- Synthesis method of 2-acetaldehyde-5-methylthiophene
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The invention relates to a synthesis method of 2-acetaldehyde-5-methylthiophene, which comprises the following steps: reacting thiophene with acetic anhydride in the presence of phosphoric acid, adding acetic anhydride, 85% phosphoric acid and thiophene into a reaction pot, stirring, gradually heating to reflux temperature of 95-100 DEG C, keeping reflux for 2-3 hours, cooling, washing with water,removing a water layer, distilling an obtained oil layer under reduced pressure after normal pressure to obtain the 2-acetaldehyde-5-methylthiophene, collecting distillate, standing, removing a waterlayer, recycling 2-acetaldehyde thiophene, removing residual oily substances in a pot, performing reduced pressure distillation, collecting a 85-90 DEG C fraction 2-acetaldehyde thiophene finished product, performing reaction reflux on the 2-acetaldehyde thiophene by using methyl iodide under the catalysis of aluminum chloride, pouring the obtained mixture into ice water dissolved with sodium hydroxide, separating out an oil layer, drying to obtain the product, and carrying out distillation to obtain a fraction of 110 DEG C. Briefly speaking, according to the technical scheme, an excellent optimization scheme is utilized, and the problems that more residues exist after synthesis, and raw material waste is large are solved.
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Paragraph 0025-0028
(2021/03/11)
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- NON-LYSOSOMAL GLUCOSYLCERAMIDASE INHIBITORS AND USES THEREOF
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The invention provides compounds for inhibiting glucosylceramidases, prodrugs of the compounds, and pharmaceutical compositions including the compounds or prodrugs of the compounds.
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Paragraph 00366
(2020/12/01)
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- Stereoselective Synthesis of Vinylboronates by Rh-Catalyzed Borylation of Stereoisomeric Mixtures
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The stereoselective preparation of vinylboronates via rhodium-catalyzed borylation of E/Z mixtures of vinyl actetates is described, and this method was also extended to synthesis of vinyldiboronates. These transformations feature high functional group compatibility and mild reaction conditions. Control experiments support a mechanism that involved a Rh-catalyzed borylation-isomerization sequence. The isomerization of (Z)-vinylboronates to (E)-isomers was also demonstrated.
- Li, Shenhuan,Li, Jie,Xia, Tianlai,Zhao, Wanxiang
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supporting information
p. 462 - 468
(2019/03/28)
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- Copper-Catalyzed Cascade Cyclization of Indolyl Homopropargyl Amides: Stereospecific Construction of Bridged Aza-[n.2.1] Skeletons
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Catalytic cycloisomerization-initiated cascade cyclizations of terminal alkynes have received tremendous interest, and been widely used in the facile synthesis of a diverse array of valuable complex heterocycles. However, these tandem reactions have been mostly limited to noble-metal catalysis, and are initiated by an exo-cyclization pathway. Reported herein is an unprecedented copper-catalyzed endo-cyclization-initiated tandem reaction of indolyl homopropargyl amides, where copper catalyzes both the hydroamination and Friedel–Crafts alkylation process. This method allows the practical and atom-economical synthesis of valuable bridged aza-[n.2.1] skeletons (n=3–6) with wide substrate scope, and excellent diastereoselectivity and enantioselectivity by a chirality-transfer strategy. Moreover, the mechanistic rationale for this novel cascade cyclization is also strongly supported by control experiments, and is distinctively different from the related gold catalysis.
- Tan, Tong-De,Zhu, Xin-Qi,Bu, Hao-Zhen,Deng, Guocheng,Chen, Yang-Bo,Liu, Rai-Shung,Ye, Long-Wu
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p. 9632 - 9639
(2019/06/27)
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- Synthetic method of 2-thiopheneacetic acid
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The invention discloses a synthetic method of 2-thiopheneacetic acid and belongs to the technical field of synthesis of intermediates. The synthetic method comprises the following steps: synthesis of3-(2-thiophene)-2,3-epoxy sodium propionate: taking 2-thiophenecarboxaldehyde and chloracetate as raw materials, carrying out Darzen reaction to synthesize epoxy acid ester and then hydrolyzing to obtain the 3-(2-thiophene)-2,3-epoxy sodium propionate; synthesis of 2-thiopheneacetic acid: acidizing the 3-(2-thiophene)-2,3-epoxy sodium propionate, carrying out decarboxylation rearrangement to obtain 2-thiophene acetaldehyde and then carrying out Pinnick oxidation reaction to obtain the 2-thiopheneacetic acid. In the synthesis method of the 2-thiopheneacetic acid provided by the invention, Darzen reaction and Pinnick oxidation reaction are adopted; due to high conversion rate of the Darzen reaction and good selectivity of Pinnick oxidation, the product has the advantages of high yield, fewercontained impurities, significant advantages and practical value.
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Paragraph 0027; 0030; 0031; 0034; 0035; 0038; 0039; 0042
(2019/07/29)
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- Photoredox Cyanomethylation of Indoles: Catalyst Modification and Mechanism
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The direct cyanomethylation of indoles at the 2- or 3-position was achieved via photoredox catalysis. The versatile nitrile synthon is introduced as a radical generated from bromoacetonitrile, a photocatalyst, and blue LED as a light source. The mechanism of the reaction is explored by determination of the Stern-Volmer quenching constants. By combining photophysical data and mass spectrometry to follow the catalyst decomposition, the catalyst ligands were tuned to enable synthetically useful yields of radical coupling products. A range of indole substrates with alkyl, aryl, halogen, ester, and ether functional groups participate in the reaction, affording products in 16-90% yields. The reaction allows the rapid construction of synthetically useful cyanomethylindoles, products that otherwise require several synthetic steps.
- O'Brien, Connor J.,Droege, Daniel G.,Jiu, Alexander Y.,Gandhi, Shivaani S.,Paras, Nick A.,Olson, Steven H.,Conrad, Jay
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p. 8926 - 8935
(2018/07/05)
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- Aryl [a] indole [2,3 - the g] and quinolizine compound, preparation method thereof, pharmaceutical compositions and uses thereof
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The invention relates to an aryl [a] indole [2,3-g] quinolizine compound as well as a preparation method, a pharmaceutical composition and application thereof, and particularly relates to a aryl [a] indole [2,3-g] quinolizine compound with a novel structure as shown in a general formula (I) and a derivative, a preparation method and a pharmaceutical composition thereof and application of the aryl [a] indole [2,3-g] quinolizine compound in preparation of a drug for treating diseases related to alpha 1-adrenoreceptor and urinary system diseases, such as benign prostatic hyperplasia, uroschesis and bladder outlet obstruction, especially.
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Paragraph 0368; 0369
(2017/01/17)
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- Pd-catalyzed C-N coupling of vinylbromides and sulfonimidamides: A facile synthesis of N′-vinylsulfonimidamides
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N′-Vinyl sulfonimidamides have been synthesized through a Pd-catalyzed C-N cross coupling between the N′-(imine nitrogen) of N′-deprotected sulfonimidamides and vinyl bromides. The hitherto unreported products were obtained in moderate to excellent yield, and the C-C double bond geometry of the vinylic substrates were retained during the course of reaction. Single crystal X-ray crystallographic analysis confirmed the product structure. Furthermore, we demonstrate that the formed N′-vinyl sulfonimidamides could undergo hydrogenation with Pd-C/H2 to provide N′-alkyl sulfonimidamides.
- Nandi, Ganesh C.,Kota, Sudhakar R.,Wakchaure, Prasad B.,Chinthakindi, Praveen K.,Govender, Thavendran,Kruger, Hendrick G.,Naicker, Tricia,Arvidsson, Per I.
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p. 62084 - 62090
(2015/08/03)
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- Copper-mediated direct alkoxylation of arenes using an N, O -bidentate directing system
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Highly effective CuCl-mediated C-H alkoxylation of arenes and heteroarenes has been developed by using a 2-aminopyridine 1-oxide moiety as an N,O-bidentate directing group. The reaction proceeds smoothly using a broad range of substrates to afford o-alkox
- Zhang, Lin-Bao,Hao, Xin-Qi,Zhang, Shou-Kun,Liu, Ke,Ren, Baozeng,Gong, Jun-Fang,Niu, Jun-Long,Song, Mao-Ping
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p. 10399 - 10409
(2015/02/19)
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- Selective reduction of carboxylic acids to aldehydes catalyzed by B(C 6F5)3
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B(C6F5)3 efficiently catalyzes hydrosilylation of aliphatic and aromatic carboxylic acids to produce disilyl acetals under mild conditions. Catalyst loadings can be as low as 0.05 mol %, and bulky tertiary silanes are favored to give selectively the acetals. Acidic workup of the disilyl acetals results in the formation of aldehydes in good to excellent yields.
- Bezier, David,Park, Sehoon,Brookhart, Maurice
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supporting information
p. 496 - 499
(2013/03/29)
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- Selective switchable iron-catalyzed hydrosilylation of carboxylic acids
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Selective reduction of carboxylic acids either to aldehydes or alcohols is achieved using a one pot procedure based on iron-catalyzed hydrosilylations. Using phenylsilane and (COD)Fe(CO)3 catalyst under UV-irradiation at rt, alcohols were obtained specifically in good yields, whereas aldehydes were selectively obtained using TMDS and (t-PBO)Fe(CO)3 catalyst under thermal activation.
- Misal Castro, Luis C.,Li, Haoquan,Sortais, Jean-Baptiste,Darcel, Christophe
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supporting information
p. 10514 - 10516,3
(2020/09/02)
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- The catalytic potential of Coptis japonica NCS2 revealed - Development and utilisation of a fluorescamine-based assay ETI
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The versatility and potential of a norcoclaurine synthase (NCS) from Coptis japonica NCS2 has been investigated, together with the development and application of a novel fluorescence-based high-throughput assay using nearly forty amines/aldehydes. The stereocontrol exerted by CjNCS2 on selected non-natural substrates has been determined, where the tetrahydroisoquinolines (THIAs) were formed as the (1S)-isomer in >95% ee, as observed with the natural product norcoclaurine. Docking calculations involving THIA mechanism intermediates, utilising the reported Thalictrum flavum NCS X-ray crystallographic structure, were carried out and combined with the CjNCS2 screening results to further understand the mode of action of NCS. These findings suggested that in addition to the key active-site residues K122 and E110, D141 is also mechanistically essential for the enzymatic transformation. The exceptional tolerance of NCS towards aldehyde substrates is furthermore supported by our proposed mechanism in which the aldehydes protrude out of the enzymatic pocket. Copyright
- Pesnot, Thomas,Gershater, Markus C.,Ward, John M.,Hailes, Helen C.
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supporting information
p. 2997 - 3008
(2013/01/15)
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- Microwave-assisted synthesis of 5-substituted 2-aminothiophenes starting from arylacetaldehydes
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An easy three-step pathway for the synthesis of arylacet-aldehydes from the corresponding carboxylic acids in very high yields is described. Their use as precursors of 5-substituted-2-aminothiophenes is illustrated via a microwave-assisted Gewald reaction. This method allows obtaining the expected compounds in a shorter time and with better yields and purities than the classical procedures. Georg Thieme Verlag Stuttgart - New York.
- Revelant, Germain,Dunand, Sandrine,Hesse, Stephanie,Kirsch, Gilbert
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p. 2935 - 2940
(2011/11/01)
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- Push-pull aminobithiophenes - Highly fluorescent stable fluorophores
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Stable 2-aminobithiophenes were prepared using the Gewald reaction. The resulting push-pull bithiophenes exhibited both unprecedented high fluorescence yields and stability in addition to demonstrating fluorescence on-off properties.
- Dong, Yanmei,Bolduc, Andreanne,McGregor, Nicholas,Skene
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supporting information; experimental part
p. 1844 - 1847
(2011/06/22)
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- One-pot synthesis of imidazole-4-carboxylates by microwave-assisted 1,5-electrocyclization of azavinyl azomethine ylides
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Diversely functionalized imidazole-4-carboxylates were synthesized by microwave-assisted 1,5-eletrocyclization of 1,2diaza-l,3-diene-derived azavinyl azomethine ylides. 1,2-Diaza-1,3-dienes were treated with primary aliphatic or aromatic amines and subjected to microwave irradiation in the presence of aldehydes. 3-Alkyl- and 3-arylimidazole-4-carboxylates were prepared in good yields through a one-pot multicomponent procedure. Modulation of the substituents at C-2, N-3, and C-5 was possible, and 2-unsubstituted imidazoles were obtained when paraformaldehyde was used.
- Preti, Lisa,Attanasi, Orazio A.,Caselli, Emilia,Favi, Gianfranco,Ori, Claudia,Davoli, Paolo,Felluga, Fulvia,Prati, Fabio
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supporting information; experimental part
p. 4312 - 4320
(2010/10/21)
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- Biologically active compounds
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The present invention relates to compounds of formula (I), and pharmaceutically acceptable salts thereof. The invention further relates to pharmaceutical compositions comprising compounds of formula (I), and the use of such compounds in the treatment of a disease selected from osteoporosis, Paget's disease, Chagas's disease, malaria, gingival diseases, hypercalaemia, metabolic bone disease and diseases involving matrix or cartilate degradation.
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Page/Page column 29
(2009/05/28)
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- New volatile sulfur-containing constituents in a simultaneous distillation-extraction extract of red bell peppers (Capsicum annuum)
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An extract of red bell peppers (Capsicum annuum) was prepared by simultaneous distillation-extraction (SDE, Likens-Nickerson). In addition to the already known (3E)-hepten-2-one (1), the unsaturated C9-ketones 1-nonen-4-one (2), (2E)-2-nonen-4-one (3), and (2E,5E)-2,5-nonadien-4-one (4), 2-methoxy-3-isobutylpyrazine (5), and heptane-2-thiol (6), we identified 19 new thiols (the aliphatic saturated and unsaturated thiols 14-16, and 22-27, the mercapto-ketones 12 and 13, the mercapto-alcohols 17, 18, and 30, the dithiols 19 and 28, the methylthio-thiols 20 and 21, and the thiophene-thiol 31) and the two new dithiolanes 10 and 29. All of them are structurally related to the unsaturated C7-and C9-ketones 1-4. The free thiols were enriched using Affi-Gel 501 (p-aminophenyl-mercuric acetate grafted on an agarose gel). The new compounds were confirmed by syntheses and were organoleptically evaluated.
- Naef, Regula,Velluz, Alain,Jaquier, Alain
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experimental part
p. 517 - 527
(2009/04/10)
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- Properties of Triflic Anhydride. Oxidation of Alcohols and Sulfides
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The reaction of dimethyl sulfide with triflic anhydride leads to the formation of the corresponding dimethyl(trifluoromethanesulfonyl)sulfonium salt. The latter can be used in the mild oxidation of primary and secondary alcohols including unsaturated and natural ones to the corresponding carbonyl compounds in 34-75% yield. The reaction of various sulfides with triflic anhydride was studied. It was found that the reactions give rise to the corresponding dialky(trifluoromethane- sulfonyl)sulfonium salts. Succeeding treatment with water leads to the formation of sulfoxides in 25-73% yield. Formation of sulfones does not proceed.
- Nenajdenko, Valentine G.,Vertelezkij, Pavel V.,Koldobskij, Andrej B.,Alabugin, Igor V.,Balenkova, Elizabeth S.
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p. 2483 - 2486
(2007/10/03)
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- Synthesis of aldehydes from oxiranes using silica gel as reagent
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The rearrangement of some 2-aryl monosubstituted and 2-aryl, 2-methyl disubstituted oxiranes to aldehydes using silica gel in very mild conditions is reported.
- Lemini,Ordonez,Perez-Flores,Cruz-Almanza
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p. 2695 - 2702
(2007/10/02)
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- Synthesis of aldehydes by a one-carbon homologation of ketones and aldehydes via --α,β-unsaturated isocyanides
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Ketones and aldehydes react via a Wittig-Horner-Emmons reaction using diethyl(isocyanomethyl)phosphonate to form α,β-unsaturated isocyanides (4), which are either hydrolyzed as such, under acid conditions, or hydrolyzed after oxidation to α,β-unsaturated isocyanates (6) to give aldehydes containing one additional carbon atom.The scope of the reaction is demonstrated by 20 examples.
- Moskal, Janusz,Leusen, Albert M. van
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p. 137 - 141
(2007/10/02)
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