- Mechanochemical Syntheses of N-Containing Heterocycles with TosMIC
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A mechanochemical van Leusen pyrrole synthesis with a base leads to 3,4-disubstitued pyrroles in moderate to excellent yields. The developed protocol is compatible with a range of electron-withdrawing groups and can also be applied to the synthesis of oxazoles. Attempts to mechanochemically convert the resulting pyrroles into porphyrins proved to be difficult.
- Bolm, Carsten,Molitor, Claude,Rissanen, Kari,Schumacher, Christian,Smid, Sabrina,Truong, Khai-Nghi
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p. 14213 - 14222
(2021/09/07)
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- Silver-Catalyzed Acyl Nitrene Transfer Reactions Involving Dioxazolones: Direct Assembly of N-Acylureas
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Dioxazolones and isocyanides are useful synthetic building blocks, and have attracted significant attention from researchers. However, the silver-catalyzed nitrene transfer reaction of dioxazolones has not been investigated to date. Herein, a silver-catalyzed acyl nitrene transfer reaction involving dioxazolones, isocyanides, and water was realized in the presence of Ag2O to afford a series of N-acylureas in moderate to good yields.
- Yang, Zheng-Lin,Xu, Xin-Liang,Chen, Xue-Rong,Mao, Zhi-Feng,Zhou, Yi-Feng
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supporting information
p. 648 - 652
(2020/12/21)
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- Phenyl pyrrole compound and application thereof in bactericidal activity
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The invention provides a novel phenyl pyrrole compound, and the phenyl pyrrole compound shows good bactericidal activity and can be used for preparing a broad-spectrum plant bactericide. In addition,the synthesis route is simple, the operation is convenient, the synthesis cost is reduced, and ecological environment pollution to soil, surface water, underground water and the like is avoided.
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Paragraph 0137; 0140
(2020/08/17)
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- Nitrogen-substituted phenyl pyrrole compound and application thereof in plant sterilization
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The invention provides a novel nitrogen-substituted phenyl pyrrole compound. The phenyl pyrrole compound shows good bactericidal activity and can be used for preparing bactericides with high-selectivity sterilization. Moreover, the synthesis route is simple, the operation is convenient, the synthesis cost is reduced, and ecological environment pollution to soil, surface water, underground water and the like is avoided.
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Paragraph 0143; 0152; 155
(2020/07/21)
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- Silver-catalyzed [3+2+1] annulation of aryl amidines with benzyl isocyanide
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A silver-catalyzed [3+2+1] annulation of amidines with benzyl isocyanide toward 2,4-diaryl-1,3,5-triazines was developed. A variety of symmetrical and unsymmetrical products were obtained in moderate to good yields. This work also features an oxidant-free approach to 2,4-disubstituted triazines.
- Lu, Xiaodong,Xin, Xiaoyi,Wan, Boshun
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supporting information
p. 361 - 364
(2018/01/08)
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- Catalytic Enantio- and Diastereoselective Mannich Addition of TosMIC to Ketimines
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Chiral amines bearing a stereocenter in the α position are ubiquitous compounds with many applications in the pharmaceutical and agrochemical sectors, as well as in catalysis. Catalytic asymmetric Mannich additions represent a valuable method to access such compounds in enantioenriched form. This work reports the first enantio- and diastereoselective addition of commercially available p-toluenesulfonylmethyl isocyanide (TosMIC) to ketimines, affording 2-imidazolines bearing two contiguous stereocenters, one of which is fully-substituted, with high yields and excellent stereocontrol. The reaction, catalyzed by silver oxide and a dihydroquinine-derived N,P-ligand, is broad in scope, operationally simple, and scalable. Derivatization of the products provides enantioenriched vicinal diamines, precursors to NHC ligands and sp3-rich heterocyclic scaffolds. Computations are used to understand catalysis and rationalize stereoselectivity.
- Franchino, Allegra,Chapman, Jack,Funes-Ardoiz, Ignacio,Paton, Robert S.,Dixon, Darren J.
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supporting information
p. 17660 - 17664
(2018/11/10)
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- SUBSTITUTED IMIDAZO[1,5-A]PYRIMIDINES AND THEIR USE IN THE TREATMENT OF MEDICAL DISORDERS
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The invention provides substituted imidazo[1,5-a]pyrimidines and related organic compounds, compositions containing such compounds, medical kits, and methods for using such compounds and compositions to treat medical disorders, e.g., Gaucher disease, Parkinson's disease, Lewy body disease, dementia, or multiple system atrophy, in a patient. Exemplary substituted imidazo[1,5-a]pyrimidine compounds described herein include substituted 2,4-dimethyl-N-phenylimidazo[1,5-a]pyrimidine-8-carboxamide compounds and variants thereof.
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Paragraph 00242
(2016/06/01)
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- A 2-fluoro-4-methyl sulfonyl methyl isonitriles method for the synthesis of
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The invention discloses a synthesis method of 2-fluoro-4-toluenesulfonylmethyl isocyanide. The method comprises the following steps: with sodium p-tolylsulfinate as a raw material, carrying out similar Mannich condensation and amide dehydration reaction to prepare tolylsulfonylmethyl isocyanide; adding a hydrofluoric acid aqueous solution and an Ni-CO catalyst to tolylsulfonylmethyl isocyanide; and fully reacting under nitrogen protection, and carrying out suction filtration, washing and drying to obtain faint yellow crystal 2-fluoro-4-toluenesulfonylmethyl isocyanide, wherein the yield reaches over 92%, and the purity is 99.8%. The synthesis method has the advantages of being available in reaction raw materials, mild in condition, high in yield, suitable for industrial production and the like.
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Paragraph 0021; 0022
(2017/03/08)
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- 4 - (2,2-difluoro -1,3-Benzodioxole-4-yl) pyrrole-3-nitrile synthetic method
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The invention discloses a synthetic method of 4-(2,2-difluoro-1,3-benzodioxole-4-yl)pyrrole-3-nitrile. The method comprises the following steps of: preparing an intermediate 2,2-difluorobenz-1,3-dioxole through reacting catechol with dibromodifluoromethane, and preparing an intermediate 2-cyano-3-(2,2-difluorobenz-1,3-dioxole-4-yl)-2-acrylate. The fludioxonil prepared by the synthetic method provided by the invention has the purity of more than 99.0% and the total yield of more than 45.0%; the synthetic method has the advantages of cheap and easily available raw materials, simple process, high product yield in each step, good purity, low production cost, applicability to batch industrial production and the like.
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Paragraph 0046; 0061; 0077
(2018/07/10)
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- COMPOSITION, SYNTHESIS, AND USE OF NEW ARYLSULFONYL ISONITRILES
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This invention relates to novel isonitriles, including arylsulfonyl isonitriles, and methods for their synthesis. The isonitriles include a conjugated ring system. The structure is designed with the flexibility to have multiple substitution patterns. The isonitriles may be used in applications including, but not limited to, pharmaceutical compositions.
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Paragraph 0182
(2015/09/23)
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- Alkyl sulfinates: Formal nucleophiles for synthesizing TosMIC analogs
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Alkyl sulfinates function as formal nucleophiles in Mannich-type reactions to give sulfonyl formamides, which are readily dehydrated to the corresponding sulfonylmethyl isonitriles. The efficient, two-step synthesis provides a general route to sulfonylmethyl isonitriles from readily available methyl sulfinates or thiols. Mechanistic analysis reveals that the unusual nucleophlicity of the alkyl sulfinates arises from the in situ release of sulfinic acids.
- Lujan-Montelongo, J. Armando,Estevez, Angel Ojeda,Fleming, Fraser F.
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supporting information
p. 1602 - 1605
(2015/03/04)
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- Synthesis and thermal stability of imino-1,3-dithietanes. Influence of structural factors
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The reaction of 1,2-dithiol-3-thiones with isonitriles at room temperature affords imino-1,3-dithietanes. The reaction is reversible. According to 1H NMR spectroscopy, the rise of the temperature shifts the equilibrium to the starting compounds
- Ogurtsov,Karpychev, Yu. V.,Belyakov,Nelyubina, Yu. V.,Lyssenko,Rakitin
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scheme or table
p. 430 - 436
(2010/07/09)
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- Ketone compounds and compositions for cholesterol management and related uses
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The present invention relates to novel ketone compounds, compositions comprising ketone compounds, and methods useful for treating and preventing cardiovascular diseases, dyslipidemias, dysproteinemias, and glucose metabolism disorders comprising administering a composition comprising a ketone compound. The compounds, compositions, and methods of the invention are also useful for treating and preventing Alzheimer's Disease, Syndrome X, peroxisome proliferator activated receptor-related disorders, septicemia, thrombotic disorders, obesity, pancreatitis, hypertension, renal disease, cancer, inflammation, and impotence. In certain embodiments, the compounds, compositions, and methods of the invention are useful in combination therapy with other therapeutics, such as hypocholesterolemic and hypoglycemic agents.
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- Synthesis of a 10-oxo-bilirubin: Effects of the oxo group on conformation, transhepatic transport, and glucuronidation
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Bilirubin, the yellow pigment of jaundice, is a linear tetrapyrrole with a methylene group at its center, C(10), a position of crucial importance to its conformation and metabolism. The presence of the central methylene group allows the bilirubin to fold into an intramolecularly hydrogen-bonded conformation. This paper describes the first synthesis of a bilirubin analogue with an oxo group at C(10). The change from CH2 to C=O, from sp3 to sp2, is designed to stress the molecule at its hinge and relax its conformation. Such compounds have been suggested as potential oxidative metabolites of bilirubin in vivo. 10-Oxo-mesobilirubin-XIIIα (1) is a red crystalline solid, unlike its parent, mesobilirubin-XIIIα, which is a bright yellow solid. It is surprisingly polar, relative to the parent, yet it does not exhibit a significantly larger bicarbonate/chloroform partition coefficient. Like the parent, 1 appears to adopt an intramolecularly hydrogen-bonded ridge-tile-like conformation. In normal rats, 1 is metabolized to acylglucuronides, which are secreted into bile, but a portion of the administered dose is secreted into bile intact. In mutant rats (Gunn rats) lacking bilirubin glucuronyl transferase, 1 was excreted efficiently in bile in unchanged form, unlike the parent with a methylene group at C(10). Thus, introduction of the oxygen function at C(10) has little effect on hepatic uptake but a dramatic effect on canalicular secretion into bile.
- Chen, Qingqi,Huggins, Michael T.,Lightner, David A.,Norona, Wilma,McDonagh, Antony F.
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p. 9253 - 9264
(2007/10/03)
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- Syntheses, Structures, and Reactivity of Dinuclear Molybdenum-Platinum and Tungsten-Platinum Complexes with Bridging Carbonyl, Sulfur Dioxide, Isonitrile, and Aminocarbyne Ligands and a dppa Backbone (dppa = Ph2PNHPPh2)
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The heterodinuclear μ-carbonyl complexes [(OC)4M(μ-CO)(μ-dppa)Pt(PPh3)] (3a, M = Mo; 3b, M = W) are formed upon the reaction of [(OC)5M(η1-dppa)] (1a, M = Mo; 1b, M = W) with [Pt(C2H4)(PPh3)2]. After addition of p-tosylmethyl isonitrile to 3, the CO bridge is replaced by a bridging isonitrile ligand to afford [(OC)4W(μ-C=NCH2SO 2p-tolyl)(μ-dppa)Pt-(PPh3)] (4a, M = Mo; 4b, M = W). If stronger electron-donating isonitriles such as benzyl or 2,6-xylyl isonitrile are added to 3, fragmentation into mononuclear complexes occurs. Protonation of 4 leads to the μ-aminocarbyne complexes [(OC)4M{μ-CN(H)CH2SO 2p-tolyl}-(μ-dppa)Pt(PPh3)][BF4] (5a, M = Mo; 5b, M = W), which react further with isonitriles to yield the μ-aminocarbyne complexes [(OC)3(RNC)W{μ-CN(H)CH2SO 2p-tolyl}(μ-dppa)Pt-(PPh3)][BF4] 6, (R = 2,6-xylyl, benzyl). Purging a solution of 4a with SO2 yields the complex [(OC)4Mo(μ-SO2)(μ-dppa)Pt(PPh3)], 7a, in which a triphenylphosphine oxide ligand is bound via a hydrogen bridge to the N-H group of the dppa backbone. X-ray diffraction studies performed on 4b and 7a reveal that the μ-CNR and the μ-SO2 ligands bridge the metal centers in an asymmetric manner, the Pt-μ-C or Pt-μ-S distances being significantly shorter than the corresponding W-μ-C or Mo-μ-S distances, respectively.
- Knorr, Michael,Strohmann, Carsten
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p. 248 - 257
(2008/10/08)
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- Synthesis of L-histidine specifically labelled with stable isotopes
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(2'-13C)-, (1'-15N)- and (3'-15N)-L-Histidine were prepared according to a synthetic scheme that allows the 13C or 15N labelling of all carbon and nitrogen positions or any combination of positions.A 1,5-disubstituted imidazole ring was constructed via condensation of tosylmethyl isocyanide with 3-phenylpropenal and subsequent cycloaddition of benzylamine.The imidazole intermediate was converted into 1-benzyl-5-(chloromethyl)-imidazolium chloride which was coupled to a glycine moiety via an enantioselective coupling with the bislactim ether of cyclo-D-valylglycine.Deprotection of the coupling product afforded L-histidine in high optical purity.Syntheses for the isotopically labelled synthons were developed starting from simple, comercially available, highly enriched compounds.The labelled L-histidines were characterized by mass spectrometry and 1H-, 13C- and 15N-NMR spectroscopy.
- Cappon, J. J.,Witters, K. D.,Baart, J.,Verdegem, P. J. E.,Hoek, A. C.,et al.
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p. 318 - 328
(2007/10/02)
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- Substituted alkylamine derivatives
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The substituted alkylamine derivatives represented by formula (I) STR1 wherein R1 represents (a) substituted or unsubstituted C2-6 alkenyl group, (b) substituted or unsubstituted C3-6 cycloalkenyl group, (c) substituted or unsubstituted C2-6 alkynyl group, (d) substituted or unsubstituted aryl group, (e) substituted or unsubstituted heterocyclic group, (f) fused heterocyclic group which may be substituted, or (g) group represented by the formula Ru11 -Ar wherein R11 is a heterocyclic group and Ar is a 5- or 6-membered aromatic ring which may contain a hetero N, O or S atom, and which may be substituted; STR2 represents a 5- or 6-membered aromatic ring which may contain a hetero N, O or S atom, and may be substituted by R7, X and Y are linking groups, R2 is H or lower alkyl, R3 is hydrogen, lower alkyl, lower alkenyl, lower alkynyl or lower cycloalkyl, R4 and R5 are independently hydrogen or halogen atoms, R6 represents (a) substituted or unsubstituted acyclic hydrocarbon group which may be unsaturated, (b) substituted or unsubstituted cycloalkyl group, or (c) substituted or unsubstituted phenyl group, or non-toxic salts thereof. (E)-N-(6-6-dimethyl-2-hepten-4-ynyl)-N-ethyl-3-[4-(3-thienyl)-2-thienyl-methyloxy]benzylamine hydrochloride is a representative example. The substituted alkylamine derivatives are useful as pharmaceuticals, particularly for the treatment and prevention of hypercholesterolemia, hyperlipemia and arteriosclerosis.
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