- An Application of nJ(CH2,H) and 5J(OH,H) Long-Range Couplings in the Conformational Analysis of 2-Hydroxybenzyl Methyl Ether in Various Solvents. Computational Strategies for Spectral Analysis and Determination of Association Thermod
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1H NMR spectra of 2-hydroxy- and 2-methoxy-benzyl methyl ethers were measured in various solvents and solvent mixtures.Precise nJ(CH2,H), where n = 4, 5 or 6, and 5J(OH,H) long-range couplings were applied to the characterization of
- Laatikainen, Reino
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Read Online
- Ligand-Promoted Non-Directed C?H Cyanation of Arenes
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This article reports the first example of a 2-pyridone accelerated non-directed C?H cyanation with an arene as the limiting reagent. This protocol is compatible with a broad scope of arenes, including advanced intermediates, drug molecules, and natural products. A kinetic isotope experiment (kH/kD=4.40) indicates that the C?H bond cleavage is the rate-limiting step. Also, the reaction is readily scalable, further showcasing the synthetic utility of this method.
- Liu, Luo-Yan,Yeung, Kap-Sun,Yu, Jin-Quan
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supporting information
p. 2199 - 2202
(2019/01/24)
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- Methoxymethylation and benzyloxymethylation of aryl bromides
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The methoxymethylation and benzyloxymethylation of aryl bromides methodology was reported here. The transition metal free, high yielding one pot procedure will be useful for synthetic community.
- Panda, Biswajit
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p. 981 - 985
(2020/06/26)
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- A synthetic method of the compound animal pen ether class
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The invention relates to a synthetic method of a benzyl ether compound. The synthetic method is used for avoiding environmental pollution caused by conventional benzyl ether compound synthetic methods. The synthetic method comprises following steps: step 1, a benzyl silane compound, an oxidizing agent, and a light reaction catalyst are delivered into a reactor, the reactor is vacuumized, and is filled with nitrogen for protection, an alkali compound and an alcohol reagent are delivered into the reactor through syringes, the reactor is exposed to visible light, reaction is carried out at room temperature with magnetic stirring, after reaction, an obtained reaction solution is filtered, and a liquid obtained via filtration is subjected to condensation so as to remove solvents and obtain a concentrated solution; and step 2, the concentrated solution is subjected to silica-gel column chromatography for separation and purification so as to obtain the benzyl ether compound, wherein a mixed solution of petroleum ether and ethyl acetate is taken as an eluent. Reaction conditions are mild; operation is simple and convenient; reaction yield is high; and the maximum reaction yield can be 93%.
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Paragraph 0099; 0100; 0101; 0102; 0103-0110
(2017/04/27)
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- Lewis acid promoted ruthenium(II)-catalyzed etherifications by selective hydrogenation of carboxylic acids/esters
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Ethers are of fundamental importance in organic chemistry and they are an integral part of valuable flavors, fragrances, and numerous bioactive compounds. In general, the reduction of esters constitutes the most straightforward preparation of ethers. Unfortunately, this transformation requires large amounts of metal hydrides. Presented herein is a bifunctional catalyst system, consisting of Ru/phosphine complex and aluminum triflate, which allows selective synthesis of ethers by hydrogenation of esters or carboxylic acids. Different lactones were reduced in good yields to the desired products. Even challenging aromatic and aliphatic esters were reduced to the desired products. Notably, the in situ formed catalyst can be reused several times without any significant loss of activity. An assist from Al: A bifunctional catalyst system consisting of a Ru/phosphine complex and aluminum triflate allows selective hydrogenation of esters to ethers. A variety of lactones were reduced to the desired products in good yields. The catalyst further provides a general method for the reduction of linear esters and reductive etherification of carboxylic acids with alcohols.
- Li, Yuehui,Topf, Christoph,Cui, Xinjiang,Junge, Kathrin,Beller, Matthias
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supporting information
p. 5196 - 5200
(2015/04/27)
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- Methoxy-substituted α, n-didehydrotoluenes. photochemical generation and polar vs diradical reactivity
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The photoreactivity of differently substituted (chloromethoxybenzyl)trimethylsilanes in alcohols and alcohol/water mixtures has been investigated by means of a combined computational and experimental approach. Subsequent elimination of the chloride anion and the trimethylsilyl cation gives the corresponding methoxy-substituted α,n-didehydrotoluenes (α,n-MeO-DHTs). The rate of desilylation is evaluated through the competition with arylation via phenyl cation (ca. 108s-1). α,2-MeO- and α,4-MeO-DHTs show a purely radical behavior (H abstraction from the solvent, methanol), while α,3-MeO-DHT shows mainly a ionic chemistry, as when the parent α,3-DHT is thermally generated. This is likely due to triplet-singlet surfaces crossing occurring during desilylation.
- Raviola, Carlotta,Ravelli, Davide,Protti, Stefano,Fagnoni, Maurizio
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supporting information
p. 13874 - 13881
(2015/02/05)
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- TiCl4-activated selective nucleophilic substitutions of tert-butyl alcohol and benzyl alcohols with π-donating substituents
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TiCl4-activated selective nucleophilic substitution reactions of tert-butyl alcohol and benzyl alcohols with π-donating substituents in the presence of primary and secondary alcohols can be carried out with various oxygen, nitrogen and carbon nucleophiles in good yields.
- Tsai, Chen-Yu,Sung, Robert,Zhuang, Bo-Ren,Sung, Kuangsen
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experimental part
p. 6869 - 6872
(2010/09/18)
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- HYDROXYMETHYLBORON COMPOUNDS
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The present invention provides compounds which are useful as safe substitutes for the organotin reagent used in coupling reaction for the oxymethylation of aromatic rings, such as alkoxymethylation or hydroxymethylation, with a palladium catalyst and which can dispense with chromatographic purification with silica gel in the production and are suitable for mass production; and compounds applicable even to the oxymethylation of aromatic ring substrates which do not permit coupling reaction by conventional technique or have low reactivity.
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Page/Page column 35-36
(2010/11/29)
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- [1,2]-Wittig rearrangement from chloromethyl ethers
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The reaction of different chloromethyl ethers 1 with an excess of lithium powder and a catalytic amount of 4,4′-di-tert-butylbiphenyl (2.5 mol %) in THF at 0 °C leads to the corresponding α-lithiomethyl ether intermediates, through a chlorine-lithium exchange, which spontaneously undergo a clean [1,2]-Wittig rearrangement affording the expected homobenzylic alcohols 2. This is the first version of this rearrangement starting from easily available chloromethyl ethers.
- Gómez, Cecilia,Maciá, Beatriz,Lillo, Victor J.,Yus, Miguel
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p. 9832 - 9839
(2007/10/03)
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- Solid state S-methylation of thiols and O-methylation of phenols and naphthols with dimethyl sulfate under microwave irradiation
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Mild and efficient S-methylation of thiols and o-methylation of phenols and naphthals occurs with dimethyl sulfate (DMS) supported on basic alumina under microwave irradiation in solventless system. Copyright Taylor & Francis Inc.
- Heravi, Majid M.,Ahari, Neda Zamani,Oskooie, Hossein A.,Ghassemzadeh, Mitra
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p. 1701 - 1712
(2007/10/03)
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- Reductive etherification of aromatic aldehydes with decaborane
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Aromatic aldehydes were easily convened to the corresponding ethers in methanol or ethanol using decaborane at r.t. under nitrogen in high yields.
- Lee, Seung Hwan,Park, Yong June,Yoon, Cheol Min
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p. 6049 - 6050
(2007/10/03)
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- Asymmetric synthesis of (R)-(+)-α-methyl-o-methoxybenzyl methyl ether via the stereoselective benzylic elaboration of tricarbonyl (η6-o-methoxybenzyl methyl ether)chromium(o)
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Treatment of tricarbonyl (η6-o-methoxybenzyl methyl ether)chromium(o) with t-butyllithium followed by an electrophile gives a single diastereoisomer of the corresponding alpha substituted complex. The relative configuration within the product f
- Davies,Goodfellow,Sutton
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p. 1303 - 1316
(2007/10/02)
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- SUBSTITUENT EFFECTS IN THE PHOTOSOLVOLYSIS OF BENZYL DERIVATIVES. GENERAL STRUCTURE-REACTIVITY RELATIONSHIPS.
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The relative reactivity of photosolvolysis of a number of substituted benzyl acetates is in the order ortho > meta > para, these substitutent effects being apparently additive, as suggested by the relative reactivity of photomethanolysis of several dimethoxy-susbstituted benzyl alcohols.
- Wan, Peter,Chak, Becky,Li, Carrier
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p. 2937 - 2940
(2007/10/02)
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- Structure-Reactivity Studies and Catalytic Effects in the Photosolvolysis of Methoxy-substituted Benzyl Alcohols
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The photosolvolysis of several methoxy-, dimethoxy-, and hydroxy-substituted benzyl alcohols has been studied in aqueous solution.The primary photochemical event is photodehydroxylation, to give a benzyl cation intermediate, which can be trapped by added external nucleophiles.The reaction is via the singlet excited state, based on observation of fluorescence quenching by hydronium ion in a complementary manner with acid catalysis of reaction observed for several derivatives.Solvent isotope effects on fluorescence efficiency and reaction for (7) and (8) provide additional support of singlet-state reactivity for these compounds.Dimethoxy-substituted alcohols are more reactive than monosubstituted compounds, with quantum yields of methanolysis of up to 0.31 for the most reactive compound, 2,6-dimethoxybenzyl alcohol (8).Using a kinetic argument, the quantum yields of the primary photodehydroxylation process has been estimated to be 1.0 +/- 0.1 for this compound.The results observed for the dimethoxy-substituted derivatives suggest the existence of additivity of substituent effects in these photodehydroxylation reactions.
- Wan, Peter,Chak, Becky
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p. 1751 - 1756
(2007/10/02)
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- A NOVEL METHOXYMETHYLATION OF ARYL BROMIDE BY METHOXYMETHYLTRIBUTYLTIN IN THE PRESENCE OF PALLADIUM COMPLEX
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The reaction of aryl bromides with methoxymethyltributyltin in the presence of a catalytic amount of dichlorobis(triphenylphosphine)palladium was found to give arylmethyl methyl ether.The reaction is a novel aromatic methoxymethylation.
- Kosugi, Masanori,Sumiya, Takashi,Ogata, Toshimi,Sano, Hiroshi,Migita, Toshihiko
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p. 1225 - 1226
(2007/10/02)
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- Long-chain Phenols. Part 18. Conversion of Anacardic Acid into Urushiol
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(15:0)-Anacardic acid (6-pentadecylsalicylic acid), prepared by reduction of unsaturated anacardic acid from Anacardium occidentale, has been converted into anacardic alcohol (6-pentadecylsalicylic alcohol) and thence by oxidation at carbon into anacardaldehyde.Phenolic oxidation of anacardic alcohol led to 8-pentadecyl-1-oxaspiroocta-5,7-dien-4-one, itself readily convertible photochemically, but less so thermally, into anacardaldehyde.Reaction of thionyl chloride with anacardic acid led mainly to the anhydride, which by hydride reduction gave anacardaldehyde less satisfactorily.Dakin oxidation of anacardaldehyde furnished (15:0)-urushiol (3-pentadecylcatechol) identical chemically and from argentation t.l.c. with the hydrogenated natural product from Rhus vernicifera. (15:0)-Cardanol (3-pentadecylphenol) has been detected in hydrogenated urushiol.The composition of the unsaturated constituents of urushiol from Rhus vernicifera and Rhus toxicodendron and its mode of formation have been discussed.An improved synthesis of (15:0)-urushiol has been devised based on an organo-lithium route.Aromatic methyl ether and ester formation in this series is greatly facilitated by phase-transfer catalysis.
- Kiong, Lam Soot,Tyman, John H. P.
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p. 1942 - 1952
(2007/10/02)
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