- Transformation of Unsaturated Fatty Acids/Esters to Corresponding Keto Fatty Acids/Esters by Aerobic Oxidation with Pd(II)/Lewis Acid Catalyst
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Utilization of renewable biomass to partly replace the fossil resources in industrial applications has attracted attention due to the limited fossil feedstock with the increased environmental concerns. This work introduced a modified Wacker-type oxidation for transformation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, in which Cu2+ cation was replaced with common nonredox metal ions, that is, a novel Pd(II)/Lewis acid (LA) catalyst. It was found that adding nonredox metal ions can effectively promote Pd(II)-catalyzed oxidation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, even much better than Cu2+, and the promotional effect is highly dependent on the Lewis acidity of added nonredox metal ions. The improved catalytic efficiency is attributed to the formation of heterobimetallic Pd(II)/LA species, and the oxidation mechanism of this Pd(II)/LA catalyst is also briefly discussed.
- Senan, Ahmed M.,Zhang, Sicheng,Zeng, Miao,Chen, Zhuqi,Yin, Guochuan
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- Fatty ketones from the rearrangement of epoxidized vegetable oils
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The rearrangement of epoxidized vegetable oils to produce fatty ketones, catalyzed by acidic resins, is disclosed. The non-microbial production of fatty ketones from epoxidized vegetable oils has not been previously reported. Some of the variables affecti
- Rios, Luis A.,Llano, Biviana A.,Hoelderich, Wolfgang F.
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- Diethylene Glycol/NaBr Catalyzed CO2 Insertion into Terminal Epoxides: From Batch to Continuous Flow
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CO2 insertion reactions on terminal epoxides (styrene oxide, 1,2-epoxyhexane and butyl glycidyl ether) were performed in a binary homogeneous mixture comprising NaBr as the nucleophilic catalyst and diethylene glycol (DEG) as both solvent and catalyst activator (cation coordinating agent). The reaction protocol was initially studied under batch conditions either in autoclaves and glass reactors: quantitative formation of the cyclic organic carbonate products (COCs) were achieved at T=100 °C and p0(CO2)=1–40 bar. The process was then transferred to continuous-flow (CF) mode. The effects of the reaction parameters (T, p(CO2), catalyst loading, and flow rates) were studied using microfluidic reactors of capacities variable from 7.85 ? 10?2 to 0.157 cm3. Albeit the CF reaction took place at T=220 °C and 120 bar, CF improved the productivity and allowed catalyst recycle through a semi-continuous extraction procedure. For the model case of 1,2-epoxyhexane, the (non-optimized) rate of formation of the corresponding carbonate, 4-butyl-1,3-dioxolan-2-one, was increased up to 27.6 mmol h?1 equiv.?1, a value 2.5 higher than in the batch mode. Moreover, the NaBr/DEG mixture was reusable without loss of performance for at least 4 subsequent CF-tests.
- Rigo, Davide,Calmanti, Roberto,Perosa, Alvise,Selva, Maurizio,Fiorani, Giulia
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- A General Approach to Intermolecular Olefin Hydroacylation through Light-Induced HAT Initiation: An Efficient Synthesis of Long-Chain Aliphatic Ketones and Functionalized Fatty Acids
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Herein, an operationally simple, environmentally benign and effective method for intermolecular radical hydroacylation of unactivated substrates by employing photo-induced hydrogen atom transfer (HAT) initiation is described. The use of commercially available and inexpensive photoinitiators (Ph2CO and NHPI) makes the process attractive. The olefin hydroacylation protocol applies to a wide array of substrates bearing numerous functional groups and many complex structural units. The reaction proves to be scalable (up to 5 g). Different functionalized fatty acids, petrochemicals and naturally occurring alkanes can be synthesized with this protocol. A radical chain mechanism is implicated in the process.
- Guin, Joyram,Paul, Subhasis
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supporting information
p. 4412 - 4419
(2021/02/05)
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- Synthesis of fatty ketoesters by tandem epoxidation-rearrangement with heterogeneous catalysis
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Unsaturated fatty esters can be easily transformed into ketoesters through a two-step process. The highly efficient epoxidation is carried out with tert-butyl hydroperoxide (TBHP) in α,α,α-trifluorotoluene (TFT) using a Ti-silica heterogeneous catalyst. The formed epoxide is easily rearranged by a heterogeneous Br?nsted acid, with Nafion-silica SAC13 as the most efficient one. Both reactions can be combined in a tandem process, with separation of the Ti-silica catalyst by filtration from the reaction medium and addition of the second acid catalyst to perform the second reaction. Each catalyst is separated individually and can be reused, with or without re-activation, under the same conditions to maximize the productivity.
- Dorado, Vicente,Fraile, José M.,Gil, Lena,Herrerías, Clara I.,Mayoral, José A.
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p. 1789 - 1795
(2020/04/09)
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- A Two-Step Oxidative Cleavage of 1,2-Diol Fatty Esters into Acids or Nitriles by a Dehydrogenation–Oxidative Cleavage Sequence
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Dehydrogenative oxidation of vicinal alcohols catalyzed by a commercially 64 wt.% Ni/SiO2 catalyst leads to the formation of α-hydroxyketone. This first step was developed without additional solvent according to two protocols: “under vacuum” or “with an olefin scavenger”. The synthesis of ketols was carried out with good conversions and selectivities. The recyclability of the supported nickel was also studied. Acyloin was then cleaved with oxidative reagent “formic acid/hydrogen peroxide”, which is cheap and can be used on a large scale for industrial oxidation processes. The global yield of this sequential system was up to 80 % to pelargonic acid and azelaic acid monomethyl ester without intermediate purification. By treating the acyloin intermediate with hydroxylamine, nitriles were obtained with a good selectivity.
- Guicheret, Boris,Bertholo, Yann,Blach, Philippe,Raoul, Yann,Métay, Estelle,Lemaire, Marc
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p. 3431 - 3437
(2018/09/06)
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- Homogeneous and heterogeneous catalytic (dehydrogenative) oxidation of oleochemical 1,2-diols to α-hydroxyketones
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Herein, the preparation of methyl oleate α-hydroxyketone from the corresponding 1,2-diol was investigated using both homogeneous and heterogeneous systems. Homogeneous conditions using a Pd(OAc)2/neocuproine complex were first developed using oxygen as a sole oxidant under mild conditions (MeOH, 50 °C). Under these conditions, the conversion of diol reached 95%, and α-hydroxyketone was obtained with 97% selectivity. The access to α-hydroxyketone has also been studied by dehydrogenation using a range of heterogeneous catalysts under solvent-free conditions at high temperatures (160-180 °C). Dehydrogenation using activated Ru/C under vacuum provided α-hydroxyketone with 93% conversion and 82% GC yield. The optimized conditions were applied to a range of oleochemical diols, including a vegetable oil derivative, to obtain the corresponding α-hydroxyketones with up to 74% isolated yields.
- Vu, Nam Duc,Guicheret, Boris,Duguet, Nicolas,Métay, Estelle,Lemaire, Marc
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p. 3390 - 3399
(2017/07/28)
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- Process For Preparing A Carboxylic Acid
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A process for preparing a carboxylic acid, including a step of bringing at least one vicinal diol or at least one vicinal polyol into contact with an atmosphere including oxygen, and a catalyst, and in the absence of additional solvent.
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Paragraph 0114-0116
(2017/04/14)
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- Cooperative catalyst system for the synthesis of oleochemical cyclic carbonates from CO2 and renewables
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Phosphonium salts and various (transition-) metals were studied as catalysts in the synthesis of carbonated oleochemicals from the corresponding epoxides and carbon dioxide. In combination with tetra-n-butylphosphonium bromide molybdenum compounds were identified as highly active co-catalysts for the formation of cyclic carbonates. The co-catalyst accelerates the conversion of the epoxidized fatty acid ester considerably. The chemo- as well as the stereoselectivity of the carbonated oleochemicals can be controlled by the choice of the catalyst and the reaction conditions. Under optimized reaction conditions this new catalyst system allows the conversion of both mono- and polyepoxidized oleo compounds into the corresponding carbonates in good to excellent yields up to >99% under comparatively mild reaction conditions. This procedure has been applied to the synthesis of a potential renewable plasticizer and works well even at larger scale (200 g).
- Tenhumberg, Nils,Büttner, Hendrik,Sch?ffner, Benjamin,Kruse, Daniela,Blumenstein, Michael,Werner, Thomas
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p. 3775 - 3788
(2016/07/07)
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- Highly efficient nano-sized TS-1 with micro-/mesoporosity from desilication and recrystallization for the epoxidation of biodiesel with H2O2
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The epoxidation of the unsaturated fatty acid methyl esters (FAME) in biodiesel with H2O2 was investigated at 323 K in the liquid phase over microporous nano-sized TS-1 as well as micro-/mesoporous nano-sized TS-1. Nano-sized TS-1 with stacked morphology exhibits a catalytic activity per number of Ti sites up to 30% higher than a conventional, industrial TS-1 catalyst. Mesoporosity was successfully introduced by a desilication-recrystallization approach. Desilication by alkaline treatment in the presence of the structure-directing agent tetrapropylammonium cation (TPA+) or NaOH leads to the generation of undefined mesopores (10-40 nm), probably accompanied by an increase of the surface hydrophilicity. Consequently, the alkaline-treated materials show a two times lower catalytic activity in the epoxidation of biodiesel than the purely microporous parent material. The surfactant-assisted recrystallization of the alkaline-treated materials results in more uniform and smaller mesopores (3-10 nm). In the epoxidation, the recrystallized materials are remarkably more active with respect to both the purely microporous parent and alkaline-treated materials reaching a FAME conversion of 65% with an epoxide selectivity of 82%.
- Wilde,Pelz,Gebhardt,Gl?ser
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p. 3378 - 3389
(2015/06/25)
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- Process to prepare a phosphorous containing vegetable oil based lubricant additive
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Chemically-modified triglycerides are prepared by reacting epoxidized triglyceride oils with phosphorus-based acid hydroxide or esters. The phosphorus-containing triglyceride derivatives are of the formula: wherein R1″, R2″ and R3″ are independently selected from C3 to C29 aliphatic fatty acid residues, at least one of which comprising one or both of the derivatized methylene groups of the formula: wherein m is 0, 1 or 2, n is 0 or 1, q is 1, 2 or 3, and R and R′ are independently selected from the group consisting of H, straight, branched or cyclic hydrocarbons and substituted hydrocarbons, and aryl groups. The phosphorus-containing triglyceride derivatives so produced have utility as antiwear/antifriction additives for industrial oils and automotive applications.
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Page/Page column 9; 10; 11
(2014/09/16)
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- PROCESS FOR THE SYNTHESIS OF KETONES FROM INTERNAL ALKENES
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The present invention is directed to methods for oxidizing internal olefins to ketones. In various embodiments, each method comprising contacting an organic substrate, having an initial internal olefin, with a mixture of (a) a biscationic palladium salt; and (b) an oxidizing agent; dissolved or dispersed in a solvent system to form a reaction mixture, said solvent system comprising at least one C2-6 carbon nitrile and optionally at least one secondary alkyl amide, said method conducted under conditions sufficient to convert at least 50 mol % of the initial internal olefin to a ketone, said ketone positioned on a carbon of the initial internal olefin. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed oil derivatives and a bioactive natural product are described.
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Page/Page column 0122; 0136; 0149
(2014/07/22)
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- Highly efficient oxyfunctionalization of unsaturated fatty acid esters: An attractive route for the synthesis of polyamides from renewable resources
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An efficient and environmentally benign strategy for the oxyfunctionalization of fatty acid methyl esters (FAMEs) employing molecular oxygen as an oxidizing agent is described. Keto-fatty acid esters were directly synthesized by co-catalyst-free Wacker oxidations employing oxygen as a sole re-oxidant. Amine functionalization of the thus obtained keto-fatty acid esters was achieved by reductive amination. The prepared renewable AB-type monomers were studied in homopolymerizations as well as in copolymerization reactions with hexamethylendimethylamine and dimethyl adipate to modify the properties of conventional Nylon 6,6. The obtained (co)-polymers were characterized by SEC, NMR and DSC analysis as well as water uptake tests. the Partner Organisations 2014.
- Winkler, Matthias,Meier, Michael A. R.
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supporting information
p. 1784 - 1788
(2014/04/17)
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- Practical and general palladium-catalyzed synthesis of ketones from internal olefins
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Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features. Copyright
- Morandi, Bill,Wickens, Zachary K.,Grubbs, Robert H.
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supporting information
p. 2944 - 2948
(2013/04/10)
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- Enzymatic kinetic resolution of hydroxystearic acids: A combined experimental and molecular modelling investigation
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Enantioenriched 7-, 8-, 9-, and 10-hydroxystearic acids (HSA) were obtained, for the first time, by kinetic resolution of their racemates with lipases CALB and PS, in the presence of vinyl acetate. Among them, the best results were obtained for 7-HSA and 9-HSA, whose enantiomeric excess was around 55%. The same resolutions carried out on the hydroxy esters completely failed. For the acid substrates neither the Kazlauskas' rule nor the 3D-QSAR model could be applied, since both models are focused on the CALB alcohol-pocket evaluation and not on the acyl-pocket one. Therefore, a semiquantitative approach was used, whose results were in accordance with our findings, as far as the absolute configuration of the product is concerned.
- Ebert, Cynthia,Felluga, Fulvia,Forzato, Cristina,Foscato, Marco,Gardossi, Lucia,Nitti, Patrizia,Pitacco, Giuliana,Boga, Carla,Caruana, Paolo,Micheletti, Gabriele,Calonghi, Natalia,Masotti, Lanfranco
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- Epoxidation of methyl oleate with hydrogen peroxide. the use of Ti-containing silica solids as efficient heterogeneous catalysts
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Titanium-silica catalysts, obtained by grafting titanocene dichloride onto mesoporous silica (MCM-41 and MCM-48) and onto nanosized pyrogenic silica, were tested in the epoxidation of methyl oleate using aqueous hydrogen peroxide. All titanium-containing materials, combined with the slow addition of hydrogen peroxide, showed good catalytic activity and comparable behaviour in terms of conversion, selectivity and yield of methyl epoxystearate, notwithstanding the morphology and the texture of the silica support. By optimizing the reaction conditions (especially, the catalyst to substrate ratio), high yields up to 91% in epoxide were obtained for Ti/MCM-41 with a high stereoselectivity (80%) for the cis-epoxide. The formation of the cis/trans-epoxide and the nature of the catalytic reaction pathway are also discussed.
- Guidotti, Matteo,Gavrilova, Elena,Galarneau, Anne,Coq, Bernard,Psaro, Rinaldo,Ravasio, Nicoletta
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experimental part
p. 1806 - 1811
(2011/09/16)
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- An efficient ring opening reaction of methyl epoxystearate promoted by synthetic acid saponite clays
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The acid-catalysed reaction of methyl 9,10-epoxystearate ring opening using synthetic saponite acid clay as catalyst, has been studied for the first time. In the presence of methanol, 90% of the epoxide substrate is converted after 5 min and the main reaction product is the vicinal hydroxyether, methyl methoxyhydroxystearate, with 84% of selectivity. In the absence of alcohol the ring opening reaction proceeds slower, leading to a mixture of methyl 9- and 10-oxostearate as main products, and a 9,10-epoxystearate conversion of 66% after 1 h. The performance of acid saponite, an environmentally benign catalyst, is exceedingly higher than those of strong mineral acids, such as H 2SO4, widely used for this reaction.
- Guidotti, Matteo,Psaro, Rinaldo,Ravasio, Nicoletta,Sgobba, Maila,Carniato, Fabio,Bisio, Chiara,Gatti, Giorgio,Marchese, Leonardo
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experimental part
p. 1173 - 1178
(2010/05/18)
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- Anti-inflammatory constituents of the Red Alga Gracilaria verrucosa and their synthetic analogues
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A chemical study on the anti-inflammatory components of the red alga Gracilaria verrucosa led to the isolation of new 11-deoxyprostaglandins (1-4), a ceramide (5), and a C16 keto fatty acid (6), along with known oxygenated fatty acids (7-14). Their structures were elucidated on the basis of NMR and MS data. The absolute configurations of compounds 1-5 were determined by Mosher's method. The anti-inflammatory activity of the isolated compounds (1-14) was evaluated by determining their inhibitory effects on the production of pro-inflammatory mediators (NO, IL-6, and TNF-α) in lipopolysaccharide (LPS)-activated RAW 264.7 murine macrophage cells. Compounds 9 and 10 exhibited the most potent activity. In the evaluation of these two compounds and derivatized analogues (15-40), the anti-inflammatory activity was enhanced in some synthetic analogues. These enone fatty acids were investigated as potential anti-inflammatory leads for the first time.
- Hung, The Dang,Hye, Ja Lee,Eun, Sook Yoo,Shinde, Pramod B.,Yoon, Mi Lee,Hong, Jongki,Dong, Kyoo Kim,Jung, Jee H.
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p. 232 - 240
(2008/12/22)
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- Regiospecific oxidation of unsaturated fatty esters with palladium(II) chloride/p-benzoquinone: a sonochemical approach
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Oxidation of unsaturated fatty esters to the corresponding oxo derivatives was accomplished in moderate to high yields when the substrates were treated with palladium(II) chloride and p-benzoquinone in aqueous tetrahydrofuran (THF/H2O, 4:1 v/v) under ultrasound (20 kHz).Methyl 10-undecanoate furnished methyl 10-oxoundecanoate in 92percent yield.Methyl oleate and trans-2-hexadecenoate furnished methyl 9(10)-oxostearate (65percent) and methyl 3-oxohexadecanoate (41percent) respectively.Unsaturated fatty esters with a terminal double bond were more readily oxidized than those containing an internal double bond.Methyl trans-3,12-tridecadienoate gave only methyl 12-oxo-trans-3-tridecenoate (86percent), while a cyclopentenoic fatty ester (methyl chaulmoograte) furnished a mixture of positional oxo-isomers: viz. methyl 1-oxocyclopentane-2-tridecanoate and 1-oxocyclopentane-3-tridecanoate (51.5percent total).Oxidation of methyl 12-hydroxy-, 12-azido-, 12-chloro- and 12-oxo-cis-9-octadecanoate furnished the corresponding 9-oxo-derivatives only.Methyl iso-ricinoleate (methyl 9-hydroxy-cis-12-octadecenoate) gave exclusively methyl 9-hydroxy-12-oxostearate.Without ultrasonication the same oxidation reactions at room temperature furnished low yields (30percent) of the corresponding oxo derivatives after prolonged stirring at room temperature.Aqueous THF is a superior solvent system than the commonly used aqueous N,N-dimethylformmaide (DMF). - Keywords: Aqueous THF; p-Benzoquinone; Oxidation; Oxo fatty esters; Palladium(II) chloride; Ultrasound; Unsaturated fatty esters; Wacker reaction
- Jie, Marcel S. F. Lie Ken,Lam, C. K.
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- Selective oxidation of primary-secondary diols with methyl hypochlorite in acid buffered medium
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A convenient, low cost method was developed for the selective oxidation of secondary alcohols, leaving primary alcohol functions intact. Methyl hypochlorite, generated from chlorine or trichloroisocyanuric acid in methanol, is used as a 'positive chlorine' reagent in the presence of an appropriate buffer which is acidic enough to warrant good transfer of 'positive chlorine'. 1,9(R)-octadecanediol was converted to 1-hydroxy-9-octadecanone with 98% selectivity.
- Tassignon, Patrick S. G.,De Wit, Dick,De Rijk, Theo C.,De Buyck, Laurent F.
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p. 11863 - 11872
(2007/10/02)
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- Silver Chromate-Iodine Oxidation of Olefinic Compounds: An Ideal Method for the Synthesis of α-Iodohydrins
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Silver chromate-iodine has been used for the direct synthesis of α-iodohydrins from olefins for which a mechanism has been proposed.Terminal (1) and internal (5) olefinic esters on treatment with silver chromate-iodine under anhyd. conditions yield the ex
- Khan, Mushfiquddin,Agarwal, Rajiv,Ahmad, Suhail,Ahmad, F.,Osman, S. M.
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p. 430 - 434
(2007/10/02)
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- Synthesis, Characterisation, and Transformations of a Lipid Cyclic Peroxide
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Photosensitised oxidation of (9E,11E)-methyl octadeca-9,11-dienoate gave an unsaturated cyclic peroxide (epidioxide) in high yield.This was characterised spectroscopically.The peroxide underwent facile rearrangement to a furanoid ester under a variety of reaction conditions.Catalytic reduction of the unsaturated peroxide cleaved the O-O bond.Bromination and epoxidation gave dibromo and epoxy esters respectively with the peroxide group still intact.
- Bascetta, Emanuele,Gunstone, Frank D.,Scrimgeour, Charles M. S.
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p. 2199 - 2206
(2007/10/02)
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- A NEW HYDROXYOLEFINIC ACID FROM PLANTAGO MAJOR SEED OIL
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Key Word Index - Plantago major; Plantaginaceae; greater plantain; seed oil; 9-hydroxy-cis-11-octadecenoic acid.A new isomer of ricinoleic acid has been found as a minor constituent (1.5percent) of the seed oil of Plantago major.This previously unknown β-hydroxyolefinic acid, 9-hydroxy-cis-11-octadecenoic, was characterized by IR, 1H NMR and oxidative cleavage, and the structure was supported by MS.
- Ahmad, Mohammad Shamim,Ahmad, Moghis U.,Osman, S. M.
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p. 2137 - 2140
(2007/10/02)
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