- The synthesis of two long-chain N-hydroxy amino coumarin compounds and their applications in the analysis of aldehydes
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Herein, two N-substituted coumaryl hydroxylamines (compounds 1a and 1b) with long aliphatic chains were prepared in 8 steps with a novel synthetic protocol. They served as derivatization agents for aldehydes by the formation of nitrones under mild conditions, which can be readily analysed by LC-MS with good chromatographic performance, excellent fluorescent response, and high ionization strength. We successfully used compounds 1a and 1b in the analysis of furfuraldehydes in raisins, based on the derivatization reactions of standard furfural (F), 5-methylfurfural (5-MF) and 5-(hydroxymethyl)furfural (5-HMF) samples. It proved that they are excellent agents for the analysis of aldehydes in foodstuffs. The derivatization reaction between compound 1a and hexanal suggested that the applications of our designed derivatization agents can be further extended to the analysis of aliphatic aldehydes. This study demonstrated that the designed N-substituted coumaryl hydroxylamines are excellent probes for the analysis of various aldehydes which are important in multiple research areas.
- Guan, Zhaobing,Ding, Manman,Sun, Yao,Yu, Sisi,Zhang, Ao,Xia, Shuguang,Hu, Xiaosong,Lin, Yawei
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Read Online
- Fluorescent derivative reagent for detecting aldehyde substances, and preparation method and application thereof (by machine translation)
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The invention provides a fluorescent derivative reagent for detecting aldehyde substances, a preparation method thereof and application, of the reagent which comprises 4 - hydroxybutyl-butyl - 7 7-coumarin, which is a novel hydroxylamine derivative reagent; shown in structural formula HAMC, wherein fluorescence, is detected by the fluorescent derivative reagent for detecting aldehyde substances and an aldehyde compound standard sample, is detected under a high performance liquid chromatography (HPLC) fluorescence detector for detecting an aldehyde substance, and the detection reagent kit is used for detecting the aldehyde substance as shown in the structural structural formula shown in the following structural formula I. The detection reagent kit can detect, aldehydes . with fluorescein. (by machine translation)
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Paragraph 0042-0046
(2020/05/02)
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- COMPOUND, RESIN, RESIST COMPOSITION AND PRODUCTION METHOD OF RESIST PATTERN
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PROBLEM TO BE SOLVED: To provide a compound, a resin and a resist composition containing the resin, from which a resist pattern having good CD uniformity (CDU) can be produced. SOLUTION: The compound is represented by formulae (I-1) to (I-4), or the like;
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Paragraph 0201
(2020/10/27)
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- COMPOUND, RESIN, RESIST COMPOSITION AND PRODUCTION METHOD OF RESIST PATTERN
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PROBLEM TO BE SOLVED: To provide a compound from which a resist pattern with good line edge roughness (LER) can be produced. SOLUTION: The compound is represented by formula (I). In the formula, R1 represents an alkyl group having 1 to 6 carbon atoms, H, or a halogen atom; X1 represents a connecting group such as -COO-C6H5-COO-; A1 represents a single bond or the like; A3 represents an alkanediyl group having 1 to 6 carbon atoms; W represents a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms; and R2 represents a substituted/unsubstituted hydrocarbon group having 1 to 28 carbon atoms. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPO&INPIT
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Paragraph 0223
(2020/10/27)
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- BENZOIMIDAZOL-1,2-YL AMIDES AS Kv7 CHANNEL ACTIVATORS
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Optionally substituted benzoimidazol-1,2-yl amides, such as compounds of Formula 1 or Formula 2, can be used to treat disorders associated with a Kv7 potassium channel activator. Compositions, medicaments, and dosage forms related to the treatment are als
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Paragraph 0259; 0260
(2016/04/09)
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- Synthesis of oxazolidin-2-ones and imidazolidin-2-ones directly from 1,3-diols or 3-amino alcohols using iodobenzene dichloride and sodium azide
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A general and efficient method for the synthesis of oxazolidin-2-ones and imidazolidin-2-ones directly from 1,3-diols and 3-amino alcohols has been developed using the same reagent combination of iodobenzene dichloride (PhICl2) and sodium azide (NaN3).
- He, Tian,Gao, Wen-Chao,Wang, Wei-Kun,Zhang, Chi
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supporting information
p. 1113 - 1118
(2014/04/03)
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- Application of sulfuryl chloride for the quick construction of β-chlorotetrahydrofuran derivatives from homoallylic alcohols under mild conditions
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An efficient and mild method is reported for the construction of β-chlorotetrahydrofuran derivatives by 5-endo chlorocycloetherification of homoallylic alcohols. The system employs sulfuryl chloride as the chlorinating agent under catalyst-free conditions. A variety of homoallylic alcohols with aryl or alkyl substituents were smoothly converted into β- chlorotetrahydrofurans in yields up to 98%.
- Zeng, Xianghua,Miao, Chengxia,Wang, Shoufeng,Xia, Chungu,Sun, Wei
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supporting information
p. 2391 - 2396
(2013/09/23)
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- Quinolone derivatives containing strained spirocycle as orally active glycogen synthase kinase 3β (GSK-3β) inhibitors for type 2 diabetics
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The design, synthesis, and evaluation of 6-6-7 tricyclic quinolones containing the strained spirocycle moiety aiming at the GSK-3β inhibitor were described. Among the synthesized compounds, 44, having a cyclobutane ring on a spirocycle, showed excellent GSK-3β inhibitory activity in both cell-free and cell-based assays (IC50 = 36 nM, EC50 = 3.2 μM, respectively). Additionally, 44 decreased the plasma glucose concentration dose-dependently after an oral glucose tolerance test in mice.
- Seto, Shigeki,Yumoto, Kazuhiko,Okada, Kyoko,Asahina, Yoshikazu,Iwane, Aya,Iwago, Maki,Terasawa, Reiko,Shreder, Kevin R.,Murakami, Koji,Kohno, Yasushi
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experimental part
p. 1188 - 1200
(2012/03/26)
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- CATHEPSIN S INHIBITORS
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Compounds of the formula (I) where R1 is C1-C4 straight or branched alkyl, optionally substituted with up to three substituents selected from halo and hydroxy; R2 is halo, hydroxy, methyloxy, or C1-C2 alkyl, which alkyl is optionally substituted with up to three halogens or an hydroxy or a methyloxy; D is - C3-C7 alkylene-, thereby defining a cycloalkyl ring; E is -C(=O)-, -S(=O)m-, -NRdS(=O)m-, -NRaC(=O)-, -OC(=O)-, R3 is an optionally substituted carbocyclic or heterocyclic ring R10 is H, ORc, SRc or together with the gem H is =O or (ORc)2; Ra is independently selected from H, C1-C4 alkyl; have utility in the inhibition of cathepsin S and are thus useful pharmaceuticals against disorders such as autoimmune disorders and chronic pain.
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Page/Page column 55-56
(2010/11/08)
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- New application of bromotrimethylsilane: Elaboration of aldehydes/ketones into homologous α,β-unsaturated esters via β-hydroxy esters
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α,β-Unsaturated esters are formed when β-hydroxy esters react with bromotrimethylsilane which is generated from chlorotrimethylsilane- lithium bromide in acetonitrile. Copyright Taylor & Francis, Inc.
- Suri, Suresh C.,Marcischak, Jacob C.
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p. 379 - 387
(2007/10/03)
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- A Direct Retro-Reformatsky Fragmentation: Formal Ring Enlargement of Cyclic Ketones for Novel and Practical Synthesis of Heterocyclic Enamines
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A novel and practical synthesis of heterocyclic enamines has been developed from the formal ring enlargement of cyclic ketones, which comprised the retro-Reformatsky fragmentation reaction as a key step. Under alkaline bromination conditions, the Reformat
- Zhao, Mei-Xin,Wang, Mei-Xiang,Yu, Chu-Yi,Huang, Zhi-Tang,Fleet, George W. J.
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p. 997 - 1000
(2007/10/03)
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- PROCESS FOR PRODUCING FUSED IMIDAZOLE COMPOUND, REFORMATSKY REAGENT IN STABLE FORM, AND PROCESS FOR PRODUCING THE SAME
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The present invention provides an industrially advantageous process for producing a steroid C17,20 lyase inhibitor represented by the general formula (I): and a Reformatsky reagent in a stable form suitable for the process.In the present invention, a compound represented by the general formula (I) is produced by reducing a specific β-hydroxy ester compound derivative or a salt thereof obtained from a specific carbonyl compound in a Reformatsky reaction in the presence of a metal hydride complex and a metal halide, and then subjecting it to a ring-closing reaction. In the above Reformatsky reaction, it is useful to use a stable solution of a compound represented by the general formula BrZnCH2COOC2H5 or a crystal of the compound which is represented by the formula (BrZnCH2COOC2H5·THF)2.
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- Unique Molecular Discrimination in Europium Complex-Catalyzed Reactions of Saturated and α,β-Unsaturated Ketones with Ketene Silyl Acetals
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The unique molecular discriminations are observed in the Eu(III)-catalyzed reactions of saturated ketones, α,β-enones, and α,β-ynones with ketene silyl acetals and discussed in terms of the discriminating ability of the Eu-catalyst at the complexation sta
- Hanyuda, Kiyoshi,Hirai, Kei-Ichi,Nakai, Takeshi
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- Intramolecular cyclization of 2,7- or 2,8-bis-unsaturated esters mediated by (η2-propene)Ti(O-i-Pr)2. Facile construction of mono- and bicyclic skeletons with stereoselective introduction of a side chain. A synthesis of d-sabinene
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tert-Butyl 2-en-7-ynoate 6 was treated with (η2-propene)Ti(O-i-Pr)2 (3), generated in situ from Ti(O-i-Pr)4 or Ti(O-i-Pr)3Cl and i-PrMgCl, in ether at -50 to -20°C to afford the product 8 in good yield. The presence of the intermediate titanabicycle 7 was verified by bis-deuterolysis with excess D2O. When the titanabicycle 7 was treated with 1.1 equiv of i-PrOD and then worked up as usual, the monodeuterated product 10 was obtained with high sight selectivity and stereoselectivity. Other electrophiles such as aldehydes and ketones also reacted with the titanabicycle in a highly stereoselective manner to give cyclopentanes having a stereo-defined side chain. On the contrary, treatment of the corresponding ethyl ester, ethyl 8-(trimethylsilyl)-(E)-2-octen-7-ynoate (28), with 3 under the same conditions followed by the addition of 1.1 equiv of s-BuOH afforded 2-(trimethylsilyl)-1-bicyclo[3.3.0]- octen-3-one (32) in 80% yield. Quenching the same reaction mixture with i-PrOD, EtCHO, and Et2CO in place of s-BuOH gave 4-deuterio (with exclusive deuterium incorporation), 4-(1-hydroxypropyl), and 4-(1-ethyl-1-hydroxypropyl) derivatives of the above bicyclic ketone (34, 35, and 36) in good yields. These electrophiles were always introduced from the convex face of the bicyclic skeleton. The stereochemistry of the cyclization could be controlled by an allylic substituent such as (tert-butyl)dimethylsiloxy or butyl group to a high degree yet with a reversal diastereoselection to give 45 or 47. The reaction of ethyl 7-octen-2-ynoate (56) and 3 at -50 to 0°C took place in a quite different way to afford 1-[(ethoxycarbonyl)methyl]bicyclo[3.1.0]hexane (64) in 74% yield after hydrolysis. If the simple hydrolysis is replaced by deuterolysis or the action of diethylketone, 1-[(ethoxycarbonyl)dideuteriomethyl] (with 99% deuterium incorporation), or 1-[(ethoxycarbonyl)(3-pentylidene)methyl] derivative of the above product (65 or 66) was obtained in good yields. A 7-en-2-ynoate having an internal Z-double bond such as 80 afforded a single stereoisomer 82 with the substituent at the endo position, of the bicyclic skeleton, suggesting that the stereochemical integrity of the Z-double bond of the starting material was retained in the product. An alkyl substituent at the allylic position of the substrates like 74 and 76 nicely controlled the stereochemistry of the cyclization to afford single products 75 and 77 with the substituent being placed in the exo orientation of the bicyclic structure. This high diastereoselectivity was successfully applied to an enantioselective synthesis of d-sabinene from an optically active enynoate via nearly complete chirality transfer.
- Urabe,Suzuki,Sato
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p. 10014 - 10027
(2007/10/03)
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- 2,2-Di(ethoxy)vinyllithium: Reactions with carbonyl compounds
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2,2-Di(ethoxy)vinyllithium 2 generated from bromo ketene acetal 1 reacts with carbonyl compounds to give either β-hydroxy esters 5 or conjugated esters 6 or hydroxy ketene acetals 7 according to the work up.
- Hiouni, Abdelaziz,Duhamel, Lucette
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p. 5507 - 5510
(2007/10/03)
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- One-pot Preparation of β-Hydroxy Esters Catalysed by a Bis(cyclopentadienyl)titanium(IV) Dichloride-Zinc System
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The reaction of α-haloesters with carbonyl compounds catalysed by Cp2TiCl2(cat.)-Zn gives β-hydroxy esters.
- Ding, Yu,Zhao, Gang
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p. 941 - 942
(2007/10/02)
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- Homolytic Displacement at Saturated Carbon: Part 5. Synthesis of Cyclopropylmethyl, Bicyclohex-2-yl, Bicyclohept-2-yl and Cyclohexanespirocycloprop-2-yl Sulphones from the Corresponding But-3-enylcobaloximes
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But-3-enylcobaloxime reacts with arenesulphonyl chlorides under thermal and photochemical conditions to give cyclopropylmethyl sulphones.The yields depend upon the reaction conditions used.Similar reactions of cyclopent-2-enylmethylcobaloxime and cyclohex-2-enylmethylcobaloximes under photochemical conditions form a mixture of cis and trans isomers of bicyclohex-2-yl and bicyclohept-2-yl sulphones in (50:50) and (70:30) isomeric ratios respectively.However, cyclohex-3-enylcobaloximes form only the trans-bicyclohex-2-yl sulphone.Exclusive formation of cycloalkanespirocycloprop-2-yl sulphones is observed in the reactions of 2-(cyclo alk-1-enyl)ethylcobaloximes with arenesulphonyl chlorides.The reactions are free radical in nature and are believed to take place by a chain mechanism.In the key step a homolytic attack of the RSO2 radical at the terminal (δ) carbon of the butenyl ligand leads to the cyclized product.The exact nature of the ring closure step is uncertain, as both concerted and stepwise mechanisms are possible.
- Gupta, B. Dass,Das, Indira,Dixit, Vandana
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p. 2409 - 2446
(2007/10/02)
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- A Barbier allylation and a Reformatsky reaction of carbonyl compounds mediated by indium(I) iodide
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Indium(I) iodide was found to mediate in the Barbier allylation and in the Reformatsky reaction of aldehydes and ketones to give homoallylic alcohols and β-hydroxy esters, respectively, presumably via allylindium(III) diiodide.
- Araki, Shuki,Ito, Hirokazu,Katsumura, Nobuhito,Butsugan, Yasuo
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p. 291 - 296
(2007/10/02)
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- Cyclic Ether Formation in Superacid Media
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The formation of ethers in superacids by interaction of a primary hydroxy group with a carbocation centre has been investigated by a study of cyclisation of suitable substrates, mainly 1-(2-hydroxyethyl)cyclohexanols to give hydrobenzofurans.Cyclisation traps thermodynamically stable ionic species, with rates of reaction dependent upon the size of the ether ring formed.Three- and four-membered ether rings were not formed, five-membered ether rings formed readily, the reaction being comparable in rate with a 1,2-methyl shift.Six-membered rings formed a little less readily and seven-membered rings less readily still, though a yield of 34 percent from a suitable substrate has been recorded.An unexpected feature of the reactions was their stereospecificity; in one case, this is believed to result from a methyl shift concerted with attack of the primary hydroxy group, the reaction proceeding through hindered transition state, in which methyl loss, probably as CH3+, competes with a 1,2-methyl shift.
- Carr, Graham,Whittaker, David
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p. 359 - 366
(2007/10/02)
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- REFORMATSKY REACTION USING Zn/Ag COUPLE
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The Reformatsky reaction is easy to run in ethereal solvents in the presence of Zn/Ag couple.From methyl γ-bromocrotonate and krtones, remified esters are fromed in refluxing Et2O, linear ones in refluxing THF.
- Bortolussi, Michel,Seyden-Penne, Jacqueline
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p. 2355 - 2362
(2007/10/02)
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- HOMOLYTIC DISPLACEMENT AT CARBON. X. TOLUENESULPHONYL IODIDE AS A SOURCE OF TOLUENESULPHONYL RADICALS FOR THE FORMATION OF ALLYL-, BENZYL-, CYCLOPROPYLCARBINYL-, SPIROCYCLOPROPYLCYCLOALKYL-, BICYCLOALKYL-, AND BICYCLOALKYL-4-TOLYLSULPHONES FROM ORGANOCOBALOXIMES
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4-Toluenesulphonyl iodide reacts thermally at alkylsulphone.Spiro- and bicyclo-alkyl compounds are also formed with other free radical precursors.The reactions are believed to take place through a chain mechanism in which cobaloxime(II), present adventitiously or formed by partial homolysis of the substrate, abstracts iodine from the toluenesulphonyl iodide to give the toluenesulphonyl radical, which attacks the organic ligand of the cobaloxime, preferably at the terminal olefinic carbon, thereby displacing cobaloxime(II) and giving the observed organic product.
- Ashcroft, Martyn R.,Bougeard, Peter,Bury, Adrian,Cooksey, Christopher J.,Johnson, Michael D.
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p. 403 - 416
(2007/10/02)
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