- Ring-Closing Metathesis of Aliphatic Ethers and Esterification of Terpene Alcohols Catalyzed by Functionalized Biochar
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Functionalized biochars, renewable carbon materials prepared from waste biomass, can catalyze transformations of a range of oxygen-containing substrates via hydrogen-bonding interactions. Good conversions (up to 75.2 %) to different O-heterocycles are obtained from ring-closing C?O/C?O metathesis reactions of different aliphatic ethers under optimized conditions using this heterogeneous, metal-free, and easy separable catalyst. The diversity in the sorts of O-containing feedstocks is further demonstrated by the utilization of functionalized biochar to promote the esterification of terpene alcohols, an important reaction in food and flavor industries. Under the optimized conditions, full conversions to various terpene esters are obtained. Moreover, both of the reactions studied herein are performed under neat conditions, thus increasing the overall sustainability of the process described.
- Kerton, Francesca M.,MacQuarrie, Stephanie L.,Vidal, Juliana L.,Wyper, Olivia M.
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supporting information
p. 6052 - 6056
(2021/12/10)
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- A Modified Synthesis of Oxetan-3-ol
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Abstract: A highly regioselective ring opening reaction of terminal epoxides with 2-bromobenzoic acid catalyzed by tetrabutylammonium bromide was accomplished. The procedure is operationally simple and practical for the synthesis of a series of β-hydroxy esters. Using this protocol, oxetan-3-ol could be prepared efficiently in a good yield.
- Feng, Y.,He, W.,Luo, Y.,Sun, W.,Xia, X. Y.,Zhan, L.
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p. 877 - 883
(2020/07/03)
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- Novel method for synthesizing 3-oxacyclobutanol
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The invention provides a novel method for synthesizing 3-oxacyclobutanol. The novel method is characterized in that epoxy chloropropane and glacial acetic acid are taken as raw materials, a catalyst is used for catalyzing the ring-opening reaction; under an organic strong acid condition, vinyl ethyl ether is added to perform upper protecting group reaction; under a strong-alkaline condition, ring-forming reaction is performed to obtain a key intermediate solution; the intermediate solution is extracted, concentrated and rectified to obtain an intermediate; catalysis amount of organic strong acid is used in the solvent by the intermediate to perform deprotection to obtain a 3-oxacyclobutanol crude product; the crude product is neutralized to be meta-alkalescent with weak alkaline, and is concentrated and rectified to obtain the 3-oxacyclobutanol product. The novel method has the characteristics of being cheap in raw materials, short in route, free of dangerous reagent, avoiding use of dangerous chemicals such as diazomethane, butyl lithium or 1,3-dichloroacetone, so that the synthesis method for 3-oxacyclobutanol can be safely amplified, and therefore, large-scale production can beperformed; and moreover, the 3-oxacyclobutanol is low in price, and is convenient to popularize.
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Paragraph 0016; 0019; 0020; 0023; 0024; 0027
(2019/02/19)
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- A method for synthesis of oxetane butanone (by machine translation)
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The present invention provides a method for synthesis of oxetane butanone, the method is used in the organic solvent, diluent, organic alkali exist under the conditions, by dehydrating the oxidizing agent will be 3 - oxygen heterocyclic butanol oxidation, further separation and purification to obtain 3 - oxetanone; the organic solvent as chain alkanes, halogenated hydrocarbon, alcohol, ethers in a; the thinner is dimethyl sulfoxide, N, N - dimethyl formamide in a; the organic base is triethylamine, ethylenediamine, diisopropyl ethylamine in a; the dehydration of the oxidizing agent is P2 O5 , P2 O3 In a. The present invention uses a phosphorus pentoxide system to oxidation to produce 3 - oxetanone, materials used in the cheap, is relatively simple in operation, avoids the use of hazardous chemicals, friendly to the environment, there are higher reaction yield, conducive to 3 - oxetanone in organic chemical and biological medicinal further application and development. (by machine translation)
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Paragraph 0029; 0033; 0037
(2019/03/26)
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- 3-oxetanone synthesis method
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The invention provides a 3-oxetanone synthesis method, which comprises: removing the protection group from an intermediate in an organic solvent I by using an organic strong acid, neutralizing with aweak alkali to achieve an alkaline pH value, carrying out concentration distillation on the solvent to obtain a oxetan-3-ol crude product, oxidizing the oxetan-3-ol with an oxidizing agent in the presence of a catalyst I, a halide and an alkali, and carrying out separating purification to obtain the 3-oxetanone product, wherein the intermediate preparation method comprises: carrying out a ring opening reaction by using epichlorohydrin and glacial acetic acid as raw materials under the catalysis of a catalyst II, adding ethyl vinyl ether under an organic strong acid condition, carrying out a protection group forming reaction, and carrying out a ring formation reaction under a strong alkali condition so as to obtain the key intermediate solution. According to the present invention, the oxetan-3-ol preparation process is combined without the purifying of oxetan-3-ol so as to eliminate the oxetan-3-ol purifying step; and the method has characteristics of inexpensive raw materials, short route, no use of dangerous reagents and the like.
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Paragraph 0018; 0020
(2019/05/04)
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- Discovery of Novel 1-Cyclopentenyl-3-phenylureas as Selective, Brain Penetrant, and Orally Bioavailable CXCR2 Antagonists
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CXCR2 has emerged as a therapeutic target for not only peripheral inflammatory diseases but also neurological abnormalities in the central nervous system (CNS). Herein, we describe the discovery of a novel 1-cyclopentenyl-3-phenylurea series as potent and CNS penetrant CXCR2 antagonists. Extensive SAR studies, wherein molecules' property forecast index (PFI) was carefully optimized for overall balanced developability profiles, led to the discovery of the advanced lead compound 68 with a desirable PFI. Compound 68 demonstrated good in vitro pharmacology with excellent selectivity over CXCR1 and other chemokine receptors. Rat and dog pharmacokinetics (PK) revealed good oral bioavailability, high oral exposure, and desirable elimination half-life of the compound in both species. In addition, the compound demonstrated dose-dependent efficacy in the in vivo pharmacology neutrophil infiltration "air pouch" model in rodents after oral administration. Further, compound 68 is a CNS penetrant molecule with high unbound fraction in brain tissue.
- Lu, Hongfu,Yang, Ting,Xu, Zhongmiao,Lin, Xichen,Ding, Qian,Zhang, Yueting,Cai, Xin,Dong, Kelly,Gong, Sophie,Zhang, Wei,Patel, Metul,Copley, Royston C. B.,Xiang, Jianing,Guan, Xiaoming,Wren, Paul,Ren, Feng
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supporting information
p. 2518 - 2532
(2018/03/26)
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- 3-hydroxyl oxygen heterocyclic butane preparation method of compound
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The invention discloses a synthetic method of a 3-hydroxy oxetane compound shown as a formula I. The method provided by the invention employs substituted glycerol I-1 as a raw material, which is subjected to condensation with aldehydes and ketones compounds to obtain a compound I-2; the I-2 is subjected to R2 protection to obtain a compound I-3; the compound I-3 is subjected to removal of aldehydes and ketones protecting groups to obtain a compound I-4; the compound I-4 is subjected to intramolecular cyclization to obtain a compound I-5; and the compound I-5 is subjected to removal of R2 protection to obtain a target compound I. Although the method has a long route, the reaction conditions are mild, and the post treatment and detection are convenient; therefore, the method is suitable for industrialized production.
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Paragraph 0031; 0032; 0041; 0042
(2016/10/07)
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- 1 -(CYCLOPENT-2-EN-1 -YL)-3-(2-HYDROXY-3-(ARYLSULFONYL)PHENYL)UREA DERIVATIVES AS CXCR2 INHIBITORS
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The invention relates to 1-(3-sulfonylphenyl)-3-(cyclopent-2-en-1-yl)urea derivatives, and their use in treating or preventing diseases and conditions mediated by the CXCR2 receptor. In addition, the invention relates to compositions containing the derivatives and processes for their preparation.
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Page/Page column 169
(2015/12/18)
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- FeCl3/pyridine: Dual-activation in opening of epoxide with carboxylic acid under solvent free condition
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Inexpensive, non-toxic, and readily available catalyst system FeCl 3/pyridine was found to be highly efficient for the opening of a wide variety of epoxides with carboxylic acid under solvent free conditions.
- Zhao, Yichao,Wang, Wen,Li, Jian,Wang, Feng,Zheng, Xiufang,Yun, Hongying,Zhao, Weili,Dong, Xiaochun
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supporting information
p. 5849 - 5852
(2013/10/21)
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- NOVEL GLUCOKINASE ACTIVATORS AND METHODS OF USING SAME
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Compounds are provided which are phosphonate and phosphinate activators and thus are useful in treating diabetes and related diseases and have the structure wherein is a heteroaryl ring; R4 is —(CH2)n-Z-(CH2)m—PO(OR7)(OR8), —(CH2)nZ-(CH2)m—PO(OR7)Rg, —(CH2)n-Z-(CH2)m—OPO(OR7)Rg, —(CH2)nZ—(CH2)m—OPO(R9)(R10), or —(CH2)nZ—(CH2)m—PO(R9)(R10);R5 and R6 are independently selected from H, alkyl and halogen;Y is R7(CH2)s or is absent; andX, n, Z, m, R4, R5, R6, R7, and s are as defined herein; or a pharmaceutically acceptable salt thereof. A method for treating diabetes and related diseases employing the above compounds is also provided.
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Page/Page column 82
(2008/06/13)
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- 1-alkyl-4-benzoyl-5-hydroxypyrazole compounds and their use as herbicides
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1-Alkyl-4-benzoyl-5-hydroxy-1H-pyrazole compounds in which the benzoyl moiety is substituted in the 2-position with groups such as halo or alkyl, in the 4-position with an alkylsulfonyl group, and in the 3-position with a 3-oxetanyloxy or an oxetanylmethoxy substituent were prepared and found to be useful for the control of a variety of broadleaf and grassy weeds. The compounds have favorable environmental and toxicological properties and can be used to control undesirable vegetation in crops.
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- Preparation and Characterization of Side-Chain Liquid-Crystalline Polyoxetanes Anchoring a Pendant Spacer-Separated Mesogen at the Tertiary-Like C-3 Carbon of the Oxetane Unit
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Polyoxetanes anchoring a pendant spacer-separated mesogen at the tertiary-like C-3 carbon of the oxetane unit were prepared by cationic ring-opening polymerization of the corresponding oxetane derivatives. The resulting polymers were liquid-crystalline substances showing textures assignable to the nematic or smectic mesophase over a wide temperature range from about 260 ° C to room temperature. These mesogens also behaved in the manner similar to that of the mesogens in the analogous polyoxetanes attached by a methyl side chain at the quaternary C-3 carbon, although the less bulky polymer backbone in the present work indicated a somewhat higher Isotropic phase-transition temperature than that of the methyl-substituted analogs. In both types of the polyoxetanes, their mesophase patterns were influenced by the core structure and alkoxy tail length in the pendant mesogen, but not by the bulkiness of the second side chains, H and CH3, attached at the C-3 carbon of the polyoxetane unit.
- Ogawa, Hiroshi,Kodera, Yasutake,Kanoh, Shigeyoshi,Ueyama, Akihiko,Motoi, Masatoshi
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p. 433 - 442
(2007/10/03)
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- Process for the preparation of 3-hydroxyoxetanes
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A process for the preparation of 3-hydroxyoxetanes of formula I STR1 wherein R9 and R10 are each independently of the other hydrogen or C1 -C4 alkyl, by (1) reaction of a carboxylic acid R--CO2 H, wherein R is branched alkyl, with an epichlorohydrin of formula II STR2 wherein R9 and R10 are as defined hereinbefore, to form an ester of formula III STR3 wherein R, R9 and R10 are as defined hereinbefore, (2) reaction of that ester with an ether of formula IV wherein R1 is hydrogen or methyl, R2 is C1 -C6 alkyl, or R1 and R2 together form a radical of formula --(CH2)3 --, in the presence of a catalyst, to form an ester of formula V STR4 (3) hydrolysis and cyclization of that ester in the presence of a base to form a compound of formula VI STR5 wherein R1, R2, R9 and R10 are as defined hereinbefore, (4) acetal cleavage in the presence of an acid to form the corresponding 3-hydroxyoxetane and (5) isolation of that 3-hydroxyoxetane.
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- Herbicidal oxetane and thiaetane derivatives
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Oxetane and thiaetane derivatives of the formula I in which, Q is oxygen, sulfur, -COO-, -Z-CH(R3)-COO-, or CO-Y4-CH(R10)-COO-;, W is and R1 is hydrogen or fluorine; R2 is halogen or cyano; R3 and R10 independently of one another are hydrogen or C1-C3alkyl; R4 is hydrogen, fluorine, chlorine, bromine, C1-C4alkyl or trifluoromethyl; R5 and R7 independently of one another are C1-C4alkyl; R6 and R8 independently of one another are hydrogen or C1-C4alkyl; R9 is hydrogen, C1-C6alkyl, C3-C7cycloalkyl, C1-C4alkoxy-C1-C4alkyl or C1-C7haloalkyl; X is oxygen or sulfur; Y1, Y2, Y3, Y4, Y5 and Y6 independently of one another are oxygen or sulfur; Z is oxygen or sulfur; n is 0; 1, 2, 3 or 4; and q is 1 or 2, have good selective herbicidal properties when used pre- or post-emergence.
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- Synthesis of 3-hydroxyoxetane
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A process for preparing 3-hydroxyoxetane comprising the following steps in order (1) reacting a carboxylic acid of the formula CH3 (CH2)n COOH with epichlorohydrin in the presence of anhydrous ferric chloride to produce an ester of the formula STR1 wherein n is an integer of from 0 to 3; (2) protecting the secondary hydroxy group of the ester with a blocking group, Z, that is stable to bases; thus forming a blocked ester of the formula STR2 (3) hydrolyzing the blocked ester formed in step (2) with an aqueous base to remove the carboxylic acid and form a 3-hydroxyoxetane derivative of the formula STR3 in which Z represents the blocking group; (4) removing the blocking group from the 3-hydroxyoxetane derivative by heating it with an alcohol and an acid to form the product 3-hydroxyoxetane, STR4
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- Synthesis of Electron-Deficient Oxetanes. 3-Azidooxetane, 3-Nitrooxetane, and 3,3-Dinitrooxetane
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A facile synthesis of 3-hydroxyoxetane is described and is based on the addition of acetic acid to epichlorohydrin, protection of the resulting primary alcohol as an acetal, basic acetate hydrolysis and ring closure, and removal of the protecting group. 3-Azidooxetane was prepared from 3-(tosyloxy)oxetane and sodium azide.Reduction of the azide with triphenylphosphine or hydrogen gave 3-aminooxetane, and oxidation of the amine with m-chloroperbenzoic acid gave 3-nitrooxetane.Oxidative nitration or reaction with tetranitromethane gave 3,3-dinitrooxetane. 3-Azidooxetane and 3,3-dinitrooxetane were polymerized with Lewis acids.
- Baum, Kurt,Berkowitz, Phillip T.,Grakauskas, Vytautas,Archibald, Thomas G.
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p. 2953 - 2956
(2007/10/02)
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