- Studies on the synthesis of Schisandraceae natural products: Exploring a cyclopropylcarbinol ring expansion strategy
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Acid mediated cyclopropylcarbinol ring expansion has been shown to be a viable method for the construction of the AB ring framework of lancifodilactone F and related terpenoids of the Schisandraceae family of natural products. We found that this rearrangement proceeds with good stereochemical control based on inversion of the C10 cyclopropyl center. Our studies indicate that the cis-decalin motif of 31 could be used as a key synthetic precursor of certain Schisandraceae metabolites. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Fischer, Derek,Theodorakis, Emmanuel A.
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Read Online
- 1,5,7-TRISUBSTITUTED ISOQUINOLINE DERIVATIVES, PREPARATION THEREOF, AND USE THEREOF IN MEDICINES
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The present disclosure relates to 1,5,7-trisubstituted isoquinoline derivatives, their preparation and pharmaceutical use. In particular, the present disclosure discloses a compound of formula (I) or a pharmaceutically acceptable salt, stereoisomer, solvate or prodrug thereof, and a preparation method and use thereof. The definitions of the groups in the formula can be found in the specification and claims.
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Paragraph 0150; 0259-0260; 0262-0263
(2020/08/30)
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- Synthesis method of 1,4-cyclohexanedione monoethylene ketal
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The invention relates to the technical field of organic synthesis, and particularly discloses a synthesis method of 1,4-cyclohexanedione monoethylene ketal. The synthesis method comprises the following step: with dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate, ethylene glycol and water as raw materials and acidic ionic liquid as a reaction medium and a catalyst, sequentially carrying out heatingto 105-120 DEG C and 130-140 DEG C for reactions respectively to obtain the 1,4-cyclohexanedione monoethylene glycol ketal. According to the synthesis method disclosed by the invention, one-pot synthesis from dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate to 1,4-cyclohexanedione monoethylene glycol ketal is realized, and the problems of low industrial production efficiency and low yield of 1,4-cyclohexanedione monoethylene glycol ketal in the prior art are solved.
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Paragraph 0007; 0026; 0027; 0028; 0029; 0030
(2020/10/21)
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- Method for preparing 1,4-cyclohexanedione monoethylene glycol ketal
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The invention relates to the technical field of chemical synthesis and particularly discloses a method for preparing 1,4-cyclohexanedione monoethylene glycol ketal. The method comprises the steps of producing an eutectic system from ammonium methyltriethylchloride and ethylene glycol, and then, directly adding 1,4-cyclohexanedione for a reaction. According to the method disclosed by the invention,produced monoketal is high in selectivity, the yield can reach 90% or more, and other reaction solvents are not required to be used, so that the production cost is reduced; after the reaction ends up, the product is easy to separate, and the operation is simple.
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Paragraph 0016-0021; 0023; 0024; 0026; 0027
(2019/04/04)
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- An investigation into the role of 2,6-lutidine as an additive for the RuCl3-NaIO4 mediated oxidative cleavage of olefins to ketones
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2,6-Lutidine has been identified as a beneficial additive for the oxidative cleavage of olefins to ketones by NaIO4 in the presence of catalytic RuCl3, improving the yield and shortening the reaction times. In the absence of 2,6-lutidine reactions stalled at the diol intermediate with incomplete conversion to the desired ketones. The reaction protocol described herein also avoids the use of harmful solvents such as CCl4 and DCE and is tolerant of a range of functional groups.
- Watson, David W.,Gill, Matthew,Kemmitt, Paul,Lamont, Scott G.,Popescu, Mihai V.,Simpson, Iain
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supporting information
p. 4479 - 4482
(2018/11/23)
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- Hypervalent-Iodine-Mediated Formation of Epoxides from Carbon(sp2)-Carbon(sp3) Single Bonds
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We have developed an efficient method for direct formation of epoxide groups from carbon(sp2)-carbon(sp3) single bonds of β-keto esters; the reaction is mediated by the water-soluble hypervalent iodine(V) reagent AIBX (5-trimethylammonio-1,3-dioxo-1,3-dihydro-1λ5-benzo[d][1,2]iodoxol-1-ol anion). On the basis of the results of density functional theory calculations and experimental studies, we propose that the reaction proceeds by a two-stage mechanism involving dehydrogenation of the β-keto ester substrates and epoxidation of the resulting enone intermediates. The rate-limiting step is abstraction of the β′-C-H (calculated free energy of activation, 24.5 kcal/mol).
- Jiang, Shan,Yan, Tai-Shan,Han, Yong-Chao,Cui, Li-Qian,Xue, Xiao-Song,Zhang, Chi
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p. 11691 - 11702
(2017/11/24)
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- Alcohol Oxidations Using Reduced Polyoxovanadates
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A full account of our recently communicated room temperature alcohol oxidation using reduced polyoxovanadates (r-POVs) is presented. Extensive optimizations revealed optimal conditions employing 0.02 equiv. of r-POV catalyst Cs5(V14As8O42Cl), 5 equiv. tert-butyl hydrogen peroxide (tBuOOH) as the terminal co-oxidant, in an acetone solvent for the quantitative oxidation of aryl-substituted secondary alcohols to their ketone products. The substrate scope tolerates most aryl substituted secondary alcohols in good to quantitative yields while alkyl secondary and primary activated alcohols were sluggish in comparison under similar conditions. Catalyst recyclability was successful on a 1.0?mmol scale of starting alcohol 1-phenylethanol. The oxidation was also successfully promoted by the VIV/VV mixed valent polyoxovanadate (POV) Cs11Na3Cl5(V15O36Cl). Finally, a third POV, Cs2.64(V5O9)(AsO4)2, was investigated for catalytic activity using our established reaction protocol, but proved ineffective as compared to the other two r-POV catalysts. This study expands the field of POM-mediated alcohol oxidations to include underexplored r-POV catalysts. While our catalysts do not supplant the best catalysts known for the transformation, their study may inform the development of other novel oxidative transformations mediated by r-POVs.
- Campbell, McKenzie L.,Sulejmanovic, Dino,Schiller, Jacqueline B.,Turner, Emily M.,Hwu, Shiou-Jyh,Whitehead, Daniel C.
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- Oxidation of Secondary Methyl Ethers to Ketones
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We present a mild way of converting secondary methyl ethers into ketones using calcium hypochlorite in aqueous acetonitrile with acetic acid as activator. The reaction is compatible with various oxygen- and nitrogen-containing functional groups and afforded the corresponding ketones in up to 98% yield. The use of this methodology could expand the application of the methyl group as a useful protecting group.
- Gilissen, Pieter J.,Blanco-Ania, Daniel,Rutjes, Floris P. J. T.
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p. 6671 - 6679
(2017/07/15)
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- Room-temperature catalytic oxidation of alcohols with the polyoxovanadate salt Cs5(V14As8O42Cl)
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While many known methods for oxidation mediated by polyoxometalates (POMs) employ environmentally friendly co-oxidants, they tend to employ large catalyst loadings (e.g. 40 mol%) and costly high reaction temperatures (~90-135 °C) that potentially contribute to the degradation of the catalyst and reduce their effectiveness. Herein, we present some initial results demonstrating a room temperature catalytic oxidation using the reduced salt-inclusion polyoxometalate, Cs5(V14As8O42Cl), that contains polyoxovanadate (POV) clusters as an efficient catalyst (e.g., 2 mol%) in the transformation of secondary alcohols to their corresponding ketones in very good to quantitative yields. Further, the catalyst can be suspended on celite and recycled.
- Campbell, McKenzie L.,Sulejmanovic, Dino,Schiller, Jacqueline B.,Turner, Emily M.,Hwu, Shiou-Jyh,Whitehead, Daniel C.
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p. 3208 - 3213
(2016/05/24)
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- KINASE INHIBITORS AND METHODS OF USE
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The present invention provides chemical entities or compounds and pharmaceutical compositions thereof that are capable of modulating certain protein kinases such as mTor, tyrosine kinases, and/or lipid kinases such as PI3 kinase. Also provided in the present invention are methods of using these compositions to modulate activities of one or more of these kinases, especially for therapeutic applications.
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Page/Page column 87-88
(2010/04/03)
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- Method for the Production of Substituted and Unsubstituted Cyclohexanone Monoketals
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The invention relates to a novel process for preparing and isolating known substituted and unsubstituted 1,4-cyclohexanone monoketals.
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Page/Page column 4
(2010/09/05)
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- 2-iodoxybenzenesulfonic acid as an extremely active catalyst for the selective oxidation of alcohols to aldehydes, ketones, carboxylic acids, and enones with oxone
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Electron-donating group-substituted 2-iodoxybenzoic acids (IBXs) such as5-Me-IBX (1g), 5-MeO-IBX (1h), and 4,5-Me2-IBX were superior to IBX 1a as catalysts for the oxidation of alcohols with Oxone (a trad emark of DuPont) under nonaqueous conditions, although Oxone was almost insoluble in most organic solvents. The catalytic oxidation proceeded more rapidly and cleanly in nitromethane. Furthermore, 2-iodoxybenzenesulfonic acid (IBS, 6a) was much more active than modified IBXs. Thus, we established a highly efficient and selective method for the oxidation of primary and secondary alcohols to carbonyl compounds such as aldehydes, carboxylic acids, and ketones with Oxone in nonaqueous nitromethane, acetonitrile, or ethyl acetate in the presence of 0.05-5molpercentof 6a, which was generated in situ from 2-iodobenzenesulfonic acid (7a) or its sodium salt. Cycloalkanones could be further oxidized to α,β- cycloalkenones or lactones by controlling the amounts of Oxone under the same conditions as above. When Oxone was used under nonaqueous conditions, Oxone wastes could be removed by simple filtration. Based on theoretical calculations, we considered that the relatively ionic character of the intramolecular hypervalent iodine-OSO2 bond of IBS might lower the twisting barrier of the alkoxyperiodinane intermediate 16.
- Uyanik, Muhammet,Akakura, Matsujiro,Ishihara, Kazuaki
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supporting information; experimental part
p. 251 - 262
(2009/06/28)
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- METHOD FOR PRODUCING CARBONYL COMPOUND AN PRO-OXIDANT USED FOR PRODUCTION OF CARBONYL COMPOUND
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The invention provides a process for the preparation of a carbonyl compound in high efficiency by oxidizing an alcohol. The process for the preparation of a carbonyl compound of the present invention includes a step of oxidizing an alcohol in the presence of a compound of the formula (I) or a derivative or a salt thereof, and an oxidant, wherein R1 and R2 independently represent hydrogen, a halogen, a nitro or acidic group, or an alkyl or alkoxy group, each of which optionally has a substituent, or R1 and R2 combine the two carbon atoms to which they are boned to form an aromatic ring.
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Page/Page column 12; 14-15
(2009/08/16)
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- A new efficient deprotection of azines, hydrazones and oximes. An excellent route for exchanging oxygen isotopes in carbonyls
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Carbonyls, protected as azines or other C=N derivatives can be deprotected by HOF·CH3CN in seconds to the corresponding ketone or aldehyde in very good yields. This reaction also offers a very efficient route for replacing the oxygen atom of most carbonyls with any other oxygen isotope, for example, [18]O.
- Carmeli, Mira,Rozen, Shlomo
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p. 763 - 766
(2007/10/03)
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- Rodlike molecules and singlet energy transfer
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In continuing our investigations on rodlike molecules composed of bicyclo[2.2.2]octane units, we studied the effect of interposing a single aromatic ring in the rod. Thus, two [3]-rods were synthesized with the two outer units being bicyclooctyls, the central unit being benzenoid, and with one terminal unit bearing an α-naphthyl moiety and the other terminus bearing an acetyl or benzoyl group. Excitation of the α-naphthyl group led to fluorescence emission by both the naphthyl and the acetyl units. However, compared to the [1]- and [2]-rods previously studied, transmission of singlet excitation proved to be less efficient as determined by the fluorescence emission and also by the singlet lifetimes obtained from single photon counting measurement. Transmission to the benzoyl group proved more rapid than to the acetyl moiety. In assessing the factors controlling energy transmission, Δ-density determinations were employed to describe the distribution of electronic excitation in such systems. It was observed that despite most of the energy being located in the terminal chromophores, some is distributed in the bicyclooctyl units. The extent of this distribution provides a guide to the facility of through-bond energy transfer. Evidence is presented that energy transfer in the short rods is mainly through-bond while in the longer rods Forster through-space transfer is involved.
- Zimmerman,Lapin,Nesterov,Sereda
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p. 7740 - 7746
(2007/10/03)
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- Aminooxyamide tricyclic inhibitors of farnesyl-protein transferase
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Novel aminooxyamide tricyclic compounds and pharmaceutical compositions are disclosed which are inhibitors of the enzyme, farnesyl protein transferase. Also disclosed is a method of inhibiting Ras function and therefore inhibiting the abnormal growth of cells. The method comprises administering the novel aminooxyamide tricyclic compound to a biological system. In particular, the method inhibits the abnormal growth of cells in a mammals such as a human.
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- Dicobaltoctacarbonyl-mediated deoximation
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Treatment of oxime O-acetates with Co2(CO)8 in the presence of a base, followed by H2O at room temperature efficiently afforded the parent carbonyl compounds in high yields. Direct regeneration of carbonyl functionalities from the corresponding oxime derivatives was realized by successive exposure to acetylation conditions, Co2(CO)8 in the presence of base, and H2O. In addition, N-monosubstituted hydrazone derivatives could generate the parent carbonyl compound under the above conditions.
- Mukai, Chisato,Nomura, Izumi,Kataoka, Osamu,Hanaoka, Miyoji
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p. 1872 - 1874
(2007/10/03)
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- Direct evidence for anchimeric assistance in alcohol elimination from gas-phase MH+ ions of 1,4-dialkoxycyclohexanes under chemical ionisation. Experiment and theory
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trans-1,4-Dialkoxycyclohexanes afford very abundant [MH - ROH]+ ions upon chemical ionisation (CI), in contrast to the cis-isomers, suggesting anchimeric assistance in the alcohol elimination from the MH+ ions of the trans-diethers. Collision induced dissociation (CID) measurements of the [MH - ROH]+ ions, obtained from various suitably deuterium labelled stereoisomeric 1-ethoxy-4-methoxycyclohexanes, indicated fromation of symmetrical bicyclic ethyl and methyl oxonium ions by an anchimerically assisted alcohol elimination from the trans-diethers. On the other hand these measurements suggest that the cis-isomers afford isomeric monocyclic O-protonated 4-alkoxycyclohexene cations, in which the hydrogens at positions 2 and 3 (as well as those at positions 5 and 6, and 1 and 4) are not equivalent. The two results, namely the symmetrical bicyclic structure and the high abundance of the [MH - ROH]+ ions in the CI mass spectra of the trans-diethers, in contrast to the non-symmetrical monocyclic structure and low abundance of these ions in the cis-isomers, are suggested to be direct evidence for anchimeric assistance in a gas-phase ion dissociation process. Ab initio calculations at the MP3/6-31G*//6-31G* level support the anchimerically assisted elimination mechanism observed in trans-1-ethoxy-4-methoxycyclohexane, but also show that the energy difference between the anchimerically assisted and non-assisted elimination mechanisms is small (ca. 2-3 kcal mol-1)(1 cal = 4.184 J).
- Shvily, Ronit,Mueller, Thomas,Apeloig, Yitzhak,Mandelbaum, Asher
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p. 1221 - 1234
(2007/10/03)
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- Deblocking of dithioacetals and oxathioacetals using periodic acid under mild nonaqueous conditions
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A novel method for the deblocking of the dithioacetals and oxathioacetals is described. Periodic acid under nonaqueous conditions has been used for the deprotection of the dithio- and oxathio-derivatives to the corresponding carbonyl compounds. This simple high-yield transformation is conveniently carried out in nonaqueous medium and works well with complex sensitive aldehydes and in the presence of other protective groups.
- Shi, Xiao-Xin,Khanapure, Subhash P.,Rokach, Joshua
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p. 4331 - 4334
(2007/10/03)
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- PIPERAZINYL-AND PIPERIDINYL-CYCLOHEXANOLS
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Novel piperazinyl-and piperidinyl-cyclohexanols of the following formula are useful as anxiolytic agents and have other psychotropic properties STR1
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- The protection of ketones and aldehydes as 4-trimethylsilylmethyl-1,3- dioxolanes
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The 1,3-dioxolanation of carbonyl compounds with 2,3- bis(trimethylsilyloxy)-trimethylsilylpropane (BTTP) in the presence of catalytic amounts of trimethylsilyl trifluoromethanesulfonate (TMSOTf) has been investigated. BTTP readily converted unhindered ketones and aldehydes to their corresponding 4-trimethylsilylmethyl-1,3-dioxolanes, but failed for more hindered substrates. The 4-trimethylsilylmethyl-1,3-dioxolane can be selectively cleaved to regenerate the carbonyl compound in the presence of a 1,3-dioxolane using either LiBF4 or HF in acetonitrile.
- Lillie,Avery
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p. 969 - 972
(2007/10/02)
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- Simple and Chemoselective Deprotection of Acetals Using Aqueous Dimethyl Sulfoxide
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Deprotection of acetals was achieved in aqueous dimethyl sulfoxide under neutral reaction condition.Selective cleavage of acyclic acetals bearing various types of acid labile protecting groups was also reported.
- Kametani, Tetsuji,Kondoh, Hirotsune,Honda, Toshio,Ishizone, Hiroyuki,Suzuki, Yukio,Mori, Wakako
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p. 901 - 904
(2007/10/02)
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- 1,2,4-TRIOXANES AS MASKED, DUAL PURPOSE, FUNCTIONAL GROUPS
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1,2,4-Trioxanes readily undergo reductive cleavage upon treatment with zinc and acetic acid to furnish the corresponding 1,2-diols and C3-derived carbonyl compounds in high yield.
- Jefford, Charles W.,Rossier, Jean-Claude,Boukouvalas, John
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p. 673 - 676
(2007/10/02)
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- Anhydrous Iron(III) Chloride Dispersed on Silica Gel; III. A Convenient and Mild Reagent for Deacetalization in Dry Medium
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Acetals of various structures are conveniently cleaved under mild conditions by anhydrous iron(III) chloride dispersed on silica gel in the absence of any solvent.
- Fadel, Antoine,Yefsah, Ramdane,Salauen, Jacques
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- ALDEHYDE AND KETONE SYNTHESES USING METHYLTHIOMETHYL p-TOLYL SULFONE
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Methylthiomethyl p-tolyl sulfone (1) was conveniently alkylated to give mono- and dialkylated products (2 and 4).Reaction conditions for the transformation of 2 and 4 into aldehydes (3) and ketones (5), respectively, were exploited.
- Ogura, Katsuyuki,Ohtsuki, Kazuo,Nakamura, Masami,Yahata, Nobuhiro,Takahashi, Kazumasa,Iida, Hirotada
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p. 2455 - 2458
(2007/10/02)
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- Condensations of 1,4-Cyclohexanediones and Secondary Aromatic Amines. The Formation of Alkyldiarylamines and Triarylamines
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Condensation of 1,4-cyclohexanedione with N-alkylarylamines gives N-alkyl-N-arylanilines, and that with diarylamines gives triarylamines.A mechanism involving dehydration of monoenamines of the 1,4-dione is proposed for the reaction.Relative rates of substituted N-ethylanilines on competitive reactions plotted vs.Hammet's ? values gave -2.0 as the ρ value.In separate reactions, however, a different tendency is noted for the yield, that is, the ease of reactions with p-chloro and p-nitro derivatives.This discrepancy is explained in terms of acidities of the conjugate acids of the amines used as the actual catalysts.
- Haga, Kazuo,Oohashi, Masayuki,Kaneko, Ryohei
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p. 1586 - 1590
(2007/10/02)
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- Preparation et isolement du mono-acetal de la cyclohexadienone-1,4
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We report that 1,4-dioxa(4,5)spiro-8-decanone 1 (the monoketal of 1,4-cyclohexadione) obtained by way of transketalisation can be separated from the starting materials by filtration and crystallisation through a process allowing them to be easily recycled.The interest of the process lies in the simple separation increase of the compound in the medium due to better experimental conditions (temperature, time, stoechiometry).
- Kamenka, Jean-Marc,Geneste, Patrick,El Harfi, Ahmed
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- 1,2-Disubstituted Ethanes As Possible Precursors For The Synthesis of Cannabis Spirans
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Three possible methods for converting suitable 1,2-disubstituted ethanes into Cannabis spirans have been investigated. 4',5-Dihydroxy-3-methoxybibenzyl underwent intramolecular o-p- and p-p-coupling with ferricyanide in a chloroform-aqueous potassium carbonate system, but yields were low: certain other oxidants did not succeed or gave only traces of product.A method for making 1-hydroxy-1-(3,5-dimethoxyphenylethyl)cyclohexan-4-one ethylene acetal or thioacetal via a Birch reaction is described: despite favourable precedent, acid-catalysed cyclisation led to octahydrophenanthrenones rather than spiro-ketones, whilst N,N-dimethylformamide dineopentyl acetal gave two olefins.Jacquesy's super-asid method for making spirocyclohexenones from a methoxylated bibenzyl was not applicable to the 3,4',5-trimethoxy-case, which would have given cannabispirenone methyl ether, presumably because of protonation of both aromatic systems.
- Crombie, Leslie,Crombie, W. Mary L.,Jamieson, Sally V.,Tuchinda Patoomratana,Whitaker, Alison J.
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p. 1485 - 1492
(2007/10/02)
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- Phenylacetamide derivative analgesics
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N-[(1-Amino-4-(mono or di-oxygen-group-substituted)cyclohex-1-yl)methyl]phenylacetamide derivatives of the formula 1 STR1 wherein R, R1, R2, R3, P, Q, X and Y are defined in the specification, e.g., 2-(3,4-dichlorophenyl)-N-[[8-(1-pyrrolidinyl)-1,4-dioxaspiro[4.5]dec.-8-yl]methyl]acetamide, and their pharmacologically acceptable salts, have analgesic drug properties with lower physical dependence liability characteristics than morphine or methadone, for use as analgesic drugs in mammalian animals including humans.
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