- Microwave assisted rapid synthesis of phenoxazines and benzopyridoxazines
-
A facile protocol for the synthesis of phenoxazines and benzopyridoxazines by Smiles rearrangement have been demonstrated in short reaction time under microwave irradiation. The control experiments suggest that a reaction proceeds through Smiles rearrangement followed SNAr ring closure by in situ cascade process. In our present work, both the electron donating and electron withdrawing groups were tolerant and provided a corresponding phenoxazine/benzopyridoxazine in good to moderate yields.
- Anchan, Kavitha,Puttappa, Nagaswarupa H.,Poongavanam, Baburajan,Sarkar, Sujit Kumar
-
p. 635 - 646
(2020/11/27)
-
- Combined KOH/BEt3Catalyst for Selective Deaminative Hydroboration of Aromatic Carboxamides for Construction of Luminophores
-
The selective catalytic C-N bond cleavage of amides into value-added amine products is a desirable but challenging transformation. Molecules containing iminodibenzyl motifs are prevalent in pharmaceutical molecules and functional materials. Here we established a combined KOH/BEt3 catalyst for deaminative hydroboration of acyl-iminodibenzyl derivatives, including nonheterocyclic carboxamides, to the corresponding amines. This novel transition-metal-free methodology was also applied to the construction of Clomipramine and luminophores.
- Li, Jinshan,Wang, Jiali,Yang, Jianguo,Yao, Wubing,Zhong, Aiguo
-
p. 8086 - 8090
(2020/11/03)
-
- Hydride-catalyzed selectively reductive cleavage of unactivated tertiary amides using hydrosilane
-
The first hydride-catalyzed reductive cleavage of various unactivated tertiary amides, including the biologically active aryl-phenazine carboxamides and the challenging non-heterocyclic carbonyl functions, using low-cost hydrosilane as a reducing reagent has been developed. The novel catalyst system exhibits high efficiency and exclusive selectivity, providing the desired amines in useful to excellent yields under mild conditions. Overall, this transition metal-free process may offer a versatile alternative to currently employed expensive reducing reagents, high-pressure hydrogen or metal systems for the selective reductive cleavage of amides.
- Yao, Wubing,Li, Rongrong,Yang, Jianguo,Hao, Feiyue
-
p. 3874 - 3878
(2019/08/07)
-
- A disubstituted amide derivatives decarbonylation hydrogenation green new method (by machine translation)
-
The invention relates to a high efficiency, high selectivity of the disubstituted amide derivatives of decarbonylation hydrogenation reaction green new method. For the first time to the metallic compound triethylborane as catalyst, under mild conditions can be conveniently catalytic N, N - di-aryl substituted amide and its derivative and cheap and easy to obtain organic silicon reagent selective preparation of secondary organic amine product. Compared with the traditional method, the new method generally has the wide substrate universality, functional group compatibility outstanding, simple operation and the like. For the first time in order to realize the organic silicon reagent as reducing agent and amide compounds decarbonylation hydrogenation reaction, is the reduction of amides and derivatives thereof, in particular the organic light-emitting diodes (OLEDs) material unit - diaryl amine compound of the laboratory preparation or industrial production provides a brand-new "green" response strategies. (by machine translation)
- -
-
Paragraph 0054; 0055; 0056; 0057
(2018/02/04)
-
- Characterization of HJ-PI01 as a novel Pim-2 inhibitor that induces apoptosis and autophagic cell death in triple-negative human breast cancer
-
Aim: Pim-2 is a short-lived serine/threonine kinase, which plays a key role in metastasis of breast cancer through persistent activation of STAT3. Although the crystal structure of Pim-2 has been reported, but thus far no specific Pim-2-targeted compounds have been reported. In this study, we identified a novel Pim-2 inhibitor, HJ-PI01, by in silico analysis and experimental validation. Methods: The protein-protein interaction (PPI) network, chemical synthesis, molecular docking, and molecular dynamics (MD) simulations were used to design and discover the new Pim-2 inhibitor HJ-PI01. The anti-tumor effects of HJ-PI01 were evaluated in human breast MDA-MB-231, MDA-MB-468, MDA-MB-436, MCF-7 cells in vitro and in MDA-MB-231 xenograft mice, which were treated with HJ-PI01 (40 mg·kg-1 ·d-1, ig) with or without lienal polypeptide (50 mg·kg-1 ·d-1, ip) for 10 d. The apoptosis/autophage-inducing mechanisms of HJ-PI01 were elucidated using Western blots, immunoblots, flow cytometry, transmission electron microscopy and fluorescence microscopy. Results: Based on the PrePPI network, the potential partners interacting with Pim-2 in regulating apoptosis (160 protein pairs) and autophagy (47 protein pairs) were identified. Based on the structural characteristics of Pim-2, a total of 15 compounds (HJ-PI01 to HJ-P015) were synthesized, which showed moderate or remarkable anti-proliferative potency in the human breast cancer cell lines tested. The most effective compound HJ-PI01 exerted a robust inhibition on MDA-MB-231 cells compared with chlorpromazine and the pan-Pim inhibitor PI003. Molecular dynamics (MD) simulation revealed that HJ-PI01 had a good binding score with Pim-2. Moreover, HJ-PI01 (300 nmol/L) induced death receptor-dependent and mitochondrial apoptosis as well as autophagic death in MDA-MB-231 cells. In MDA-MB-231 xenograft mice, administration of HJ-PI01 remarkably inhibited the tumor growth and induced tumor cell apoptosis in vivo. Co-administration of HJ-PI01 with lienal polypeptide could improve the anti-tumor activity of HJ-PI01 and reduce its toxicity. Conclusion: The newly synthesized compound, HJ-PI01, can induce death receptor/mitochondrial apoptosis and autophagic cell death by targeting Pim-2 in human breast cancer cells in vitro and in vivo.
- Zhao, Yu-Qian,Yin, Yi-Qiong,Liu, Jie,Wang, Gui-Hua,Huang, Jian,Zhu, Ling-Juan,Wang, Jin-Hui
-
p. 1237 - 1250
(2016/09/09)
-
- Transition-metal-free intramolecular N-arylations
-
N-Substituted phenoxazines and related aza analogs have been prepared from N-acetylated aryloxy anilides by transition-metal-free, base-catalyzed cyclization reactions. In the presence of a mixture of 10 mol % of N,N′-dimethylethylenediamine (DMEDA) and 2 equiv of K2CO 3 in toluene at 135 °C the products are obtained in high yields.
- Thome, Isabelle,Bolm, Carsten
-
scheme or table
p. 1892 - 1895
(2012/05/20)
-
- NOVEL AROMATIC COMPOUND AND POLYARYLENE COPOLYMER HAVING NITROGEN-CONTAINING HETEROCYCLE INCLUDING SULFONIC ACID GROUP IN SIDE CHAIN
-
Provided is a solid polymer electrolyte having increased heat resistance and high proton conductivity and a proton conductive membrane composed of the electrolyte. Also provided is a copolymer having a sulfonic acid group. The copolymer includes a repeating unit represented by Formula (1): (in the formula, Y denotes at least one kind of structure selected from the group consisting of —CO—, —SO2—, —SO—, —CONH—, —COO—, —(CF2)l— (l is an integer of 1 to 10), and —C(CF3)2—; W denotes at least one kind of structure selected from the group consisting of a direct bond, —CO—, —SO2—, —SO—, —CONH—, —COO—, —(CF2)l— (l is an integer of 1 to 10), —C(CF3)2—, —O—, and —S—; Z denotes a direct bond or at least one kind of structure selected from the group consisting of —(CH2)l—(l is an integer of 1 to 10), —C(CH3)2—, —O—, —S—, —CO—, and —SO2—; R30 denotes a nitrogen-containing aromatic ring having a substituent represented by —SO3H, —O(CH2)hSO3H, or —O(CF2)hSO3H (h is an integer of 1 to 12); p is an integer of 0 to 10; q is an integer of 0 to 10; r is an integer of 1 to 5; and k is an integer of 0 to 4).
- -
-
-
- Heterocyclization of N-propenyl-substituted phenothiazines and phenoxazines using electrophiles in an anhydrous medium
-
10-Propenylphenothiazine reacts with a catalytic amount of BF 3·Et2O in dry ethyl acetate via intramolecular heterocyclization of an intermediate dimeric cation to give mainly 1-ethyl-2-methyl-3-(phenothiazin-10-yl)-2,3-dihydro-1H-pyrido[3,2,1-k,l] phenothiazine and a minor product through fission of phenothiazine which is 1-ethyl-2-methyl-1H-pyrido[3,2,1-k,l]phenothiazine. Under similar conditions 10-propenylphenoxazine gave an oligomer (degree of polymerization 4.4) and the minor product 1-ethyl-2-methyl-1H-pyrido[3,2,1-k,l]phenoxazine likely formed similarly to the phenothiazine analog from the corresponding product of intramolecular heterocyclization (the latter not being observed in the reaction mixture).
- Sirotkina,Khlebnikov,Napilkova
-
experimental part
p. 1505 - 1509
(2009/07/04)
-
- Substituted quinobenzoxazine analogs
-
The present invention relates to quinobenzoxazines analogs having the general formula: and pharmaceutically acceptable salts, esters and prodrugs thereof; wherein A, U, V, W, X and Z are substituents. The present invention also relates to methods for using such compounds.
- -
-
-
- Novel derivatives and analogues of galanthamin
-
New compounds of general formula I 1
- -
-
-
- Piperadinyl-substituted pyridylalkane, alkene and alkine carboxamides
-
The invention relates to new piperidinyl-substituted pyridyl carboxamides of the general formula (I), wherein the structure element E has meanings (E1) or (E2) and whereby the heterocyclic ring can optionally have a double bond. These substances have especially high cytostatic activities and pronounced immunosuppressive properties which make them suitable for therapeutic treatment in broad tumor spectrum.
- -
-
-
- Polyadducts produced from nonlinear-optically active copolymers and polymerizable nonlinear-optically active monomers
-
The present invention relates to nonlinear-optically active copolymers which are composed of a chromophore acrylate, a glycidyl-functional acrylate, and a further acrylate unit, and to polyadducts produced from them by crosslinking with a carboxyl-functional polyester. The nonlinear-optical copolymers of the present invention, and the polyadducts prepared from them, possess an orientation stability in the crosslinked state, and a thermal stability, which makes them highly suitable for producing electrooptical and photonic components.
- -
-
-
- Cyclic di[(o-polyethyleneglycoxy)phenyl]amine: New members in the crown ether family
-
The synthesis of cyclic ethers based on polyethyleneglycol chains grafted on di(o-hydroxyphenyl)amine is described. The starting diarylamine is obtained from a melted salt procedure and coupled to the tosylated tri-, tetra- and pentaethyleneglycol. The X-ray crystal structure of the tetraethyleneglycol derivative was determined. For the triethyleneglycol compound, alkylation of the nitrogen atom with 5-bromomethyl-5'-methyl-2,2'- bipyridine (excess or 1 equiv.) led either to the quaternary ammonium salt or to the tertiary amine derivatives, respectively. The latter reacted with [Re(CO)5Cl] to give the corresponding Re(I) complex in a facial configuration. (C) 2000 Elsevier Science Ltd.
- Charbonnière, Lo?c J.,Ziessel, Raymond F.
-
p. 2373 - 2376
(2007/10/03)
-
- N-Hetarylethylenes. XII. Influence of the Substituent at the Double Bond and the Nature of the Heterocycle on the Acid Hydrolysis of N-Alkenyl Derivatives of Phenoxazine, Phenothiazine, and Carbazole
-
The kinetics of acid hydrolysis of N-vinylphenothiazine, N-vinylphenoxazine, N-isopropenylcarbazole, N-isopropenylphenoxazine, N-(1-phenylvinyl)phenothiazine, and N-(1-phenylvinyl)phenoxazine in 60% aqueous dioxane have been studied. The activation parameters and kinetic isotope effects (kH/kD = 3.1-5.2) indicate that the hydrolysis follows ASE2 mechanism with proton transfer from the medium to substrate in the rate-determining stage. The results are compared with the previous data for N-alkenyl derivatives of carbazole, phenothiazine, and phenoxazine. The existence of isokinetic relationship in the coordinates In k (313 K) - In k (334 K) provides an additional evidence for the similarity of the mechanisms of hydrolysis of these compounds. 10-Phenothiazinyl substituent exerts the strongest activating effect on the double bond. In the series of compounds with the same substituents, the rate of hydrolysis increases in going from cis to trans and then to geminal arrangement of the substituents at the double bond.
- Anfinogenov,Okhtemenko,Khlebnikov,Filimonov
-
p. 1027 - 1032
(2007/10/03)
-
- Studies on Intramolecular NH-Bridging in Aromatic Compounds.
-
A study was made of the use of calcium oxide as a catalyst at a temperature of 400 - 700 deg for the dehydrocyclization of four primary arylamines: 2-aminobiphenyl, 1-aminotriphenylene (5c), 2-phenoxyaniline, and N-(2-aminophenyl)pyrrole.Maximal yields of cyclized products isolated were 53percent (carbazole), 52percent (4H-naphthocarbazole), 18percent (phenoxazine), and 0percent, respectively.Comparison is made with reported cyclizations of the corresponding nitro and azido starting materials.In one case, treatment of 1-nitrotriphenylene with triethyl phosphite produced mainly diethyl N-(1-triphenylenyl)phosphoramidate (51percent).Mono- and hemihydrochlorides of 5c are described.A mechanism for the catalyzed dehydrocyclization is proposed.
- Horaguchi, Takaaki,Klemm, L. H.,Norris, Eric S.
-
p. 797 - 802
(2007/10/03)
-
- Regiospecific Lithiation of Phenoxazine Ortho to the Oxygen Atom. Synthesis of 4-Mono- and 4,6-Disubstituted Phenoxazine Derivatives
-
Under appropriate conditions, phenoxazine bearing a sterically demanding, bulky N-substituent (e.g., α-methylbenzyl or tert-butyldimethylsilyl) undergoes lithiation at C-4 or at C-4 and C-6 with n-butyllithium in THF solution.The lithiated species react with a variety of electrophilic reagents and upon subsequent N-deprotection provide access to 4-mono- or 4,6-disubstituted phenoxazines.This process is of particular synthetic utility (36-54percent yields) when the N-substituent is tert-butyldimethylsilyl.
- Antonio, Yulia,Barrera, Patricia,Contreras, Olga,Franco, Fidencio,Galeazzi, Edvige,et al.
-
p. 2159 - 2165
(2007/10/02)
-
- PREPARATIVE ELECROCHEMICAL LIBERATION OF ARENES AND HETEROCYCLES FROM THEIR RESPECTIVE IRONCYCLOPENTADIENYL COMPLEXES
-
Electrolysis of arene and heterocycle cyclopentadienyliron hexafluorophosphates led to the liberation of arenes or heterocycles in 69-90percent yield.The procedure described gives yields comparable with or superior to the yields obtained from pyrolytic sublimation used previously.
- Sutherland, Ronald G.,Abd-El-Aziz, Alaa S.,Piorko, Adam,Baranski, Andrzej S.,Lee, Choi Chuck
-
p. 189 - 196
(2007/10/02)
-
- N-HETEROARYLETHYLENES. IV. THE EFFECT OF THE NATURE OF THE HETEROCYCLE ON THE REACTIVITY OF cis- AND trans-N-PROPENYL-SUBSTITUTED PHENOXAZINE, PHENOTHIAZINE, AND CARBAZOLE IN ACID HYDROLYSIS
-
The kinetics of the acid hydrolysis of cis- and trans-N-propenylphenoxazines in 60percent aqueous dioxane were studied.The kinetic isotope effects, the first orders of the reaction with respect to the catalyst and the substrate, and the negative values of the entropy of activation are consistent with proton transfer from the medium to the substrate in the controlling stage.The difference in the reactivity of the cis and trans isomers is determined to a significant degree by the entropy factor.The effect of the heterocyclic fragment of the molecule on the hydrolysis rate was established.For the cis isomers the reactivity decreases in the following order: 10-Propenylphenothiazine > 10-propenylphenoxazine > 10-propenylphenothiazine S-oxide.For the trans isomers it decreases in the order: 10-Propenylphenothiazine > 10-propenylphenoxazine > 9-propenylcarbazole.
- Khlebnikov, A. I.,Anfinogenov, V. A.,Filimonov, V. D.,Sokolova, I. V.
-
p. 1396 - 1401
(2007/10/02)
-
- Molecular Rearrangement. XXI. Photolysis and Thermolysis of Hydroxylamine Derivatives
-
Photolysis of N-phenylhydroxylamine for 10 h at 0 deg C in acetone or cyclohexane solution gives o- and p-aminophenol, azobenzene, azoxybenzene and aniline.On the other hand, on thermolysis in a sealed tube, phenoxazine, ammonia and water are obtained in addition to the previous products.Thermolysis of N-hydroxyphthalimide affords hydroxylation of nitrobenzene and/or naphthalene when supplied as solvents.Moreover, phthalimidation of naphthalene has also been observed mainly in the β-position.From these results a free radical mechanism has been postulated to take place through the initial homolysis of the N-O bond.
- Fahmy, A. M.,Aly, M. M.,Badr, M. Z. A.,Abd El-Gawad, A. M.
-
-
- Molecular Rearrangements. XXVIII. Thermolysis and Photolysis of Some Hydroxamic Acid Derivatives
-
Thermolysis and photolysis of benzohydroxamic acid and some of its derivatives have been investigated.Thermolysis of benzohydroxamic acid (BHA) either by heating in air or in a sealed tube gives NH3, H2O, CO, benzil, aniline, o- and p-aminophenols, phenoxazine, benzanilide, and benzoic acid.Whereas, thermolysis of N-(benzyloxy)benzamide (BBA) affords toluene, benzaldehyde, bibenzyl, stilbene, phenanthrene, acridine, and o- and p-aminodiphenylmethane in addition to the previous products.Analogous products were also obtained on pyrolysis of phenylacetohydroxamic acid.Photolysis of BHA and BBA in acetonitrile gives similar results to those of pyrolysis.A free-radical mechanism involving homolysis at different sites was postulated to account for the formation of such products.
- Badr, M. Z. A.,Fahmy, A. M.,Mahgoub, S. A.,Aly, M. M.
-
p. 2629 - 2634
(2007/10/02)
-
- Reaction of o-Aminophenol and p-Benzoquinone in Acetic Acid
-
The reaction of o-aminophenol and p-benzoquinone in acetic acid yields phenoxazinones 1, 5 and 6, phenoxazine 7, triphenodioxazine 2, ditriphenodioxazine 3 and the phenoxazinonyltriphenodioxazine 4.
- Bolognese, Adele,Scherillo, Giulia,Schaefer, Wolfram
-
p. 1003 - 1006
(2007/10/02)
-
- ARENE COMPLEXES OF TRANSITION METALS IN REACTIONS WITH NUCLEOPHILIC REAGENTS. XI. SYNTHESIS OF HETEROCYCLIC COMPOUNDS BY NUCLEOPHILIC SUBSTITUTION OF CHLORINE ATOMS IN η6-o-DICHLOROBENZENECHROMIUM TRICARBONYL
-
A method was developed for the synthesis of dibenzo-1,4-dioxin, phenoxazine, and phenoxathiin and also their chromium tricarbonyl complexes by the reaction of η6-o-dichlorobenzenechromium tricarbonyl with the alkali-metal salts of pyrocatechol, o-aminophenol, and o-mercaptophenol in HMPTA.The composition of the reaction products and the yield of the heterocyclic compounds depend significantly on the nature of the solvent, the nucleophile, the condensing agent, and the reaction conditions.
- Litvak, V. V.,Goryunov, L. I.,Shteingarts, V. D.
-
p. 138 - 144
(2007/10/02)
-
- Zinc chloride complex compounds
-
Zinc chloride complex compounds to which the structure of the general formula (1) STR1 can be assigned, in which the individual radicals in the formula have the following meanings: Rhu 1 is a hydrogen atom or an optionally substituted lower alkyl group; R2 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted phenyl radical; R3 is a hydrogen atom or an optionally substituted lower alkyl group; R4 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted phenyl radical; R5 is a hydrogen atom or a halogen atom or a lower alkyl group or a lower alkoxy group, or R1 and R5 together form the o-phenylene radical; R6 is a hydrogen atom or a halogen atom or a lower alkyl group or a lower alkoxy group; Z is a hydrogen atom or a halogen atom or a lower alkyl group or a cyano, carboxylic acid, carbamoyl or sulfamoyl group or a carbamoyl or sulfamoyl group which is monosubstituted or disubstituted by lower alkyl, or a trifluoromethyl or lower carbalkoxy group, a lower alkoxy group which can be substituted by cyano, an acyloxy group, an acylamino group, a lower alkylamino group or a lower dialkylamino group. They are prepared by reacting a nitroso compound of the formula (2) STR2 in which R3, R4, R6 and Z have the meanings mentioned above, with an m-aminophenol of the formula (3) STR3 in which R1, R2 and R5 have the meanings mentioned above, in the presence of zinc chloride and in the absence of a base. The zinc chloride complex compounds of the formula (1) can be converted by eliminating the radical Z in the formula or by removing, by oxidative means, this radical Z, in the formula, which is in the ortho-position in relation to the nitrogen atom, or the other hydrogen atom which is in the ortho-position, into the phenoxazine dyestuffs of the formula (4) STR4 in which R1, R2, R3, R4, R5 and R6 have the meanings mentioned above and Z1 denotes a halogen atom, a lower alkyl group, a cyano, carboxylic acid, carbamoyl or sulfamoyl group, a carbamoyl or sulfamoyl group which is monosubstituted or disubstituted by lower alkyl, or a trifluoromethyl or lower carbalkoxy group or a hydrogen atom and X(-) represents and anion.
- -
-
-
- Synthesis and Some Heterocyclic Systems from Nucleophilic Substitution Reactions with η6-o-Dichlorobenzene-η5-cyclopentadienyliron Hexafluorophosphate
-
A method for the synthesis of heterocyclic systems related to 9,10-dihydroanthracene with two hetero-atoms at the 9,10-positions is described.It involves the nucleophilic substitution reaction of η6-o-dichlorobenzene-η5-cyclopentadienyliron hexafluorophosphate with two nucleophilic groups (OH, SH and/or NH2) located in the 1,2-positions of a benzene ring to give a cyclopentadienyliron complexed heterocycle.Upon pyrolytic sublimation of the complex, the free heterocyclic compound is then obtained.
- Sutherland, Ronald G.,Piorko, Adam,Gill, Udai S.,Lee, Choi Chuck
-
p. 801 - 803
(2007/10/02)
-
