- A new synthesis of α,β-unsaturated aldehydes: Synthesis of traumatin and bombykol
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A novel conversion of an alkene to a higher homologue α,β-unsaturated aldehyde was achieved in three steps. The aldehydes were used for the synthesis of traumatin, a wound hormone and bombykol, the pheromone of bombyx mori.
- Dasaradhi,Neelakantan,Jagadishwar,Bhalerao
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- Copper-catalyzed method for preparing aldehyde or ketone compound by oxidizing alcohol with oxygen as oxidizing agent and application
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The invention discloses a copper-catalyzed method for preparing an aldehyde or ketone compound by oxidizing alcohol with oxygen as an oxidizing agent. Reaction is performed in an organic solvent for 4-48 hours at room temperature by using copper salt and nitroxide free radicals as catalysts and oxygen or air as an oxidizing agent to efficiently oxidize an alcohol compound into the corresponding aldehyde or ketone compound. The method is simple to operate, free of chlorides corrosive to equipment, available in raw materials and reagents, mild in reaction conditions, wide in substrate universality, good in functional group compatibility, convenient in separation and purification, environmentally friendly in the whole process and free of pollution, and is a method suitable for industrial production.
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Paragraph 0028-0030; 0145-0147; 0181-0183
(2020/08/18)
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- Formation of potentially toxic carbonyls during oxidation of triolein in the presence of alimentary antioxidants
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Abstract: A relation between oil uptake and cancer as well as induction of hepatic inflammation was shown earlier. It is discussed that the main oil oxidation products—hydroperoxides and carbonyls—might be the reason for the mentioned diseases. In this manuscript quantitative determination of aldehydes which are formed during oxidation of triolein—as a model substance—using the Rancimat 679 is described. The oxidation of 11?g of triolein is carried out at 120?°C sparging air with a flow of 20?dm3/h for 10?h. A series of aliphatic aldehydes starting from hexanal to decanal as well as decenal was identified by LC–MS/MS and quantified as DNPH derivatives. In addition, the total amount of carbonyls was determined. Based on the calibration with hexanal, all other dominant substances were in the similar concentration range with maximum concentrations of 1.6?μmol/cm3 of hexanal, 2.3?μmol/cm3 of heptanal, 2.5?μmol/cm3 of octanal, 3.2?μmol/cm3 of nonanal, 4.0?μmol/cm3 of decanal after 6?h. The total amount of carbonyls reached a maximum after 6?h being 27?μmol/cm3 for triolein without antioxidant. The results of this investigation will be a basis for further toxicological studies on oxidized oils.
- Damanik, Marini,Murkovic, Michael
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p. 2031 - 2035
(2017/10/26)
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- Method to oxidize alcohols selectively to aldehydes and ketones with heterogeneous supported ruthenium catalyst at room temperature in air and catalyst thereof
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The present invention relates to a method for selectively oxidizing alcohol by using a heterogeneous catalyst for producing aldehyde and ketone in an organic synthesis process used in the laboratory and chemical industries, and a catalytic system thereof. The method can be used as an intermediate product for synthesizing medicine, scent, fragrance, and precise chemical products, and can use a heterogeneous catalyst at room temperature in air by using the catalytic system and producing alcohol and ketone.COPYRIGHT KIPO 2016
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Paragraph 0021; 0022
(2016/10/07)
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- Selective oxidation of styrene catalyzed by cerium-doped cobalt ferrite nanocrystals with greatly enhanced catalytic performance
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The rare earth metal Ce-doped cobalt ferrite samples CexCo1?xFe2O4 (x?=?0.1, 0.3, 0.5) were prepared by the sol–gel autocombustion route. The as-prepared samples were characterized by X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, ICP–atomic emission spectroscopy, and N2 physisorption. Their catalytic performance was evaluated in oxidation of styrene using hydrogen peroxide (30%) as oxidant. Compared with pristine CoFe2O4, the Ce-doped samples were found to be more efficient catalysts for the oxidation of styrene to benzaldehyde, with greatly enhanced catalytic performance. Especially, when Ce0.3Co0.7Fe2O4 was used as catalyst, 90.3% styrene conversion and 91.5% selectivity for benzaldehyde were obtained at 90?°C for 9?h reaction. The catalyst can be magnetically separated easily for reuse, and no obvious loss of activity was observed when it was reused in five consecutive runs.
- Tong, Jinhui,Li, Wenyan,Bo, Lili,Wang, Huan,Hu, Yusen,Zhang, Zhixia,Mahboob, Abdulla
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p. 474 - 481
(2016/11/18)
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- 1H-pyrrole-2,4-dicarbonyl-derivatives and their use as flavoring agents
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The present invention primarily relates to 1H-pyrrole-2,4-dicarbonyl-derivatives of Formula (I) wherein R1, R2, R3, Z. Z' and J are as defined in the description, to mixtures thereof and to the use thereof as flavoring agents. The compounds in accordance with the present invention are suitable for producing, imparting, or intensifying an umami flavor. The invention further relates to flavoring mixtures, compositions for oral consumption as well as ready-to-eat, ready-to-use and semifinished products, comprising an effective amount of the compound of Formula (I) or of a mixture of compounds of Formula (I) and to specific methods for producing, imparting, modifying and/or intensifying specific flavor impressions.
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- Imidazo[1,2-a]pyridine-ylmethyl-derivatives and their use as flavoring agents
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The present invention primarily relates to imidazo[1,2-a]pyridine-ylmethyl-derivatives of Formula (I) wherein R1, R2, X, W e J are as defined in the description, to mixtures thereof and to the use thereof as flavoring agents. The compounds in accordance with the present invention are suitable for producing, imparting, or intensifying an umami flavor. The invention further relates to flavoring mixtures, compositions for oral consumption as well as ready-to-eat, ready-to-use and semifinished products, comprising an effective amount of the compound of Formula (I) and to specific methods for producing, imparting, modifying and/or intensifying specific flavor impressions.
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- Synthesis of α,β-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs' catalysts
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A series of α,β-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs' catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (≥90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids.
- Rountree, Sandra M.,Taylor, Sarah F.R.,Hardacre, Christopher,Lagunas, M. Cristina,Davey, Paul N.
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- Iron-catalyzed aerobic oxidation of allylic alcohols: The issue of C=C bond isomerization
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An aerobic oxidation of allylic alcohols using Fe(NO3) 3·9H2O/TEMPO/NaCl as catalysts under atmospheric pressure of oxygen at room temperature was developed. This eco-friendly and mild protocol provides a convenient pathway to the synthesis of stereodefined α,β-unsaturated enals or enones with the retention of the C-C double-bond configuration.
- Liu, Jinxian,Ma, Shengming
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supporting information
p. 5150 - 5153
(2013/11/06)
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- A detailed identification study on high-temperature degradation products of oleic and linoleic acid methyl esters by GC-MS and GC-FTIR
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GC-MS and GC-FTIR were complementarily applied to identify oxidation compounds formed under frying conditions in methyl oleate and linoleate heated at 180 °C. The study was focused on the compounds that originated through hydroperoxide scission that remain attached to the glyceridic backbone in fats and oils and form part of non-volatile molecules. Twenty-one short-chain esterified compounds, consisting of 8 aldehydes, 3 methyl ketones, 4 primary alcohols, 5 alkanes and 1 furan, were identified. In addition, twenty non-esterified volatile compounds, consisting of alcohols, aldehydes and acids, were also identified as major non-esterified components. Furanoid compounds of 18 carbon atoms formed by a different route were also identified in this study. Overall, the composition of the small fraction originated from hydroperoxide scission provides a clear idea of the complexity of the new compounds formed during thermoxidation and frying.
- Berdeaux, Olivier,Fontagné, Stéphanie,Sémon, Etienne,Velasco, Joaquin,Sébédio, Jean Louis,Dobarganes, Carmen
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experimental part
p. 338 - 347
(2012/06/29)
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- Structure-Activity relationship of aliphatic compounds for nematicidal activity against pine wood nematode (Bursaphelenchus xylophilus)
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Nematicidal activity of aliphatic compounds was tested to determine a structure-activity relationship. There was a significant difference in nematicidal activity among functional groups. In a test with alkanols and 2E-alkenols, compounds with C8-C11 chain length showed 100% nematicidal activity against pine wood nematode, Bursaphelenchus xylophilus, at 0.5 mg/mL concentration. C6-C10 2E-alkenals exhibited >95% nematicidal activity, but the other compounds with C 11-C14 chain length showed weak activity. Nematicidal activity of alkyl acetates with C7-C11 chain length was strong. Compounds belonging to hydrocarbons, alkanals, and alkanoic acetates showed weak activity at 0.5 mg/mL concentration. Nematicidal activity of active compounds was determined at lower concentrations. At 0.25 mg/mL concentration, whole compounds except C8 alkanol, C8 2E-alkenol, and C7 alkanoic acid showed >80% nematicidal activity. C 9-C11 alkanols, C10-C11 2E-alkenols, C8-C9 2E-alkenals, and C9-C10 alkanoic acids showed >80% nematicidal activity at 0.125 mg/mL concentration. Only C11 alkanol exhibited strong nematicidal activity at 0.0625 mg/mL concentration, the lowest concentration that was tested. 2010 American Chemical Society.
- Seo, Seon-M.I.,Junheon, Kim,Eunae, Kim,Park, Hye-M.I.,Kim, Young-Joon,Park, I.L.-Kwon
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experimental part
p. 1823 - 1827
(2010/09/09)
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- PpoC from Aspergillus nidulans is a fusion protein with only one active haem
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In Aspergillus nidulans Ppos [psi (precocious sexual inducer)-producing oxygenases] are required for the production of so-called psi factors, compounds that control the balance between the sexual and asexual life cycle of the fungus. The genome of A. nidulans harbours three different ppo genes: ppoA, ppoB and ppoC. For all three enzymes two different haem-containing domains are predicted: a fatty acid haem peroxidase/ dioxygenase domain in the N-terminal region and a P450 haem-thiolate domain in the C-terminal region. Whereas PpoA was shown to use both haem domains for its bifunctional catalytic activity (linoleic acid 8-dioxygenation and 8-hydroperoxide isomerization), we found that PpoC apparently only harbours a functional haem peroxidase/dioxygenase domain. Consequently, we observed that PpoC catalyses mainly the dioxygenation of linoleic acid (18:2Δ 9Z,12Z), yielding 10-HPODE (10-hydroperoxyoctadecadienoic acid). No isomerase activity was detected. Additionally, 10-HPODE was converted at lower rates into 10-KODE (10-keto-octadecadienoic acid) and 10-HODE (10-hydroxyoctadecadienoic acid). In parallel, decomposition of 10-HPODE into 10-ODA (10-octadecynoic acid) and volatile C-8 alcohols that are, among other things, responsible for the characteristic mushroom flavour. Besides these principle differences we also found that PpoA and PpoC can convert 8-HPODE and 10-HPODE into the respective epoxy alcohols: 12,13-epoxy-8-HOME (where HOME is hydroxyoctadecenoic acid) and 12,13-epoxy-10-HOME. By using site-directed mutagenesis we demonstrated that both enzymes share a similar mechanism for the oxidation of 18:2Δ9Z,12Z; they both use a conserved tyrosine residue for catalysis and the directed oxygenation at the C-8 and C-10 is most likely controlled by conserved valine/leucine residues in the dioxygenase domain. The Authors Journal compilation
- Brodhun, Florian,Schneider, Stefan,Goebel, Cornelia,Hornung, Ellen,Feussner, Ivo
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experimental part
p. 553 - 565
(2011/02/23)
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- Copper-catalyzed rearrangement of vinyl oxiranes
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A novel copper-catalyzed vinyl oxirane ring expansion protocol has been developed. A wide range of vinyl oxiranes can be rearranged to 2,5-dihydrofurans in excellent yields in the presence of electrophilic copper(II) acetylacetonate catalysts. Regioisomeric vinyl oxiranes can be converted to a single dihydrofuran product using these conditions. This method uses low catalyst loadings (0.5-5 mol %), has good tolerance of substitution patterns, and can be done in the absence of solvent. Copyright
- Batory, Lindsay A.,McInnis, Christine E.,Njardarson, Jon T.
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p. 16054 - 16055
(2007/10/03)
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- γ-p-toluenesulfonyl-α,β-epoxysilane: A new and practical acrolein β-anion equivalent
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(Chemical Equation Presented) Reaction of γ-p-toluenesulfonyl- α,β-epoxysilane with alkyl halides and aldehydes followed by treatment with n-Bu4NF affords α,β-unsaturated aldehydes via a Brook rearrangement-mediated tandem process under extremely mild conditions.
- Sasaki, Michiko,Takeda, Kei
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p. 4849 - 4851
(2007/10/03)
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- Synthesis of α,β-unsaturated aldehydes and methyl carboxylic esters from 2-acetylenic phenyl sulfides
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2-Alkynylthio benzenes were reduced to 2-Alkenylthio benzenes with diisobutyl aluminum hydride. Mono chlorination of these compounds with sulfuryl chloride and pyridine followed by hydrolysis, in the presence of Cu(II) salts, gave α,β-unsaturated aldehydes. 2-Alkynylthio benzenes were converted into 2-Alkynyl 1,1-bis thiobenzenes by monochlorination with sulfuryl chloride and pyridine followed by treatment with thiophenol and triethylamine. These substances were then converted to α,β-unsaturated methyl carboxylic esters by way of isomerization with sodium methoxide to the corresponding allene and treatment with hydrochloric acid and methanolysis in the presence of iodine.
- Fortes, Carlos C.,Garrote, Clevia F. D.
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p. 3917 - 3941
(2007/10/03)
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- Synthesis of (2E,4E)-dienals by double formyl-olefination with an arsonium salt and its application in the syntheses of lipoxygenase metabolites of arachidonic acid
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A new facile route to (2E,4E)-dienals by a double formyl-olefination with arsonium salts has been developed. By this method and with other arsonium reagents in the key step some lipoxygenase metabolites of arachidonic acid, lipoxin A4 and B4 and leukotriene B4, have been synthesized.
- Peng, Zhi-Hui,Li, Yun-Long,Wu, Wen-Lian,Liu, Cui-Xian,Wu, Yu-Lin
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p. 1057 - 1066
(2007/10/03)
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- Synthesis of carbonyl and dicarbonyl compounds from organometallic reagents and N-imidazolium-N-methyl amides and bis-amides
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A new method for the synthesis of selective acylating agents is described from the reaction of carboxylic acids with 3-methyl-1-methylamino-3H-imidazol-1-ium salts in the presence of appropriate coupling reagents. The amides and bis-amides thus prepared reacted selectively with organometallics to afford ketones and diketones and with DIBALH to give aldehydes and dialdehydes in high yields.
- De Las Heras, Maria A.,Vaquero, Juan J.,Garcia Navio, Jose L.,Alvarez-Builla, Julio
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p. 14297 - 14310
(2007/10/03)
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- A Simple, Effective, New, Palladium-Catalyzed Conversion of Enol Silanes to Enones and Enals
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Enol silanes derived from aldehydes and ketones are readily converted to the corresponding α,β-unsaturated carbonyl compounds by 10percent Pd(OAc)2 in the presence of one atmosphere of oxygen in DMSO as the solvent.
- Larock, Richard C.,Hightower, Timothy R.,Kraus, George A.,Hahn, Pat,Zheng, Deye
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p. 2423 - 2426
(2007/10/02)
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- Two- and Four-Carbon Homologation of Aldehyde by AgClO4-Catalyzed Addition of Alkoxyalkenylzirconocene Chloride
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Two-and four-carbon homologation of aldehyde is described, which is based on the AgClO4-catalyzed addition of zirconocene complexes, derived from hydrozirconation of 1-ethoxyethyne (1) and (Z)-1-methoxy-1-buten-3-yne (2) with Cp2Zr(H)Cl, followed by acidic hydrolysis.
- Maeta, Hideki,Suzuki, Keisuke
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p. 341 - 344
(2007/10/02)
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- β-Phenylseleno α,β-unsaturated aldehydes, efficient three carbon homologating agents. 1,3-carbonyl transposition
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The easily obtained β-phenylseleno α,β-unsaturated aldehydes react with Grignard reagents and with n-butyllithium leading to the 1,2-addition products, which upon acidic hydrolysis in the presence of silica gel afford the selenium-free α,β-unsaturated carbonyl compounds with 1,3-carbonyl transposition.
- Arrua,Comasseto
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p. 1663 - 1666
(2007/10/02)
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- SYNTHESIS OF 4,6-DIALKYL-1,3-DIOXINS. VERSATILE INTERMEDIATES FOR THE PREPARATION OF (E)-ALKENONES, anti,anti-1,2,3-TRIOLS AND syn-1,3-DIOLS
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The title compounds 4 are prepared from 4-alkyldioxins 2 via a metalation, alkylation sequence.The dialkyl dioxins 4 are thermally labile (providing enones) and undergo highly stereoselective hydroboronation or hydrogenation reactions to provide anti,anti-1,2,3-triols and syn-1,3-diols, respectively.This methodology has been exploited in the synthesis of (+/-)-endo-1,3-dimethyl-2,9-dioxabicyclononane.
- Funk, Raymond L.,Bolton, Gary L.
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p. 1111 - 1114
(2007/10/02)
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- Oxidative Breaking of Long-Chain Acetylenic Enol Ethers of Glycerol of the Marine Sponges Raspailia pumila and R. ramosa and of Model Compounds with Aerial Oxygen
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The raspailynes (novel long-chain enol ethers of glycerol having the enol ether double bond conjugated, in sequence, to an acetylenic and an olefinic bond, isolated from the North-East-Atlantic sponges Raspailia pumila and R. ramosa) are stable under normal hydrolytic conditions for enol ethers.In contrast, when their solutions are evaporated, these lipids such as raspailyne B1 (=(-)-3--1,2-propanediol; (-)-2) rapidly react with aerial O2 under normal laboratory-daylight conditions, with rupture of the C=C enol ether bond to give 1-O-formylglycerol (3) and an aldehyde (such as tridec-4-en-3-ynal(4) from (-)-2).This reaction must be caused by triplet O2, since thermally generated singlet O2 has no effect on (-)-2 in solution.That the mere presence of an enol-ether moiety conjugated to an acetylenic group is responsible for such a behaviour is demonstrated with the model compounds 1-methoxypentadec-1-en-3-yn-5-ol (6a) and its 5-O-acetyl or 5-O-tetrahydropyranyl derivatives 6b and 6c, respectively.Resistance to both hydrolytic conditions and singlet O2 of these compounds is thought to arise from electron depletion at the enol-ether C(β) atom by the acetylenic group.Plausible reaction pathways for enol-ether bond rupture in these compounds by aerial O2 are outlined.
- Guella, Graziano,Mancini, Ines,Pietra, Francesco
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p. 1400 - 1411
(2007/10/02)
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- ANION OF 1--2-PHENYLSULFONYLCYCLOPROPANE AS A NEW d3-REAGENT: PREPARATION OF β-SUBSTITUTED α,β-UNSATURATED ALDEHYDES
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Preparation of β-alkylsubstituted α,β-unsaturated aldehydes using a new d3-reagent is described.
- Pohmakotr, Manat,Pisutjaroenpong, Somchai
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p. 3613 - 3616
(2007/10/02)
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- FACILE FORMYLOLEFINATION OF ALDEHYDES BY MEANS OF ARSONIUM SALT
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A facile formylolefination of a variety of aldehydes was achieved by using formylmethyltriphenylarsonium bromide with K2CO3 (trace H2O) at room temperature to give highly stereoselectively (E) α,β-unsaturated aldehydes in excellent yields.
- Huang, Yaozeng,Shi, Lilan,Yang, Jianhua
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p. 6447 - 6448
(2007/10/02)
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- Reactions with Phosphine Alkylenes, 44. A Further Synthesis of (Z)-α,β-Unsaturated Aldehydes
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Reaction of phosphorus ylides 4, especially such with electron donating groups R, with the glyoxal semiacetal 5 leads Z-stereospecifically to the formation of the acetals 3, which can be cleaved to the (Z)-α,β-unsaturated aldehydes 6.
- Bestmann, Hans Juergen,Ermann, Peter
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p. 3264 - 3266
(2007/10/02)
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- Cumulated Ylides, XII. A Stereoselective Synthetic Method for (Z)-α,β-Unsaturated Aldehydes
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(2-Ethoxyvinyl)triphenylphosphonium bromide (5) is converted with sodium amide into the corresponding phosphaallenylide 6 which adds ethanol forming the ylide 7. 7 is also obtained by the reaction of 5 with sodium ethanolate.The Wittig reaction of 7 with aldehydes 2 proceeds with high (Z)-stereoselectivity to give (Z)-α,β-unsaturated acetals 8 which are cleaved under well defined conditions with p-toluenesulfonic acid or with wet silica gel to (Z)-α,β-unsaturated aldehydes 9.
- Bestmann, Hans Juergen,Roth, Kurt,Ettlinger, Manfred
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p. 161 - 171
(2007/10/02)
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