strong top note. The fragrance compounds can be used alone or incorporated into a fragrance composition and/or consumer product to modify or enhance the odor of the fragrance composition and/or consumer product.
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Page/Page column 21; 22
(2018/01/15)
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- Molybdenum carbonyl grafted onto silicate intercalated cobalt-aluminum hydrotalcite: A new potential catalyst for the hydroformylation of octene
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We present the first example of molybdenum carbonyl grafted on diaminosiloxane-functionalized cobalt-aluminum hydrotalcite (CA-HTSi-DA-Mo) as a promising catalyst for the hydroformylation of olefins. The catalyst showed 80% conversion with selective formation of branched aldehyde. About 70% of the catalytic activity retains even after three cycles.
- Sakthivel, Ayyamperumal,Mahato, Nihar Ranjan,Baskaran, Thangaraj,Christopher, Jayaraj
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- Palladium-catalyzed desulfinylative C-C allylation of Grignard reagents and enolates using allylsulfonyl chlorides and esters
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2-Methylprop-2-ene-, prop-2-ene-, 1-methylprop-2-ene-, and (E)-but-2-enesulfonyl chlorides have been used as electrophilic partners in desulfinylative palladium-catalyzed C-C coupling with Grignard reagents and sodium salts of dimethyl malonate and methyl
- Rao Volla, Chandra M.,Dubbaka, Srinivas Reddy,Vogel, Pierre
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experimental part
p. 504 - 511
(2009/04/07)
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- A remarkable catalytic activity of [Cu(NCMe)2(PPh 3)2]BF4 in conjugate addition of organomanganese reagents to α,β-unsaturated ester, enone and allyl chloride
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A simple and convenient method of conjugate addition of alkyl and aryl organomanganese reagents to α,β-unsaturated ester and enone and allyl chloride in presence of Cu(I) salts is described. Conjugated products result with [Cu(NCMe)2(PPh3)2]BF4 as a catalyst along with chlorosilane as an accelerator at -10 to 0 °C.
- Deshmukh,Jadhav, Sunil,Anbhule,Mali,Suryawanshi
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p. 248 - 250
(2007/10/03)
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- Reactions of Saturated and Unsaturated Tertiary Alkyl Halides and Saturated Secondary Alkyl Iodides with Lithium Aluminum Deuteride. Convincing Evidence for a Single-Electron-Transfer Pathway
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Reactions of saturated secondary and tertiary alkyl halides with LiAlH4 (LAH) and LiAlD4 (LAD) have been carried out, and convincing evidence for a single-electron-transfer (SET) pathway has been obtained. Reactions involving saturated alkyl halides with LAD provide a model system in which a halogen-atom radical chain process is not possible, and therefore, the observation of large quantities (in some cases >90 percent) of protium in the reduction product provides strong evidence for a radical intermediate and a SET pathway. Specifically, the reaction of 2-iodooctane (10) with LAD produced octane with a deuterium content as low as 21 percent. Also, the reaction of the tertiary halide 2-iodo-2-methylheptane (15) with LAD produced 2-methylheptane (16) with a deuterium content as low as 8 percent. The effect of stoichiometry, halogen type, and reaction vessel surface on these reactions was studied. Reaction of the unsaturated tertiary halide 6-iodo-6-methyl-1-heptene (25) with LAD was also studied and was found to proceed predominantly by a SET process involving a halogen-atom radical chain process. The possibility of a carbocation intermediate in all of these reactions is discussed.
- Ashby, E. C.,Welder, Catherine O.
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p. 7707 - 7714
(2007/10/03)
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- The Synthetic Potential of the Isocyanide-Cyanide Rearrangement
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Excellent chemical and optical yields (>96percent retention) of cyanides are achieved by vapor phase thermolysis or short contact flow thermolysis of isocyanides. trans-2-Butenyl isocyanide rearranges without concomitant allylic isomerization to trans-2-butenyl cyanide.Optically active 1-(formyloxymethyl)-2-phenylethyl cyanide is obtained from optically active L-phenylalanine as a new type of chiral pool synthon.
- Meier, Michael,Ruechardt, Christoph
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- Preparation of 1-Alkenes by the Palladium-Catalyzed Hydrogenolysis of Terminal Allylic Carbonates and Acetates with Formic Acid-Triethylamine
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A useful method for the preparation of 1-alkenes from terminal allylic carbonates and acetates by the palladium-catalyzed reaction with formates is described.Formic acid-triethylamine is a suitable reductant.As catalyst, Pd2(dba)3CHCl3-P(n-Bu)3 gave the best result, 0.05-0.2 molpercent being sufficient (turnover 500-2000).Using this method, various 1-alkenes were prepared in good yields with high selectivity.
- Tsuji, Jiro,Minami, Ichiro,Shimizu, Isao
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p. 623 - 627
(2007/10/02)
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- ORGANIC PHOTOCHEMISTRY WITH 6.7eV PHOTONS: DECOMPOSITION OF 1,1-DISUBSTITUTED CYCLOPROPANES IN SOLUTION
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The course of the two-bond cleavage reactions of cyclopropanes in photolysis at 185nm in solution is strikingly influenced by disubstitution of one of the carbons in the ring.
- Srinivasan, R,Baum, Thomas,Ors, Jose A.
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p. 4795 - 4798
(2007/10/02)
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- Photochemistry of Alkenes. 6. Direct Irradiation of 1,5-Hexadienes: and Sigmatropic Allyl Shifts
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The photochemical behavior of a series of alkyl-substituted 1,5-hexadienes has been studied.Competing allylcyclopropane formation and rearrangement to an isomeric 1,5-hexadiene via competing and sigmatropic allyl shifts, respectively, were observed.In one case a product (30 from 27) and in another a product (35 from 31) was obtained, but only in low yield.Extensive cis trans isomerization competed with the allyl shifts, and, in addition, other products were obtained which are characteristic of the photochemical behavior of isolated double bonds.At low conversion diene 10t underwent stereoselective rearrangement to 8t and 11t, whereas the cis isomer 10c afforded mixtures of the cis and trans isomers of 8 and 11.Attempts to induce the allyl migrations by sensitization with p-xylene or by irradiation at 254 nm afforded only cis trans isomerization.It is concluded that the allyl migrations occur via an excited state involving interaction between the double bonds and requiring a conformation in which the central C3-C4 bond is in a plane orthogonal to both double bonds, as proposed previously.In contrast with the acyclic dienes, 1,5-cyclooctadiene (50) afforded products 51-53 from competing , , and allyl shifts, respectively.The divergent behavior in this case apparently arises because appropriate interaction between the two double bonds can occur only in the boat conformation.
- Manning, T. D. R.,Kropp, Paul J.
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p. 889 - 897
(2007/10/02)
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