- Substituent effects of iridium complexes for highly efficient red OLEDs
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This study reports substituent effects of iridium complexes with 1-phenylisoquinoline ligands. The emission spectra and phosphorescence quantum yields of the complexes differ from that of tris(1-phenylisoquinolinato-C 2, N) iridium(in) (Irpiq) depending on the substituents. The maximum emission peak, quantum yield and lifetime of those complexes ranged from 598-635 nm, 0.17-0.32 and 1.07-2.34 μs, respectively. This indicates the nature of the substituents has a significant influence on the kinetics of the excited-state decay. The substituents attached to phenyl ring have an influence on a stability of the HOMO. Furthermore, those substituents have effect on the contribution to a mixing between 3π-π and 3MLCT for the lowest excited states. Some of the complexes display the larger quantum yield than Irpiq, which has the quantum yield of 0.22. The organic light emitting diode (OLED) device based on tris [1-(4-fluoro-5-methylphenyl) isoquinolinato-C2,N]iridium(III) (Ir4F5Mpiq) yielded high external quantum efficiency of 15.5% and a power efficiency of 12.41m W-1 at a luminance of 218 cd m-2. An emission color of the device was close to an NTSC specification with CIE chromaticity characteristics of (0.66, 0.34). The Royal Society of Chemistry 2005.
- Okada, Shinjiro,Okinaka, Keiji,Iwawaki, Hironobu,Furugori, Manabu,Hashimoto, Masashi,Mukaide, Taihei,Kamatani, Jun,Igawa, Satoshi,Tsuboyama, Akira,Takiguchi, Takao,Ueno, Kazunori
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Read Online
- Design, synthesis, and biological evaluation of isoquinolin-1(2H)-one derivates as tankyrase-1/2 inhibitors
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To investigate structure-activity relationships of tankyrase (TNKS) inhibitors, twelve new derivatives of isoquinolin- 1(2H)-one were designed and synthesized, and biological assessments were conducted. Several potent TNKS inhibitors with single- or double-digit nanomolar IC50 values were identified using enzymatic assays. Compound 11c was the most potent compound of this series and inhibited TNKS1 and TNKS2 at an IC50 of 0.009 and 0.003 μM, respectively, and showed an IC50 of 0.029 μM in a DLD-1 SuperTopFlash assay. Molecular docking results showed that compound 11c occupied a unique subpocket and formed a hydrogen bond with Glu1138 of TNKS2, which was not consistent with the patterns of known TNKS inhibitors and thus warrants further research.
- MO, JIANGWEN,PENG, YAN,WANG, YANYAN,WANG, ZHU,YAO, HAIPING
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p. 132 - 137
(2021/05/31)
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- Preparation method of formaldehyde-substituted aza-condensed ring compound
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The invention provides a preparation method of a formaldehyde-substituted aza-condensed ring compound, comprising the following steps: by using an aza-condensed ring lactam compound as a starting material, carrying out halogenation reaction, methylation reaction and methyl oxidation reaction to obtain the formaldehyde-substituted aza-condensed ring compound. According to the preparation method ofthe formaldehyde-substituted aza-condensed ring compound, the whole synthesis route is good in step repeatability, mild in operation condition and high in safety, and large-scale production and industrial popularization are facilitated; post-treatment energy consumption is low, a large amount of toxic wastewater is not generated, no pollution is caused to the environment, the production safety level and the production cost are reduced, application of green and environment-friendly industrial production is facilitated, and wide application prospects are achieved.
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Paragraph 0141-0143
(2020/06/02)
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- Transition-metal-free decarboxylative halogenation of 2-picolinic acids with dihalomethane under oxygen conditions
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A convenient and efficient method for the synthesis of 2-halogen-substituted pyridines is described. The decarboxylative halogenation of 2-picolinic acids with dihalomethane proceeded smoothly via N-chlorocarbene intermediates to afford 2-halogen-substituted pyridines in satisfactory to excellent yields under transition-metal-free conditions. This new type of decarboxylative halogenation is operationally simple and exhibits high functional-group tolerance.
- Zhang, Xitao,Feng, Xiujuan,Zhang, Haixia,Yamamoto, Yoshinori,Bao, Ming
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supporting information
p. 5565 - 5570
(2019/10/22)
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- Site-Selective C–H Functionalization of (Hetero)Arenes via Transient, Non-symmetric Iodanes
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Fosu, Hambira, and colleagues describe the direct C–H functionalization of medicinally relevant arenes or heteroarenes. This strategy is enabled by transient generation of reactive, non-symmetric iodanes from anions and PhI(OAc)2. The site-selective incorporation of Cl, Br, OMs, OTs, and OTf to complex molecules, including within medicines and natural products, can be conducted by the operationally simple procedure included herein. A computational model for predicting site selectivity is also included. The discovery of new medicines is a time- and labor-intensive process that frequently requires over a decade to complete. A major bottleneck is the synthesis of drug candidates, wherein each complex molecule must be prepared individually via a multi-step synthesis, frequently requiring a week of effort per molecule for thousands of candidates. As an alternate strategy, direct, post-synthetic functionalization of a lead candidate could enable this diversification in a single operation. In this article, we describe a new method for direct manipulation of drug-like molecules by incorporation of motifs with either known pharmaceutical value (halides) or that permit subsequent conversion (pseudo-halides) to medicinally relevant analogs. This user-friendly strategy is enabled by combining commercial iodine reagents with salts and acids. We expect this simple method for selective, post-synthetic incorporation of molecular diversity will streamline the discovery of new medicines. A strategy for C–H functionalization of arenes and heteroarenes has been developed to allow site-selective incorporation of various anions, including Cl, Br, OMs, OTs, and OTf. This approach is enabled by in situ generation of reactive, non-symmetric iodanes by combining anions and bench-stable PhI(OAc)2. The utility of this mechanism is demonstrated via para-selective chlorination of medicinally relevant arenes, as well as site-selective C–H chlorination of heteroarenes. Spectroscopic, computational, and competition experiments describe the unique nature, reactivity, and selectivity of these transient, unsymmetrical iodanes.
- Fosu, Stacy C.,Hambira, Chido M.,Chen, Andrew D.,Fuchs, James R.,Nagib, David A.
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supporting information
p. 417 - 428
(2019/02/14)
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- Rh(III)-Catalyzed [4 + 2] Self-Annulation of N-Vinylarylamides
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An efficient rhodium(III)-catalyzed self-annulation of N-vinylarylamide has been developed. This reaction features a simple system and good reactivity with complete regioselectivity. The protocol provides easy access to an aminal incorporated dihydroisoqu
- Sun, Rui,Yang, Xiao,Chen, Xue,Zhang, Chunchun,Zhao, Xiaoyu,Wang, Xin,Zheng, Xueli,Yuan, Maolin,Fu, Haiyan,Li, Ruixiang,Chen, Hua
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supporting information
p. 6755 - 6759
(2018/11/21)
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- Regioselective Chlorination of Quinoline N-Oxides and Isoquinoline N-Oxides Using PPh3/Cl3CCN
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A novel method for the regioselective C2-chlorination of heterocyclic N-oxides has been developed. PPh3/Cl3CCN were used as chlorinating reagents and the desired N-heterocyclic chlorides were obtained smoothly in satisfactory yields. The reactions proceeded in a highly efficient and selective manner across a broad range of substrates demonstrating excellent functional group tolerance. In addition, this chlorination reaction can be used for the modification of N-heterocyclic scaffolds of appealing ligands and pharmaceuticals.
- Qiao, Kai,Wan, Li,Sun, Xiaoning,Zhang, Kai,Zhu, Ning,Li, Xin,Guo, Kai
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p. 1606 - 1611
(2016/04/05)
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- Application of 1,1-ADEQUATE, HMBC, and Density Functional Theory to Determine Regioselectivity in the Halogenation of Pyridine N-Oxides
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The 1,1-ADEQUATE spectrum clearly shows specific two-bond proton to carbon correlations to unequivocally distinguish the major and minor regioisomers of ortho-halogenated pyridines and to aid in assignment of the corresponding proton and carbon chemical shifts. M06-2X/6-31+G(d,p) free energies of the regioisomeric intermediates arising from deprotonation correctly predict the experimentally observed preference and thus can be used to tune the substituent pattern to yield a desired regiochemical outcome.
- Hwang, Tsang-Lin,Bartberger, Michael D.,Chen, Ying
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p. 1956 - 1959
(2016/06/01)
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- Development of a facile and inexpensive route for the preparation of α-halobenzopyridines from α-unsubstituted benzopyridines
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A facile and inexpensive route for the preparation of α-halobenzopyridines from α-unsubstituted benzopyridines via N-methylbenzopyridin-α-ones was developed. α-Unsubstituted benzopyridines were converted easily into the corresponding N-methylbenzopyridin-α-ones, which were halogenated using PPh3-TCICA or PPh3-DBICA without using solvent to give α-halobenzopyridines.
- Sugimoto, Osamu,Iwasaki, Hyuma,Tanji, Ken-Ichi
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p. 1445 - 1454
(2015/07/15)
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- Highly Regioselective Halogenation of Pyridine N -Oxide: Practical Access to 2-Halo-Substituted Pyridines
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A highly efficient and regioselective halogenation reaction of unsymmetrical pyridine N-oxide under mild conditions is described. The methodology provides a practical access to various 2-halo-substituted pyridines, which are pharmaceutically important intermediates.
- Chen, Ying,Huang, Jinkun,Hwang, Tsang-Lin,Chen, Maosheng J.,Tedrow, Jason S.,Farrell, Robert P.,Bio, Matthew M.,Cui, Sheng
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supporting information
p. 2948 - 2951
(2015/06/30)
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- Discovery of a 4-aryloxy-1H-pyrrolo[3,2-c]pyridine and a 1-aryloxyisoquinoline series of TRPA1 antagonists
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A series of TRPA1 antagonists is described having a 4-aryloxy-1H-pyrrolo[3,2-c]pyridine or a 1-aryloxyisoquinoline scaffold. These compounds have high ligand efficiency and favorable physical properties and may thus serve as scaffolds for further optimization.
- Hu, Yun-Jin,St.-Onge, Miguel,Laliberté, Sébastien,Vallée, Frédéric,Jin, Shujuan,Bedard, Leanne,Labrecque, Jean,Albert, Jeffrey S.
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supporting information
p. 3199 - 3203
(2015/02/19)
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- A practical and mild chlorination of fused heterocyclic N-oxides
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Fused azine N-oxides were selectively chlorinated at C2 in moderate to excellent yields, employing Vilsmeier reagent as both the activating agent and the nucleophilic chloride source. Remarkable features of the method include simple operation, mild reaction conditions, a wide substrate scope, and the use of only stoichiometric amount of POCl3. The potential extension of this method to a one-pot oxidation/chlorination sequence that obviates the need for isolation of the N-oxide intermediates is also validated.
- Wang, Dong,Jia, Hailing,Wang, Wuchang,Wang, Zhe
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supporting information
p. 7130 - 7132
(2015/02/02)
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- ALPHA-AMINO BORONIC ACID DERIVATIVES, SELECTIVE IMMUNOPROTEASOME INHIBITORS
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The present invention provides compounds of Formula (I) as inhibitors of LMP7 for the treatment of autoimmune and inflammatory diseases. In formula (I), Rb and Rc are independently selected from one another from H or C1-C6-alkyl; whereby Rb and Rc may be linked to form a 5 or 6 membered-ring containing the oxygen atoms to which they are linked; Q denotes Ar, Het or cycloalkyl; R1 R2 independently from each other denotes H, ORa, Hal, C1-C6-alkyl wherein 1 to 5 H atoms may be independently replaced by OH or Hal; Y denotes CR 3R4, preferably CH2 or C(CH3)2; R 3, R4 independently of one another denote H or C1-C6-alkyl; L denotes L1 or L2 or alkyl; n is an integer selected from 0 to 3; L 1 is Q1-CO-M- wherein Q 1 is Ar or Het, preferably, phenyl, naphthyl or pyridine, optionally substituted with 1 to 5 groups independently selected from ORa, Hal, phenyl, and C1-C6-alkyl wherein 1 to 5 H atoms may be independently replaced by OH or Hal; L2 is Q2-M- wherein Q 2 is a fused bicyclic system containing 1 nitrogen atom and 1 to 3 additional groups independently selected from O, S, N, or CO, and wherein at least one of the rings is aromatic whereby the fused bicyclic system is optionally substituted with 1 to 5 groups independently selected from ORa, Hal, phenyl, and C1-C6-alkyl wherein 1 to 5 H atoms may be independently replaced by OH or Hal; or Q 2 is unsaturated or aromatic 5 membered-ring system containing 1 to 3 heteroatoms selected from N, O, S and CO, and optionally substituted with a phenyl ring or pyridine ring whereby phenyl ring and pyridine ring are optionally substituted with 1 to 4 groups independently selected from ORa, Hal, phenyl, and C1-C6-alkyl wherein 1 to 5 H atoms may be independently replaced by OH or Hal; M is a linear or branched alkylene having 1 to 5 carbon atoms wherein 1 or 2 H atoms may be replaced by OR a or a phenyl ring optionally substituted with 1 to 5 groups independently selected from Hal, ORa, and C1-C6-alkyl optionally substituted with 1 to 5 groups independently selected from OH, and Hal; or M denotes a cycloalkylene having 3 to 7 carbon atoms; or M denotes a thiazolidinyl group; R a is H or C1-C6-alkyl wherein 1 to 5 H atom may be independently replaced by OH or Hal; Ar denotes a 6 membered-aromatic carbocyclic ring optionally fused with another carbocyclic saturated, unsaturated or aromatic ring having 5 to 8 carbon atoms; Het denotes a 5- or 6-membered saturated, unsaturated or aromatic heterocyclic ring having 1 to 3 heteroatoms independently selected from N, N+O-, O, S, SO, and SO 2, and optionally fused with another saturated, unsaturated or aromatic ring having 5 to 8 atoms and optionally containing 1 to 3 heteroatoms selected from N, O, and S; Hal denotes CI, Br, I of F; preferably CI or F.
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Page/Page column 54
(2013/07/05)
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- Phosphonium chloride as a non-volatile chlorinating reagent: Preparation and reaction in no solvent or ionic liquid
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Reaction of triphenylphosphine with trichloroisocyanuric acid in no solvent or an ionic liquid gave the corresponding phosphonium chloride, which can be used as a cheap and safe chlorinating reagent. Conversion of hydroxyheterocycles to chloroheterocycles, carboxylic acids to carboxylic acid chlorides, and primary amides to nitriles were accomplished by using the phosphonium chloride in excellent to good yields.
- Sugimoto, Osamu,Harada, Yukihiro,Tanji, Ken-Ichi
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p. 1583 - 1590
(2013/08/15)
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- Palladium-catalyzed C-H oxidation of isoquinoline N-oxides: Selective alkylation with dialkyl sulfoxides and halogenation with dihalo sulfoxides
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A novel palladium-catalyzed C-H oxidation of isoquinoline N-oxides has been developed for regioselectively synthesizing substituted isoquinolines. The method represents the first example of using dialkyl sulfoxides as the alkyl sources for the construction of 1-alkylated isoquinolines. Moreover, the regioselective halogenation of isoquinoline N-oxides is also successful using dihalo sulfoxides as the halide sources. Copyright
- Yao, Bo,Song, Ren-Jie,Liu, Yan,Xie, Ye-Xiang,Li, Jin-Heng,Wang, Meng-Ke,Tang, Ri-Yuan,Zhang, Xing-Guo,Deng, Chen-Liang
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supporting information; experimental part
p. 1890 - 1896
(2012/09/22)
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- On the mechanism of asymmetric allylation of aldehydes with allyltrichlorosilanes catalyzed by QUINOX, a chiral isoquinoline N-oxide
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Allylation of aromatic aldehydes 1a-m with allyl- and crotyl- trichlorosilanes 2-4, catalyzed by the chiral N-oxide QUINOX (9), has been found to exhibit a significant dependence on the electronics of the aldehyde, with p-(trifluoromethyl)benzaldehyde 1g
- Malkov, Andrei V.,Ramirez-Lopez, Pedro,Biedermannova, Lada,Rulisek, Lubomir,Dufkova, Lenka,Kotora, Martin,Zhu, Fujiang,Kocovsky, Pavel
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p. 5341 - 5348
(2008/12/21)
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- Efficient one-pot transformation of aminoarenes to haloarenes using halodimethylisulfonium halides generated in situ
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Halodimethylsulfonium halide 1, which is readily formed in situ from hydrohaloic acid and DMSO, is a good nucleophilic halide. This activated nucleophilic halide rapidly converts aryldiazonium salt prepared in situ by the same hydrohaloic acid and nitrite ion to aryl chlorides, bromides, or iodides in good yield. The combined action of nitrite ion and hydrohaloic acid in DMSO is required for the direct transformation of aromatic amines, which results in the production of aryl halides within 1 h. Substituted compounds with electron-donating or -withdrawing groups or sterically hindered aromatic amines are also smoothly transformed to the corresponding aromatic halides. The only observed by-product is the deaminated arene (usually 7%). The isolated aryldiazonium salts can also be converted to the corresponding aryl halides using 1. The present method offers a facile, one-step procedure for transforming aminoarenes to haloarenes and lacks the environmental pollutants that usually accompany the Sandmeyer reaction using copper halides.
- Baik, Woonphil,Luan, Wanqiang,Lee, Hyun Joo,Yoon, Cheol Hun,Koo, Sangho,Kim, Byeong Hyo
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p. 213 - 219
(2007/10/03)
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- Reaction of N-fluoropyridinium fluoride with isonitriles: A convenient route to picolinamides
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Reaction of N-fluoropyridinium fluoride generated in situ with a series of isonitriles led to the formation of the corresponding picolinamides in good yields. A similar reaction sequence for quinoline yielded the respective derivatives of 2-quinoline carboxylic acid. The proposed reaction mechanism involves the intermediate formation of a highly reactive carbene species.
- Kiselyov, Alexander S.
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p. 2279 - 2282
(2007/10/03)
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- MICROPOROUS STRUCTURE OF AN ORGANIC METAL COMPLEX
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A porous structure includes an organic metal complex represented by the following general formula (1):M·EL(A,B)3 (1)(where M represents a metal atom; L (A, B) represents a ligand constituted of A and B; and A and B respectively represent cyclic groups which may have or may not have one or more substituents).
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- Discovery of quinazolines as a novel structural class of potent inhibitors of NF-κB activation
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We disclose here a new structural class of low-molecular-weight inhibitors of NF-κB activation that were designed and synthesized by starting from quinazoline derivative 6a. Structure-activity relationship (SAR) studies based on 6a elucidated the structural requirements essential for the inhibitory activity toward NF-κB transcriptional activation, and led to the identification of the 6-amino-4-phenethylaminoquinazoline skeleton as the basic framework. In this series of compounds, 11q, containing the 4-phenoxyphenethyl moiety at the C(4)-position, showed strong inhibitory effects on both NF-κB transcriptional activation and TNF-α production. Furthermore, 11q exhibited an anti-inflammatory effect on carrageenin-induced paw edema in rats.
- Tobe, Masanori,Isobe, Yoshiaki,Tomizawa, Hideyuki,Nagasaki, Takahiro,Takahashi, Hirotada,Fukazawa, Tominaga,Hayashi, Hideya
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p. 383 - 391
(2007/10/03)
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- Structure-activity relationships for pyrido-, imidazo-, pyrazolo-, pyrazino-, and pyrrolophenazinecarboxamides as topoisomerase-targeted anticancer agents
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Heterocyclic phenazinecarboxamides were prepared by condensation of aminoheterocycles and 2-halo-3-nitrobenzoic acids, followed by reductive ring closure and amidation. They showed similar inhibition of paired cell lines that underexpressed topo II or overexpressed P-glycoprotein, indicating a non topo II mechanism of cytotoxicity and indifference to P-glycoprotein mediated multidrug resistance. Compounds with a fused five-membered heterocyclic ring were generally less potent than the pyrido[4,3-a]phenazines. A 4-methoxypyrido[4,3-a]phenazine (IC50s 2.5-26 nM) gave modest (ca. 5 day) growth delays in H69/P xenografts with oral dosing.
- Gamage, Swarna A.,Spicer, Julie A.,Rewcastle, Gordon W.,Milton, John,Sohal, Sukhjit,Dangerfield, Wendy,Mistry, Prakash,Vicker, Nigel,Charlton, Peter A.,Denny, William A.
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p. 740 - 743
(2007/10/03)
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- Base and cation effects on the suzuki cross-coupling of bulky arylboronic acid with halopyridines: Synthesis of pyridylphenols
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Strong base and large size cation have been shown to accelerate the rate and the yield of Suzuki coupling of a sterically bulky boronic acid with halopyridines in DME for the synthesis of pyridylphenols.
- Zhang, Huichang,Kwong, Fuk Yee,Tian, Yuan,Chan, Kin Shing
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p. 6886 - 6890
(2007/10/03)
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- Preparation of substituted 2-chloropyridines
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A process for the preparation of a substituted 2-chloropyridine derivatives of the formula STR1 in which R1, R2, R3 and R4 represent hydrogen or various other radicals, which comprises reacting a pyridine-1-oxide of the formula STR2 with an aromatic carbonyl chloride in the presence of an inert organic solvent and in the presence of an acid acceptor at a temperature between about -20° C. and 200° C.
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- Synthesis and Resolution of 1-(2-Diphenylphosphino-1-naphthyl)isoquinoline; a P-N Chelating Ligand for Asymmetric Catalysis
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A multistep synthesis resulting in a good yield of the title compound has been developed based on the Pd-catalysed coupling of 1-chloroisoquinoline and 2-methoxy-1-naphthylboronic acid (5).The product is converted into the corresponding trifluoromethanesu
- Alcock, Nathaniel W.,Brown, John M.,Hulmes, David I.
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p. 743 - 756
(2007/10/02)
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- Heteroaromatic N-oxide rearrangements. Reinvestigation of 1,3 tosyloxy migration in the reaction of isoquinoline N-oxide with tosyl chloride
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Isoquinoline N-oxide (2) reacts with 18O-enriched tosyl chloride to furnish 18O-labeled 4-tosyloxy-isoquinoline (4), which was assessed for oxygen isotopic enrichment by NMR and mass spectrometry. The 30-45% 18O incorporation at the bridging oxygen is inconsistent with a high level of the intramolecular tight-ion-pair ('sliding') mechanism. A combination of two intramolecular mechanisms is probably operative.
- Maryanoff,Zhang,Reitz,Leo,Jones
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p. 7247 - 7250
(2007/10/02)
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- Molecular yardsticks. Rigid probes to define the spatial dimensions of the benzodiazepine receptor binding site
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A series of rigid planar azadiindoles (8a, 8b, and 8d), benzannelated pyridodiindoles (11a, 11b, and 11d), and indolopyridoimidazoles (11c, 20, and 24) were synthesized from 4-oxo-1,2,3,4-tetrahydro-β-carboline 5 via the Fischer indole cyclization with the appropriate arylhydrazines. These analogues were employed as probes ('molecular yardsticks') to define the spatial dimensions of the lipophilic regions of the benzodiazepine receptor (BzR) binding cleft. Benzannelated indoles 11a-d and indolopyridoimidazoles 20 and 24 were important in establishing an area of negative interaction (S1, see Figure 6, part b) in the binding cleft common to the interactions of both inverse agonists and agonists. Data from this chemical and computer- assisted analysis of the pharmacophore (see Figure 6) indicates that inverse agonists and agonists bind to the same binding region, but the pharmacophoric descriptors required for the two activities are different, in keeping with previous studies with these planar ligands. However, the hydrogen bond donating site H1 and the lipophilic region L1 in the receptor binding site are common interactions experienced by both series of ligands. The low affinities of both indolo[3,2-c]carbazole (3a) and indolo[3,2-b]isoquinoline (3b) for the BzR are consonant with the requirements of a hydrogen bond acceptor interaction at donor site H1 and a hydrogen bond donor interaction at acceptor site A2 for potent inverse agonist activity in the β-carboline series. The hydrochloride salts of 1-aza- 8a (IC50 10.6 nM), 2-aza- 8b (IC50 51.5 nM), and 4-azadiindole 8d (IC50 11.2 nM) were found to be much more soluble in water than the corresponding salt of the parent diindole 2. Moreover, aza analogues 8a and 8b were shown to be partial inverse agonists with proconvulsant potencies comparable to that of the parent diindole 2.
- Martin,Trudell,Arauzo,Allen,LaLoggia,Deng,Schultz,Tan,Bi,Narayanan,Dorn,Koehler,Skolnick,Cook
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p. 4105 - 4117
(2007/10/02)
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- Process for the preparation of substituted 2-chloropyridines
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A new process has been found for the preparation of substituted 2-chloropyridine derivatives of the formula (I) STR1 wherein R1 to R4 have the meanings as defined in the description. The new process is characterized in that pyridine 1-oxides of the formula II STR2 are reacted with a chlorine-containing phosphoric acid derivative from the series of the chlorophosphoric esters and chlorophosphoramides in the presence of an inert organic solvent and in the presence of an acid acceptor at temperatures between -20° C. and 200° C., and the resulting product is separated further, if appropriate. Compound (I) is known as an intermediate product for medicaments (cf.DE-A 2,812,585) or for insecticidel nitromethylene derivatives (cf. EP-A 163,855).
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- PHOTODECARBOXYLATIVE CHLORINATION OF CARBOXYLIC ACIDS VIA THEIR BENZOPHENONE OXIME ESTERS
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Decarboxylative chlorination of various aromatic and aliphatic carboxylic acids is performed successfully by the photolysis of their benzophenone oxime esters in carbon tetrachloride and corresponding chloro compounds are prepared in good yields.High selective generation of the certain radical and efficiency of the stable radical precursor, benzophenone oxime ester, afford much advantage for radical chemistry.
- Hasebe, Masato,Tsuchiya, Takashi
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p. 6287 - 6290
(2007/10/02)
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- Process for production of decahydroisoquinoline
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A process for the production of decahydroisoquinoline is disclosed which comprises hydrogenating isoquinoline or partially hydrogenated isoquinoline in the presence of a ruthenium catalyst at a temperature of 110° C. to 230° C. under a hydrogen pressure of at least 10 kg/cm2 *G.
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- The Mechanism of Thermal Eliminations. Part 21. Rate Data for Pyrolysis of 2-Ethoxyquinoline, 1-and 3-Ethoxyisoquinoline, and 1-Ethoxythiazole: Correlation of Reactivities with ?-Bond Order of the C=N Bond
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We have measured the rates of thermal elimination of ethylene from the title compounds between 587.3 and 722.9 K.The reactivities relative to 2-ethoxypyridine at 650 K are: 3-ethoxyisoquinoline (0.21), 2-ethoxyquinoline (3.13), 1-ethoxyisoquinoline (6.47), 2-ethoxythiazole (63.1).These reactivities parallel the ?-bond order of the C=N bond, though the exceptional reactivity of 2-ethoxythiazole is attributed to additional acceleration through +M electron release from sulphur to nitrogen.This emphasizes the greater relative importance of nucleophilic attack by the nitrogen upon the β-hydrogen atom as compared with the analogous mechanism for pyrolysis of esters.Because of semi-concentrated nature of the reaction, interruption of aromaticity is much less significant than in, for example, electrophilic aromatic substitution.Thus retention of the benzenoid character of the ring not involved in the elimination is not an important rate-determining feature, as shown by the lower reactivity of 3-ethoxyisoquinoline relative to 2- ethoxypyridine.The unimportance of the interruption of aromaticity of the benzenoid ring means that conjugative effects are better relayed to nitrogen in the β-naphthalene-like position (isoquinoline) than in the α-naphthalene-like position (quinoline).This is the reverse of the familiar pattern for reactions of naphthalene-like systems where full charges are involved, and may be an additional factor contributing to the higher reactivity of 1-ethoxyisoquinoline than of 2-ethoxyquinoline, as may also be the -I effect of the benzo substiutent.The conclusions are used to predict elimination rates for alkoxyheterocycles not yet studied.
- Al-Awadi, Nouria,Taylor, Roger
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p. 1589 - 1592
(2007/10/02)
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