- CANNABINOID DERIVATIVES, PRECURSORS AND USES
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The present disclosure relates to new cannabinoid derivatives and precursors and processes for their preparation. The disclosure also relates to pharmaceutical and analytical uses of the new cannabinoid derivatives.
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Page/Page column 21; 25-26
(2021/03/19)
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- Synthesis of gasoline and jet fuel range cycloalkanes and aromatics from poly(ethylene terephthalate) waste
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For the first time, gasoline and jet fuel range C7-C8 cycloalkanes and aromatics were selectively synthesized by the alcoholysis of poly(ethylene terephthalate) (PET) waste, followed by solvent-free hydrogenation and hydrodeoxygenation (HDO). It was found that methanol is highly reactive for the alcoholysis of PET waste. In the absence of any catalyst, a high yield of dimethyl terephthalate (97.3%) was achieved under mild conditions (473 K, 3.5 h). Dimethyl terephthalate exists as a solid and can be automatically separated from methanol with a decrease in temperature. Subsequently, dimethyl terephthalate was liquefied to dimethyl cyclohexane-1,4-dicarboxylate by hydrogenation over noble metal catalysts. Among the investigated catalysts, Pt/C exhibited the highest activity. Finally, the dimethyl cyclohexane-1,4-dicarboxylate as obtained was further hydrodeoxygenated to C7-C8 cycloalkanes and aromatics that can be used as gasoline or additives to improve the densities (or volumetric heat value) and sealabilities of current bio-jet fuels. Bimetallic Ru-Cu/SiO2 was found to be a promising HDO catalyst. According to the characterization results, the excellent HDO performance of Ru-Cu/SiO2 can be explained by the formation of smaller Ru-Cu alloy particles during the catalyst preparation. In real applications, dimethyl cyclohexane-1,4-dicarboxylate can also be simultaneously hydrodeoxygenated with biomass derived oxygenates to produce jet fuel with a suitable content of cycloalkanes and aromatics.
- Tang, Hao,Li, Ning,Li, Guangyi,Wang, Aiqin,Cong, Yu,Xu, Guoliang,Wang, Xiaodong,Zhang, Tao
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supporting information
p. 2709 - 2719
(2019/06/03)
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- Ni-Catalyzed chemoselective alcoholysis of: N -acyloxazolidinones
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Although N-acyloxazolidinone-based (catalytic) asymmetric synthetic methodologies occupy an important position in modern organic synthesis, the catalytic cleavage of a chiral auxiliary remains underdeveloped. We report the Ni(cod)2/bipyr.-catalyzed alcoholysis of N-acyloxazolidinones to deliver esters. The reaction is broad in scope for both N-acyloxazolidinone substrates and alcohol nucleophiles, and displays good functional group tolerance and excellent chemoselectivity. A gram-scale methanolysis allowed the enantioselective synthesis of the C22-C26 segment of a close analogue of the potent immunosuppressant agent FK506.
- Huang, Pei-Qiang,Geng, Hui
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supporting information
p. 593 - 599
(2018/02/14)
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- Borenium ionic liquids as catalysts for Diels-Alder reaction: Tuneable Lewis superacids for catalytic applications
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Ionic liquids based on the tricoordinate borenium cation were used for the first time as Lewis acid catalysts for a model Diels-Alder reaction. The conversion of the dienophile was successfully correlated with the Gutmann acceptor number values of the ionic liquids. Borenium ionic liquids exceeded the performance of catalysts reported in the literature.
- Matuszek,Coffie,Chrobok,Swad?ba-Kwa?ny
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p. 1045 - 1049
(2017/08/15)
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- METHODS OF SYNTHESIS OF (1R,2R,5R)-5-AMINO-2-METHYLCYCLOHEXANOL HYDROCHLORIDE AND INTERMEDIATES USEFUL THEREIN
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Provided herein are methods and intermediates for making (lR,2R,5R)-5-amino-2- methylcyclohexanol hydrochloride, which are useful for the preparation of compounds useful for the treatment of a disease, disorder, or condition associated with the JNK pathwa
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Paragraph 0046
(2017/02/24)
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- Polyelectrolyte-catalyzed Diels–Alder reactions
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Imidazolium-based poly(ionic liquids) bearing bromide and bis(trifluoromethane)sulfonimide as counteranions [poly(ViEIm)Br and poly(ViEIm)NTf2] derived from reversible addition fragmentation chain transfer (RAFT) polymerization techniques are u
- Pothanagandhi, Nellepalli,Sivaramakrishna, Akella,Vijayakrishna, Kari
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p. 132 - 136
(2016/08/05)
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- Silica-supported chlorometallate(iii) ionic liquids as recyclable catalysts for Diels-Alder reaction under solventless conditions
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A range of Lewis acidic metal chlorides were tested as homogeneous catalysts in a model Diels-Alder reaction; AlCl3and GaCl3performed best in terms of conversion andendo : exoselectivity. Based on this outcome, the corresponding chlorometallate(iii) ionic liquids were tested as homogeneous catalysts, without a decrease in performance compared to the chlorides. Finally, these ionic liquids were heterogenised by covalent tethering of the cation onto a multimodal porous silica support; such supported chlorogallate(iii) ionic liquids are reported for the first time. Supported chlorometallate(iii) ionic liquids were used as recyclable heterogeneous catalysts for the Diels-Alder reaction under solventless conditions. High yields (99%) and highendo-selectivities (95%) were obtained after very short reaction times (5 min) at near-ambient temperature (25 °C).
- Chrobok, Anna,Jarz?bski, Andrzej,Latos, Piotr,Markiton, Magdalena,Matuszek, Karolina,Swad?ba-Kwa?ny, Ma?gorzata,Szymańska, Katarzyna
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p. 8129 - 8137
(2020/10/19)
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- Method for producing terephthalic acid
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A method for producing terephthalic acid comprises the steps of: subjecting methyl acrylate to contact with aluminum chloride so as to form a complex; adding isoprene to the complex to result in a Diels-Alder reaction which is kept at a temperature no higher than 50° C. by cooling so as to obtain a cyclic adduct product; subjecting the cyclic adduct product to separation so as to obtain a cyclic para-precursor; and subjecting the cyclic para-precursor to a chemical reaction so as to obtain terephthalic acid.
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Page/Page column 3 - 5
(2015/07/02)
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- Bis(phosphine)cobalt dialkyl complexes for directed catalytic alkene hydrogenation
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Planar, low-spin cobalt(II) dialkyl complexes bearing bidentate phosphine ligands, (P - P)Co-(CH2SiMe3)2, are active for the hydrogenation of geminal and 1,2-disubstituted alkenes. Hydrogenation of more hindered internal and endocyclic trisubstituted alkenes was achieved through hydroxyl group activation, an approach that also enables directed hydrogenations to yield contrasteric isomers of cyclic alkanes.
- Friedfeld, Max R.,Margulieux, Grant W.,Schaefer, Brian A.,Chirik, Paul J.
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supporting information
p. 13178 - 13181
(2015/03/30)
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- Diels-alder reaction between isoprene and methyl acrylate over different zeolites: Influence of pore topology and acidity
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The Diels-Alder reaction between isoprene and methyl acrylate over several zeolites was thoroughly investigated. ZSM-5 zeolites provided the highest productivity in methyl 4-methylcyclohex-3-enecarboxylate isomer, achieving 0.219mmol product per mmolHsup
- Bernardon, Claire,Louis, Benoit,Beneteau, Valerie,Pale, Patrick
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p. 1134 - 1141
(2013/09/24)
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- Impact of carbon dioxide pressurization on liquid phase organic reactions: A case study on Heck and Diels-Alder reactions
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Heck coupling reactions of methyl acrylate with various aryl bromides have been investigated using a Pd/TPP catalyst in toluene under pressurized CO 2 conditions up to 13 MPa. Although CO2 is not a reactant, the pressurization of the reaction liquid phase with CO2 has positive and negative impacts on the rate of Heck coupling depending on the structures of the substrates examined. In the case of either 2-bromoacetophenone or 2-bromocinnamate, the conversion has a maximum at a CO2 pressure of about 3 MPa; for the former, it is much larger by a factor of 3 compared with that under ambient pressure. For 2-bromobenzene, in contrast, the conversion is minimized at a similar CO2 pressure, being half compared with that at ambient pressure. In the other substrates, including the other isomers of these three aryl bromides, the conversion simply decreases or does not change so much with the CO2 pressure. To examine the factors responsible for the effects of CO2 pressurization, the phase behavior and the molecular interactions with dense phase CO2 have also been studied by visual observation and in situ high pressure FT-IR spectroscopy. In addition, impact of CO2 pressurization was also studied for the Diels-Alder reactions of isoprene with a few dienophiles like methyl acrylate, methyl vinyl ketone, and acrolein in the same solvent, toluene, but a heterogeneous silica-alumina catalyst was used (the reaction system was liquid-solid biphasic). When the CO2 pressure is raised, the conversion monotonously decreases for the three dienophiles; however, the product selectivity changes with the pressure, in particular for acrolein. The FT-IR spectroscopic measurements suggest that its reactivity is altered by interactions with CO2 molecules under pressurized conditions.
- Fujita,Tanaka,Akiyama,Asai,Hao,Zhao,Arai
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experimental part
p. 1615 - 1625
(2009/07/01)
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- Active ray curable ink-jet composition, image forming method using the same, ink-jet recording apparatus, and triarylsulfonium salt compound
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An active ray curable ink-jet ink composition comprising a photo-induced acid generating agent containing an onium salt which does not generate benzene under active ray radiation, and a photopolymerizable compound containing a compound having an oxetane ring in the molecule.
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- High-pressure effect on organic reactions in fluorophobic media
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The kinetic effect of fluorophobic interactions was examined in Diels-Alder reactions and the conjugate addition of amines to acrylonitrile at different pressures. Its magnitude is lower than for other solvophobic media (water, ethylene glycol). Activatio
- Jenner, Gerard,Gacem, Badra
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p. 265 - 270
(2007/10/03)
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- Nanoporous solid acid catalyst for the Diels-Alder reaction of 1,3-dienes with acrylates
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Nanoporous aluminosilicate, Al-HMS with a high aluminum content, strong acidity, and nanoporosity was found to catalyze the Diels-Alder reaction of 1,3-dienes with methacrylate and acrylate, and turned out to be a green alternative to homogeneous acid catalysts.
- Onaka, Makoto,Hashimoto, Naoki,Yamasaki, Ryota,Kitabata, Yasuyoshi
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p. 166 - 167
(2007/10/03)
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- Phosphonium tosylates as solvents for the Diels-Alder reaction
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Phosphonium tosylates have been investigated as solvents for the Diels-Alder reactions of isoprene with methyl acrylate, but-3-en-2-one and acrylonitrile. The reactions with oxygen-containing dienophiles showed high regioselectivity.
- Ludley, Petra,Karodia, Nazira
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p. 2011 - 2014
(2007/10/03)
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- A practical new chiral controller for asymmetric Diels-Alder and alkylation reactions
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(formula presented) The enantiomerically pure hydroxy sulfones (+)- and (-)-2 have been prepared from 1,2-epoxycyclohexane by a simple and practical procedure. The acrylate esters of these alcohols undergo BCl3-catalyzed Diels-Alder reactions with a variety of dienes at -78 to -55°C in CH2Cl2 or C7H8 with high dienophile face selectivity (Table 1). The chiral esters so formed are readily cleaved with recovery of the controllers (+)- or (-)-2. Esters of (+)- and (-)-2 can be converted to Z-polassium enolates and alkylated with high face selectivity.
- Sarakinos, Georgios,Corey
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p. 1741 - 1744
(2008/02/11)
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- Construction of bicyclo[2.2.2]octane ring system via homoallyl-homoallyl radical rearrangement
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We designed a sequential three-step, one-pot reaction (homoallyl- homoallyl radical rearrangement reaction) to generate highly functionalized bicyclo[2.2.2]octane ring system, and succeeded in developing a novel synthetic method to bicyclo[2.2.2]octane compounds from simple cyclohexene derivatives.
- Toyota, Masahiro,Yokota, Masahiro,Ihara, Masataka
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p. 1551 - 1554
(2007/10/03)
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- Silica-Promoted Diels-Alder Reactions in Carbon Dioxide from Gaseous to Supercritical Conditions
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Amorphous fumed silica (SiO2) was shown to increase yields and selectivities of several Diels-Alder reactions in gaseous and supercritical CO2. Pressure effects on the Diels-Alder reaction were explored using methyl vinyl ketone and penta-1,3-diene at 80°C. The selectivity of the reaction was not affected by pressure/ density. As pressure was increased, the yield decreased. At the reaction temperature, adsorption isotherms at various pressures were obtained for the reactants and the Diels-Alder adduct. As expected when pressure is increased, the ratio of the amount of reactants adsorbed to the amount of reactants in the fluid phase decreases, thus causing the yield to decrease. The Langmuir adsorption model fit the adsorption data. The Langmuir equilibrium partitioning constants all decreased with increasing pressure. The effect of temperature on adsorption was experimentally determined and traditional heats of adsorption were calculated. However, since supercritical CO2 is a highly compressible fluid, it is logical to examine the effect of temperature at constant density. In this case, entropies of adsorption were obtained. The thermodynamic properties that influence the real enthalpy and entropy of adsorption were derived. Methods of doping the silica and improving yields and selectivities were also explored.
- Weinstein, Randy D.,Renslo, Adam R.,Danheiser, Rick L.,Tester, Jefferson W.
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p. 2878 - 2887
(2007/10/03)
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- Selectivities of Diels-Alder reactions catalyzed by highly acidic boronated aluminas
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A series of boronated aluminas was prepared by the reaction of BX3 (X= F, Cl, Br) with alumina or by a two-step synthesis involving the reaction of BH3*Me2S with alumina and then with I2.The modified aluminas, BXn/Al2O3, were found to have n = 3 (F), n =
- McGinnis, Michael B.,Vagle, Kurt,Green, James F.,Tan, Lay Choo,Palmer, Ronald,et al.
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p. 3497 - 3500
(2007/10/03)
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- Zeolite and Lewis Acid Catalysis in Diels-Alder Reactions of Isoprene
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The use of zeolites as catalysts in Diels-Alder reactions of isoprene, 2, has been studied.The regioselectivity in zeolite-catalyzed reactions was compared with the regioselectivity of the same reaction using Lewis acid catalysts.The reaction was studied with seven dienophiles: but-3-en-one (1a), 3-bromobut-3-en-2-one (1b), methyl propenoate (1c), cyclohex-2-enone (1d), phenylethene (1e), ethyl propynoate (1f) and propenenitrile (1g).The following catalysts were investigated: zeolites: ZSM-5, mordenite, zeolite Y-152, zeolite Y-45, and zeolite β Lewis acids: aluminum tribromide, aluminum trichloride, antimony pentachloride, antimony triiodide, boron trifuoride-diethyl ether, manganese difluoride and zinc dichloride.The zeolite-catalyzed reactions afforded the Diels-Alder product with the denophiles 1a-1d, but not with the other dienophiles, 1e-1g.The dienophiles which failed to undergo cycloaddition in the presence of zeolites also did so or afforded poor results with the Lewis acid catalysts.With the exception of the reaction of 1b catalyzed by ZSM-5, which afforded a regioisomeric ratio of 13/87, the other zeolite-catalyzed reactions afforded regioisomeric ratios in the range 6/94-0/100 which is similar to that obtained by Lewis acid catalysis.The experimental conditions were studied in detail for two zeolite catalysts (mordenite, zeolite beta) in the reaction of isoprene with 1d.The optimum experimental conditions with respect to yield and selectivity were established by multivariate techniques.In this reaction, zeolite catalysis was found to afford high yields of cis-6-methyl-6(7)-1-octalone.Under Lewis acid catalyzed conditions, this product is rapidly epimerized into the trans isomer.Full experimental details are given for the preparative use of the method.Examples are provided by the reactions with the dienophiles 1a, 1c and 1d catalyzed by zeolite beta.Factors determining the regioselectivity of zeolite-catalyzed Diels-Alder reaction are briefly discussed.
- Eklund, Lars,Axelsson, Anna-Karin,Nordahl, Ake,Carlson, Rolf
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p. 581 - 591
(2007/10/02)
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- Silica and Alumina Modified by Lewis Acids as Catalysts in Diels-Alder Reactions of Carbonyl-Containing Dienophiles
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Several aluminium and titanium derivatives are supported on silica and alumina.Some of the solids obtained contain strong Lewis acids sites and are efficient catalysts in Diels-Alder reactions of carbonyl-containing dienophiles.In cyclopentadiene reaction
- Cativiela, Carlos,Fraile, Jose M.,Garcia, Jose I.,Mayoral, Jose A.,Pires, Elisabet,et al.
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p. 4073 - 4084
(2007/10/02)
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- Supercritical Carbon Dioxide as Reaction Medium: Examination of Its Solvent Effects in the Near-Critical Region
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The consequence of the compressible properties of supercritical carbon dioxide on the Diels-Alder reaction between isoprene and methyl acrylate in the solvent is discussed on the basis of IR spectroscopic data.The transition activation volume of the react
- Ikushima, Yutaka,Saito, Norio,Arai, Masahiko
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p. 2293 - 2297
(2007/10/02)
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- Unsaturated acid derivatives in Diels-Alder cycloadditions: Effect of the extended or cross conjugation
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Beahvior of pentadienoic acid derivatives in Diels-Alder cycloadditions has been examined in the light of experimental results and theoretical calculations. The effect of cross conjugation to an electron-releasing group has also been investigated for these systems and for simple acrylic acid derivatives.
- Branchadell,Oliva,Ortuno,Rafel,Ventura
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p. 9001 - 9012
(2007/10/02)
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- CATALYSIS OF DIELS-ALDER REACTIONS BY METALLOPORPHYRINS
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Aluminium (III) tetraphenyl porphyrin chloride (AITPPCl) has been shown to catalyze Diels-Alder reactions of α,β-unsaturated carbonyl compounds in moderate yield.Selectivity based on electronic effects is exhibited which is different from that seen with catalysts such as diethylaluminium chloride.
- Bartley, David W.,Kodadek, Thomas J.
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p. 6303 - 6306
(2007/10/02)
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- Diels-Alder Reaction in the Presence of Zeolite
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Cu(I) ion exchanged Y-zeolite catalyzed Diels-Alder reaction of furan, cyclopentadiene, 1,3-cyclohexadiene, isoprene and 2,3-dimethylbutadiene with a series of acrylic and acetylenic dienophiles is reported.The cycloadducts are obtained in high yield and selectivity. - Keywords: Cycloaddition Reactions, Copper(I)-zeolite
- Ipaktschi, Junes
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p. 496 - 498
(2007/10/02)
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- STEREOCHEMICAL CONTROL BY CARBOXYLATE GROUPS IN HOMOGENEOUS HYDROGENATION
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The stereochemistry of hydrogenation of a range of unsaturated cyclohexane-carboxylic acids and their esters has been investigated, employing either bis(1,4-diphenylphosphino)butanerhodium or pyridine(tricyclohexylphosphine)iridium based cationic catalysts in CH2Cl2.For methyl 3-methylcyclohex-2-enecarboxylate, highly selective reduction to the trans-product was achieved in both cases, whereas the isomeric methyl 3-methylenecyclohexanecarboxylate gave appreciable amounts of the cis-isomer.A predominance of trans-isomer was also achieved in the reduction of methyl 4-methylcyclohex-3-ene carboxylate, in a rather slower reaction.Reductions with D2 revealed that considerable isomerisation of the olefinic double bond occurred during hydrogenation.The corresponding unsaturated acids were reduced with moderate to high selectivity but reaction was either very slow, or ceased after a few turnovers.Related cyclohexadienecarboxylates were unreactive to homogeneous hydrogenation with cationic catalysts.
- Brown, John M.,Hall, Stephen A.
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p. 333 - 342
(2007/10/02)
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- HIGHLY REGIOSELECTIVE DIELS-ALDER REACTIONS OF 2-TRIMETHYLSILYLMETHYL- AND 2-TRIMETHYLSTANNYLMETHYL-1,3-BUTADIENE
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2-Trimethylsilylmethyl and 2-trimethylstannylmethyl-1,3-butadiene undergo facile cycloaddition with dienophiles, and show high regioselectivity with unsymmetrical dienophiles.
- Hosomi, Akira,Saito, Masaki,Sakurai, Hideki
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p. 355 - 358
(2007/10/02)
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